Reverse water-gas shift reaction method with metalloid promoted supported catalysts; metalloid promoted supported co2 conversion catalysts

Abstract

The present disclosure relates generally to supported CO2 conversion catalyst comprising: a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; at least one of cobalt, nickel, ruthenium, and rhodium, present in an amount in the range of 0.05 to 16 wt% of the catalyst, based on the total weight of the catalyst; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst.

Description

REVERSE WATER-GAS SHIFT REACTION METHOD WITH METALLOID PROMOTED SUPPORTED CATALYSTS; METALLOID PROMOTED SUPPORTED CO2CONVERSION CATALYSTSCROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application claims the benefit of priority of European Patent Application no. 24222575.3, filed December 20, 2024, which is hereby incorporated herein by reference in its entirety.1. Field

[0002] The present disclosure relates generally to CO2conversion catalysts, methods of making the same, and methods for performing reverse water-gas shift reactions.2. Technical Background

[0003] The reverse water-gas shift reaction (rWGS) is an advantageous route to obtain carbon monoxide from carbon dioxide for further chemical processing. The rWGS converts carbon dioxide and hydrogen to carbon monoxide and water, as shown in Equation (1).Eq. (1)This can be used, for example, to modify the CO:H2ratio of a gas mixture for further processing. The carbon monoxide and hydrogen so formed is a valuable feedstock for a number of chemical processes, for example, the well-known Fischer-Tropsch process, shown in Equation (2).Eq. (2)

[0004] However, the rWGS reaction is not favored in all circumstances. For example, a competing reaction is the Sabatier reaction (Equation (3)), which decreases carbon monoxide yield in favor of methane production.Eq. (3)The strongly exothermic Sabatier reaction is thermodynamically favored over the endothermic rWGS reaction at lower reaction temperatures. As such, minimizing the methanation during rWGS, especially at low temperatures, can become a significant challenge.

[0005] Similarly, the carbon monoxide product from rWGS can be hydrogenated to methane, as shown in Equation (4).Eq. (4)Hydrogenation of carbon monoxide to methane is also an exothermic reaction, so it too is favored at lower temperatures. The stoichiometry of the reaction requires at least a 3:1 ratio of hydrogen to carbon monoxide. This means that performing the rWGS reaction with alarge excess of hydrogen to drive the equilibrium toward carbon monoxide (see Equation (1)) is not always ideal because it runs the risk of hydrogenating the carbon monoxide product to form methane.

[0006] Coupled with equations (3) and (4), further undesirable side reactions can occur. These side reactions can form undesirable carbon deposits on the surface of catalysts used to promote rWGS. Examples of these carbon-producing side reactions are shown in Equations (5), (6), and (7). All three of these reactions are endothermic and are favored at higher temperatures, just like the rWGS reaction.Eq. (5)Eq. (6)Eq. (7)Accordingly, because the carbon-producing side reactions (Equations (5)-(7)) are also endothermic and are favored at higher temperatures, operation at higher temperatures to favor the desired carbon monoxide product can severely impact catalyst lifetime through the deposition of carbon.

[0007] Given the multiple reactions and competing thermodynamics at play, there remains a need in the art for new CO2conversion catalysts and processes.SUMMARY

[0008] In one aspect, the present disclosure provides for a supported CO2conversion catalyst comprising: a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; at least one of cobalt, nickel, ruthenium, and rhodium, present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst.

[0009] In another aspect, the present disclosure provides for a method of making the catalyst as described herein, the method comprising: providing a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, asilicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; contacting the support with one or more liquids each comprising one or more cobalt- containing, nickel-containing, ruthenium-containing, or rhodium-containing compounds and / or one or more tellurium-containing, bismuth-containing, tin- containing, antimony-containing, germanium-containing, selenium-containing, arsenic-containing, boron-containing compounds, indium-containing compounds, or silicon-containing compounds dispersed in a solvent(s); allowing the solvent(s) to evaporate to provide a catalyst precursor; and

[0010] calcining the catalyst precursor. In another aspect, the present disclosure provides for a catalyst as described herein made by the method as described herein.

[0011] In another aspect, the present disclosure provides a method for performing a reverse water-gas shift reaction, the method comprising contacting at a temperature in the range of 200-700 °C a catalyst as described herein with a feed stream comprising CO2and H2, to provide a product stream comprising CO and H2, the product stream having a lower concentration of CO2and a higher concentration of CO than the feed stream.BRIEF DESCRIPTION OF FIGURES

[0012] The accompanying drawings are included to provide a further understanding of the methods of the disclosure, and are incorporated in and constitute a part of this specification. The drawings are not necessarily to scale, and sizes of various elements may be distorted for clarity. The drawings illustrate one or more embodiment(s) of the disclosure and together with the description serve to explain the principles and operation of the disclosure.

[0013] FIG. 1 is a schematic of the reverse water-gas shift reaction as described herein.

[0014] FIG. 2A is a High angle annular darkfield scanning transmission electron microscopy and energy dispersive X-ray elemental mapping (HAADF-STEM EDX) micrographs of a Co / TiO2catalyst.

[0015] FIG. 2B is a HAADF-STEM EDX micrographs of a CoTe / TiO2catalyst, as described herein.

[0016] FIG. 2C is a HAADF-STEM EDX micrographs of a Ni / TiO2catalyst.

[0017] FIG. 2D is a HAADF-STEM EDX micrographs of a NiTe / TiO2catalyst, as described herein.

[0018] FIG. 3 are Powder X-Ray Diffraction (PXRD) diffractograms of Co / TiO2, Ni / TiO2, CoTe / TiO2, and NiTe / TiO2catalysts as described herein. Marked reflexes originate from the metal and metal telluride nanoparticles. All other reflexes come from the TiO2P25 support.

[0019] FIG. 4A is the Co K edge X-Ray Absorption Spectroscopy (XAS) spectra of Co / TiO2and CoTe / TiO2catalysts as described herein in their calcined and reduced states.

[0020] FIG. 4B is the first derivative spectra of the XAS spectra of Co / TiO2and CoTe / TiO2catalysts as described herein in their calcined and reduced states.

[0021] FIG. 4C is the R-space spectra of the XAS spectra of Co / TiO2and CoTe / TiO2catalysts as described herein in their calcined and reduced states.

[0022] FIG. 4D is the Ni K edge XAS spectra of Ni / TiO2and NiTe / TiO2catalysts as described herein in their calcined and reduced states.

[0023] FIG. 4E is the first derivative spectra of the XAS spectra of Ni / TiO2and NiTe / TiO2catalysts as described herein in their calcined and reduced states.

[0024] FIG. 4F is the R-space spectra of the XAS spectra of Ni / TiO2and NiTe / TiO2catalysts as described herein in their calcined and reduced states.

[0025] FIG. 5A is the overlaid XAS spectra of pristine and spent CoTe / TiO2catalysts as described herein. Reference spectra for Co(0) (bottom) and Co(ll) (top) are provided.

[0026] FIG. 5B is the first derivate spectra of the overlaid XAS spectra of pristine and spent CoTe / TiO2catalysts as described herein. Reference spectra for Co(0) (bottom) and Co(ll) (top) are provided.

[0027] FIG. 6A is a graph of the CO2conversion as a function of temperature shown for CoTe / TiO2and NiTe / TiO2catalysts as described herein with the dotted line marking the equilibrium conversion for rWGS.

[0028] FIG. 6B is a graph of the product selectivity and conversion of a CoTe / TiO2catalyst as described herein, a NiTe / TiO2catalyst as described herein, and their monometallic variants at 450 °C and 40 bar.

[0029] FIG. 6C is a graph of the stability date of a CoTe / TiO2catalyst as described herein at 400 °C and 40 bar over 150 h time on stream.

[0030] FIG. 6D is a graph of the stability date of a NiTe / TiO2catalyst as described herein at 400 °C and 40 bar over 150 h time on stream.

[0031] FIG. 7A is a graph of the CO2conversion as a function of temperature shown for CoTe / TiO2, NiTe / TiO2, RuTe / TiO2, and RhTe / TiO2catalysts as described herein with the dotted line marking the equilibrium conversion for rWGS.

[0032] FIG. 7B is a graph of the CO selectivity as a function of temperature shown for CoTe / TiO2, NiTe / TiO2, RuTe / TiO2, and RhTe / TiO2catalysts as described herein with dashed lines representing monometallic catalysts..

[0033] FIG. 7C is a graph comparing the CO selectivity and CO2conversion of CoTe / TiO2, NiTe / TiO2, RuTe / TiO2, and RhTe / TiO2catalysts as described versus monometallic catalysts under rWGS conditions at 450 °C and 40 bar.DETAILED DESCRIPTION

[0034] As discussed above, the reverse gas-water shift reaction reacts carbon dioxide with hydrogen to form carbon monoxide and water, and can be useful in providing a feedstock containing carbon monoxide and hydrogen -- often called “synthesis gas” -- for use in processes such as the Fischer-Tropsch process. However, the Sabatier reaction, carbon monoxide methanation, and carbon-producing side reactions can interfere with the rWGS reaction. The Sabatier reaction and CO methanation are exothermic and favored at lower temperatures, while the rWGS and carbon-producing side reactions are endothermic and favored at higher temperatures. Accordingly, there remains a need for CO2conversion catalysts that can provide good performance in spite of these complicating factors. Here, the present inventors have provided supported CO2conversion catalysts that include a metal oxide support, at least one of cobalt, nickel, ruthenium, and rhodium, and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon that can meet the requirements necessary for a commercially-useful rWGS process.

[0035] In one aspect, the present disclosure provides a supported CO2conversion catalyst including a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support including a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; at least one of cobalt, nickel ruthenium, and rhodium, present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon present in an amount in the range of 0.5 to 20 wt% of the catalyst, based on the total weight of the catalyst.

[0036] As described above, the CO2conversion catalysts of the present disclosure are supported catalysts. In various embodiments as otherwise described herein, the supportmakes up at least 70 wt%, e.g., at least 75 wt%, or 80 wt%, or 85 wt%, or 90 wt% of the catalyst on an oxide basis.

[0037] In various embodiments as otherwise described herein, the support is a cerium oxide support. As used herein, a "cerium oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt% cerium oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the cerium oxide support includes at least 60 wt% cerium oxide, e.g., at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide. In some such embodiments, at least a surface layer of the cerium oxide support includes at least 90 wt% cerium oxide. For example, in some embodiments, at least a surface layer of the cerium oxide support includes at least 95 wt% cerium oxide or at least 98 wt% cerium oxide. In various examples, the cerium oxide support contains cerium oxide substantially throughout, e.g., at least 50 wt% of the cerium oxide support is cerium oxide on an oxide basis. For example, in various embodiments, the cerium oxide support includes at least 60 wt% cerium oxide, e.g., at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide. In various embodiments, the cerium oxide support includes at least 90 wt% cerium oxide, e.g., at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide. In some embodiments, the cerium oxide support may further include additional metals or metal oxides.

[0038] In various embodiments as otherwise described herein, the support is a titanium oxide support. As used herein, a "titanium oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt% titanium oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the titanium oxide support includes at least 60 wt% titanium oxide, e.g., at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide. In some such embodiments, at least a surface layer of the titanium oxide support includes at least 90 wt% titanium oxide. For example, in some embodiments, at least a surface layer of the titanium oxide support includes at least 95 wt% titanium oxide or at least 98 wt% titanium oxide. In various examples, the titanium oxide support contains titanium oxide substantially throughout, e.g., at least 50 wt% of the titanium oxide support is titanium oxide on an oxide basis. For example, in various embodiments, the titanium oxide support includes at least 60 wt% titanium oxide, e.g., at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide. In various embodiments, the titanium oxide support includes at least 90 wt% titanium oxide, e.g., at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide. In some embodiments, the titanium oxide support may further include additional metals or metal oxides.

[0039] In various embodiments as otherwise described herein, the support is an aluminum oxide support. As used herein, an "aluminum oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt% aluminum oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the aluminum oxide support includes at least 60 wt% aluminum oxide, e.g., at least 70 wt% aluminum oxide, or at least 80 wt% aluminum oxide. In some such embodiments, at least a surface layer of the aluminum oxide support includes at least 90 wt% aluminum oxide. For example, in some embodiments, at least a surface layer of the aluminum oxide support includes at least 95 wt% aluminum oxide or at least 98 wt% aluminum oxide. In various examples, the aluminum oxide support contains aluminum oxide substantially throughout, e.g., at least 50 wt% of the aluminum oxide support is aluminum oxide on an oxide basis. For example, in various embodiments, the aluminum oxide support includes at least 60 wt% aluminum oxide, e.g., at least 70 wt% aluminum oxide, or at least 80 wt% aluminum oxide. In various embodiments, the aluminum oxide support includes at least 90 wt% aluminum oxide, e.g., at least 95 wt% aluminum oxide, or at least 98 wt% aluminum oxide. In some embodiments, the aluminum oxide support may further include additional metals or metal oxides.

[0040] In various embodiments as otherwise described herein, the support is a zirconium oxide support. As used herein, a "zirconium oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt% zirconium oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the zirconium oxide support includes at least 60 wt% zirconium oxide, e.g., at least 70 wt% zirconium oxide, or at least 80 wt% zirconium oxide. In some such embodiments, at least a surface layer of the zirconium oxide support includes at least 90 wt% zirconium oxide. For example, in some embodiments, at least a surface layer of the zirconium oxide support includes at least 95 wt% zirconium oxide or at least 98 wt% zirconium oxide. In various examples, the zirconium oxide support contains zirconium oxide substantially throughout, e.g., at least 50 wt% of the zirconium oxide support is zirconium oxide on an oxide basis. For example, in various embodiments, the zirconium oxide support includes at least 60 wt% zirconium oxide, e.g., at least 70 wt% zirconium oxide, or at least 80 wt% zirconium oxide. In various embodiments, the zirconium oxide support includes at least 90 wt% zirconium oxide, e.g., at least 95 wt% zirconium oxide, or at least 98 wt% zirconium oxide. In some embodiments, the zirconium oxide support may further include additional metals or metal oxides.

[0041] In various embodiments as otherwise described herein, the support is a zinc oxide support. As used herein, a "zinc oxide” support is a support that presents at least asurface layer (e.g., 50 microns in thickness) that is at least 50 wt% zinc oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the zinc oxide support includes at least 60 wt% zinc oxide, e.g., at least 70 wt% zinc oxide, or at least 80 wt% zinc oxide. In some such embodiments, at least a surface layer of the zinc oxide support includes at least 90 wt% zinc oxide. For example, in some embodiments, at least a surface layer of the zinc oxide support includes at least 95 wt% zinc oxide or at least 98 wt% zinc oxide. In various examples, the zinc oxide support contains zinc oxide substantially throughout, e.g., at least 50 wt% of the zinc oxide support is zinc oxide on an oxide basis. For example, in various embodiments, the zinc oxide support includes at least 60 wt% zinc oxide, e.g., at least 70 wt% zinc oxide, or at least 80 wt% zinc oxide. In various embodiments, the zinc oxide support includes at least 90 wt% zinc oxide, e.g., at least 95 wt% zinc oxide, or at least 98 wt% zinc oxide. In some embodiments, the zinc oxide support may further include additional metals or metal oxides.

[0042] In various embodiments as otherwise described herein, the support is a silicon oxide support. As used herein, a "silicon oxide” support is a support that presents at least a surface layer (e.g., 50 microns in thickness) that is at least 50 wt% silicon oxide, on an oxide basis. In various embodiments of the disclosure as described herein, at least a surface layer of the silicon oxide support includes at least 60 wt% silicon oxide, e.g., at least 70 wt% silicon oxide, or at least 80 wt% silicon oxide. In some such embodiments, at least a surface layer of the silicon oxide support includes at least 90 wt% silicon oxide. For example, in some embodiments, at least a surface layer of the silicon oxide support includes at least 95 wt% silicon oxide or at least 98 wt% silicon oxide. In various examples, the silicon oxide support contains silicon oxide substantially throughout, e.g., at least 50 wt% of the silicon oxide support is silicon oxide on an oxide basis. For example, in various embodiments, the silicon oxide support includes at least 60 wt% silicon oxide, e.g., at least 70 wt% silicon oxide, or at least 80 wt% silicon oxide. In various embodiments, the silicon oxide support includes at least 90 wt% silicon oxide, e.g., at least 95 wt% silicon oxide, or at least 98 wt% silicon oxide. In some embodiments, the silicon oxide support may further include additional metals or metal oxides.

[0043] In various embodiments as otherwise described herein, the support is a mixed oxide support. These can be provided, for example, by admixture of multiple of the oxides above and formation into a support that includes both. For example, in some embodiments, the mixed oxide support is a mixture of two or more metal oxides, such as cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide. In some embodiments, at least a surface layer of the support includes at least 50 wt% total of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, andsilicon oxide on an oxide basis. In some embodiments, at least a surface layer of the mixed oxide support includes at least 60 wt% total, e.g., at least 70 wt%, or at least 80 wt% of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide. In some embodiments, at least a surface layer of the mixed oxide support includes at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of two or more cerium oxide, titanium oxide, aluminum oxide, zirconium oxide zinc oxide, and silicon oxide. In various examples, the mixed oxide support contains the oxides substantially throughout, e.g., at least 50 wt% of the mixed oxide support is two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide. In various embodiments, the mixed oxide support includes at least 60 wt% total, e.g., at least 70 wt%, or at least 80 wt% of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide. In various embodiments, the mixed oxide support includes at least 90 wt% total, e.g., at least 95 wt%, or at least 98 wt% of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide zinc oxide, and silicon oxide. In some embodiments, the mixed oxide support may further include additional metals or metal oxides.

