Compositions, methods of manufacture, and uses for catalysts

Abstract

Heterogeneous catalyst compositions that can be used for gas phase catalysis, such as for ammonia synthesis and / or hydrogenation reactions are generally provided. The catalyst composition may include a catalyst having an active component containing a base metal such as iron and, in some instances, one or more lanthanide metals (e.g., cerium and / or praseodymium). In some, but not all embodiments, a binder is present in the catalyst composition.

Description

[0001] COMPOSITIONS, METHODS OF MANUFACTURE, AND USES FOR CATALYSTS

[0002] RELATED APPLICATIONS

[0003] This application claims priority under 35 U.S.C. § 119(e) to U.S. Provisional Patent Application No. 63 / 652,225, filed May 28, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 681,253, filed August 9, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 684,469, filed August 19, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 684,474, filed August 19, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 686,806, filed August 25, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 686,809, filed August 25, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 699,368, filed September 26, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 699,392, filed September 26, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 715,134, filed November 1, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 715,139, filed November 1, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” to U.S. Provisional Patent Application No. 63 / 756,402, filed February 10 , 2025, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” and to U.S. Provisional Patent Application No. 63 / 756,406, filed February 10, 2025, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” each of which is incorporated herein by reference in its entirety for all purposes.

[0004] GOVERNMENT SPONSORSHIP

[0005] This invention was made with government support under ARPA-E OPEN 2021, Award # DE-AR0001556 awarded by the Department of Energy. The government may have certain rights in the invention.

[0006] TECHNICAL FIELD

[0007] Catalyst compositions for the synthesis of ammonia or other hydrogenation reactions and related systems and methods are generally described.

[0008] #13981562vl BACKGROUND

[0009] The Haber-Bosch (HB) process for fixing nitrogen to ammonia was a world-changing discovery, revolutionizing our global agricultural system and winning Nobel Prizes in Chemistry for both Fritz Haber (1918) and Carl Bosch (1931). This impact continues today as millions of metric tons of ammonia are produced annually, the vast majority of which is used for fertilizer. Remarkably, little about modern ammonia production would be unfamiliar to Bosch, as the basics of the industrial HB process have not changed appreciably over the past century, despite its enormous environmental impact.

[0010] Specifically, there has been very little progress on the catalytic materials that may promote the HB process, even though a catalyst with high efficiency under ambient conditions would significantly reduce the environmental impact of global ammonia production. As was the case in Bosch’s time, today’s iron catalysts are made by fusing potassium oxide and aluminum oxide with magnetite (FC3O4) at -1600 °C followed by hydrogen reduction, which may also contain oxides of calcium, magnesium, and / or silicon depending on reaction conditions. While ruthenium has been commercialized for ammonia catalysis, nothing to date has replaced iron as the catalyst of choice in industry, due to the combination of iron’s low cost and high productivity. Accordingly, there exists a need for efficient and economically viable catalysts for producing ammonia at more mild conditions (i.e. lower temperatures and pressures). In a similar vein, there is a need for more higher yielding and more selective catalysts for the production of carbon-based sustainable fuels from CO2 and sustainable H2 feedstocks.

[0011] One of the major advances in the ammonia industry in recent years is the use of ammonia in the energy industry. Ammonia may be used as a fuel for electricity generation

[0012] SUMMARY

[0013] The subject matter of the present disclosure involves, in some cases, interrelated products, alternative solutions to a particular problem, and / or a plurality of different uses of one or more systems and / or articles.

[0014] In certain embodiments, a catalyst for the synthesis of ammonia or other hydrogenation reactions is described. The catalyst may comprise an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising: 50-94 at% Fe, 0.5-30 at% of one or more lanthanide metals, 0-40 at% of Co, 0.1-20 at% of one or more

[0015] #13981562vl promoter metals selected from the group comprising Ca, Al, K, Li, Na, Cs, and / or Ba, 2-30 at% of Mg, and 0-0.5 at% additional metal elements (trace). In some embodiments, the one or more promoter metals are selected from the group comprising: Ca, Al, K, Cs, and / or Ba.

[0016] In some embodiments, the catalyst comprises an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising: 50-94 at% Fe, 5-50 at% of one or more lanthanide metals, 0-40 at% of Co, 0.1-20 at% of one or more promoter metals selected from the group comprising Ca, Al, Mg, K, Li, Na, Cs, and / or Ba, and 0-0.5 at% additional metal elements (trace).

[0017] In some embodiments, the catalyst comprises an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising: 50-94 at% Fe, X at% of one or more lanthanide metals, 0-40 at% of Co, 0.1-20 at% of one or more promoter metals selected from the group comprising Ca, Al, K, Li, Na, Cs, and / or Ba, 0-0.5 at% additional metal elements (trace), and J at% of Mg, wherein X > 0, J > 0, 5 < (X + J) < 50, and 2.5 < (J / X) < 3.5 when J > 0.

[0018] In some embodiments, the catalyst comprises an active component comprising a base metal, wherein the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within the temperature range of greater than or equal to 125 degrees C and less than or equal to 200 degrees C.

[0019] In some embodiments, the catalyst comprises an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising Q at% of Fe, 0.5-50 at% of one or more lanthanide metals, Z at% of Co, 0.1-20 at% of one or more promoter metals selected from the group comprising Ca, Al, Mg, K, Li, Na, Cs, and / or Ba, and 0-0.5 at% additional metal elements (trace), wherein 50 < Q < 94, 0 < Z < 40, and 1.5 < (Q / Z) < 20.

[0020] In some embodiments, the catalyst comprises an active component, having metal content (measured as at% of total metal content) in either its finished form or as a sum of the metal

[0021] #13981562vl content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP- MS), ICP-OES, or an equivalent method of elemental analysis, comprising 50-94 at% Fe, 0.5-30 at% of Ce and / or Pr, 0-40 at% of Co, 0.1-20 at% of one or more promoter metals selected from the group comprising Ca, Al, K, Cs, and / or Ba, and 0-0.5 at% additional metal elements (trace). In some embodiments, an optional binder comprising binding materials well known in the heterogeneous catalyst art is included. The binder may contain metal elements including but not limited to Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis.

[0022] In certain embodiments, a method of manufacturing of the active component of the catalyst described herein is described. In some embodiments, the method involves one or more of the following catalyst manufacturing techniques: fusion, coprecipitation, incipient wetness impregnation, combustion synthesis, Pechini process, and / or pulsation reaction.

[0023] In certain embodiments, a method of combining the active component with an optional binder described herein is described. According to some embodiments, the method involves one or more of the following catalyst formulation and shaping techniques: extrusion, pelletizing, tablet-moulding, spheronizing, or others to make different granules. The different granules may have a shape selected from the group comprising: rings, spheres, tablets, pellets, tripods, in both solid and hollowed forms.

[0024] In certain embodiments, a method of producing ammonia is described. The method may comprise contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising an active component capable of catalyzing the production of ammonia having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising 50-94 at% Fe, 0.5-30 at% of one or more lanthanide metals, 0-40 at% of Co, 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba, 2-30 at% of Mg, and 0-0.5 at% additional metal elements (trace). In some embodiments, the one or more promoter metals are selected from the group comprising: Ca, Al, K, Cs, and / or Ba.