[0044] The present inventors have found that cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide can provide good performance in the absence of substantial amounts of other metals in the support. For example, in various embodiments of the disclosure as otherwise described herein, the support does not include additional metals in a total amount of additional metals in excess of 2 wt%, e.g., in excess of 1 wt% or in excess of 0.5 wt%, on an oxide basis.

[0045] However, the inventors have noted that in many cases performance can be desirably effected by the inclusion of other metals in the support. Accordingly, in other embodiments as otherwise described herein, the support includes at least one additional metal. In various embodiments, the total amount of the at least one additional metal is in the range of 0.5-20 wt%, e.g., 1-20 wt%, or 2-20 wt%, or 0.5-15 wt%, or 1-15 wt%, or 2-15 wt%, or 0.5-10 wt%, or 1-10 wt%, or 2-10 wt%, or 0.5-5 wt%, or 1-5 wt%, on an oxide basis.

[0046] Supports suitable for use herein can be provided with a range of pore volumes. The person of ordinary skill in the art will select a pore volume appropriate for a desired catalytic process. For example, in various embodiments as otherwise described herein, the pore volume is at least 0.05 mL / g, e.g., at least 0.1 mL / g. In various embodiments as otherwise described herein, the pore volume is at most 1.5 mL / g, e.g., at most 1 mL / g. In various embodiments of the present disclosure as described herein, the pore volume is in the range of 0.05-1.5 mL / g, e.g., 0.1 mL / g to 1 mL / g. Pore volumes are measured by mercury porosimetry as measured according to ASTM D4284-12.

[0047] As described above, the supported CO2conversion catalysts of the disclosure include at least one of cobalt, nickel, ruthenium, and rhodium. In some embodiments, the supported CO2conversion catalysts of the disclosure include one of cobalt, nickel, ruthenium, and rhodium. In some embodiments, the supported CO2conversion catalysts of the disclosure include only one of cobalt, nickel, ruthenium, and rhodium.

[0048] For example, in various embodiments as otherwise described herein, cobalt is present in the catalyst. For the purposes of this disclosure, the amount of cobalt present is calculated as a weight percentage of cobalt atoms in the catalyst based on the total weight of the catalyst, despite the form in which that cobalt may be present. The cobalt may be present in the catalyst in a variety of forms; most commonly, cobalt is principally present as metal, metal oxide, or a combination thereof. In some embodiments of the present disclosure as described herein, cobalt is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, cobalt is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, cobalt is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, cobalt is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, cobalt is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, cobalt is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0049] In various embodiments as otherwise described herein, nickel is present in the catalyst. For the purposes of this disclosure, the amount of nickel present is calculated as a weight percentage of nickel atoms in the catalyst based on the total weight of the catalyst, despite the form in which that nickel may be present. The nickel may be present in the catalyst in a variety of forms; most commonly, nickel is principally present as metal, metal oxide, or a combination thereof. In some embodiments of the present disclosure as described herein, nickel is present in the catalyst in an amount in the range of 0.05-15 wt%,e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, nickel is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, nickel is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, nickel is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, nickel is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, nickel is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst. In some embodiments, the catalyst of the disclosure is as otherwise described herein with the proviso that if an amount of nickel is at least 0.05 wt%, an amount of cobalt is no more than 0.1 wt%. In some embodiments, the catalyst of the disclosure is as otherwise described herein with the proviso that if an amount of nickel is at least 0.05 wt%, an amount of ruthenium is no more than 0.1 wt%.

[0050] In various embodiments as otherwise described herein, ruthenium is present in the catalyst. For the purposes of this disclosure, the amount of ruthenium present is calculated as a weight percentage of ruthenium atoms in the catalyst based on the total weight of the catalyst, despite the form in which that ruthenium may be present. The ruthenium may be present in the catalyst in a variety of forms; most commonly, ruthenium is principally present as metal, metal oxide, or a combination thereof. In some embodiments of the present disclosure as described herein, ruthenium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, ruthenium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, ruthenium is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, ruthenium is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, ruthenium is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, ruthenium is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0051] In various embodiments as otherwise described herein, rhodium is present in the catalyst. For the purposes of this disclosure, the amount of rhodium present is calculated as a weight percentage of rhodium atoms in the catalyst based on the total weight of the catalyst, despite the form in which that rhodium may be present. The rhodium may be present in the catalyst in a variety of forms; most commonly, rhodium is principally present as metal, metal oxide, or a combination thereof. In some embodiments of the present disclosure as described herein, rhodium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, rhodium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, rhodium is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, rhodium is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, rhodium is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, rhodium is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst. In some embodiments, the catalyst of the disclosure is as otherwise described herein with the proviso that if an amount of rhodium is at least 0.05 wt%, an amount of cobalt is no more than 0.1wt%. In some embodiments, the catalyst of the disclosure is as otherwise described herein with the proviso that if an amount of rhodium is at least 0.05 wt%, an amount of ruthenium is no more than 0.1 wt%.

[0052] As described above, the supported CO2conversion catalyst of the disclosure includes at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon. In some embodiments, the supported CO2conversion catalyst of the disclosure includes one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon. In some embodiments, the supported CO2conversion catalyst of the disclosure includes at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, and boron (e.g., present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst). In some embodiments, the supported CO2conversion catalyst of the disclosure includes one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, and boron (e.g., present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst). The present inventors have determined that inclusion of metalloids in the catalyst can provide improved performance. In particular, the present inventors have found that the inclusion of a metalloid in the cobalt, nickel, ruthenium, and rhodium based catalysts switches the selectivities of the catalysts from methane to CO, essentially turning off Fischer-Tropsch activity in favor of rWGS activity.

[0053] For example, in some embodiments, the supported CO2conversion catalysts of the disclosure may include tellurium. The present inventors have determined that inclusion of tellurium in the catalyst can provide improved performance, as described in the Examples below. For the purposes of this disclosure, the amount of tellurium present is calculated as a weight percentage of tellurium atoms in the catalyst based on the total weight of the catalyst, despite the form in which that tellurium may be present. The tellurium may be present in the catalyst in a variety of forms; most commonly, tellurium is principally present as metal oxide, metal, or a combination thereof. In various embodiments of the present disclosure as otherwise described herein, tellurium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, tellurium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, tellurium is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the totalweight of the catalyst. In various embodiments of the present disclosure as described herein, tellurium is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, tellurium is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, tellurium is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0054] The cobalt, nickel, ruthenium, and / or rhodium and the tellurium can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium is at least 0.5:1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium is at least 0.8:1, or at least 1:1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium is at most 10: 1 or 5: 1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1 , or 0.2:1 to 5:1 , or 0.5:1 to 15:1, or 0.5:1 to 10:1, or 0.5:1 to 5:1, or 0.8:1 to 15:1, or 0.8:1 to 10:1 , or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium is in the range of 0.2:1 to 1.5:1 , or 0.2:1 to 1 :1 , or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1.

[0055] In some embodiments, the supported CO2conversion catalysts of the disclosure may include bismuth. The present inventors have determined that inclusion of bismuth in the catalyst can provide improved performance, as described in the Examples below. For the purposes of this disclosure, the amount of bismuth present is calculated as a weight percentage of bismuth atoms in the catalyst based on the total weight of the catalyst, despite the form in which that bismuth may be present. The bismuth may be present in the catalyst in a variety of forms; most commonly, bismuth is principally present as metal oxide, metal, ora combination thereof. In various embodiments of the present disclosure as otherwise described herein, bismuth is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, bismuth is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, bismuth is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, bismuth is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, bismuth is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, bismuth is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0056] The cobalt, nickel, ruthenium, and / or rhodium and the bismuth can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to bismuth present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to bismuth is at least 0.5:1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to bismuth is at least 0.8:1, or at least 1:1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to bismuth present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to bismuth is at most 10:1 or 5:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to bismuth present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to bismuth is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1 , or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to bismuth is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel,ruthenium, and / or rhodium to bismuth is in the range of 0.2: 1 to 1.5:1, or 0.2: 1 to 1:1, or 0.5:1 to 2:1, or 0.5:1 to 1.5:1, or 0.5:1 to 1:1, or 0.8:1 to 2:1, or 0.8:1 to 1.5:1, or 0.8:1 to 1:1.

[0057] In some embodiments, the supported CO2conversion catalysts of the disclosure also include tin. For the purposes of this disclosure, the amount of tin present is calculated as a weight percentage of tin atoms in the catalyst based on the total weight of the catalyst, despite the form in which that tin may be present. The tin may be present in the catalyst in a variety of forms; most commonly, tin is principally present as metal oxide, metal, or a combination thereof. In various embodiments of the present disclosure as otherwise described herein, tin is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, tin is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, tin is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, tin is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, tin is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, tin is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0058] The cobalt, nickel, ruthenium, and / or rhodium and the tin can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tin present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tin is at least 0.5:1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tin is at least 0.8:1, or at least 1 :1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tin present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tin is at most 10:1 or 5:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium,and / or rhodium to tin present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tin is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1 , or 0.2:1 to 5:1, or 0.5:1 to 15:1 , or 0.5:1 to 10:1, or 0.5:1 to 5:1, or 0.8:1 to 15:1, or 0.8:1 to 10:1 , or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tin is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tin is in the range of 0.2:1 to 1.5:1 , or 0.2:1 to 1 :1 , or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1.

[0059] In some embodiments, the supported CO2conversion catalysts of the disclosure may include antimony. For the purposes of this disclosure, the amount of antimony present is calculated as a weight percentage of antimony atoms in the catalyst based on the total weight of the catalyst, despite the form in which that antimony may be present. The antimony may be present in the catalyst in a variety of forms; most commonly, antimony is principally present as metal oxide, metal, or a combination thereof. In various embodiments of the present disclosure as otherwise described herein, antimony is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, antimony is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, antimony is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, antimony is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, antimony is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, antimony is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0060] The cobalt, nickel, ruthenium, and / or rhodium and the antimony can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosureas described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony is at least 0.5:1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony is at least 0.8:1, or at least 1:1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony is at most 10:1 or 5:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1 , or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to antimony is in the range of 0.2:1 to 1.5:1, or 0.2:1 to 1:1, or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1.

[0061] In some embodiments, the supported CO2conversion catalysts of the disclosure may include germanium. For the purposes of this disclosure, the amount of germanium present is calculated as a weight percentage of germanium atoms in the catalyst based on the total weight of the catalyst, despite the form in which that germanium may be present. The germanium may be present in the catalyst in a variety of forms; most commonly, germanium is principally present as metal oxide, metal, or a combination thereof. In various embodiments of the present disclosure as otherwise described herein, germanium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, germanium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, germanium is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, germanium is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%,or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, germanium is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, germanium is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0062] The cobalt, nickel, ruthenium, and / or rhodium and the germanium can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium is at least 0.5: 1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium is at least 0.8:1 , or at least 1 :1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium is at most 10:1 or 5:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1 , or 0.5:1 to 10:1, or 0.5:1 to 5:1, or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to germanium is in the range of 0.2: 1 to 1.5: 1 , or 0.2: 1 to 1 : 1 , or 0.5: 1 to 2: 1 , or 0.5: 1 to 1.5: 1 , or 0.5:1 to 1:1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1.

[0063] In some embodiments, the supported CO2conversion catalysts of the disclosure may include selenium. For the purposes of this disclosure, the amount of selenium present is calculated as a weight percentage of selenium atoms in the catalyst based on the total weight of the catalyst, despite the form in which that selenium may be present. The selenium may be present in the catalyst in a variety of forms; most commonly, selenium is principally present as metal oxide, metal, or a combination thereof. In various embodiments of the present disclosure as otherwise described herein, selenium is present in the catalyst in an amount in the range of 0.05 to 15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on thetotal weight of the catalyst. In various embodiments of the present disclosure as described herein, selenium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, selenium is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, selenium is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, selenium is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, selenium is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0064] The cobalt, nickel, ruthenium, and / or rhodium and the selenium can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium is at least 0.5:1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium is at least 0.8:1, or at least 1:1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium is at most 10: 1 or 5: 1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1 , or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium is in the range of 0.2:1 to 2: 1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to selenium is in the range of 0.2:1 to 1.5:1, or 0.2:1 to 1:1, or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1.

[0065] In some embodiments, the supported CO2conversion catalysts of the disclosure may include arsenic. For the purposes of this disclosure, the amount of arsenic present is calculated as a weight percentage of arsenic atoms in the catalyst based on the total weight of the catalyst, despite the form in which that arsenic may be present. The arsenic may be present in the catalyst in a variety of forms; most commonly, arsenic is principally present as metal oxide, metal, or a combination thereof. In various embodiments of the present disclosure as otherwise described herein, arsenic is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, arsenic is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, arsenic is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, arsenic is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, arsenic is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, arsenic is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0066] The cobalt, nickel, ruthenium, and / or rhodium and the arsenic can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to arsenic present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to arsenic is at least 0.5:1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to arsenic is at least 0.8:1, or at least 1:1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to arsenic present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to arsenic is at most 10:1 or 5:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to arsenic present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / orrhodium to arsenic is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1 , or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to arsenic is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to arsenic is in the range of 0.2: 1 to 1.5: 1 , or 0.2: 1 to 1 : 1 , or 0.5: 1 to 2:1, or 0.5:1 to 1.5:1 , or 0.5:1 to 1:1, or 0.8:1 to 2:1, or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1.

[0067] In some embodiments, the supported CO2conversion catalysts of the disclosure may include boron. For the purposes of this disclosure, the amount of boron present is calculated as a weight percentage of boron atoms in the catalyst based on the total weight of the catalyst, despite the form in which that boron may be present. The boron may be present in the catalyst in a variety of forms; most commonly, boron is principally present as metal oxide, metal, or a combination thereof. In various embodiments of the present disclosure as otherwise described herein, boron is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, boron is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, boron is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, boron is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, boron is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, boron is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0068] The cobalt, nickel, ruthenium, and / or rhodium and the boron can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron is at least 0.5:1. In someembodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron is at least 0.8:1, or at least 1:1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron is at most 10:1 or 5:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1 , or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to boron is in the range of 0.2:1 to 1.5:1, or 0.2:1 to 1:1, or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1:1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1.

[0069] In some embodiments, the supported CO2conversion catalysts of the disclosure may include indium. For the purposes of this disclosure, the amount of indium present is calculated as a weight percentage of indium atoms in the catalyst based on the total weight of the catalyst, despite the form in which that indium may be present. The indium may be present in the catalyst in a variety of forms; most commonly, indium is principally present as metal oxide, metal, or a combination thereof. In various embodiments of the present disclosure as otherwise described herein, indium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, indium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, indium is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, indium is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, indium is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, indium is present in an amount in the rangeof 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0070] The cobalt, nickel, ruthenium, and / or rhodium and the indium can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium is at least 0.5:1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium is at least 0.8:1, or at least 1:1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium is at most 10: 1 or 5: 1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium present in the catalyst is in the range of 0.2:1 to 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1 , or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and / or rhodium to indium is in the range of 0.2:1 to 1.5:1, or 0.2:1 to 1 :1, or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1:1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1.

[0071] However, when silicon is present in the support, silicon of the support itself can provides the active catalytic silicon, i.e. , no separate silicon need be provided. Accordingly, another aspect of the disclosure is a supported CO2conversion catalyst comprising: a support that is a silicon oxide or a mixed oxide support comprising a mixture silicon oxide with one or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide; and at least one of cobalt, nickel, ruthenium, and rhodium present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst, wherein silicon is present in an amount of at least 0.05 wt%, based on the total weight of the catalyst.For example, in various such embodiments, silicon is present in an amount of at least 0.1 wt%, based on the total weight of the catalyst. In various such embodiments, silicon is present in an amount of at least 0.4 wt%, based on the total weight of the catalyst. In various such embodiments, silicon is present in an amount of at least 0.7 wt%, based on the total weight of the catalyst. In various such embodiments, silicon is present in an amount ofat least 1 wt%, based on the total weight of the catalyst. In various such embodiments, silicon is present in an amount of at least 1.5 wt%, based on the total weight of the catalyst. Silicon can be present in relatively high proportions, e.g., forming the balance of the material other than the at least one of cobalt, nickel, ruthenium, and rhodium. Amounts of other materials can be as otherwise described herein. For example, in various embodiments of the present disclosure as otherwise described herein, silicon is present in the catalyst in an amount in the range of 0.05 to 15 wt%, based on total weight of the catalyst. For example, in various embodiments, silicon is present in the catalyst in an amount in the range of 0.05 to 15 wt%, e.g., in the range of 0.05 to 12 wt%, or 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, silicon is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, silicon is present in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure as described herein, silicon is present in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, silicon is present in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst. In various embodiments of the present disclosure, silicon is present in an amount in the range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.