[0025] In some embodiments, the method comprises contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising an active component capable of catalyzing the production of ammonia having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-

[0026] #13981562vl MS), ICP-OES, or an equivalent method of elemental analysis, comprising 50-94 at% Fe, 5-50 at% of one or more lanthanide metals, 0-40 at% of Co, 0.1-20 at% of one or more promoter metals selected from the group comprising Ca, Al, Mg, K, Li, Na, Cs, and / or Ba, and 0-0.5 at% additional metal elements (trace).

[0027] In some embodiments, the method comprises contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising an active component capable of catalyzing the production of ammonia having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP- MS), ICP-OES, or an equivalent method of elemental analysis, comprising 50-94 at% Fe, X at% of one or more lanthanide metals, 0-40 at% of Co, 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba, 0-0.5 at% additional metal elements (trace), and J at% of Mg, wherein X > 0, J > 0, 5 < (X + J) < 50, and 2.5 < (J / X) < 3.5 when J > 0.

[0028] In some embodiments, the method comprises contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising an active component comprising a base metal, wherein the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within the temperature range of greater than or equal to 125 degrees C and less than or equal to 200 degrees C.

[0029] In some embodiments, the method comprises contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising an active component capable of catalyzing the production of ammonia having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP- MS), ICP-OES, or an equivalent method of elemental analysis, comprising Q at% of Fe, 0.5-50 at% of one or more lanthanide metals, Z at% of Co, 0.1-20 at% of one or more promoter metals selected from the group comprising Ca, Al, Mg, K, Li, Na, Cs, and / or Ba, and 0-0.5 at% additional metal elements (trace), wherein 50 < Q < 94, 0 < Z < 40, and 1.5 < (Q / Z) < 20.

[0030] Embodiments may provide a catalyst for the synthesis of ammonia or other hydrogenation reactions. Catalyst productivity has been measured at various conditions for different catalyst compositions. The addition of Co to the composition in specific Fe:Co ratios greatly improves catalyst productivity. Specifically, based on testing at different Fe:Co ratios, an advantageous ratio, in some instances, of 1.5:1 to 20:1 is identified to promote strong catalyst performance. As a more specific example, based on testing at different Fe:Co ratios, an

[0031] #13981562vl advantageous ratio, in some instances, of 5:1 is identified to improve catalyst performance. Further testing has identified how the presence of cerium (Ce) or praseodymium (Pr) in the catalyst composition improves catalyst performance, with an advantageous Ce mol% of 0-30 up to a plateau beyond 20%. It should be appreciated that references to mol% herein refer to a molar percent of the total metal content (i.e. excluding oxygen and other non-metal content). In addition, inclusion of a promoter metal such as K or Cs may improve catalyst performance. Testing shows that impressive performance is attained when K is around 0.25 mol%. Inclusion of additional metals such as Mg in the catalyst composition also may improve catalyst performance with impressive performance when Mg = 6 mol%. An advantageous ratio of 2.5- 3.5:1 has been identified to improve catalyst performance. Each of the catalyst productivities discussed herein are characterizable via temperature programmed desorption (TPD) in embodiments of the present disclosure.

[0032] Embodiments may provide a catalyst for the synthesis of ammonia or other hydrogenation reactions. Catalyst productivity has been measured at various conditions for different catalyst compositions. In some embodiments, the addition of Co to the composition in specific Fe:Co ratios greatly improves catalyst productivity. Specifically, based on testing at different Fe:Co ratios, a ratio of 5:1 is identified to afford impressive catalyst performance. Further testing has identified how the presence of Ce or Pr in the catalyst composition improves catalyst performance in some instances, with an advantageous Ce mol% of 0-30 up to a plateau beyond 20%. It should be appreciated that references to mol% herein refer to a molar percent of the total metal content (i.e. excluding oxygen content). In addition, inclusion of a promoter metal such as K or Cs may improve catalyst performance. Testing shows that beneficial performance is attained, in some instances, when K is around 0.25 mol%. Each of the catalyst productivities discussed herein are characterizable via temperature programmed desorption (TPD) in embodiments of the present disclosure.

[0033] Embodiments may provide a catalyst for the synthesis of ammonia or other hydrogenation reactions, comprising an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP- OES, or an equivalent method of elemental analysis, comprising: 50-94 at% Fe; 0.5-30 at% of one or more lanthanide metals; 0-40 at% of Co; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Cs, and / or Ba; 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace).

[0034] #13981562vl Embodiments may provide a catalyst for the synthesis of ammonia or other hydrogenation reactions, comprising an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP- OES, or an equivalent method of elemental analysis, comprising: 50-94 at% Fe; 5-50 at% of one or more lanthanide metals; 0-40 at% of Co; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and 0-0.5 at% additional metal elements (trace). An optional binder may comprise binding materials including one or more of the following: carbon black, graphite, stearic acid, acrylic glass (poly(methyl methacrylate)), fumed silica, glucose, hydroxyethyl cellulose, formaldehyde, alumina (e.g., boehmite), silica (e.g., silanes, tetraethyl orthosilicate (TEOS), bentonite), alite (SCaO-SiCE), belite ( CaO-SiCE), tricalcium aluminate or celite (3CaO- AI2O3), brownmillerite (4CaO- AhO3-Fe2O3), water- soluble alumina-silica dispersions (e.g., DISPAL®, SIRAL), titania (metatitanic acid, titanium tetraethoxide (TEOT)), zirconia (zirconyl acetate), calcium aluminate (cement), magnesium aluminate (hydrotalcite), and / or aluminum phosphates, and combinations thereof. The binder may include metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS or an equivalent method of elemental analysis. The ratio of the active component to a total mass of the catalyst may be between 0.5-1: 1.

[0035] Embodiments may provide a catalyst for the synthesis of ammonia or other hydrogenation reactions comprising: an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), comprising: 25-94 at% Fe; 5-50 at% lanthanide metals; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, and / or Ba; and 0-1 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials well known in the heterogeneous catalyst art containing metal elements including Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS.

[0036] The at% of Fe is in one or more of the following ranges: 55-94, 60-94, 65-94, 70-94, and 75-94. The metal content of the one or more lanthanide metals is in one or more of the following ranges: 0.5-1 at%, 0.5-2 at%, 0.5-3 at%, 0.5-4 at%, 0.5-5 at%, 0.5-6 at%, 0.5-7 at%, 0.5-8 at%, 0.5-9 at%, 0.5-10 at%, 1-2 at%, 1-3 at%, 1-4 at%, 1-5, at%, 1-6 at%, 1-7 at%, 1-8 at%, 1-9 at%, 1-10 at%, 2-3 at%, 2-4 at%, 2-5 at%, 2-6 at%, 2-7 at%, 2-8 at%, 2-9 at%, 2-10 at%, 3-4 at%, 3-5 at%, 3-6 at%, 3-7 at%, 3-8 at%, 3-9 at%, 3-10 at%, 4-5 at%, 4-6 at%, 4-7 at%,

[0037] #13981562vl 4-8 at%, 4-9 at%, 4-10 at%, 5-6 at%, 5-7 at%, 5-8 at%, 5-9 at%, 5-10 at%, 6-7 at%, 6-8 at%, 6-9 at%, 6-10 at%, 7-8 at%, 7-9 at%, 7-10 at%, 8-9 at%, 8-10 at%, 9-10 at%, 0.5-15 at%, 0.5-20 at%, 0.5-25 at%, 5-15 at%, 10-20 at%, 10-25 at%, and 0.5-30 at%.