[0072] The cobalt, nickel, ruthenium, and rhodium and the silicon can be provided in a variety of weight ratios. For example, in some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon present in the catalyst is at least 0.2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon is at least 0.5:1. In some embodiments, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon is at least 0.8:1, or at least 1:1. In various embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon present in the catalyst is at most 15:1. For example, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon is at most 10:1 or 5:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon present in the catalyst is in the range of 0.2:1 to 15:1. Forexample, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1 , or 0.2:1 to 10:1 , or 0.2:1 to 5:1 , or 0.5:1 to 15:1, or 0.5:1 to 10:1, or 0.5:1 to 5:1 , or 0.8:1 to 15:1 , or 0.8:1 to 10:1, or 0.8:1 to 5:1. In some embodiments of the present disclosure as described herein, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon is in the range of 0.2:1 to 2:1. For example, in various embodiments, the weight ratio of cobalt, nickel, ruthenium, and rhodium to silicon is in the range of 0.2:1 to 1.5:1 , or 0.2:1 to 1 :1 , or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2: 1 , or 0.8: 1 to 1.5: 1 , or 0.8: 1 to 1 : 1.

[0073] The present inventors have determined that suitable CO2conversion catalysts can be formed of one or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide as a support, with cobalt, nickel, ruthenium, and / or rhodium in combination with tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and / or silicon included in / on the catalyst. As would be understood by the person of ordinary skill in the art, the amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium can be quantified on a metallic basis regardless of the form in which these metals may be present. For example, the amount of these metals can be calculated as a weight percentage based on the total weight of metals in the catalysts (i.e., on a metallic basis), without the inclusion of oxygen or non-metallic counterions in the calculation. Accordingly, in various embodiments of the present disclosure as described herein, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. For example, in some particular embodiments, the total amount of cerium, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In other embodiments, the total amount of titanium, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In other embodiments, the total amount of aluminum, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In other embodiments, the total amount of zirconium, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt%of the catalyst, on a metallic basis. In other embodiments, the total amount of zinc, silicon, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In other embodiments, the total amount of silicon, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0074] As described above, in some embodiments, the supported CO2conversion catalysts of the disclosure include a metal oxide support, one of cobalt, nickel, ruthenium, and rhodium, and one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon. Accordingly, in various embodiments, the catalysts of the disclosure include cobalt. For example, in some embodiments, the catalyst of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0075] In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and tellurium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and bismuth, present in an amountas described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and tin, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and antimony, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and germanium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and selenium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of thedisclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and arsenic, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and boron, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and indium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; cobalt, present in an amount in an amount as described herein; and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, and cobalt in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0076] In particular embodiments of the present disclosure, the support is a titanium oxide support as described herein. For example, in various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt,present in an amount in an amount as described herein; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0077] In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and tellurium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and bismuth, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and tin, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and antimony, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and germanium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and selenium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, thecatalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and arsenic, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and boron, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and indium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; cobalt, present in an amount in an amount as described herein; and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, cobalt, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0078] In various embodiments, the catalysts of the disclosure include nickel. For example, in some embodiments, the catalyst of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0079] In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount asdescribed herein; and tellurium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and bismuth, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and tin, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and antimony, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and germanium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and selenium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and arsenic, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and boron, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and indium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide,zirconium oxide, zinc oxide, and silicon oxide; nickel, present in an amount in an amount as described herein; and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, and nickel, in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0080] In particular embodiments of the present disclosure, the support is a titanium oxide support as described herein. For example, in various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0081] In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and tellurium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and bismuth, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and tin, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and antimony, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and germanium,present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and selenium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and arsenic, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and boron, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and indium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; nickel, present in an amount in an amount as described herein; and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, nickel, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0082] In various embodiments, the catalysts of the disclosure include ruthenium. For example, in some embodiments, the catalyst of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium,zinc, silicon, ruthenium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0083] In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and tellurium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and bismuth, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and tin, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and antimony, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or atleast 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and germanium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and selenium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and arsenic, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and boron, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide supportcomprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and indium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; ruthenium, present in an amount in an amount as described herein; and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, and ruthenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0084] In particular embodiments of the present disclosure, the support is a titanium oxide support as described herein. For example, in various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0085] In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and tellurium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and bismuth, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and tin, present in an amount as described herein. For example, in someembodiments, the total amount of titanium, ruthenium, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and antimony, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and germanium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and selenium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and arsenic, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and boron, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and indium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; ruthenium, present in an amount in an amount as described herein; and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, ruthenium, and silicon in thecatalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0086] In various embodiments, the catalysts of the disclosure include rhodium. For example, in some embodiments, the catalyst of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0087] In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and tellurium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and bismuth, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and tin,present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and antimony, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and germanium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and selenium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and arsenic, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. Invarious embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and boron, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and indium, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; rhodium, present in an amount in an amount as described herein; and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, and rhodium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0088] In particular embodiments of the present disclosure, the support is a titanium oxide support as described herein. For example, in various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0089] In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount asdescribed herein; and tellurium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and bismuth, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and tin, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and antimony, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and germanium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and selenium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and arsenic, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and boron, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and boron in the catalyst is atleast 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and indium, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis. In various embodiments, the catalysts of the disclosure include a support that is a titanium oxide support as described herein; rhodium, present in an amount in an amount as described herein; and silicon, present in an amount as described herein. For example, in some embodiments, the total amount of titanium, rhodium, and silicon in the catalyst is at least 90 wt%, e.g., at least 95 wt%, or at least 98 wt% of the catalyst, on a metallic basis.

[0090] In some embodiments as described herein, the catalyst as described herein an additional metal content of no more than 10 wt%, based on the total weight of the catalyst. The additional metal may be any metal that is not cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, or silicon. For example, the additional metal may be selected from alkali metals, alkaline earth-metals, lanthanide metals, coinage metals, noble metals, or other transition metals. For example, in various embodiments, the catalyst has an additional metal content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has an alkali metal content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has an alkali metal content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has an alkaline-earth metal content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has an alkaline- earth metal content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has a lanthanide metal content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has a lanthanide metal content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.

[0091] In some embodiments as described herein, the catalyst has a copper content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has a copper content of no more than 5 wt%, or no more than 2wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has a silver content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has a silver content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has a gold content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has a gold content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has a platinum content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has a platinum content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has a palladium content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has a palladium content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.

[0092] In some embodiments as described herein, the catalyst has a manganese content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has a manganese content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has a molybdenum content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has a molybdenum content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst. In some embodiments as described herein, the catalyst has an iron content of no more than 10 wt%, based on the total weight of the catalyst. For example, in various embodiments, the catalyst has an iron content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.

[0093] As described above, the supported catalyst includes at least one (or one) of cobalt, nickel, ruthenium, and rhodium and at least one (or one) of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon. Depending on the method of synthesis, these species, which will typically be principally present in metallic formand / or oxide form, can be disposed at a variety of different places on the support. For example, they can be found in pores of the support and on the outer surface of the support. They may be found substantially throughout the support, e.g., as when a large volume of impregnation liquid is used, or only in a surface layer of the support, e.g., when impregnation liquid does not infiltrate into the entirety of the support, such as when using an incipient wetness technique.

[0094] Without intending to be bound by theory, it is believed that the active form of cobalt, nickel, rhodium, and ruthenium is typically a substantially metallic form. As described below, as cobalt, nickel, rhodium, and ruthenium may be present substantially in an oxide form after catalyst preparation and during shipment and storage, it is typically desirable to activate the catalyst by contacting it with a reductant, e.g., hydrogen gas, to convert a substantial fraction of such oxide to metallic form. However, the person of ordinary skill in the art will appreciate that the present disclosure contemplates the usefulness of a wide variety of cobalt, nickel, rhodium, and ruthenium forms in its catalysts, as these can be active or can be conveniently transformed to active forms.

[0095] The tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon will typically be provided in oxide form after catalyst preparation and during shipment and storage. Without intending to be bound by theory, the present inventors believe that these metalloids acts to improve the catalytic activity of the supported catalysts by reducing CO methanation that can occur over the typical reverse water-gas shift reaction temperature range, which impacts CO selectivity. The present inventors believe that the improved activity can be attributed to the metalloid interfacing with both the cobalt, nickel, ruthenium, and / or rhodium and the support (e.g., cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, or a mixed oxide). The present inventors contemplate that it is possible that some of the metalloid oxide may be converted to metallic form during the activation of the cobalt, nickel, ruthenium, and / or rhodium species, and / or form an alloy with the tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and / or silicon. However, the person of ordinary skill in the art will appreciate that the present disclosure contemplates the usefulness of a wide variety of metalloid forms in its catalysts, as these can provide a promoting effect or can be conveniently transformed to forms that will.

[0096] The person of ordinary skill in the art will appreciate that the catalysts of the disclosure can be provided in many forms, depending especially on the particular form of the reactor system in which they are to be used, e.g., in a fixed bed or as a fluid bed. The supports themselves can be provided as discrete bodies of material, e.g., as porous particles, pellets or shaped extrudates, with cobalt, nickel, rhodium, ruthenium, tellurium,bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon provided thereon to provide the catalyst. However, in other embodiments, a catalyst of the disclosure can itself be formed as a layer on an underlying substrate. The underlying substrate is not particularly limited. It can be formed of, e.g., a metal or metal oxide, and can itself be provided in a number of forms, such as particles, pellets, shaped extrudates, or monoliths. Of course, as would be understood by the person of ordinary skill in the art, other embodiments may be possible.

[0097] Another aspect of the present disclosure provides for a method of making the catalyst as described herein. As described above, the method includes providing a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support including a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; contacting the support with one or more liquids each including one or more cobalt-containing, nickel-containing, ruthenium- containing, and rhodium-containing compounds and / or one or more tellurium-containing, bismuth-containing, tin-containing, antimony-containing, germanium-containing, selenium- containing, arsenic-containing, boron-containing, indium-containing, or silicon-containing compounds dispersed in a solvent; allowing the solvent(s) to evaporate to provide a catalyst precursor; and calcining the catalyst precursor. The person of ordinary skill in the art will appreciate, of course, that other methods can be used to make the catalysts described herein.

[0098] In some embodiments of the present disclosure as described herein, contacting the support with the liquid includes adding the liquid in an amount about equal to (i.e., within 25% of, or within 10% of) the pore volume of the support. In other embodiments, contacting the support with the liquid includes adding the liquid in an amount greater than the pore volume of the support. For example, in some embodiments, the ratio of the amount of liquid to the amount of support on a mass basis is in the range of 0.75:1 to 5:1 , e.g., in the range of 0.9:1 to 3:1. In some embodiments, contacting the support with the liquid provides a slurry.

[0099] In various embodiments of the present disclosure as described herein, allowing the solvent to evaporate is conducted at ambient temperature. In various embodiments, allowing the solvent to evaporate is conducted at an elevated temperature for a drying time. The person of ordinary skill in the art would be able to select appropriate apparatuses or instruments to allow the solvent to evaporate, and such apparatuses or instruments are not particularly limited. Additionally, the person of ordinary skill in the art would understand that the elevated temperature that will allow the solvent to evaporate depends on the boiling point of the solvent. As such, the person of ordinary skill in the art would be able to select anappropriate elevated temperature. For example, in some embodiments, the elevated temperature is in the range of 50-150 °C, e.g., in the range of 50-120 °C, or 50-100 °C, or 100-150 °C, or 100-120 °C. In some embodiments, the drying time is in the range of 1 to 48 hours, e.g., in the range of 10 to 36 hours, or 12 to 24 hours. For example, in particular embodiments, the drying time is about 24 hours. In some embodiments, allowing the solvent to evaporate is conducted under vacuum and at an elevated temperature for a drying time, as described herein. In some embodiments, allowing the solvent to evaporate is conducted in a stirring drybath at an elevated temperature, for example, in the range of 30-100 °C.

[0100] In some embodiments of the present disclosure as described herein, calcining the catalyst precursor is conducted in a furnace for a calcining time and at a calcining temperature. For example, in some embodiments, the calcining time is in the range of 0.5 to 24 hours, or 0.5 to 15 hours, or 0.5 to 10 hours, or 0.5 to 5 hours. In some embodiments, the calcining temperature is in the range of 100-600 °C, e.g., in the range of 120-500 °C.

[0101] As described above, the method of making the catalyst as described herein includes contacting the support with one or more liquids each including one or more cobalt- containing, nickel-containing, ruthenium-containing, and rhodium-containing compounds and / or one or more tellurium-containing, bismuth-containing, tin-containing, antimony- containing, germanium-containing, selenium-containing, arsenic containing, boron- containing, indium-containing, or silicon-containing compounds dispersed in a solvent. The cobalt-, nickel-, ruthenium-, rhodium-, tellurium-, bismuth-, tin-, antimony-, germanium-, selenium-, arsenic-, boron-, indium-, and silicon-containing compounds are not particularly limited and the person of ordinary skill in the art would be able to choose appropriate compounds that are soluble in the solvent. For example, in some embodiments of the disclosure as described herein, the cobalt-, nickel-, ruthenium-, rhodium-, tellurium-, bismuth-, tin-, antimony-, germanium-, selenium-, arsenic-, boron-, indium-, and silicon- containing compounds may be selected from metal salts (e.g., nitrates and acetates). The solvent is also not particularly limited and the person of ordinary skill in the art would be able to choose an appropriate solvent that can be absorbed by the support. For example, in some embodiments of the disclosure as described herein, the solvent is water. As the person of ordinary skill in the art will appreciate, these metal species are conveniently provided in the same liquid, so that only one step of contacting the support with liquid is required. However, other schemes are possible.

[0102] In another aspect, the present disclosure provides a catalyst as described herein made by the methods as described herein.

[0103] Another aspect of the present disclosure provides a method for performing a reverse water-gas shift reaction. As described above, the method includes contacting at a temperature in the range of 200-799 °C a catalyst as described herein with a feed stream that includes CO2and H2, to provide a product stream that includes CO and H2, the product stream having a lower concentration of CO2and a higher concentration of CO than the feed stream. An example of such a method is shown schematically in FIG. 1. In FIG. 1, the method 100 includes performing a reverse water-gas shift reaction by providing a feed stream 111 comprising H2and CO2, here, to a reaction zone, e.g., a reactor 110. A CO2conversion catalyst 113, as described herein, is contacted at a temperature in the range of 200-700 °C with the feed stream 111 to provide a product stream 112 comprising CO and H2. The product stream has a lower concentration of CO2and a higher concentration of CO than the feed stream.

[0104] As used herein, a “feed stream” is used to mean the total material input to a process step, regardless of whether provided in a single physical stream or multiple physical streams, and whether through a single inlet or multiple inlets. For example, H2and CO of the feed stream can be provided to the CO2conversion catalyst in a single physical stream (e.g., in a single pipe to reactor 110), or in multiple physical streams (e.g., separate inlets for CO and H2, or one inlet for fresh CO and H2and another for recycled CO and / or H2). Similarly, a “product stream” is used to mean the total material output from a process step, regardless of whether provided in a single physical stream or multiple physical streams, and whether through a single outlet or multiple outlets.

[0105] In various embodiments of the present disclosure as described herein, the reverse water-gas shift reaction has a CO selectivity of at least 90%. As used herein, a “selectivity” for a given reaction product is the molar fraction of the feed (here, CO2) that is converted to the product (for “CO selectivity,” CO). The present inventors have determined that the present catalysts, even when operating at lower temperatures than many conventional reverse water-gas shift catalysts, can provide excellent selectivity for CO, despite the potential for competition by the Sabatier reaction and the methanation of CO. . In some embodiments as otherwise described herein, the reverse water-gas shift reaction has a CO selectivity of at least 92% or at least 95%. For example, in some embodiments as otherwise described herein, the reverse water-gas shift reaction has a CO selectivity of at least 97%, e.g., or at least 98%.

[0106] Notably, even at relatively low temperatures in the range of 200-700 °C, the catalysts described herein can be operated to provide carbon monoxide with only a very minor degree of methane formation. For example, in various embodiments of the present disclosure as otherwise described herein, the reverse water-gas shift reaction has amethane selectivity of no more than 5%, e.g., no more than 4%. For example, in some embodiments, the reverse water-gas shift reaction has a methane selectivity of no more than 2%, e.g., no more than 1%.

[0107] The present inventors have determined that the catalysts described here can provide desirably high CO selectivity and desirably low methane selectivity at commercially relevant conversion rates. As used herein, a “conversion” is a molar fraction of a feed that is reacted (be it to desirable products or undesirable species). In various embodiments of the present disclosure as described herein, the reverse water-gas shift reaction has a CO2conversion of at least 5%, e.g., at least 10%, or 20%. For example, in some embodiments, the reverse water-gas shift reaction has a CO2conversion of at least 30%, e.g., at least 40%. In various embodiments of the present disclosure as described herein, the reverse water-gas shift reaction has a CO2conversion of no more than 80%, e.g., no more than 70%. For example, in some embodiments, the reverse water-gas shift reaction has a CO2conversion of no more than 65%, e.g., no more than 60%. For example, in various embodiments as otherwise described herein, the CO2conversion is in the range of 10-80%, e.g., 10-70%, or 10-60%, or 10-65%, or 20-80%, or 20-70%, or 20-60%, or 20-65%, or 30- 80%, or 30-70%, or 30-60%, or 30-65%, or 40-80%, or 40-70%, or 40-60%, or 40-65%. The person of ordinary skill in the art will, based on the disclosure herein, operate at a degree of conversion that provides a desirable product. And of course, in other embodiments, e.g., when in a stacked-bed or mixed-bed system, the CO2conversion may be even higher than described here.

[0108] Advantageously, the processes described herein can be performed at temperatures that are lower than temperatures used in many conventional reverse water-gas shift processes. As described above, various processes of the disclosure can be performed in a temperature range of 200-700°C. For example, in some embodiments, the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 250-700 °C, or 250-650 °C, or 250-600 °C. In some embodiments of the present disclosure as described herein, the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 300-700 °C, or 300-650 °C, or 300-600 °C. In some embodiments of the present disclosure as described herein, the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 350-700 °C, or 350-650 °C, or 350-600 °C. In some embodiments, the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 400-700 °C, or 400-650 °C, or 400-600 °C. In some embodiments, the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 450-700 °C, or 450- 650 °C, or 450-600 °C. In some embodiments, the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 500-700 °C, or 500-650 °C, or 500-600 °C. In some embodiments, the method for performing the reverse water-gas shift reaction is conducted at a temperature in the range of 550-700 °C, or 550-650 °C, or 550-600 °C.

[0109] As described above, the feed stream includes CO2and H2. Advantageously, the present inventors have recognized that both of these can come from renewable or otherwise environmentally responsible sources. For example, at least part of the H2can be so-called “green” hydrogen, e.g., produced from the electrolysis of water operated using renewable electricity (such as wind, solar, or hydroelectric power). In other embodiments, at least part of the H2may be from a so-called “blue” source, e.g., from a natural gas reforming process with carbon capture. Of course, other sources of hydrogen can be used in part or in full. For example, in some embodiments, at least a portion of the H2of the feed stream is grey hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen. CO2can be captured from the environment generally, or more directly from processes that form CO2(especially in difficult-to-abate sectors), making a product that is later made from the CO at least carbon-neutral. For example, in some embodiments, at least part of the CO2is from direct air capture, or from a manufacturing plant such as a bioethanol plant (e.g., CO2produced fermentation), a steel plant, or a cement plant. Accordingly, the rWGS reaction can be not only carbon neutral, but in some cases a net consumer of carbon dioxide. These benefits in particular makes the rWGS reaction highly attractive for decarbonizing transportation fuels, for both automotive and aviation sectors, since the carbon monoxide produced in the reaction can be readily utilized by well-established technologies to synthesize liquid hydrocarbon fuels.

[0110] The feed stream contains both H2and CO2(e.g., provided to a reaction zone in a single physical stream or multiple physical streams). As used herein, the feed stream includes all feeds to the process, regardless of whether provided as a mixture of gases or as gases provided individually to a reaction zone. In various embodiments as otherwise described herein, the molar ratio of H2to CO2in the feed stream is at least 0.1:1 , e.g., at least 0.5:1. In some embodiments, the molar ratio of H2to CO2in the feed stream is at least 0.9:1 , e.g., at 1:1 or least 1.5:1. In some embodiments, the molar ratio of H2to CO2in the feed stream is at least 2:1, e.g., at least 2.5:1. In some embodiments, the molar ratio of H2to CO2in the feed stream is no more than 100:1 , e.g., no more than 75:1, or 50:1. In some embodiments, the molar ratio of H2to CO2in the feed stream is no more than 20:1, e.g., no more than 15:1 , or 10:1. For example, in some embodiments, the molar ratio of H2to CO2in the feed stream is in the range of 0.5:1 to 10:1. The person of ordinary skill in the art will provide a desired ratio of H2:CO2in the feed stream, based on the disclosure herein, thatprovides a desirable conversion and selectivity; excess H2can, if consistent with a desirable conversion and selectivity, be provided to flow through the system and provide a product stream with a desirable ratio of H2to CO for a downstream process.

[0111] Other gases may also be included in the feed stream. For example, in some embodiments, the feed stream further comprises CO. In some embodiments of the disclosure as otherwise described herein, the feed stream further comprises one or more inert gases. For example, in some embodiments, the feed stream further comprises nitrogen and / or methane.

[0112] The processes described herein can be performed at a variety of pressures, as would be appreciated by the person of ordinary skill in the art. In various embodiments of the present disclosure, the method for performing the reverse water-gas shift reaction is conducted at a pressure in the range of 1 to 100 barg. For example, the method is conducted at a pressure in the range of 1 to 70 barg, or 1 to 50 barg, or 1 to 40 barg, or 1 to 35 barg, or 5 to 70 barg, or 5 to 50 barg, or 5 to 40 barg, or 5 to 35 barg, or 10 to 70 barg, 10 to 50 barg, or 10 to 40 barg, or 10 to 35 barg, or 20 to 70 barg, 20 to 50 barg, or 20 to 40 barg, or 20 to 35 barg, or 25 to 70 barg, 25 to 50 barg, or 25 to 40 barg, or 25 to 35 barg.

[0113] The processes described herein can be performed at a variety of GHSV (gas hourly space velocity), as would be appreciated by the person of ordinary skill in the art. As such, the GHSV for performing the reverse water-gas shift reaction is not particularly limited. For example, in some embodiments of the present disclosure, the method for performing the reverse water-gas shift reaction is conducted at a GHSV in the range of 1,000 to 2,000,000 h’1. In various embodiments, the method for performing the reverse water-gas shift reaction is conducted at a GHSV in the range of 1,000 to 1 ,200,000 IT1, or 1 ,000 to 500,000 IT1, or 1,000 to 100,000 IT1, or 5,000 to 1,200,000 IT1, or 5,000 to 500,000 IT1, or 5,000 to 100,000 IT1, or 10,000 to 1,200,000 IT1, or 10,000 to 500,000 IT1, or 10,000 to 100,000 IT1. In various embodiments of the present disclose, the method for performing the reverse water-gas shift reaction is conducted at a GHSV in the range of 1 ,000 to 50,000 IT1, or 2,000 to 50,000 IT1, or 5,000 to 50,000 IT1, or 10, 000 to 50,000, or 1,000 to 40,000 IT1, or 2,000 to 40,000 IT1, or 5,000 to 40,000 IT1, or 10, 000 to 40,000 IT1, or 1,000 to 30,000 IT1, or 2,000 to 30,000 IT1, or 5,000 to 30,000 IT1, or 10,000 to 30,000 IT1.

[0114] The CO2conversion catalyst described herein is based in part on cobalt, nickel, ruthenium, and / or rhodium. It will typically be desirable to activate the CO2conversion catalyst, e.g., before contacting with the feed stream. Thus in some embodiments of the present disclosure as described herein, the method comprises activating the CO2conversion catalyst prior to contacting the catalyst with the feed stream. For example, in someembodiments, activating the catalyst comprises contacting the catalyst with a reducing stream comprising a reductive gas, e.g., hydrogen. In various embodiments of the present disclose, the reducing stream comprises hydrogen in an amount of at least 25 mol%, e.g., at least 50 mol%, or 75 mol%, or 90 mol%. The person of ordinary skill in the art will determine suitable conditions for activation of the CO2conversion catalyst. As such, the person or ordinary skill in the art would be able to choose an appropriate temperature, pressure, and time for activating the CO2conversion catalyst. For example, in various embodiments activating the catalyst is conducted at a temperature in the range of 200 °C to 800 °C. In some embodiments, activating the catalyst is conducted at a temperature in the range of 250 °C to 800 °C, or 300 °C to 800 °C, or 200 °C to 700 °C, or 250 °C to 800 °C, or 300 °C to 700 °C. In some embodiments of the present disclosure as described herein, activating the catalyst provides a catalyst that is at least 10% reduced (e.g., at least 25%, or at least 50% reduced).

[0115] The present inventors have found that contacting the CO2conversion catalysts as described herein with a feed stream can provide a product stream with advantageously high CO selectivity and low methane selectivity. The amount of CO in the product stream can be further controlled by the rWGS reaction conditions, as described above. But in general, the methods for performing the rWGS reaction as described herein, provide a product stream comprising F^and CO, with the product stream having a lower concentration of CO2and a higher concentration of CO than the feed stream, as is consistent with the degrees of conversion described herein. For example, in various embodiments, the product stream includes no more than 95 mol% CO2, or no more than 90 mol% CO2. In some embodiments, the product stream includes no more than 85 mol% CO2, or no more than 80 mol% CO2. In other examples, the product stream includes no more than 75 mol%, or no more than 70 mol% CO2. However, as described above, the present inventors have determined that it can be desirable to perform the processes at intermediate degrees of conversion to provide desirably high CO selectivities and desirably low methane selectivities. Accordingly, in various embodiments as otherwise described herein, the product stream includes an amount of CO2together with the CO.

[0116] Other gases may also be included in the product stream. In some embodiments of the disclosure as otherwise described herein, the product stream further comprises one or more inert gases. These inert gases may be included from the feed stream or provided from a source other than the feed stream. For example, in some embodiments, the product stream further comprises nitrogen and / or methane.

[0117] Depending on, inter alia, the degree of conversion, the CO selectivity, the relative amounts of H2and CO2in the feed stream, and the reaction conditions, the product streamcan include H2in combination with CO, in a variety of ratios. For example, in some embodiments, the ratio of H2:CO in the product stream is in the range of 0.1 :1 to 100:1 (e.g., in the range of 0.1:1 to 50:1 , or 0.1:1 to 25:1, or 0.1 :1 to 10:1 , or 0.1:1 to 5:1 , or 1:1 to 100:1, or 1 :1 to 50:1 , or 1:1 to 25:1 , or 1:1 to 10:1, or 1:1 to 5:1).

[0118] The person of ordinary skill in the art would appreciate that, based on the methods as described herein, the product stream may include H2, CO, and CO2and other components in various amounts. Components of the product stream may be separated and used for various purposes in the rWGS process.

[0119] For example, in various embodiments of the present disclosure as described herein, the method further comprises separating the product stream to recycle at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) of one or more components of the product stream to the feed stream. For example, when the product stream includes CO2, the method can include recycling at least a portion (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%. at least 75 mol%, or at least 90 mol%) of the CO2of the product stream to the feed stream. The product stream may also include H2; in some embodiments, the method further includes recycling at least a portion of H2of the product stream (e.g., at least 5 mol%, at least 10 mol%, at least 25 mol%, at least 50 mol%, at least 75 mol%, or at least 90 mol%) to the feed stream.

[0120] Such recycling is shown in the process 100 of FIG. 1. Here, the process 100 includes separating from the product stream 112 at least a portion of CO2(stream 114) to recycle to the feed stream 111. Similarly, the process 100 includes separating from the product stream 112 at least a portion of H2(stream 115) to recycle to the product stream 111. While stream 115 is depicted as entering reactor 110 through a different inlet than the rest of the feed stream 111, it is considered to be part of the feed stream, as it is part of the material input to the process step.

[0121] As noted above, one competing reaction in the reverse water-gas shift reaction is the Sabatier reaction, which makes methane. While in various embodiments the reverse water-gas shift processes described herein can be performed without forming large amounts of methane, in some embodiments there can be some methane formed. Accordingly, in various embodiments of the method as described herein, the product stream comprises one or more light hydrocarbons. For example, in some embodiments, the product stream may include one or more of methane, ethane, propane, or combinations thereof. As would be understood by the person of ordinary skill in the art, it may be desirable to operate the reverse water-gas shift reaction to provide higher amounts of light hydrocarbons in theproduct feed. For example, such light hydrocarbons may be inert in further processing of the product stream and so may be acceptable at higher amounts. The person of ordinary skill in the art would be able to select appropriate reaction conditions (e.g., temperature, pressure, feed stream composition) to provide a product stream that includes methane at a desired amount. For example, in various embodiments as otherwise described herein, the product stream includes no more than 20 mol% methane or no more than 15 mol%. As noted above, when lower amounts of methane are desired in the product stream, the catalysts of the disclosure can provide very low methane selectivity. Accordingly, in various embodiments as otherwise described herein, the product stream includes no more than 10 mol% methane. For example, in various embodiments, the product stream includes no more than 5 mol%, or 1 mol%, or 0.5 mol%, or no more than 0.1 mol% methane.

[0122] The light hydrocarbons of the product stream can be separated and used for other purposes. For example, in various embodiments, the method further includes separating at least a portion of one or more light hydrocarbons from the product stream to provide a light hydrocarbon stream. For example, in method 100 of FIG. 1 , at least a portion of one or more light hydrocarbons are separated from the product stream 112 to provide a light hydrocarbon stream 116. The light hydrocarbon stream, for example, can be used to provide other products, can be partially oxidized to form CO, can be steam reformed to provide hydrogen, and / or can be burned to provide heat or other energy (e.g., electricity for electrolysis) for use in the rWGS method or otherwise.

[0123] The person of ordinary skill in the art will provide the materials and perform the methods described herein based on the general disclosure above, and with reference to the Examples below.EXAMPLES

[0124] The Examples that follow are illustrative of specific embodiments of the catalysts and processes of the disclosure, and various uses thereof. They are set forth for explanatory purposes only, and are not to be taken as limiting the scope of the disclosure.

[0125] Example 1. Catalyst Preparation

[0126] Both monometallic catalysts, tellurium promoted catalysts, and bismuth promoted were prepared using incipient wetness impregnation (IWI). For all of the catalysts, Titania (Aeroxide® TiO2P25, 48 m2g-1) was compacted with deionized water and dried at 100 °C for 7 days. The obtained agglomerates were crushed and sieved for the fraction between 250 and 400 microns, yielding a free-flowing powder to allow for easier handling.

[0127] To prepare the monometallic catalyst, a solution of the active metal nitrates (e.g., Co, Ni, Ru, or Rh) was prepared in deionized water to target 2 wt% of metal and a metal density of 0.34 mmol / g, meas.: 1.68wt% (Co), 2.15wt% (Ni)). The solution of active metal nitrate was added to titanium oxide powder. For the cobalt catalyst, an aqueous stock solution of cobalt nitrate hexahydrate (Co(NO)3, 6 H2O, >99%, SigmaAldrich), was prepared by dissolving 1233 mg (4.24 mmol) of Co(NO3)2.6 H2O in 5 mL deionized water. 0.4 ml (0.334 mmol Co(NO3)2) of stock solution was used for IWI on 1 g of TiO2- For the nickel catalyst, an aqueous stock solution of nickel nitrate hexahydrate (Ni(NO)3.6 H2O, >98%, AlfaAesar) was prepared by dissolving 1238.6 mg (4.26 mmol) of Ni(NO3)2.6 H2O in 5 mL deionized water. 0.4 ml g-1(0.334 mmol Ni(NO3)2) of stock solution was used for IWI on 1 g of TiO2. For the ruthenium catalyst, an aqueous stock solution of ruthenium nitrosyl nitrate (RU(NO)(NO3)3, 31.3% Ru in nitric acid, ABCR) was prepared by dissolving 95.4 mg (0.3 mmol Ru) of Ru(NO)(NO3)3in 2 mL deionized water. 0.4 ml g-1(0.06 mmol Ru) of stock solution was used for IWI on 1 g of TiO2. For the rhodium catalyst, an aqueous stock solution of rhodium nitrate (Rh(NO3)3, 36wt% Rh , SigmaAldrich) were used as received was prepared by dissolving 85.8 mg (0.3 mmol) of Rh(NO3)3in 2 mL deionized water. 0.4 ml g-1(0.06 mmol Rh) of stock solution was used for IWI on 1 g of TiO2.

[0128] To prepare the tellurium promoted catalyst, a solution of the active metal nitrates (e.g., Co, Ni, Ru, or Rh) and telluric acid was prepared in deionized water to target 2 wt% of metal and an equimolar amount of tellurium to obtain a metal density of ca. 0.34 mmol / g (ca.5 atoms nm-2, meas.: CoTe: 1.54wt% Co and 3.94wt% Te; meas.: NiTe: 1.95% Ni and 3.95% Te). The solution of active metal nitrate and tellurium was added to titanium oxide powder. For the cobalt and tellurium catalyst, an aqueous stock solution of Co(NO3)2.6 H2O and Telluric acid (Te(OH)e, >99%, SigmaAldrich), where both metals are in the same solution, was prepared by dissolving 1233 mg (4.24 mmol) of Co(NO3)2.6 H2O and 973.1 mg (4.24 mmol) of Te(OH)e in 5 mL deionized water. 0.4 ml (0.334 mmol Co(NO3)2& Te(OH)e) of stock solution was used for IWI on 1 g of TiO2. For the nickel and tellurium catalyst, an aqueous stock solution of Ni(NO3)2.6 H2O and Telluric acid (Te(OH)e, >99%, SigmaAldrich), where both metals are in the same solution, was prepared by dissolving 1238.6 mg (4.26 mmol) of Ni(NO3)2.6 H2O and 973.1 mg (4.24 mmol) of Te(OH)e in 5 mL deionized water. 0.4 ml g-1(0.334 mmol Ni(NO3)2& Te(OH)6) of stock solution was used for IWI on 1 g of TiO2- For the ruthenium and tellurium catalyst, an aqueous stock solution of Ru(NO)(NO3)3and Telluric acid (Te(OH)e, >99%, SigmaAldrich), where both metals are in the same solution, was prepared by dissolving 95.4 mg (0.3 mmol Ru) of Ru(NO)(NO3) and 68.9 mg (0.3 mmol) of Te(OH)6in 2 mL deionized water. 0.4 ml g-1(0.06 mmol Ru & Te(OH)6) of stock solution was used for IWI on 1 g of TiO2- For the rhodium and tellurium catalyst, an aqueous stocksolution of Rh(NO3)3and Telluric acid (Te(OH)e, >99%, SigmaAldrich), where both metals are in the same solution, was prepared by dissolving 85.75 mg (0.3 mmol) of Rh(NO3)3and 68.9 mg (0.3 mmol) of Te(OH)e in 2 mL deionized water. 0.4 ml g-1(0.06 mmol Rh(NO3)3& Te(OH)e) of stock solution was used for IWI on 1 g of TiO2.