[0038] The metal content of the single lanthanide metal in the active component may be 8% in an embodiment of the present disclosure. The metal content of lanthanide metals in the active component may be in one or more of the following ranges: 5-10 at%, 5-15 at%, 5-20 at%, 5-30 at%, 5-35 at%, 5-40 at%, 5-45 at%, 5-50 at%, 10-20 at%, 10-30 at%, 10-40 at%, 10-50 at%, 15- 50 at%, and / or 20-50 at%. The transition metal content excluding iron in the active component may be in one or more of the following ranges: 0.5-10 at%, 10-20 at%, 20-30 at%, and / or 30-40 at%. The catalyst also may include non-metal elements, as determined by ICP-MS, comprising oxygen (O) and optionally one or more of the following elements: hydrogen (H), carbon (C), nitrogen (N), phosphorus (P), silicon (Si), and trace (<1 at%) amounts of other non-metal elements. In some embodiments, the active component may contain 0.5-40 at% of Co. In other embodiments, the active component may contain no more than trace amounts (i.e. <1 at%) of lanthanides other than Ce. In some embodiments, the single lanthanide metal may be Ce or La. The ratio of the active component to a total mass of the catalyst may be between 0.5-1. The catalyst may have a BET surface area of 1-100 m2 / g or 1-500 m2 / g. A density may fall between the ranges of 0.5-1 g / cc, the ranges of 1-3 g / cc, or the ranges of 3-5 g / cc.

[0039] The catalyst also may include non-metal elements, as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis, comprising oxygen (O) and optionally one or more of the following elements: hydrogen (H), carbon (C), nitrogen (N), phosphorus (P), silicon (Si), and trace (<0.5 at%) amounts of other non-metal elements. The active component contains no more than trace amounts (e.g., <0.5 at%, 1 at%) of lanthanides other than Ce or Pr measured as at% of total metal content. The one or more lanthanide metals may consist of Ce and Pr. In some embodiments, the one or more lanthanide metals consists of Ce, wherein the one or more promoter metals is K or Cs and the additional metal elements (trace) is O. In some embodiments, the one or more lanthanide metals consists of Pr, wherein the one or more promoter metals is K or Cs.

[0040] The at% of Co is in one or more of the following ranges: 0-40, 0-20, 0-30, 5-40, 5-20, 5- 30, 10-20, 10-30, 10-40, 15-20, 15-30, and 15-40. In an embodiment, the active component may contain 0.5-40 at% of Co. The Co content in the active component may be in one or more of the following ranges: 0.5-10 at%, 10-20 at%, 20-30 at%, and / or 30-40 at%. The ratio of the mass of the active component to the total mass of the catalyst is in one or more of the following ranges: 0.5:1 to 1:1, 0.6:1 to 1:1, 0.7:1 to 1:1, 0.8:1 to 1:1, 0.9:1 to 1:1, and 0.95:1 to 1:1. In some

[0041] #13981562vl embodiments, the ratio of the active component to a total mass of the catalyst may be between 0.5-1: 1. The at% of the one or more promoter metals is in one or more of the following ranges: 0.1-20, 0.2-20, 0.1-10, 0.2-10, 0.1-5, and 0.2-5. The at% of Mg is in one or more of the following ranges: 2-30, 2-25, 2-20, 2-10, 3-30, 3-25, 3-20, 3-15, 3-10, 4-30, 4-25, 4-20, 4-10, 5- 30, 5-25, 5-20, 5-15, 5-10, 6-30, 6-25, 6-20, 6-15, and 6-10. The metal content of the single lanthanide metal in the active component may fall in one or more of the following ranges: 0.5-1 at%, 0.5-2 at%, 0.5-3 at%, 0.5-4 at%, 0.5-5 at%, 0.5-6 at%, 0.5-7 at%, 0.5-8 at%, 0.5-9 at%, 0.5- 10 at%, 10-15 at%, 15-20 a%, 20-25 at%, and / or 25-30 at %. In other embodiments, the active component may contain no more than trace amounts (e.g., <1 at%) of lanthanides other than Ce.

[0042] Embodiments may optionally include a binder comprising binding materials including one or more of the following: carbon black, graphite, stearic acid, acrylic glass (poly(methyl methacrylate)), fumed silica, glucose, hydroxyethyl cellulose, formaldehyde, alumina (e.g., boehmite), silica (e.g., silanes, tetraethyl orthosilicate (TEOS), bentonite), alite CaO-SiCE), belite (2CaO SiO2), tricalcium aluminate or celite (3CaO- AI2O3), brownmillerite (4CaO-A12O3-Fe2O3), water-soluble alumina- silica dispersions (e.g., DISPAL®, SIRAL), titania (metatitanic acid, titanium tetraethoxide (TEOT)), zirconia (zirconyl acetate), calcium aluminate (cement), magnesium aluminate (hydrotalcite), and / or aluminum phosphates, and combinations thereof. The binder may include metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis. The ratio of the active component to a total mass of the catalyst may be between 0.5-1: 1.

[0043] The catalyst may have a BET surface area in the range of 1-100 m2 / g, 10-20 m2 / g, 1-20 m2 / g, 1-30 m2 / g, 10-20 m2 / g, 10-30 m2 / g, 10-50 m2 / g, or 1-500 m2 / g. A density of the catalyst, may fall between the ranges of 0.5-1 g / cc, the ranges of 1-3 g / cc, or the ranges of 3-5 g / cc. In some embodiments, the catalyst has a BET surface area and / or density in one of the aforementioned ranges as a powder and / or a formed shape.

[0044] Any metal element in the active component that is present at concentrations greater than 0.5% (measured as at% of total metal content) as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis may be detectable in any square region of an active material surface of dimensions larger than 50 nm by 50 nm as determined by Energy Dispersive X-ray Spectrometry (EDXS) or an equivalent technique.

[0045] Another embodiment of the present disclosure may provide a catalyst for the synthesis of ammonia or other hydrogenation reactions comprising: an active component, having metal content (measured as at% of total metal content) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry

[0046] #13981562vl (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising: 50-94 at% Fe; 0.5-30 at% of Ce and / or Pr; 0-40 at% of Co; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; 0-0.5 at% additional metal elements (trace); and optionally, a binder comprising binding materials well known in the heterogeneous catalyst art containing metal elements including but not limited to Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis.

[0047] A method of manufacturing of the active component of the catalyst may involve one or more of the following catalyst manufacturing techniques: fusion, coprecipitation, incipient wetness impregnation, combustion synthesis, Pechini process, and / or pulsation reaction. A method of combining the active component with the optional binder may involve one or more of the following catalyst formulation and shaping techniques: extrusion, pelletizing, tabletmoulding, spheronizing, or others to make different granules in shapes selected from the group comprising: rings, spheres, tablets, pellets, tripods, in both solid and hollowed forms. In some embodiments, the catalyst may enable single-pass yields of ammonia (defined as (molar flow rate of NH3 in the outlet) / (2*molar flow rate of N2 in the inlet)), synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 H2:N2 ratio in excess of 3% at 400 °C, 50 bar total pressure, and 15,000 h-1 gas hourly space velocity (GHSV). In other embodiments, the catalyst may enable single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 H2:N2 ratio in excess of 3% at 365 °C, 90 bar total pressure, and 15,000 h-1 gas hourly space velocity (GHSV). The synthesis process of the catalyst may include one or more reduction steps under 1-100% hydrogen gas at 1-100 bar pressure at temperatures between 200-1200 °C for 3-48 hours total. The catalyst may have an agglomerated particle size ranging from 25 pm to 10 mm as measured via mechanical sieving.