[0129] To prepare the bismuth promoted catalyst, a solution of the active metal nitrates (e.g., Co, Ni, Ru, or Rh) and bismuth nitrate was prepared in deionized water to target 2 wt% of metal and an equimolar amount of bismuth. The solution of active metal nitrate and bismuth was added to titanium oxide powder.

[0130] The impregnated materials were dried at room temperature and calcined under a flow of synthetic air at 300°C for 6 hours.

[0131] Example 2. Characterization of Tellurium Promoted Catalysts

[0132] The catalyst prepared in Example 1 were characterized with high-angle annular dark-field (HAADF) scanning transmission electron microscopy (STEM) coupled with electron dispersive X-ray (EDX) elemental mapping to assess particle formation and element dispersion as well as spatial localization on the mono- and bimetallic catalysts after calcination and hydrogen treatment. FIG. 2A-2D show the HAADF-STEM EDX micrographs of Co / TiO2, CoTe / TiO2, Ni / TiO2and NiTe / TiO2, respectively. Transmission electron microscopy images, were obtained using a FEI Talos F200X equipped with an X-FEG electron gun, operating at 200 kV. Elemental mapping was performed through EDX analysis, with data gathered by Super X-EDS detectors at dwell times of 10 ps. To prepare the sample holder, the powdered samples, were applied directly to a Lacey-C 400 mesh Cu grid (Ted Pella) in an inert environment and placed on a vacuum transfer tomography holder (Fischione Instruments, model #2560) for transportation and insertion into the electron microscope. The distribution of particle size was assessed by measuring individual particles and calculating the average diameters ((dTEM)) and standard deviations based on the normal distribution function. The processing of the micrographs was carried out using Imaged, a Java-based imaging processing program.

[0133] The bimetallic catalyst materials exhibit average particle sizes of 15.4 (± 3.8) nm for CoTe / TiO2and 8 ± (0.7) nm for NiTe / TiO2, while nanoparticles are homogeneously distributed on the TiO2support. Micrographs of monometallic Co / TiO2reveal the formation of significantly larger nanoparticles with particle sizes ranging from 20 to 60 nm. Due to the low number of particles present on Co / TiO2, only an estimate can be given for the average particle size at ~ 41 (± 9) nm. Monometallic Ni / TiO2exhibits significantly smaller particles at an average particle size of 12 (± 0.9) nm. Elemental maps show a strong correlation between the EDX counts for M (M=Co, Ni) and Te in both the bimetallic CoTe and NiTecatalysts, possibly indicating alloying as shown in FIG. 2B and 2D. In fact, powder X-ray diffraction (PXRD), shown in FIG. 3, confirms the formation of MTe (M=Co,Ni) crystalline phases, 1 :1 M:Te alloys with a NiAs-type structure. Overall, both Co and Ni alloy with Te, which helps forming smaller particles readily detected by microscopy due to the high contrast provided by Te. PXRD diffractograms were acquired on a Bruker AXS D8 Advance diffractometer operated at 50 kV and 40 mA at 20 (Mo Ka) = 2-68.33°. The scanning step size and speed were 0.495° and 10s per step, respectively. Crystal phases are identified with reference parameters from Co (PDF 01-090-7268), Ni (01-090-6555), CoTe (01-071- 4778) and NiTe (1-071-4779). Diffractograms were processed and compared via the Jade XRD software.

[0134] X-ray absorption spectroscopy (XAS) was next employed to assess the state of Co and Ni in the monometallic and Te-doped catalyst variants after hydrogen treatment at the Co and Ni K edge, respectively. XAS spectra are acquired in fluorescence mode due to the high absorption of TiO2, which prevents data acquisition in transmission mode (see FIG. 4). XAS spectra were acquired at the European Synchrotron Radiation Facility (ESRF) on beamline BM31 of the Swiss Norwegian Beamline (SNBL) Facility in Grenoble, France. All spectra were processed using the Demeter software package (Athena, Artemis and Heaphaestus). All samples were exclusively handled and prepared in Argon-filled gloveboxes and packed in 1 mm quartz capillaries sealed with wax and two-component epoxy glue to prevent the exposure to ambient atmosphere. All spectra were acquired at the Co or Ni K edge in either transmission or fluorescence mode, depending on the support (Transmission: SiO2, AI2O3: Fluorescence: TiO2). The XAS spectra of the catalysts are shown in FIGs. 4A-4F.

[0135] Both Co-based catalysts exhibit “metallic” Co after treatment, which is reflected in the edge position and the scattering paths found in the R-space of the respective spectra. Strikingly, CoTe / TiO2exhibits for Co an Eo shift to lower energies (-1.03 eV) with respect to monometallic, Co / TiO2and the Co foil reference, indicating increased electron density on cobalt when doped with Te (FIG. 4B and 4C). The presence of Te clearly alters the EXAFS pattern for Co in CoTe / TiO2in comparison to the two references (FIG. 4A). This is reflected by the notable different scattering paths found in the R-space of CoTe / TiO2: instead of a main path at ca. 2.2 A, representing the Co-Co path; two paths can be found, which are located at 2.0 and 2.4 A, respectively (FIG. 4C). Considering again the STEM-EDX maps and X-Ray diffraction data, these paths further support CoTe alloying, in which the original metal-metal-only path is divided into an altered Co-Co (2.0) and a new Co-Te path (2.4 A). Overall, XAS data implies that Co is electronically enriched and structurally altered by the presence of Te in CoTe / TiO2compared to its monometallic variant. XAS of a spentCoTe / TiO2catalyst indicates minor oxidation, reflecting possibly the deactivation pathway for this catalyst, while product selectivity remains almost unchanged for extended periods of time (FIGs. 5A and 5B). The Ni K edge XAS spectrum of NiTe / TiO2also exhibits the structural changes reflected in the EXAFS region (altered interference pattern) and R-space (new scattering paths at 2.0 and 2.45 A), which are likely induced by alloying with Te, the Eo shift is not observed (FIGs. 4D, 4E, and 4F). Microscopy and XAS experiments show that Co and Ni are in a metallic state in both the monometallic and Te-doped variants, while the presence of Te results in more dispersed, alloyed nanoparticles with altered structure compared to the monometallic variants.

[0136] Example 3. Performance of Metalloid Promoted Catalysts

[0137] Monometallic and metalloid promoted catalysts prepared as explained in Example 1 were then tested for their catalytic performance for reverse water-gas shift reactions. To test the catalytic performance of these catalysts, 80 mg of the catalyst was diluted with 4 g of SiC. Prior to performing the rWGS reaction, the catalysts were activated in situ in a flow of hydrogen at 400 °C for 3 hours before exposure to reaction gas. Then, the catalysts were contacted at a temperature of 450 °C with a feed stream including H2and CO2and Ar at a ratio of 3:1 :1 at 20 mL / min to conduct the rWGS reaction. The total pressure was kept at 40 bar (g). The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The catalytic performance of these catalysts are shown in Table 1. In Table 1 , and Tables 2-8 below, the amount of cobalt, nickel, ruthenium, rhodium, and tellurium present in the catalyst are shown in parenthesis. These numbers are in weight percent and based on the total weight of the catalyst. For example, Co(2)Te(2) / TiO2corresponds to a catalyst with 2 wt% Co, 4 wt% Te, and 94 wt% TiO2.

[0138] Table 1.As can be seen from Table 1, the addition of metalloids (e.g., tellurium, indium, silicon, germanium, tin, antimony, and bismuth) drastically decreases the selectivity for methane and increases the selectivity of carbon monoxide. This is an almost complete reversal of the selectivity of the monometallic catalyst tested. Accordingly, the addition of tellurium switches the reactivity of the catalyst towards the reverse water-gas shift reaction.

[0139] Example 4. Performance of Bismuth Promoted Catalysts

[0140] Monometallic and bismuth promoted catalysts prepared as explained in Example 1 were then tested for their catalytic performance for reverse water-gas shift reactions. A gallium promoted catalyst, also prepared by the method as described in Example 1, was also tested. To test the catalytic performance of these catalysts, 80 mg of the catalyst was diluted with 4 g of SiC. Prior to performing the rWGS reaction, the catalysts were activated in situ in a flow of hydrogen at 400 °C for 3 hours before exposure to reaction gas. Then, the catalysts were contacted at a temperature of 230 °C with a feed stream including H2andC02and Ar at a ratio of 3:1 :1 at 8000 GHSV to conduct the rWGS reaction. The total pressure was kept at 25 bar (g). The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The catalytic performance of these catalysts are shown in Table 2.

[0141] Table 2.

[0142] Similar to tellurium, when bismuth is added, the methane selectivity drastically decreases while the CO selectivity drastically increases. This is an almost complete reversal of the selectivity of the monometallic catalyst tested. Accordingly, the addition of bismuth switches the reactivity of the catalyst towards the reverse water-gas shift reaction.

[0143] Example 5. Performance of Metalloid Promoted Catalysts Under VariousConditions

[0144] Both monometallic and metalloid promoted catalysts prepared as explained in Example 1 were tested from their catalytic performance for reverse water-gas shift reactions under various conditions. To test the catalytic performance of these catalysts, 80 mg of the catalyst was diluted with 4 g of SiC. Prior to performing the rWGS reaction, the catalysts were activated in situ in a flow of hydrogen at 400 °C for 3 hours before exposure to reaction gas. Then, the catalysts were contacted at a temperatures ranging from 200 to 450 °C at pressures ranging from 1-40 bar (g), with a feed stream including H2and CO2and Ar at a ratio of 3:1:1 at 20 mL / min to conduct the rWGS reaction. The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The catalytic performance of these catalysts are shown in Tables 3-6, FIG. 6, and FIG. 7. Table 3 shows the results of cobalt-based catalysts, Table 4 shows the results for nickel-based catalysts, Table 5 shows the results of ruthenium-based catalysts, and Table 6 shows the results of the rhodium-based catalysts. Selectivities at conversions below 0.5% were not determined and are indicated by “n.d.” in the Table 3-6.

[0145] Table 3.

[0146] Table 4.

[0147] Table 5.

[0148] Table 6.

[0149] Generally, throughout all catalysts, an increase in reaction temperature resulted in higher levels of CO2conversion, while selectivity was not affected by temperature forbimetallic systems in contrast to monometallic variants. Notably, bimetallic Co and Ni- catalysts produce almost exclusively CO via the RWGS reaction, regardless of reaction temperature and conversion (see FIG. 7B). Both Co- and Ni-catalysts exhibit CO selectivities up to 99.5%, while not falling much below 98% CO in the product gas mixture. CoTe / TiO2and NiTe / TiO2achieve 31% and 38.5% CO2conversion at 450°C, respectively, approaching thermodynamic equilibrium for the RWGS reaction (43.7%), showcasing their high activity under relatively mild conditions (see FIG. 6A). This sharply contrasts with the known reactivity of Co and Ni: both monometallic catalysts, Co / TiO2and Ni / TiO2, convert CO2into methane as expected, the rate increasing with increasing temperatures with conversion up to 50% and 90%, respectively, (see FIG. 6B) and methane selectivity eroding at high temperatures as expected based on thermodynamics (see FIG. 7B).

[0150] The drastic change in reactivity by the presence of metalloids (e.g., tellurium, indium, silicon, germanium, tin, antimony, and bismuth) is best illustrated by comparing catalysts at 450 °C: The high methanation selectivity, typically expected for Co and Ni, is fully suppressed, with a fully inverted selectivity towards CO for the bimetallic systems (see FIG. 7B). This data highlights the dramatic promotional effect of tellurium that makes base metals like Co and Ni behave like classical Pt-based RWGS catalysts. This drastic change in reactivity is not exclusive to 3d transition metals and other well-known methanation catalysts based on Rh and Ru equally shift their reactivity to exclusively promoting RWGS upon addition of Te (see FIGs. 7A-7C). Furthermore, catalyst stability was evaluated over 150 h on stream at 400 °C and 40 bar. Following an initial deactivation, both CoTe / TiO2and NiTe / TiO2at ca. 50% (Co) and 65% (Ni) of their initial CO2conversion, the selectivity towards RWGS remains almost unchanged (See FIG. 6C and 6D). The selectivity of CoTe / TiO2for CO diminishes to 95%, while NiTe / TiO2retains unchanged selectivity for CO at 98.5% after 150 h on stream, highlighting the stable reactivity of metal telluride catalysts.

[0151] As can be seen from Tables 3-6, the addition of metalloids (e.g., tellurium, indium, silicon, germanium, tin, antimony, and bismuth) drastically decreases the selectivity for methane and increases the selectivity of carbon monoxide over all of the conditions tested for the four different active metals. This is an almost complete reversal of the selectivity of the monometallic catalyst tested. Accordingly, the addition of tellurium switches the reactivity of the catalyst towards the reverse water-gas shift reaction.

[0152] Example 6. Effect of Tellurium Loading on Catalyst Performance

[0153] Tellurium promoted catalysts with cobalt as the active metal were prepared as described in Example 1, but with varying amounts of tellurium. These catalyst were tested for their reverse water-gas shift activity. To test the catalytic performance of these catalysts,80 mg of the catalyst was diluted with 4 g of SiC. Prior to performing the rWGS reaction, the catalysts were activated in situ in a flow of hydrogen at 400 °C for 3 hours before exposure to reaction gas. Then, the catalysts were contacted at a temperature at various temperatures and pressures, with a feed stream including H2and CO2and Ar at a ratio of 3:1 :1 at 20 mL / min to conduct the rWGS reaction. The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The catalytic performance of these catalysts are shown in Table 7.

[0154] Table 7.

[0155] Over a variety of active metal and tellurium ratios, the increased CO selectivity and decreased methane selectivity is observed as described herein. Accordingly, the addition of tellurium in various amounts switches the reactivity of the catalyst towards the reverse water-gas shift reaction.

[0156] Example 7. Effect of Support on Tellurium Promoted Cobalt Catalyst Performance

[0157] Tellurium promoted catalysts with cobalt as the active metal were prepared as described in Example 1 , but with different support materials. These catalyst were tested for their reverse water-gas shift activity. To test the catalytic performance of these catalysts, 80 mg of the catalyst was diluted with 4 g of SiC. Prior to performing the rWGS reaction, the catalysts were activated in situ in a flow of hydrogen at 400 °C for 3 hours before exposure to reaction gas. Then, the catalysts were contacted at a temperature or 230 °C at a pressure of 25 bar (g), with a feed stream including H2and CO2and Ar at a ratio of 3:1 :1 at 6 mL / min to conduct the rWGS reaction. The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The catalytic performance of these catalysts are shown in Table 8.

[0158] Table 8.

[0159] For both SiO2 and AI2O3 supports, the methane selectivity remains low but not as low as the TiO2support. The CO selectivity remains high for all of the supports tested.Accordingly, the addition of tellurium independent of the support used switches the reactivity of the cobalt catalyst towards the reverse water-gas shift reaction.

[0160] Example 8. Effect of Support on Tellurium Promoted Rhenium Catalyst Performance

[0161] Tellurium promoted catalysts with rhenium as the active metal were prepared as described in Example 1 , but with different support materials. These catalyst were tested for their reverse water-gas shift activity. To test the catalytic performance of these catalysts, 80 mg of the catalyst was diluted with 4 g of SiC. Prior to performing the rWGS reaction, the catalysts were activated in situ in a flow of hydrogen at 400 °C for 3 hours before exposure to reaction gas. Then, the catalysts were contacted at a temperature or 450 °C at a pressure of 1 bar (g), with a feed stream including H2and CO2and Ar at a ratio of 3:1 :1 at 6 mL / min to conduct the rWGS reaction. The catalytic performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The catalytic performance of these catalysts are shown in Table 9.

[0162] Table 9.

[0163] For the SiO2 and AI2O3 supports, the methane selectivity remains low but not as low as the TiO2and CeO2 supports. The CO selectivity remains high for all of the supports tested. Accordingly, the addition of tellurium independent of the support used switches the reactivity of the rhodium catalyst towards the reverse water-gas shift reaction.

[0164] Example 9. Control - Tellurium on Various Supports

[0165] Tellurium without an active metal were prepared as described in Example 1 on different support materials. These material were tested for their reverse water-gas shift activity. To test the performance of these materials, 80 mg of the material was diluted with 4 g of SiC. Prior to performing the rWGS reaction, the materials were activated in situ in a flow of hydrogen at 400 °C for 3 hours before exposure to reaction gas. Then, the materials were contacted at a temperature or 450 °C at a pressure of 1 bar (g), with a feed stream includingH2and CO2and Ar at a ratio of 3:1:1 at 6 mL / min to conduct the rWGS reaction. The performance was analyzed by detecting the gas composition of the reactor outlet feed using a multi-detector gas chromatograph. The performance of these catalysts are shown in Table 10.

[0166] Table 10.

[0167] The catalyst materials that include tellurium, have low methane selectivity, high CO selectivity, but poor CO2conversion. The CO selectivity remains high for all of the supports tested. Accordingly, the addition of an active metal (e.g, cobalt, nickel, ruthenium, and rhodium), increases the CO2conversion of these materials as described in Tables 1 and 3-6.

[0168] Overall, metalloids (e.g., tellurium, indium, silicon, germanium, tin, antimony, and bismuth) are demonstrated to be an outstanding promoter, inducing RWGS reactivity in well- known methanation catalysts making base metals like Co and Ni behave like Pt, a well- known RWGS catalyst. Notably, CoTe / TiO2and NiTe / TiO2are highly active, selective, and stable catalysts for the low-temperature RWGS (up to 450 °C), almost reaching equilibrium conversion. Considering that the tellurium-doped base metal catalysts exhibited the highest activity at higher pressures (40 bar), it could readily be integrated with a Fischer-Tropsch process, thereby enabling access to fuels, long-chain olefins, and alcohols from CO2.Notably, this Te-promotion extends to other well-known methanation catalysts like Ru or Rh which are also converted into RWGS catalysts, illustrating the unique nature of Te in altering the electronic structure of transition metal elements. Electron microscopy, pXRD, and XAS data show that Te alloys with both Co and Ni result in electronically and structurally changed Co and Ni phases in the respective bimetallic catalysts, likely causing the drastic shift in reactivity. The discovery that alloying with tellurium can drastically change the property of a transition metal, opens new possibilities and indicates the need for a systematic, in-depth exploration of other promoters such as semi-metals (e.g., Bi, Sb, Ge), which as shown above also provide dramatic switching in the reactivity towards the reverse water-gas shift reaction for these materials. Understanding how specific electronic structures drive reactivity is crucial for developing predictive structure-reactivity relationships. This enables us toexplore chemical space through data-driven, high-throughput experimental approaches.Such methods are vital for the discovery of efficient and sustainable processes, including the conversion of CO2into valuable products.