[0048] A method of manufacturing of the active component of the catalyst may involve one or more of the following catalyst manufacturing techniques: fusion, coprecipitation, incipient wetness impregnation, combustion synthesis, Pechini process, and / or pulsation reaction. A method of combining the active component with the optional passive binder may involve one or more of the following catalyst formulation and shaping techniques: extrusion, pelletizing, tabletmoulding, spheronizing, or others to make different granules in shapes selected from the group comprising: rings, spheres, tablets, pellets, tripods, in both solid and hollowed forms. In some embodiments, the catalyst may enable single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 H2:N2 ratio in excess of 3% at 400 °C, 50 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV). In other embodiments, the catalyst

[0049] #13981562vl may enable single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 th:N2 ratio in excess of 3% at 365 °C, 90 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV). The synthesis process of the catalyst may include one or more reduction steps under 1-100% hydrogen gas at 1-100 bar pressure at temperatures between 200-1200 °C for 3-48 hours total. The catalyst may have an agglomerated particle size ranging from 25 pm to 10 mm as measured via mechanical sieving.

[0050] A method of producing ammonia may comprise contacting a catalyst with nitrogen and hydrogen gases. In some embodiments, a method of producing ammonia may comprise contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising: an active component capable of catalyzing the production of ammonia, having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising: 50-94 at% Fe; 0.5-30 at% of one or more lanthanide metals; 0-40 at% of Co; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Cs, and / or Ba; 2-30 at% of Mg; 0-0.5 at% additional elements (trace); and optionally, a binder comprising binding materials including one or more of the following: carbon black, graphite, stearic acid, acrylic glass (poly(methyl methacrylate)), fumed silica, glucose, hydroxyethyl cellulose, formaldehyde, alumina (e.g., boehmite), silica (e.g., silanes, tetraethyl orthosilicate (TEOS), bentonite), alite CaO SiCE), belite (2CaO SiO2), tricalcium aluminate or celite (3CaO- AI2O3), brownmillerite (4CaO- A12O3-Fe2O3), water-soluble alumina- silica dispersions (e.g., DISPAL®, SIRAL), titania (metatitanic acid, titanium tetraethoxide (TEOT)), zirconia (zirconyl acetate), calcium aluminate (cement), magnesium aluminate (hydrotalcite), and / or aluminum phosphates, and combinations thereof. The binder may include metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis. In some embodiments, a method of producing ammonia may comprise contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising: an active component capable of catalyzing the production of ammonia, having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising: 50-94 at% Fe; 5-50 at% of one or more lanthanide metals; 0-40 at% of Co; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; 0-0.5 at% additional metal elements (trace); and optionally, a

[0051] #13981562vl binder comprising binding materials including one or more of the following: carbon black, graphite, stearic acid, acrylic glass (poly(methyl methacrylate)), fumed silica, glucose, hydroxyethyl cellulose, formaldehyde, alumina (e.g., boehmite), silica (e.g., silanes, tetraethyl orthosilicate (TEOS), bentonite), alite (SCaO-SiCh), belite ( CaO-SiCh), tricalcium aluminate or celite (3CaO- AI2O3), brownmillerite (4CaO- AhO3-Fe2O3), water-soluble alumina-silica dispersions (e.g., DISPAL®, SIRAL), titania (metatitanic acid, titanium tetraethoxide (TEOT)), zirconia (zirconyl acetate), calcium aluminate (cement), magnesium aluminate (hydrotalcite), and / or aluminum phosphates, and combinations thereof. The binder may include metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis. In some embodiments, a method of producing ammonia may comprise contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising: an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), comprising: 25-94 at% Fe; 5-50 at% lanthanide metals; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, and / or Ba; and 0-1 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements including Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS.

[0052] The active component contains no more than trace amounts (e.g., <0.5 at%) of lanthanides other than Ce or Pr measured as at% of total metal content. The one or more lanthanide metals may consist of Ce and Pr. In some embodiments, the one or more lanthanide metals consist of Ce. In some embodiments, the one or more lanthanide metals consist of Pr. The ratio of the mass of the active component to the total mass of the catalyst is in one or more of the following ranges: 0.5:1 to 1:1, 0.6:1 to 1:1, 0.7:1 to 1:1, 0.8:1 to 1:1, 0.9:1 to 1:1, and 0.95:1 to 1:1.

[0053] The catalyst may include non-metal elements, as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis, comprising oxygen (O) and optionally one or more of the following elements: hydrogen (H), carbon (C), nitrogen (N), phosphorus (P), silicon (Si), and trace (e.g., <0.5 at%, <1 at%) amounts of other non-metal elements.

[0054] For use of the catalysts in the production of ammonia, the atomic ratio of H2:N2 in the feed gases may be between 2-4: 1 at the point where the feedstocks make contact with the catalyst. The ammonia production volume may be less than 100 tons / day. The catalyst may enable single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas

[0055] #13981562vl precursors at a 3:1 H2:N2 ratio in excess of 3% at 400 °C, 50 bar total pressure, and 15000 h'1gas hourly space velocity (GHSV). In other embodiments, the catalyst may enable single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 H2:N2 ratio in excess of 3% at 365 °C, 90 bar total pressure, and 15000 h'1gas hourly space velocity (GHSV).

[0056] The contacting and producing steps may be conducted at a temperature ranging from 0 °C to 750 °C. The contacting and producing steps may be conducted at a temperature ranging from 0 °C to 500 °C. The contacting and producing steps may be conducted at a temperature ranging from 0 °C to 450 °C. In some embodiments, the contacting and producing steps are conducted at an initial contact temperature ranging from 0 °C to 750 °C, 0 °C to 500 °C, or 0 °C to 450 °C. A contacting and producing step being conducted at an initial contact temperature refers to the process being performed under conditions where the temperature at the location at which the precursor gas stream first contacts the catalyst (e.g., in a reactor) is at the initial contact temperature. For example, if a precursor gas stream initially contacts that catalyst at a location where the temperature is 300 °C during the process for producing ammonia, then the contacting and producing is considered to be conducted at an initial contact temperature of 300 °C, even if other locations are at different temperatures during the process (e.g., due to a temperature gradient in a reactor housing the catalyst). In some embodiments, the contacting and producing steps is conducted at an initial contact temperature ranging from 280 °C to 300 °C. The contacting and producing steps may be conducted at an initial contact temperature ranging from 300 °C to 320 °C. The contacting and producing steps may be conducted at an initial contact temperature ranging from 320 °C to 350 °C. The contacting and producing steps may be conducted at an initial contact temperature ranging from 350 °C to 380 °C. The contacting and producing steps may be conducted at a pressure ranging from 1 bar to 200 bar. The contacting and producing steps may be conducted at a pressure ranging from 1 bar to 20 bar. The contacting and producing steps may be conducted at a pressure ranging from 20 bar to 50 bar. The contacting and producing steps may be conducted at a pressure ranging from 50 bar to 100 bar. The contacting and producing steps may be conducted at a pressure ranging from 100 bar to 150 bar. The contacting and producing steps may be conducted at a pressure ranging from 150 bar to 250 bar. The contacting and producing steps may be conducted in the absence of an electric field applied to the catalyst. The contacting and producing steps may be conducted with an electric field applied to the catalyst. The contacting and producing steps may be conducted with either a DC or AC electric field or electromagnetic radiation, including but not limited to either microwaves or visible light applied to the supported catalyst. The producing step may

[0057] #13981562vl produce ammonia at a rate of at least 1 mmol product / gram catalyst / hour for a single pass over a single bed under standard commercial reactor space velocities: conditions of 200-500 °C, 1-200 bar total pressure, and 5,000-100,000 h1GHSV. In some embodiments, the producing step produces ammonia at a rate of at least 1 mmol product / gram catalyst / hour for a single pass over a single bed at an initial contact temperature ranging from 280-300 °C, 300-320 °C, 320-350 °C, or 350-380 °C, at a pressure of 1-20, 20-50 bar, 50-100 bar, 100-150 bar, or 150-250 bar, and 5,000-100,000 h1GHSV.