[0169] Additional aspects of the disclosure are provided by the following enumerated embodiments, which may be combined in any number and in any combination that is not logically or technically inconsistent.Embodiment 1. A supported CO2conversion catalyst comprising: a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; at least one of cobalt, nickel, ruthenium, and rhodium, present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst.Embodiment 2. The catalyst of embodiment 1 , wherein the support makes up at least 70 wt% (e.g., at least 75 wt%, or 80 wt%, or 85 wt%, or 90 wt%) of the catalyst, on an oxide basis.Embodiment 3. The catalyst of embodiment 1 or embodiment 2, wherein the support is a cerium oxide support.Embodiment 4. The catalyst of embodiment 3, wherein at least a surface layer of the cerium oxide support comprises at least 60 wt% cerium oxide, e.g., at least 70 wt% cerium oxide or at least 80 wt% cerium oxide, on an oxide basis.Embodiment 5. The catalyst of embodiment 3, wherein at least a surface layer of the cerium oxide support comprises at least 90 wt% cerium oxide, e.g., at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide, on an oxide basis.Embodiment 6. The catalyst of any of embodiments 3-5, wherein the cerium oxide support comprises at least 50 wt% cerium oxide, e.g., at least 60 wt% cerium oxide, or at least 70 wt% cerium oxide, or at least 80 wt% cerium oxide, on an oxide basis.Embodiment 7. The catalyst of any of embodiments 3-5, wherein the cerium oxide support comprises at least 90 wt% cerium oxide, e.g., at least 95 wt% cerium oxide, or at least 98 wt% cerium oxide, on an oxide basis.Embodiment 8. The catalyst of embodiment 1 or embodiment 2, wherein the support is a titanium oxide support.Embodiment 9. The catalyst of embodiment 8, wherein at least a surface layer of the titanium oxide support comprises at least 60 wt% titanium oxide, e.g., at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide, on an oxide basis.Embodiment 10. The catalyst of embodiment 8, wherein at least a surface layer of the titanium oxide support comprises at least 90 wt% titanium oxide, e.g., at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide, on an oxide basis.Embodiment 11. The catalyst of any of embodiments 8-10, wherein the titanium oxide support comprises at least 50 wt% titanium oxide, e.g., at least 60 wt% titanium oxide, or at least 70 wt% titanium oxide, or at least 80 wt% titanium oxide, on an oxide basis.Embodiment 12. The catalyst of any of embodiments 8-10, wherein the titanium oxide support comprises at least 90 wt% titanium oxide, e.g., at least 95 wt% titanium oxide, or at least 98 wt% titanium oxide, on an oxide basis.Embodiment 13. The catalyst of embodiment 1 or embodiment 2, wherein the support is an aluminum oxide support.Embodiment 14. The catalyst of embodiment 13, wherein at least a surface layer of the aluminum oxide support comprises at least 60 wt% aluminum oxide, e.g., at least 70 wt% aluminum oxide or at least 80 wt% aluminum oxide, on an oxide basis.Embodiment 15. The catalyst of embodiment 13, wherein at least a surface layer of the aluminum oxide support comprises at least 90 wt% aluminum oxide, e.g., at least 95 wt% aluminum oxide, or at least 98 wt% aluminum oxide, on an oxide basis.Embodiment 16. The catalyst of any of embodiments 13-15, wherein the aluminum oxide support comprises at least 50 wt% aluminum oxide, e.g., at least 60 wt% aluminumoxide, or at least 70 wt% aluminum oxide, or at least 80 wt% aluminum oxide, on an oxide basis.Embodiment 17. The catalyst of any of embodiments 13-15, wherein the aluminum oxide support comprises at least 90 wt% aluminum oxide, e.g., at least 95 wt% aluminum oxide, or at least 98 wt% aluminum oxide, on an oxide basis.Embodiment 18. The catalyst of embodiment 1 or embodiment 2, wherein the support is a zirconium oxide support.Embodiment 19. The catalyst of embodiment 18, wherein at least a surface layer of the zirconium oxide support comprises at least 60 wt% zirconium oxide, e.g., at least 70 wt% zirconium oxide or at least 80 wt% zirconium oxide, on an oxide basis.Embodiment 20. The catalyst of embodiment 18, wherein at least a surface layer of the zirconium oxide support comprises at least 90 wt% zirconium oxide, e.g., at least 95 wt% zirconium oxide, or at least 98 wt% zirconium oxide, on an oxide basis.Embodiment 21. The catalyst of any of embodiments 18-20, wherein the zirconium oxide support comprises at least 50 wt% zirconium oxide, e.g., at least 60 wt% zirconium oxide, or at least 70 wt% zirconium oxide, or at least 80 wt% zirconium oxide, on an oxide basis.Embodiment 22. The catalyst of any of embodiments 18-21, wherein the zirconium oxide support comprises at least 90 wt% zirconium oxide, e.g., at least 95 wt% zirconium oxide, or at least 98 wt% zirconium oxide, on an oxide basis.Embodiment 23. The catalyst of embodiment 1 or embodiment 2, wherein the support is a zinc oxide support.Embodiment 24. The catalyst of embodiment 23, wherein at least a surface layer of the zinc oxide support comprises at least 60 wt% zinc oxide, e.g., at least 70 wt% zinc oxide or at least 80 wt% zinc oxide, on an oxide basis.Embodiment 25. The catalyst of embodiment 23, wherein at least a surface layer of the zinc oxide support comprises at least 90 wt% zinc oxide, e.g., at least 95 wt% zinc oxide, or at least 98 wt% zinc oxide, on an oxide basis.Embodiment 26. The catalyst of any of embodiments 23-25, wherein the zinc oxide support comprises at least 50 wt% zinc oxide, e.g., at least 60 wt% zinc oxide, or at least 70 wt% zinc oxide, or at least 80 wt% zinc oxide, on an oxide basis.Embodiment 27. The catalyst of any of embodiments 23-26, wherein the zinc oxide support comprises at least 90 wt% zinc oxide, e.g., at least 95 wt% zinc oxide, or at least 98 wt% zinc oxide, on an oxide basis.Embodiment 28. The catalyst of embodiment 1 or embodiment 2, wherein the support is a silicon oxide support.Embodiment 29. The catalyst of embodiment 28, wherein at least a surface layer of the silicon oxide support comprises at least 60 wt% silicon oxide, e.g., at least 70 wt% silicon oxide or at least 80 wt% silicon oxide, on an oxide basis.Embodiment 30. The catalyst of embodiment 28, wherein at least a surface layer of the silicon oxide support comprises at least 90 wt% silicon oxide, e.g., at least 95 wt% silicon oxide, or at least 98 wt% silicon oxide, on an oxide basis.Embodiment 31. The catalyst of any of embodiments 28-30, wherein the silicon oxide support comprises at least 50 wt% silicon oxide, e.g., at least 60 wt% silicon oxide, or at least 70 wt% silicon oxide, or at least 80 wt% silicon oxide, on an oxide basis.Embodiment 32. The catalyst of any of embodiments 28-31 , wherein the silicon oxide support comprises at least 90 wt% silicon oxide, e.g., at least 95 wt% silicon oxide, or at least 98 wt% silicon oxide, on an oxide basis.Embodiment 33. The catalyst of embodiment 1 or embodiment 2, wherein the support is a mixed oxide support having at least a surface layer comprising at least 50 wt% of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide, on an oxide basis.Embodiment 34. The catalyst of any of embodiments 1-33, wherein the support does not include additional metals in a total amount of additional metals in excess of 2 wt%, e.g., in excess of 1 wt% or in excess of 0.5 wt%, on an oxide basis.Embodiment 35. The catalyst of any of embodiments 1-24, wherein the support includes at least one additional metal.Embodiment 36. The catalyst of embodiment 35, wherein the total amount of the at least one additional metal is in the range of 0.5-20 wt%, e.g., 1-20 wt%, or 2-20 wt%, or 0.5- 15 wt%, or 1-15 wt%, or 2-15 wt%, or 0.5-10 wt%, or 1-10 wt%, or 2-10 wt%, or 0.5-5 wt%, or 1-5 wt%, on an oxide basis.Embodiment 37. The catalyst of any of embodiments 1-36, wherein the support has a pore volume of at least 0.05 mL / g.Embodiment 38. The catalyst of any of embodiments 1-37, wherein the support has a pore volume of at most 1.5 mL / g.Embodiment 39. The catalyst of any of embodiments 1-38, wherein the support has a pore volume in the range of 0.05-1.5 mL / g.Embodiment 40. The catalyst of any of embodiments 1-39, wherein the catalyst includes only one of cobalt, nickel, ruthenium, and rhodium.Embodiment 41. The catalyst of any of embodiments 1-40, wherein cobalt is present in the catalyst.Embodiment 42. The catalyst of embodiment 41 , wherein cobalt is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 43. The catalyst of embodiment 41 , wherein cobalt is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 44. The catalyst of embodiment 41 , wherein cobalt is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 45. The catalyst of embodiment 41 , wherein cobalt is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 46. The catalyst of embodiment 41 , wherein cobalt is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 47. The catalyst of embodiment 41 , wherein cobalt is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 48. The catalyst of any of embodiments 1-40, wherein nickel is present in the catalyst.Embodiment 49. The catalyst of embodiment 48, wherein nickel is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 50. The catalyst of embodiment 48, wherein nickel is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 51. The catalyst of embodiment 48, wherein nickel is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 52. The catalyst of embodiment 48, wherein nickel is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 53. The catalyst of embodiment 48, wherein nickel is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 54. The catalyst of embodiment 48, wherein nickel is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 55. The catalyst of any of embodiments 1-54 with the proviso that if an amount of nickel is at least 0.05 wt%, an amount of cobalt is no more than 0.1 wt%.Embodiment 56. The catalyst of any of embodiments 1-55 with the proviso that if an amount of nickel is at least 0.05 wt%, an amount of ruthenium is no more than 0.1 wt%.Embodiment 57. The catalyst of any of embodiments 1-40, wherein ruthenium is present in the catalyst.Embodiment 58. The catalyst of embodiment 57, wherein ruthenium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 59. The catalyst of embodiment 57, wherein ruthenium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 60. The catalyst of embodiment 57, wherein ruthenium is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 61. The catalyst of embodiment 57, wherein ruthenium is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 62. The catalyst of embodiment 57, wherein ruthenium is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 63. The catalyst of embodiment 57, wherein ruthenium is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 64. The catalyst of any of embodiments 1-40, wherein rhodium is present in the catalyst.Embodiment 65. The catalyst of embodiment 64, wherein rhodium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 66. The catalyst of embodiment 64, wherein rhodium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 67. The catalyst of embodiment 64, wherein rhodium is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 68. The catalyst of embodiment 64, wherein rhodium is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 69. The catalyst of embodiment 64, wherein rhodium is present in the catalyst in an amount in the range 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 70. The catalyst of embodiment 64, wherein rhodium is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 71. The catalyst of any of embodiments 1-70 with the proviso that if an amount of rhodium is at least 0.05 wt%, an amount of cobalt is no more than 0.1 wt%.Embodiment 72. The catalyst of any of embodiments 1-71 with the proviso that if an amount of rhodium is at least 0.05 wt%, an amount of ruthenium is no more than 0.1 wt%.Embodiment 73. The catalyst of any of embodiments 1-72, wherein at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic and boron, present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst.Embodiment 74. The catalyst of any of embodiments 1-73, wherein tellurium is present in the catalyst.Embodiment 75. The catalyst of embodiment 74, wherein tellurium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 76. The catalyst of embodiment 74, wherein tellurium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 77. The catalyst of embodiment 74, wherein tellurium is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 78. The catalyst of embodiment 74, wherein tellurium is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 79. The catalyst of embodiment 74, wherein tellurium is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 80. The catalyst of embodiment 74, wherein tellurium is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 81. The catalyst of any of embodiments 1-80, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tellurium is at least 0.2:1 , e.g., at least 0.5:1.Embodiment 82. The catalyst of any of embodiments 1-80, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tellurium is at least 0.8:1 , e.g., at least 1 :1.Embodiment 83. The catalyst of any of embodiments 1-82, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tellurium is at most 15:1 , e.g., at most 10:1 , or 5:1.Embodiment 84. The catalyst of any of embodiments 1-83, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tellurium is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1 , or 0.2:1 to 10:1 , or 0.2:1 to 5:1 , or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1, or 0.8:1 to 15:1, or 0.8:1 to 10:1 , or 0.8:1 to 5:1).Embodiment 85. The catalyst of any of embodiments 1-84, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tellurium is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1, or 0.2:1 to 1:1, or 0.5:1 to 2:1, or 0.5:1 to 1.5:1, or 0.5:1 to 1:1, or 0.8:1 to 2:1, or 0.8:1 to 1.5:1, or 0.8:1 to 1 :1).Embodiment 86. The catalyst of any of embodiments 1-73, wherein bismuth is present in the catalyst.Embodiment 87. The catalyst of embodiment 86, wherein bismuth is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 88. The catalyst of embodiment 86, wherein bismuth is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 89. The catalyst of embodiment 86, wherein bismuth is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 90. The catalyst of embodiment 86, wherein bismuth is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 91. The catalyst of embodiment 86, wherein bismuth is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 92. The catalyst of embodiment 86, wherein bismuth is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 93. The catalyst of any of embodiments 1-73 and 86-92, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to bismuth is at least 0.2:1 , e.g., at least 0.5:1.Embodiment 94. The catalyst of any of embodiments 1-73 and 86-92, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium bismuth tellurium is at least 0.8:1, e.g., at least 1:1.Embodiment 95. The catalyst of any of embodiments 1-73 and 86-92, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to bismuth is at most 15:1 , e.g., at most 10:1, or 5:1.Embodiment 96. The catalyst of any of embodiments 1-73 and 86-92, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to bismuth is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1 , or 0.2:1 to 5:1, or 0.5:1 to 15:1 , or 0.5:1 to 10:1, or 0.5:1 to 5:1, or 0.8:1 to 15:1, or 0.8:1 to 10:1 , or 0.8:1 to 5:1).Embodiment 97. The catalyst of any of embodiments 1-73 and 86-92, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to bismuth is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1 , or 0.2:1 to 1 :1 , or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1:1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1).Embodiment 98. The catalyst of any of embodiments 1-73, wherein tin is present in the catalyst.Embodiment 99. The catalyst of embodiment 98, wherein tin is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 100. The catalyst of embodiment 98, wherein tin is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 101. The catalyst of embodiment 98, wherein tin is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 102. The catalyst of embodiment 98, wherein tin is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 103. The catalyst of embodiment 98, wherein tin is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 104. The catalyst of embodiment 98, wherein tin is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 105. The catalyst of any of embodiments 1-73 and 98-104, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tin is at least 0.2:1 , e.g., at least 0.5:1.Embodiment 106. The catalyst of any of embodiments 1-73 and 98-104, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tin is at least 0.8:1, e.g., at least 1:1.Embodiment 107. The catalyst of any of embodiments 1-73 and 98-104, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tin is at most 15:1 , e.g., at most 10:1, or 5:1.Embodiment 108. The catalyst of any of embodiments 1-73 and 98-104, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tin is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1 , or 0.2:1 to 5:1 , or 0.5:1 to 15:1, or 0.5:1 to 10:1, or 0.5:1 to 5:1, or 0.8:1 to 15:1 , or 0.8:1 to 10:1, or 0.8:1 to 5:1).Embodiment 109. The catalyst of any of embodiments 1-73 and 98-104, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to tin is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1, or 0.2:1 to 1 :1, or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1, or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1, or 0.8:1 to 1 :1).Embodiment 110. The catalyst of any of embodiments 1-73, wherein antimony is present in the catalyst.Embodiment 111. The catalyst of embodiment 110, wherein antimony is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or inthe range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 112. The catalyst of embodiment 110, wherein antimony is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 113. The catalyst of embodiment 110, wherein antimony is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 114. The catalyst of embodiment 110, wherein antimony is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 115. The catalyst of embodiment 110, wherein antimony is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 116. The catalyst of embodiment 110, wherein antimony is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 117. The catalyst of any of embodiments 1-73 and 110-116, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to antimony is at least 0.2:1 , e.g., at least 0.5:1.Embodiment 118. The catalyst of any of embodiments 1-73 and 110-116, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to antimony is at least 0.8:1, e.g., at least 1:1.Embodiment 119. The catalyst of any of embodiments 1-73 and 110-116, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to antimony is at most 15:1 , e.g., at most 10:1 , or 5:1.Embodiment 120. The catalyst of any of embodiments 1-73 and 110-116, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to antimony is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1 , or 0.2:1 to 10:1 , or 0.2:1 to 5:1 , or 0.5:1 to 15:1 , or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1 , or 0.8:1 to 10:1 , or 0.8:1 to 5:1).Embodiment 121. The catalyst of any of embodiments 1-73 and 110-116, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to antimony is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1 , or 0.2:1 to 1 :1 , or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1).Embodiment 122. The catalyst of any of embodiments 1-73, wherein germanium is present in the catalyst.Embodiment 123. The catalyst of embodiment 122, wherein germanium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 124. The catalyst of embodiment 122, wherein germanium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 125. The catalyst of embodiment 122, wherein germanium is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 126. The catalyst of embodiment 122, wherein germanium is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 127. The catalyst of embodiment 122, wherein germanium is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 128. The catalyst of embodiment 122, wherein germanium is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 129. The catalyst of any of embodiments 1-73 and 122-128, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to germanium is at least 0.2:1, e.g., at least 0.5:1.Embodiment 130. The catalyst of any of embodiments 1-73 and 122-128, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to germanium is at least 0.8:1, e.g., at least 1:1.Embodiment 131. The catalyst of any of embodiments 1-73 and 122-128, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to germanium is at most 15:1, e.g., at most 10:1, or 5:1.Embodiment 132. The catalyst of any of embodiments 1-73 and 122-128, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to germanium is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1 , or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1).Embodiment 133. The catalyst of any of embodiments 1-73 and 122-128, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to germanium is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1, or 0.2:1 to 1:1, or 0.5:1 to 2:1, or 0.5:1 to 1.5:1, or 0.5:1 to 1:1 , or 0.8:1 to 2:1, or 0.8:1 to 1.5:1 , or 0.8:1 to 1:1).Embodiment 134. The catalyst of any of embodiments 1-73, wherein selenium is present in the catalyst.Embodiment 135. The catalyst of embodiment 134, wherein selenium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or inthe range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 136. The catalyst of embodiment 134, wherein selenium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 137. The catalyst of embodiment 134, wherein selenium is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 138. The catalyst of embodiment 134, wherein selenium is present in the catalyst in an amount in the range 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 139. The catalyst of embodiment 134, wherein selenium is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 140. The catalyst of embodiment 134, wherein selenium is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 141. The catalyst of any of embodiments 1-73 and 134-140, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to selenium is at least 0.2:1, e.g., at least 0.5:1.Embodiment 142. The catalyst of any of embodiments 1-73 and 134-140, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to selenium is at least 0.8:1 , e.g., at least 1:1.Embodiment 143. The catalyst of any of embodiments 1-73 and 134-140, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to selenium is at most 15:1, e.g., at most 10:1 , or 5:1.Embodiment 144. The catalyst of any of embodiments 1-73 and 134-140, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to selenium is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1 , or 0.5:1 to 10:1, or 0.5:1 to 5:1, or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1).Embodiment 145. The catalyst of any of embodiments 1-73 and 134-140, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to selenium is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1 , or 0.2:1 to 1:1, or 0.5:1 to 2:1, or 0.5:1 to 1.5:1 , or 0.5:1 to 1:1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1:1).Embodiment 146. The catalyst of any of embodiments 1-73, wherein arsenic is present in the catalyst.Embodiment 147. The catalyst of embodiment 146, wherein arsenic is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 148. The catalyst of embodiment 146, wherein arsenic is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 149. The catalyst of embodiment 146, wherein arsenic is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 150. The catalyst of embodiment 146, wherein arsenic is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 151. The catalyst of embodiment 146, wherein arsenic is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 152. The catalyst of embodiment 146, wherein arsenic is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 153. The catalyst of any of embodiments 1-73 and 146-152, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to arsenic is at least 0.2:1 , e.g., at least 0.5:1.Embodiment 154. The catalyst of any of embodiments 1-73 and 146-152, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to arsenic is at least 0.8:1 , e.g., at least 1:1.Embodiment 155. The catalyst of any of embodiments 1-73 and 146-152, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to arsenic is at most 15:1 , e.g., at most 10:1, or 5:1.Embodiment 156. The catalyst of any of embodiments 1-73 and 146-1520, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to arsenic is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1, or 0.2:1 to 5:1 , or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1).Embodiment 157. The catalyst of any of embodiments 1-73 and 146-152, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to arsenic is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1 , or 0.2:1 to 1:1 , or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1).Embodiment 158. The catalyst of any of embodiments 1-73, wherein boron is present in the catalyst.Embodiment 159. The catalyst of embodiment 158, wherein boron is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or inthe range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 160. The catalyst of embodiment 158, wherein boron is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 161. The catalyst of embodiment 158, wherein boron is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 162. The catalyst of embodiment 158, wherein boron is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 163. The catalyst of embodiment 158, wherein boron is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 164. The catalyst of embodiment 158, wherein boron is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 165. The catalyst of any of embodiments 1-73 and 158-164, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to boron is at least 0.2:1 , e.g., at least 0.5:1.Embodiment 166. The catalyst of any of embodiments 1-73 and 158-164, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to boron is at least 0.8:1, e.g., at least 1:1.Embodiment 167. The catalyst of any of embodiments 1-73 and 158-164, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to boron is at most 15:1, e.g., at most 10:1 , or 5:1.Embodiment 168. The catalyst of any of embodiments 1-73 and 158-164, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to boron is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1, or 0.2:1 to 5:1, or 0.5:1 to 15:1 , or 0.5:1 to 10:1, or 0.5:1 to 5:1, or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1).Embodiment 169. The catalyst of any of embodiments 1-73 and 158-164, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to boron is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1 , or 0.2:1 to 1:1, or 0.5:1 to 2:1, or 0.5:1 to 1.5:1 , or 0.5:1 to 1:1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1:1).Embodiment 170. The catalyst of any of embodiments 1-72, wherein indium is present in the catalyst.Embodiment 171. The catalyst of embodiment 170, wherein indium is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 172. The catalyst of embodiment 170, wherein indium is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 173. The catalyst of embodiment 170, wherein indium is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 174. The catalyst of embodiment 170, wherein indium is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 175. The catalyst of embodiment 170, wherein indium is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 176. The catalyst of embodiment 170, wherein indium is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 177. The catalyst of any of embodiments 1-72 and 170-176, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to indium is at least 0.2:1, e.g., at least 0.5:1.Embodiment 178. The catalyst of any of embodiments 1-72 and 170-176, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to indium is at least 0.8:1, e.g., at least 1:1.Embodiment 179. The catalyst of any of embodiments 1-72 and 170-176, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to indium is at most 15:1 , e.g., at most 10:1, or 5:1.Embodiment 180. The catalyst of any of embodiments 1-72 and 170-176, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to indium is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1, or 0.2:1 to 5:1 , or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1).Embodiment 181. The catalyst of any of embodiments 1-72 and 170-176, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to indium is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1 , or 0.2:1 to 1:1 , or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1).Embodiment 182. The catalyst of any of embodiments 1-72, wherein silicon is present in the catalyst.Embodiment 183. A supported CO2conversion catalyst comprising:a support that is a silicon oxide or a mixed oxide support comprising a mixture silicon oxide with one or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, and zinc oxide; and at least one of cobalt, nickel, ruthenium, and rhodium present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst, wherein silicon is present in an amount of at least 0.05 wt%, based on the total weight of the catalyst.Embodiment 184. The catalyst of embodiment 183, wherein silicon is present in an amount of at least 0.1 wt%, based on the total weight of the catalyst.Embodiment 185. The catalyst of embodiment 183, wherein silicon is present in an amount of at least 0.4 wt%, based on the total weight of the catalyst.Embodiment 186. The catalyst of embodiment 183, wherein silicon is present in an amount of at least 0.7 wt%, based on the total weight of the catalyst.Embodiment 187. The catalyst of embodiment 183, wherein silicon is present in an amount of at least 1 wt%, based on the total weight of the catalyst.Embodiment 188. The catalyst of embodiment 183, wherein silicon is present in an amount of at least 1.5 wt%, based on the total weight of the catalyst.Embodiment 189. The catalyst of embodiment 183, wherein silicon is present in the catalyst in an amount in the range of 0.05-15 wt%, e.g., in the range of 0.05 to 12 wt%, or in the range of 0.05 to 10 wt%, or 0.05 to 7 wt%, or 0.05 to 5 wt%, or 0.05 to 2 wt%, based on the total weight of the catalyst.Embodiment 190. The catalyst of embodiment 183, wherein silicon is present in the catalyst in an amount in the range of 0.1 to 15 wt%, e.g., in the range of 0.1 to 12 wt%, or 0.1 to 10 wt%, or 0.1 to 7 wt%, or 0.1 to 5 wt%, or 0.1 to 2 wt%, based on the total weight of the catalyst.Embodiment 191. The catalyst of embodiment 183, wherein silicon is present in the catalyst in an amount in the range of 0.4 to 15 wt%, e.g., in the range of 0.4 to 12 wt%, or 0.4 to 10 wt%, or 0.4 to 7 wt%, or 0.4 to 5 wt%, or 0.4 to 2 wt%, based on the total weight of the catalyst.Embodiment 192. The catalyst of embodiment 183, wherein silicon is present in the catalyst in an amount in the range of 0.7 to 15 wt%, e.g., in the range of 0.7 to 12 wt%, or 0.7 to 10 wt%, or 0.7 to 7 wt%, or 0.7 to 5 wt%, or 0.7 to 2 wt%, based on the total weight of the catalyst.Embodiment 193. The catalyst of embodiment 183, wherein silicon is present in the catalyst in an amount in the range of 1 to 15 wt%, e.g., in the range of 1 to 12 wt%, or 1 to 10 wt%, or 1 to 7 wt%, or 1 to 5 wt%, or 1 to 3 wt%, based on the total weight of the catalyst.Embodiment 194. The catalyst of embodiment 183, wherein silicon is present in the catalyst in an amount in a range of 1.5 to 15 wt%, e.g., in the range of 1.5 to 12 wt%, or 1.5 to 10 wt%, or 1.5 to 7 wt%, or 1.5 to 5 wt%, or 1.5 to 4 wt%, based on the total weight of the catalyst.Embodiment 195. The catalyst of any of embodiments 1-72 and 182-194, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to silicon is at least 0.2:1, e.g., at least 0.5:1.Embodiment 196. The catalyst of any of embodiments 1-72 and 182-194, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to silicon is at least 0.8:1, e.g., at least 1:1.Embodiment 197. The catalyst of any of embodiments 1-72 and 182-194, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to silicon is at most 15:1, e.g., at most 10:1, or 5:1.Embodiment 198. The catalyst of any of embodiments 1-72 and 182-194, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to silicon is in the range of 0.2:1 to 15:1 (e.g., in the range 0.2:1 to 15:1, or 0.2:1 to 10:1 , or 0.2:1 to 5:1 , or 0.5:1 to 15:1, or 0.5:1 to 10:1 , or 0.5:1 to 5:1 , or 0.8:1 to 15:1, or 0.8:1 to 10:1, or 0.8:1 to 5:1).Embodiment 199. The catalyst of any of embodiments 1-72 and 182-194, wherein a weight ratio of cobalt, nickel, ruthenium and / or rhodium to silicon is in the range of 0.2:1 to 2:1 (e.g., in the range 0.2:1 to 1.5:1 , or 0.2:1 to 1:1 , or 0.5:1 to 2:1 , or 0.5:1 to 1.5:1 , or 0.5:1 to 1 :1 , or 0.8:1 to 2:1 , or 0.8:1 to 1.5:1 , or 0.8:1 to 1 :1).Embodiment 200. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 201. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 202. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 203. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 204. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 205. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 206. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 207. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 208. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 209. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 210. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 211. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, and cobalt in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 212. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 213. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 214. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 215. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 216. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 217. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 218. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 219. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 220. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 221. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, nickel, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 222. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, and nickel in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 223. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 224. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 225. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and bismuth in the catalystis at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 226. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 227. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 228. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 229. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 230. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 231. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 232. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, ruthenium, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 233. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, and ruthenium, in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis. Embodiment 234. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 235. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and tellurium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 236. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and bismuth in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 237. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and tin in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 238. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and antimony in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 239. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and germanium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 240. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and selenium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 241. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and arsenic in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 242. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and boron in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 243. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, rhodium, and indium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 244. The catalyst of any of embodiments 1-199, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, and rhodium in the catalyst is at least 90 wt%, e.g., at least 95 wt% or at least 98 wt% of the catalyst, on a metallic basis.Embodiment 245. The catalyst of any of embodiments 1-244, wherein the catalyst has an additional metal content of no more than 10 wt%.Embodiment 246. The catalyst of any of embodiments 1-244, wherein the catalyst has an additional metal content of no more than 5 wt%, or no more than 2 wt%, or no more than 21wt%, based on the total weight of the catalyst.Embodiment 247. The catalyst of any of embodiments 1-244, wherein the catalyst has an alkali metal content of no more than 10 wt%.Embodiment 248. The catalyst of any of embodiments 1-244, wherein the catalyst has an alkali metal content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 249. The catalyst of any of embodiments 1-244, wherein the catalyst has an alkaline-earth metal content of no more than 10 wt%.Embodiment 250. The catalyst of any of embodiments 1-244, wherein the catalyst has an alkaline-earth metal content of no more than 5 wt%, or no more than 2 wt%, or no morethan 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 251. The catalyst of any of embodiments 1-244, wherein the catalyst has an lanthanide metal content of no more than 10 wt%.Embodiment 252. The catalyst of any of embodiments 1-244, wherein the catalyst has an lanthanide metal content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 253. The catalyst of any of embodiments 1-244, wherein the catalyst has an copper content of no more than 10 wt%.Embodiment 254. The catalyst of any of embodiments 1-244, wherein the catalyst has an copper content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 255. The catalyst of any of embodiments 1-244, wherein the catalyst has an silver content of no more than 10 wt%.Embodiment 256. The catalyst of any of embodiments 1-244, wherein the catalyst has an silver content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 257. The catalyst of any of embodiments 1-244, wherein the catalyst has an gold content of no more than 10 wt%.Embodiment 258. The catalyst of any of embodiments 1-244, wherein the catalyst has an gold content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 259. The catalyst of any of embodiments 1-244, wherein the catalyst has an platinum content of no more than 10 wt%.Embodiment 260. The catalyst of any of embodiments 1-244, wherein the catalyst has an platinum content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 261. The catalyst of any of embodiments 1-244, wherein the catalyst has an palladium content of no more than 10 wt%.Embodiment 262. The catalyst of any of embodiments 1-244, wherein the catalyst has an palladium content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 263. The catalyst of any of embodiments 1-244, wherein the catalyst has an manganese content of no more than 10 wt%.Embodiment 264. The catalyst of any of embodiments 1-244, wherein the catalyst has an manganese content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 265. The catalyst of any of embodiments 1-244, wherein the catalyst has an molybdenum content of no more than 10 wt%.Embodiment 266. The catalyst of any of embodiments 1-244, wherein the catalyst has an molybdenum content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 267. The catalyst of any of embodiments 1-244, wherein the catalyst has an iron content of no more than 10 wt%.Embodiment 268. The catalyst of any of embodiments 1-244, wherein the catalyst has an iron content of no more than 5 wt%, or no more than 2 wt%, or no more than 1 wt%, or no more than 0.5 wt%, or no more than 0.2 wt%, based on the total weight of the catalyst.Embodiment 269. A method for making the catalyst of any of embodiments 1-244, the method comprising:providing a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; contacting the support with one or more liquids each comprising one or more cobalt- containing, nickel-containing, ruthenium-containing, or rhodium-containing compounds and / or one or more tellurium-containing, bismuth-containing, tin- containing, antimony-containing, germanium-containing, selenium-containing, arsenic-containing, boron-containing compounds, indium-containing compounds, or silicon-containing compounds dispersed in a solvent(s); allowing the solvent(s) to evaporate to provide a catalyst precursor; and calcining the catalyst precursor.Embodiment 270. The method of embodiment 269, wherein contacting the support with the liquid comprises adding the liquid in an amount equal to the pore volume of the support.Embodiment 271. The method of embodiment 269, wherein contacting the support with the liquid comprises adding the liquid in an amount greater than the pore volume of the support.Embodiment 272. The method of any of embodiments 269-271 , wherein ratio of the amount liquid to the amount of support on a mass basis is in the range of 1 :1 to 5:1 (e.g., in the range of 1:1 to 3:1).Embodiment 273. The method of any of embodiments 269-272, wherein contacting the support with the liquid provides a slurry.Embodiment 274. The method of any of embodiments 269-273, wherein allowing the solvent to evaporate is conducted at ambient temperature.Embodiment 275. The method of any of embodiments 269-274, wherein allowing the solvent to evaporate is conducted at an elevated temperature (e.g., in the range of 50-150 °C) for a drying time (e.g., 24 hours).Embodiment 276. The method of embodiments 269-274, wherein allowing the solvent to evaporate is conducted under vacuum and at an elevated temperature (e.g., in the range of 50-150 °C) for a drying time (e.g., 24 hours).Embodiment 277. The method of any of embodiments 269-274, wherein allowing the solvent to evaporate is conducted in a stirring drybath at an elevated temperature (e.g., in the range of 30-100 °C).Embodiment 278. The method of any of embodiments 269-277, wherein calcining the catalyst precursor is conducted for a calcining time in the range of 0.5 to 24 hours (e.g., 0.5 to 15 hours, or 0.5 to 10 hours, or 0.5 to 5 hours).Embodiment 279. The method of any of embodiments 269-278, wherein calcining the catalyst precursor is conducted for a calcining is in the range of 100-600 °C (e.g., in the range of 120-500 °C).Embodiment 280. The catalyst of any of embodiments 1-279, made by a method according to embodiments 193-203.Embodiment 281. A method for performing a reverse water-gas shift reaction, the method comprising: contacting at a temperature in the range of 200-700 °C a catalyst according to any of embodiments 1-192 and 204 with a feed stream comprising CO2and H2, to provide a product stream comprising CO and H2, the product stream having a lower concentration of CO2and a higher concentration of CO than the feed stream.Embodiment 282. The method of embodiment 281 , wherein the reverse water-gas shift reaction has a CO selectivity of at least 90%, e.g., at least 92%, or at least 95%.Embodiment 283. The method of embodiment 281 , wherein the reverse water-gas shift reaction has a CO selectivity of at least 97%, e.g., of at least 98%.Embodiment 284. The method of any of embodiments 281-283, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 5%, e.g., no more than 4%.Embodiment 285. The method of any of embodiments 281-283, wherein the reverse water-gas shift reaction has a methane selectivity of no more than 2%, e.g., no more than 1%.Embodiment 286. The method of any of embodiments 281-285, having a CO2conversion of at least 5%, e.g., at least 10%, or 20%.Embodiment 287. The method of any of embodiments 281-285, having a CO2conversion of at least 30%, e.g., at least 40%.Embodiment 288. The method of any of embodiments 281-287, having a CO2conversion of no more than 80%, e.g., no more than 70%.Embodiment 289. The method of any of embodiments 281-287, having a CO2conversion of no more than 65%, e.g., no more than 60%.Embodiment 290. The method of any of embodiments 281-289, conducted at a temperature in the range of 250-700 °C, e.g., in the range of 250-650 °C, or 250-600 °C.Embodiment 291. The method of any of embodiments 281-289, conducted at a temperature in the range of 300-700 °C, e.g., in the range of 300-650 °C, or 300-600 °C.Embodiment 292. The method of any of embodiments 281-289, conducted at a temperature in the range of 350-700 °C, e.g., in the range of 350-650 °C, or 350-600 °C.Embodiment 293. The method of any of embodiments 281-289, conducted at a temperature in the range of 400-700 °C, e.g., in the range of 400-650 °C, or 400-600 °C.Embodiment 294. The method of any of embodiments 281-289, conducted at a temperature in the range of 450-700 °C, e.g., in the range of 450-650 °C, or 450-600 °C.Embodiment 295. The method of any of embodiments 281-289, conducted at a temperature in the range of 500-700 °C, e.g., in the range of 500-650 °C, or 500-600 °C.Embodiment 296. The method of any of embodiments 281-289, conducted at a temperature in the range of 550-700 °C, e.g., in the range of 550-650 °C, or 550-600 °C.Embodiment 297. The method of any of embodiments 281-296, wherein at least part of the H2of the feed stream is from a renewable source.Embodiment 298. The method of any of embodiments 281-297, wherein at least part of the H2of the feed stream is green hydrogen.Embodiment 299. The method of any of embodiments 281-298, wherein at least part of the H2of the feed stream is blue hydrogen.Embodiment 300. The method of any of embodiments 281-299, wherein at least a part of the H2of the feed stream is grey hydrogen, black hydrogen, brown hydrogen, pink hydrogen, turquoise hydrogen, yellow hydrogen, and / or white hydrogen.Embodiment 301. The method of any of embodiments 281-300, wherein at least part of the CO2of the feed stream is from a renewable source.Embodiment 302. The method of any of embodiments 281-301 , wherein at least part of the CO2of the feed stream is from direct air capture.Embodiment 303. The method of any of embodiments 281-302, wherein at least part of the CO2of the feed stream captured from a manufacturing plant, e.g., a bioethanol plant, a steel plant, or a cement plant.Embodiment 304. The method of any of embodiments 281-303, wherein the molar ratio of H2to CO2in the feed stream is at least 0.1 :1 , e.g., at least 0.5:1.Embodiment 305. The method of any of embodiments 281-303, wherein the molar ratio of H2to CO2in the feed stream is at least 0.9:1 , e.g., at least 1 :1 or at least 1.5:1.Embodiment 306. The method of any of embodiments 281-303, wherein the molar ratio of H2to CO2in the feed stream is at least 2:1 , e.g., at least 2.5:1.Embodiment 307. The method of any of embodiments 281-303, wherein the molar ratio of H2to CO2in the feed stream is no more than 100:1, e.g., no more than 75:1, or 50:1.Embodiment 308. The method of any of embodiments 281-303, wherein the molar ratio of H2to CO2in the feed stream is no more than 20:1, e.g., no more than 15:1 , or 10:1.Embodiment 309. The method of any of embodiments 281-303, wherein the molar ratio of H2to CO2in the feed stream is in the range of 0.5:1 to 10:1.Embodiment 310. The method of any of embodiments 281-309, conducted at a pressure in the range of 1 to 100 barg (e.g., in the range of 1 to 70 barg, or 1 to 50 barg, or 1 to 40 barg, or 1 to 35 barg, or 5 to 80 barg, or 5 to 50 barg, or 5 to 40 barg, or 5 to 35 barg, or 10 to 70 barg, 10 to 50 barg, or 10 to 40 barg, or 10 to 35 barg, or 20 to 70 barg, 20 to 50 barg, or 20 to 40 barg, or 20 to 35 barg, or 25 to 70 barg, 25 to 50 barg, or 25 to 40 barg, or 25 to 35 barg).Embodiment 311. The method of any of embodiments 281-310, conducted at a GHSV in the range of 1,000 to 2,000,000 h'1(e.g., in the range of 1 ,000 to 1 ,200,000 IT1, or 1 ,000 to 500,000 IT1, or 1 ,000 to 100,000 IT1, or 5,000 to 1 ,200,000 IT1, or 5,000 to 500,000 IT1, or 5,000 to 100,000 IT1, or 10,000 to 1 ,200,000 IT1, or 10,000 to 500,000 IT1, or 10,000 to 100,000 h’1).Embodiment 312. The method of any of embodiments 281-311 , wherein the product stream comprises no more than 95 mol% CO2(e.g., no more than 90 mol% CO2).Embodiment 313. The method of any of embodiments 281-311 , wherein the product stream comprises no more than 85 mol% CO2(e.g., no more than 80 mol% CO2).Embodiment 314. The method of any of embodiments 281-311 , wherein the product stream comprises no more than 75 mol% CO2(e.g., no more than 70 mol% CO2).Embodiment 315. The method of any of embodiments 281-314, wherein the product stream further comprises CO2, and wherein the method further comprises recycling at least a portion of the CO2of the product stream to the feed stream.Embodiment 316. The method of any of embodiments 281-315, wherein the product stream further comprises hydrogen and wherein the method further comprises recycling at least a portion of the hydrogen of the product stream to the feed stream.Embodiment 317. The method of any of embodiments 281-316, wherein a ratio of H2:CO in the product stream is in the range of 0.1 :1 to 100:1. (e.g., in the range of 0.1:1 to 50:1, or0.1 :1 to 25:1, or 0.1:1 to 10:1 , or 0.1 :1 to 5:1 , or 1:1 to 100:1 , or 1 :1 to 50:1 , or 1:1 to 25:1 , or 1:1 to 10:1, or 1 :1 to 5:1).Embodiment 318. The method of any of embodiments 281-317, wherein the product stream comprises no more than 20 mol% methane, e.g., no more than 15 mol% methane.Embodiment 319. The method of any of embodiments 281-318, wherein the product stream comprises no more than 10 mol% methane, e.g., no more than 5 mol%, or 4 mol%, or 3 mol%, or 2 mol%, or 1 mol% methane.Embodiment 320. The method of any of embodiments 281-319, wherein the method comprises activating the catalyst prior to contacting the catalyst with the feed stream.Embodiment 321. The method of embodiment 320, wherein activating the catalyst comprises contacting the catalyst with a reducing stream comprising a reductive gas (e.g., hydrogen).Embodiment 322. The method of embodiment 320 or embodiment 321 , wherein the reducing stream comprises hydrogen in an amount of at least 25 mol% (e.g., at least 50 mol%, or 75 mol%, or 90 mol%).Embodiment 323. The method of any of embodiments 320-322, wherein activating the catalyst is conducted at a temperature in the range of 200 to 800 °C. (e.g., in the range of 250 °C to 800 °C, or 300 °C to 800 °C, or 200 °C to 700 °C, or 250 °C to 800 °C, or 300 °C to 700 °C).Embodiment 324. The method of any of embodiments 320-323, wherein activating the catalyst provides a catalyst that is at least 10% reduced (e.g., at least 25%, or 50%).