[0058] The method also may include separating ammonia generating by the reaction with the catalyst from the precursor gas stream via a technique selected from the group comprising: condensation, pressure swing adsorption, temperature swing adsorption, microwave swing adsorption, vacuum swing adsorption, and combinations thereof. The contacting and producing steps may be conducted in a reactor selected from the group comprising: a batch reactor, a semibatch reactor, a continuous stirred tank reactor, a plug-flow reactor, a trickle-bed reactor, a fixed bed reactor, a moving bed reactor, a rotating bed reactor, a slurry reactor, a tubular reactor, a radial and axial packed bed reactor, a membrane reactor, and a fluidized bed reactor. Further embodiments may provide a method for production of ammonia using an advanced base-metal catalyst with higher yield compared to commercial catalysts comprising: (a) producing hydrogen at >99% purity by one of the following means combined with dehydration / purification steps: (i) Steam Methane Reformer (SMR) coupled with carbon capture, (ii) water electrolyzation, (iii) methane pyrolysis with or without carbon sequestration (iv) biomass gasification with or without carbon capture or (v) use of naturally occurring geological hydrogen; (b) compression of H2 to 1-20, 20-50 bar, 50-100 bar, 100-150 bar, or 150-250 bar via electrically powered compressors that use renewable electricity; (c) production of nitrogen of >99% purity by cryogenic separation of air, pressure swing adsorption (PSA), separation of air, vacuum pressure swing adsorption (VPSA), temperature swing adsorption (TSA) or a combination thereof; (d) compression of N2 to 1-20, 20-50 bar, 50-100 bar, 100-150 bar, or 150-250 bar via electrically powered compressors that use renewable electricity; (e) combining H2 and N2 in a reactor at elevated temperatures and pressures in the range of 250-350C, 350-380C, or 380-400C and 10-20 bar, 20- 50 bar, 50-90 bar, 90-150 bar, and 150-250 bar, a H2 / N2 molar ratio of 2-4: 1, using a catalyst that produces NH3 yields in the range of 1-5%, 5-10%, 10-15%, 15-20%, 20-25%, at an ammonia converter outlet; (f) separating NH3 in the reactor effluent via condensation, PSA, VPSA, TSA or a combination thereof; and (g) compressing and recycling the unreacted H2 and N2 back into the reactor, with an option to purge to avoid inert buildup, wherein the advanced catalyst may enable single-pass ammonia yields in excess of 3% under process conditions

[0059] #13981562vl comprising 3:1 H2:N2 ratio at 350 °C, 50 bar total pressure, and 15,000 h-1 gas hourly space velocity (GHSV). In some embodiments, ammonia comprises low-carbon ammonia.

[0060] In some embodiments, a reactor vessel may be loaded with multiple layers of catalysts across the bed height, with different levels of yield in each layer spanning 5-10%, 10-15%, 15- 20% or 20-25% at the end of each layer. In certain embodiments, the reactor vessel may be capable of adsorptive or absorptive separation of NH3 and may be capable of being loaded with multiple layers of catalysts and adsorbents or absorbents across the bed height with different levels of yield in each catalyst layer spanning 5-10%, 10-15%, 15-20%, 20-25%, or 25-50% at the end of each layer. The catalyst may enable lowering of reactor inlet temperature by 5-10 °C, 10-20 °C, 20-30 °C, 30-40 °C, 40-50 °C, 50-70 °C, or 70-100 °C and may maintain reactor outlet temperatures due to higher catalyst productivity and associated exothermicity. A reactor system may exist as a single or a series of reactor vessels. The reactor system may be in one of the following configurations: batch reactor, a semibatch reactor, a continuous stirred tank reactor, a plug-flow reactor, a trickle-bed reactor, a fixed bed reactor, a moving bed reactor, a rotating bed reactor, a slurry reactor, a tubular reactor, a radial and axial packed bed reactor, a membrane reactor, and a fluidized bed reactor, with the option of inter-vessel or intra-vessel cooling. The method may have a gas hourly space velocity (GHSV) of 5000-100,000 h’1. In some embodiments, recycle may be completely eliminated, and unreacted components may be integrated into other parts of the ammonia production process or another co-located process. No reactor feed compressor may be needed. High-pressure electrolyzers may produce H2 at 20-40 bar, 40-60 bar, or 60-100 bar. Ammonia production volume may be less than 1-10, 10-100, or 100-600 tons / day. The method may be conducted in the absence of an applied electric field applied to the catalyst in some embodiments. In other embodiments, the method may be conducted with either a DC or AC electric field or electromagnetic radiation. A plant for production of ammonia (e.g., low-carbon ammonia) may be co-located with a urea plant for the production of fertilizer, and excess energy from the production of hydrogen step (e.g., low- carbon hydrogen step) is used by the urea plant. Excess energy from the production of hydrogen step (e.g., low-carbon hydrogen step) may be used for carbon capture on one or more CO2- containing effluent or flue gas streams. Excess energy from the production of hydrogen step (e.g., low-carbon hydrogen step) may be used for cogeneration of electricity. The method may be programmable and controllable to be “load-following.”

[0061] Other advantages and novel features of the present disclosure will become apparent from the following detailed description of various non-limiting embodiments of the disclosure when considered in conjunction with the accompanying figures. In cases where the present

[0062] #13981562vl specification and a document incorporated by reference include conflicting and / or inconsistent disclosure, the present specification shall control.

[0063] BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Non-limiting embodiments of the present disclosure will be described by way of example with reference to the accompanying figures, which are schematic and are not intended to be drawn to scale unless otherwise indicated. In the figures, each identical or nearly identical component illustrated is typically represented by a single numeral. For purposes of clarity, not every component is labeled in every figure, nor is every component of each embodiment of the disclosure shown where illustration is not necessary to allow those of ordinary skill in the art to understand the disclosure. In the figures:

[0065] FIG. 1 depicts a cross-sectional schematic diagram of a reactor comprising an inlet and a reactor vessel containing a catalyst composition, according to an embodiment of the present disclosure;

[0066] FIG. 2 shows a plot of ammonia yield percentage against temperature (in Celsius) at 50 bar and 15,000 h'1GHSV, with a 3:1 Fh:N2 feed, comparing wustite, magnetite, and one or more advanced catalysts, according to an embodiment of the present disclosure;

[0067] FIG. 3 shows a TEM image showing a regular catalyst with large elemental domains, according to an embodiment of the present disclosure;

[0068] FIG. 4 shows a TEM image showing an advanced catalyst with small elemental domains, according to an embodiment of the present disclosure;

[0069] FIG. 5 shows a plot of catalyst productivity at a variety of Fe:Co ratios and at two different sets of conditions, according to an embodiment of the present disclosure; and

[0070] FIG. 6A-6K shows tables of catalysts with different properties including ammonia yield, according to an embodiment of the present disclosure.