[0170] The particulars shown herein are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of various embodiments of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for the fundamental understanding of the invention, the description taken with the drawings and / or examples making apparent to those skilled in theart how the several forms of the invention may be embodied in practice. Thus, before the disclosed processes and devices are described, it is to be understood that the aspects described herein are not limited to specific embodiments, apparatuses, or configurations, and as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and, unless specifically defined herein, is not intended to be limiting.

[0171] The terms “a,” “an,” “the” and similar referents used in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. Recitation of ranges of values herein is merely intended to serve as a shorthand method of referring individually to each separate value falling within the range. Unless otherwise indicated herein, each individual value is incorporated into the specification as if it were individually recited herein. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.

[0172] All methods described herein can be performed in any suitable order of steps unless otherwise indicated herein or otherwise clearly contradicted by context. The use of any and all examples, or exemplary language (e.g., “such as”) provided herein is intended merely to better illuminate the invention and does not pose a limitation on the scope of the invention otherwise claimed. No language in the specification should be construed as indicating any non-claimed element essential to the practice of the invention.

[0173] Unless the context clearly requires otherwise, throughout the description and the claims, the words ‘comprise’, ‘comprising’, and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”. Words using the singular or plural number also include the plural and singular number, respectively. Additionally, the words “herein,” “above,” and “below” and words of similar import, when used in this application, shall refer to this application as a whole and not to any particular portions of the application.

[0174] As will be understood by one of ordinary skill in the art, each embodiment disclosed herein can comprise, consist essentially of or consist of its particular stated element, step, ingredient or component. As used herein, the transition term “comprise” or “comprises” means includes, but is not limited to, and allows for the inclusion of unspecified elements, steps, ingredients, or components, even in major amounts. The transitional phrase “consisting of’ excludes any element, step, ingredient or component not specified. The transition phrase “consisting essentially of” limits the scope of the embodiment to thespecified elements, steps, ingredients or components and to those that do not materially affect the embodiment.

[0175] Unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained by the present invention. At the very least, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

[0176] Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

[0177] Groupings of alternative elements or embodiments of the invention disclosed herein are not to be construed as limitations. Each group member may be referred to and claimed individually or in any combination with other members of the group or other elements found herein. It is anticipated that one or more members of a group may be included in, or deleted from, a group for reasons of convenience and / or patentability. When any such inclusion or deletion occurs, the specification is deemed to contain the group as modified thus fulfilling the written description of all Markush groups used in the appended claims.

[0178] Some embodiments of this invention are described herein, including the best mode known to the inventors for carrying out the invention. Of course, variations on these described embodiments will become apparent to those of ordinary skill in the art upon reading the foregoing description. The inventor expects skilled artisans to employ such variations as appropriate, and the inventors intend for the invention to be practiced otherwise than specifically described herein. Accordingly, this invention includes all modifications and equivalents of the subject matter recited in the claims appended hereto as permitted by applicable law. Moreover, any combination of the above-described elements in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

[0179] Furthermore, it is to be understood that the embodiments of the invention disclosed herein are illustrative of the principles of the present invention. Other modifications that may be employed are within the scope of the invention. Thus, by way of example, but not of limitation, alternative configurations of the present invention may beutilized in accordance with the teachings herein. Accordingly, the present invention is not limited to that precisely as shown and described.

Claims

\Ne Claim:

1. A method for performing a reverse water-gas shift reaction, the method comprising: contacting at a temperature in the range of 200-700 °C a supported CO2conversion catalyst with a feed stream comprising CO2and H2, to provide a product stream comprising CO and H2, the product stream having a lower concentration of CO2and a higher concentration of CO than the feed stream; wherein the supported CO2conversion catalyst comprises a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a zirconium oxide support, a zinc oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, zirconium oxide, zinc oxide, and silicon oxide; at least one of cobalt, nickel, ruthenium, and rhodium present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst; and at least one of tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, boron, indium, and silicon present in an amount in the range of 0.05 to 15 wt% of the catalyst, based on the total weight of the catalyst.

2. The method of claim 1 , wherein the support is a titanium oxide support and comprises at least 90 wt% titanium oxide on an oxide basis and wherein the support makes up at least 70 wt% of the catalyst, on an oxide basis.

3. The method of claim 1 or claim 2, wherein the total amount of cerium, titanium, aluminum, zirconium, zinc, silicon, cobalt, nickel, ruthenium, rhodium, tellurium, bismuth, tin, antimony, germanium, selenium, arsenic, and boron in the catalyst is at least 90 wt%, on a metallic basis.

4. The method of any of claims 1-3, wherein a weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium, bismuth, tin, antimony, germanium, selenium, and / or boron is at least 0.8:1.

5. The method of any of claims 1-4, wherein cobalt is present in the catalyst in an amount in a range of 0.5 to 15 wt%, based on the total weight of the catalyst.

6. The method of any of claims 1-4, wherein nickel is present in the catalyst in an amount in a range of 0.5 to 15 wt%, based on the total weight of the catalyst.

7. The method of any of claims 1-4, wherein ruthenium is present in the catalyst in an amount in a range of 0.5 to 15 wt%, based on the total weight of the catalyst.

8. The method of any of claims 1-4, wherein rhodium is present in the catalyst in an amount in a range of 0.5 to 15 wt%, based on the total weight of the catalyst.

9. The method of any of claims 1-8, wherein tellurium is present in the catalyst in an amount in the range of 0.5 to 15 wt%, based on the total weight of the catalyst.

10. The method of any of claims 1-8, wherein bismuth is present in the catalyst in an amount in the range of 0.5 to 15 wt%, based on the total weight of the catalyst.

11. The method of any of claims 1-8, wherein tin is present in the catalyst in an amount in the range of 0.5 to 15 wt%, based on the total weight of the catalyst.

12. The method of any of claims 1-8, wherein antimony is present in the catalyst in an amount in the range of 0.5 to 15 wt%, based on the total weight of the catalyst.

13. The method of any of claims 1-8, wherein germanium is present in the catalyst in an amount in the range of 0.5 to 15 wt%, based on the total weight of the catalyst.

14. The method of any of claims 1-13, wherein the reverse water-gas shift reaction has a CO selectivity of at least 90% and a methane selectivity of no more than 5%, e.g., no more than 4%.

15. A supported CO2conversion catalyst comprising: a support that is a cerium oxide support, a titanium oxide support, an aluminum oxide support, a silicon oxide support, or a mixed oxide support comprising a mixture of two or more of cerium oxide, titanium oxide, aluminum oxide, and silicon oxide; one of cobalt, nickel, ruthenium, and rhodium, present in an amount in the range of 1 to 15 wt% of the catalyst, based on the total weight of the catalyst; andat least one of tellurium, bismuth, tin, antimony, germanium, selenium, indium, and silicon present in an amount in the range of 1 to 15 wt% of the catalyst, based on the total weight of the catalyst; and wherein a weight ratio of cobalt, nickel, ruthenium, and / or rhodium to tellurium, bismuth, tin, antimony, germanium, selenium, boron, indium, and / or silicon is at least 1 :1.

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