[0071] DETAILED DESCRIPTION

[0072] Heterogeneous catalyst compositions that can be used for gas phase catalysis, such as for ammonia synthesis and / or hydrogenation reactions are generally provided. The catalyst composition may include a catalyst having an active component containing a base metal such as iron and, in some instances, one or more lanthanide metals (e.g., cerium and / or praseodymium). In some, but not all embodiments, a binder is present in the catalyst composition.

[0073] #13981562vl CATALYST COMPOSITION

[0074] In one aspect, embodiments disclosed herein relate to a catalyst composition that may be used for synthesis of ammonia or other hydrogenation reactions, the catalyst composition having, in some embodiments, impressive catalyst performance resulting in higher yield in ammonia synthesis or other hydrogenation reactions.

[0075] In some embodiments, the catalyst composition comprises an active component. The active component may be a component of the catalyst composition capable of participating in the catalytic reaction (e.g., as opposed to a passive component, such as a binder and / or support). In some embodiments, the active component is a material of the catalyst that provides active sites for a heterogenous catalytic process. In some embodiments, the active component is capable of catalyzing the synthesis of ammonia or other hydrogenation reactions. In some embodiments, the active component is capable of catalyzing the synthesis of ammonia. In some embodiments, the active component is configured to catalyze the synthesis of ammonia or other hydrogenation reactions. In some embodiments, the active component is configured to catalyze the synthesis of ammonia.

[0076] In some embodiments, the active component of the catalyst composition comprises one or more transition metals. The one or more transition metals may be present in their metallic form with an oxidation state of 0 and / or present in a different oxidation state. As used herein, a transition metal element can be scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), or mercury (Hg). In some embodiments, a catalyst may optionally include 0.5-40 at% in either its finished form or as a sum of the metal content of its precursors of one or more of the following transition metals: Co, Ni, and / or Cu, preferably Co. In some embodiments, a catalyst may optionally include 0.5-40 at% of one or more of the following transition metals: Fe, Ni, and / or Cu. The transition metal content in the active component may be in one or more of the following ranges: 0-40 at%, 5-40 at%, 10-40 at%, and 15-40 at%. In some embodiments, the transition metal content in the active component excluding iron may be in one or more of the following ranges: 0-40 at%, 5-40 at%, 10-40 at%, and 15-40 at%. In some embodiments, the transition metal content in the active component excluding iron may be in one or more of the following ranges: 0.5-10 at%, 10-20 at%, 20-30 at%, and / or 30-40 at%. The Mg content in the active component may be in one or more of the following ranges: 2-30 at%, 2-25 at%, 2-20 at%, 2-10 at%, 3-30 at%, 3-25 at%, 3-20

[0077] #13981562vl at%, 3-15 at%, 3-10 at%, 4-30 at%, 4-25 at%, 4-20 at%, 4-10 at%, 5-30 at%, 5-25 at%, 5-20 at%, 5-15 at%, 5-10 at%, 6-30 at%, 6-25 at%, 6-20 at%, 6-15 at%, and 6-10 at%.

[0078] In this disclosure the at% of metals reported in the active component when discussing the content of those metals in the active component are based on the total metal content of the active component, unless explicitly indicated otherwise.

[0079] As will be explained below, the catalyst composition may be synthesized as a powder and then further processed to agglomerate the powder into larger granules or agglomerates using techniques such as granulation, extrusion, tableting / pelletizing, and milling. In some embodiments, the catalyst composition may further comprise an optional binder. In some embodiments, the catalyst composition may further comprise an optional passive binder. The binder may be selected from the group which may include one or more of the following: carbon black, graphite, stearic acid, acrylic glass (poly(methyl methacrylate)), fumed silica, glucose, hydroxyethyl cellulose, formaldehyde, alumina (e.g., boehmite), silica (e.g., silanes, tetraethyl orthosilicate (TEOS), bentonite), alite (3CaO SiO2), belite (2CaO SiO2), tricalcium aluminate or celite (3CaO- AI2O3), brownmillerite (4CaO- AhO3-Fe2O3), water-soluble alumina-silica dispersions (e.g., DISPAL®, SIRAL), titania (metatitanic acid, titanium tetraethoxide (TEOT)), zirconia (zirconyl acetate), calcium aluminate (cement), magnesium aluminate (hydrotalcite), and / or aluminum phosphates, and combinations thereof. The binder may include metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis. In some embodiments, the binder comprises a metal oxide and / or metalloid oxide. In some embodiments, the binder comprises a polymer. In some embodiments, the binder comprises a mineral. In some embodiments, the binder comprises an organic compound. According to some embodiments, the binder comprises an inorganic carbon, such as carbonaceous binder (e.g., graphite).

[0080] In embodiments in which the catalyst composition is in the form of granules or agglomerates, the catalyst composition may have an agglomerated particle size ranging from 25 pm to 10 mm as measured via mechanical sieving. For example, the agglomerated particle size may have a lower limit of any one of 25 pm, 50 pm, 100 pm, 500 pm, 750 pm, and 1.0 mm and an upper limit of any one of 750 pm, 1.0 mm, 2.0 mm. 5.0 mm, and 10 mm, where any lower limit may be paired with any mathematically compatible upper limit. In some embodiments, at least 50 wt%, at least 75 wt%, at least 90 wt%, at least 95 wt%, at least 99 wt%, or all of the granules or agglomerates of the catalyst composition have a particle size in one of the ranges listed above. The shapes of the agglomerated particles may be rings, spheres, tablets, cylinders, trilobes, quadralobes, pellets and irregularly shaped particles, among others.

[0081] #13981562vl In one aspect, embodiments disclosed herein relate to a catalyst for the synthesis of ammonia or other hydrogenation reactions. In some embodiments, the catalyst includes an active component, and optionally, a binder. The catalyst may include an active component, and optionally, a binder comprising binding materials including one or more of the following: carbon black, graphite, stearic acid, acrylic glass (poly(methyl methacrylate)), fumed silica, glucose, hydroxyethyl cellulose, formaldehyde, alumina (e.g., boehmite), silica (e.g., silanes, tetraethyl orthosilicate (TEOS), bentonite), alite (SCaO-SiCh), belite ( CaO-SiCh), tricalcium aluminate or celite (3CaO- AI2O3), brownmillerite (4CaO- AhO3-Fe2O3), water-soluble alumina-silica dispersions (e.g., DISPAL®, SIRAL), titania (metatitanic acid, titanium tetraethoxide (TEOT)), zirconia (zirconyl acetate), calcium aluminate (cement), magnesium aluminate (hydrotalcite), and / or aluminum phosphates, and combinations thereof. The binder may include metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis. In some embodiments, the binder comprises a metal oxide and / or metalloid oxide. In some embodiments, the binder comprises a polymer. In some embodiments, the binder comprises a mineral. In some embodiments, the binder comprises an organic compound. According to some embodiments, the binder comprises an inorganic carbon, such as carbonaceous binder (e.g., graphite).

[0082] In some embodiments, the active component comprises iron (Fe). In some embodiments, the active component comprises Fe (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, in an amount of 50-94 at% Fe. The at% of Fe in the active component may be in one or more of the following ranges: 55-94, 60-94, 65-94, 70-94, and 75-94. In some embodiments, the content of Fe in the active component is in the range of 70-94 at%. In some embodiments, the content of Fe in the active component is in the range of 75-94 at%. In some embodiments, the content of Fe in the active component is in the range of 72-80 at%. In some embodiments, the content of Fe in the active component is in the range of 74-80 at%.

[0083] In some embodiments, the active component comprises one or more lanthanide metals. In some such embodiments, the active component comprises only a single lanthanide metal. In some embodiments, the active component comprises one or more lanthanide metals (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, in an amount of 0.5-30 at%. In some embodiments, the active component comprises one or more lanthanide metals (measured as at% of total metal content), as determined by inductively coupled plasma mass

[0084] #13981562vl spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, in an amount of 5-50 at%.

[0085] The content of the one or more lanthanide metals in the active component may be in one or more of the following ranges: 0.5-1 at%, 0.5-2 at%, 0.5-3 at%, 0.5-4 at%, 0.5-5 at%, 0.5-6 at%, 0.5-7 at%, 0.5-8 at%, 0.5-9 at%, 0.5-10 at%, 1-2 at%, 1-3 at%, 1-4 at%, 1-5, at%, 1-6 at%, 1-7 at%, 1-8 at%, 1-9 at%, 1-10 at%, 2-3 at%, 2-4 at%, 2-5 at%, 2-6 at%, 2-7 at%, 2-8 at%, 2-9 at%, 2-10 at%, 3-4 at%, 3-5 at%, 3-6 at%, 3-7 at%, 3-8 at%, 3-9 at%, 3-10 at%, 4-5 at%, 4-6 at%, 4-7 at%, 4-8 at%, 4-9 at%, 4-10 at%, 5-6 at%, 5-7 at%, 5-8 at%, 5-9 at%, 5-10 at%, 6-7 at%, 6-8 at%, 6-9 at%, 6-10 at%, 7-8 at%, 7-9 at%, 7-10 at%, 8-9 at%, 8-10 at%, 9-10 at%, 0.5- 15 at%, 0.5-20 at%, 0.5-25 at%, 5-15 at%, 10-20 at%, 10-25 at%, and 0.5-30 at%. In some embodiments, the content of the one or more lanthanide metals in the active component is in the range of 0.5-50 at%.

[0086] In some embodiments, the content of the one or more lanthanide metals (e.g., Ce and / or Pr) in the active component is in the range of 0.5-4 at%. In some embodiments, the content of the one or more lanthanide metals (e.g., Ce and / or Pr) in the active component is in the range of 1-3 at%. In some embodiments, the content of the one or more lanthanide metals (e.g., Ce and / or Pr) in the active component is in the range of 1.5-2.5 at%. In some such embodiments, Mg is also present in the active component (e.g., at a metal content greater than that of the one or more lanthanide metals).

[0087] In some embodiments, the content of the one or more lanthanide metals (e.g., Ce and / or Pr) in the active component is the range of 1-10 at%. In some embodiments, the content of the one or more lanthanide metals (e.g., Ce and / or Pr) in the active component is the range of 2-10 at%. In some embodiments, the content of the one or more lanthanide metals (e.g., Ce and / or Pr) in the active component is the range of 5-10 at%. In some embodiments, the content of the one or more lanthanide metals (e.g., Ce and / or Pr) in the active component is the range of 7-9 at%. In some such embodiments, the active component is free of Mg or Mg is present in the active component at a content that is less than that of the one or more lanthanide metal (e.g., Ce and / or Pr).

[0088] In some embodiments, the one or more lanthanide metals comprises cerium (Ce) and / or praseodymium (Pr). In some embodiments, the active component contains no more than trace amounts (e.g., <0.5 at%) of lanthanides other than Ce or Pr measured as at% of total metal content. In some embodiments, the one or more lanthanide metals consists of Ce and Pr. In some embodiments, the one or more lanthanide metals comprises Ce in an amount of at least 95

[0089] #13981562vl at%, at least 98 at%, at least 99 at%, at least 99.9 wt%, or 100% relative to the total amount of the one or more lanthanide metals.

[0090] In some embodiments, the active component comprises cobalt (Co). In some embodiments, the active component comprises Co (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, in an amount of 0-40 at%. In an embodiment, the active component may contain 0-40 at% of Co measured as at% of total metal content. In some embodiments, the active component may contain 0.5-40 at% of Co measured as at% of total metal content. The Co at% content in the active component may be in one or more of the following ranges: 0-40, 0-20, 0-30, 5-40, 5-20, 5-30, 10-20, 10-30, 10-40, 15-20, 15-30, and 15- 40. In some embodiments, the Co content in the active component may be in one or more of the following ranges: 0.5-10 at%, 10-20 at%, 20-30 at%, and / or 30-40 at%. In some embodiments, the content of Co in the active component is in the range of 5-20 at%. In some embodiments, the content of Co in the active component is in the range of 10-20 at%. In some embodiments, the content of Co in the active component is in the range of 12-18 at%.

[0091] In some embodiments, the active component comprises one or more promoter metals, such as Ca, Al, Mg K, Cs, and / or Ba. In some embodiments, the active component comprises the one or more promoter metals (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, in an amount of 0.1-20 at%.

[0092] In some embodiments, the active component comprises magnesium (Mg). In some embodiments, the active component comprises Mg (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, in an amount of 2-30 at%. In some embodiments, the content of Mg in the active component is in the range of 3-15 at%. In some embodiments, the content of Mg in the active component is in the range of 4-10 at%. In some embodiments, the content of Mg in the active component is in the range of 5-10 at%. In some embodiments, the content of Mg in the active component is in the range of 5-8 at%.

[0093] In some embodiments, the active component comprises additional elements (trace) (e.g., additional metal traces). In some embodiments, the active component comprises additional elements (trace) (e.g., additional metal traces) (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, in an amount of and 0-0.5 at%.

[0094] #13981562vl In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), ICP-OES, or an equivalent method of elemental analysis, of 50-94 at% Fe; 0.5-30 at% of one or more lanthanide metals; 0-40 at% of Co; 0.1-20 at% of one or more promoter metals: Ca, Al, K, Cs, and / or Ba; 2-30 at% of Mg; and 0-0.5 at% additional elements (trace) (e.g., additional metal traces).

[0095] In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), ICP-OES, or an equivalent method of elemental analysis, comprising 50-94 at% Fe; 5-50 at% of one or more lanthanide metals; 0-40 at% of Co; 0.1-20 at% of one or more promoter metals: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and 0-0.5 at% additional metal elements (trace).

[0096] In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), comprising 50-94 at% Fe; 5-50 at% lanthanide metals; and optionally, 0.5-40 at% of one or more of the following transition metals: Co, Ni, and / or Cu; 1-20 at% of one or more promoter metals: Ca, Al, Mg, K, Li, Na, and / or Ba; and 0-1 at% additional metal elements (trace).

[0097] In some embodiments, the catalyst may comprise an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis, comprising: 50-94 at% Fe; 0.5-10 at% lanthanide metals; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 0.5-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, and / or Ba; and 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS or an equivalent method of elemental analysis.

[0098] In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), or an equivalent method of elemental analysis, comprising 50-94 at% Co; 0.5-10 at% lanthanide metals; and optionally, 0.5-40 at% of one or more of the following transition metals: Fe, Ni, and / or Cu; 0.5-20 at% of one or more promoter metals: Ca, Al, K, and / or Ba; 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace).

[0099] In some embodiments, the catalyst may include an active component and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art, which may contain metal elements including but not limited to Ni, Al, Ti, Zr, Ce, Mg, and / or Ca as

[0100] #13981562vl determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis. In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis, comprising 50-94 at% Co; 5-50 at% lanthanide metals; and optionally, 0.5-40 at% of one or more of the following transition metals: Fe, Ni, and / or Cu; 1-20 at% of one or more promoter metals: Ca, Al, Mg, K, Li, Na, and / or Ba; and 0-0.5 at% additional metal elements (trace).

[0101] In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), or an equivalent method of elemental analysis, of 50-94 at% Fe; 5-50 at% of a single lanthanide metal; and optionally, 0.5-40 at% of one or more of the following transition metals: Co, Ni, and / or Cu; 0.1-20 at% of one or more promoter metals: Ca, Al, Mg, K, Li, Na, and / or Ba; and 0-0.5 at% additional metal elements (trace).

[0102] In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), or an equivalent method of elemental analysis, of 50-94 at% Fe; 0.5-10 at% of a single lanthanide metal; and optionally, 0.5-40 at% of one or more of the following transition metals: Co, Ni, and / or Cu; 0.1-20 at% of one or more promoter metals: Ca, Al, K, and / or Ba; 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace).

[0103] In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), or an equivalent method of elemental analysis, of 50-94 at% Fe; 0.5-10 at% of a single lanthanide metal, which may be Ce or La in some embodiments of the present disclosure; and optionally, 0.5-40 at% of one or more of the following transition metals: Co, Ni, and / or Cu; 0.1- 20 at% of one or more promoter metals: Ca, Al, K, Cs, and / or Ba; 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace).

[0104] In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), or an equivalent method of elemental analysis, of 50-94 at% Fe; 5-50 at% of a single lanthanide metal, which may be Ce or La in some embodiments of the present disclosure; and optionally, 0.5-40 at% of one or more of the following transition metals: Co, Ni, and / or Cu; 0.1- 20 at% of one or more promoter metals: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and 0-0.5 at% additional metal elements (trace).

[0105] #13981562vl In some embodiments, the Fe content may be in one or more of the following ranges: 50- 80 at%, 60-80 at%, 70-80 at%, and / or 50-94 at%. The metal content of a single lanthanide metal in the active component may be in one or more of the following ranges: 5-10 at%, 5-15 at%, 5- 20 at%, 5-30 at%, 5-35 at%, 5-40 at%, 5-45 at%, 5-50 at%, 10-20 at%, 10-30 at%, 10-40 at%, 10-50 at%, 15-50 at%, and / or 20-50 at%.

[0106] In some embodiments in which both one or more lanthanide metals and magnesium are present in the active component, the atomic ratio of lanthanide metal atoms to magnesium atoms may be between 1:2 and 1:30. In some embodiments, the atomic ratio of lanthanide metal atoms to magnesium atoms may be between 1:2 and 1:10.

[0107] In some embodiments in which both one or more lanthanide metals and magnesium are present in the active component, the sum of the metal content of the one or more lanthanide metals and the metal content of Mg is relatively high, which has been observed to result, in some instances, in relatively high product yields (e.g., for ammonia synthesis).

[0108] In some embodiments in which the active component has a metal content of the one or more lanthanide metals (e.g., Ce and / or Pr) of X at% (where X > 0) and a metal content of Mg of J at% (where J > 0), the sum of X and J is relatively large. For example, in some embodiments in which the active component has a metal content of the one or more lanthanide metals (e.g., Ce and / or Pr) of X at% (where X > 0) and a metal content of Mg of J at% (where J > 0), the sum (X+ J) is greater than or equal to 5, greater than or equal to 6, greater than or equal to 7, greater than or equal to 7.5, or greater. In some embodiments in which the active component has a metal content of the one or more lanthanide metals (e.g., Ce and / or Pr) of X at% (where X > 0) and a metal content of Mg of J at% (where J > 0), the sum (X+ J) is less than or equal to 50, less than or equal to 20, less than or equal to 10, less than or equal to 9, less than or equal to 8.5, or less. Combinations of these ranges are possible. For example, in some such embodiments, 5 < (X + J) < 50. As another example, in some such embodiments, 5 < (X + J) < 10. As another example, in some such embodiments, 7.5 < (X + J) < 8.5. As yet another example, in some such embodiments, 6 < (X + J) < 12.

[0109] In some embodiments in which both one or more lanthanide metals and magnesium are present in the active component, the ratio of the metal content of the Mg to the metal content of the one or more lanthanides is relatively high, which has been observed to result, in some instances, in relatively high product yields (e.g., for ammonia synthesis). In some embodiments in which the active component has a metal content of the one or more lanthanide metals (e.g., Ce and / or Pr) of X at% (where X > 0) and a metal content of Mg of J at% (where J > 0), the ratio (J / X) is greater than or equal to 2.5, greater than or equal to 2.8, greater than or equal to 2.9, or

[0110] #13981562vl greater. In some embodiments in which the active component has a metal content of the one or more lanthanide metals (e.g., Ce and / or Pr) of X at% (where X > 0) and a metal content of Mg of J at% (where J > 0), the ratio (J / X) is less than or equal to 3.5, less than or equal to 3.4, less than or equal to 3.2, or less. Combinations of these ranges are possible. For example, in some such embodiments, 2.5 < (J / X) < 3.5 when J > 0. As another example, in some such embodiments, 2.8 < (J / X) < 3.2 when J > 0.

[0111] The at% of Co in the active component may be in one or more of the following ranges: 0-40, 0-20, 0-30, 5-40, 5-20, 5-30, 10-20, 10-30, 10-40, 15-20, 15-30, and 15-40.

[0112] The at% of Mg in the active component may be in one or more of the following ranges: 2-30, 2-25, 2-20, 2-10, 3-30, 3-25, 3-20, 3-15, 3-10, 4-30, 4-25, 4-20, 4-10, 5-30, 5-25, 5-20, 5- 15, 5-10, 6-30, 6-25, 6-20, 6-15, and 6-10.

[0113] The catalyst also may include non-metal elements, as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis, comprising oxygen (O) and optionally one or more of the following elements: hydrogen (H), carbon (C), nitrogen (N), phosphorus (P), silicon (Si), and trace (e.g., <0.5 at%, < 1 at%) amounts of other non-metal elements. It should be appreciated that the non-metal elements may be part of the active component, part of the binder, or part of both the active component and the binder in embodiments of the present disclosure.

[0114] In some embodiments, in which the active component comprises both Fe and Co, the ratio of metal content of Fe to that of Co is relatively high, which in some instances has been observed in the context of this disclosure to result in advantageous catalyst performance (e.g., for ammonia synthesis). In some embodiments in which the active component has an Fe metal content of Q at% (e.g., where 50 < Q < 94) and a Co metal content of Z at% (e.g., where 0 < Z < 40), the ratio (Q / Z) is greater than or equal to 1.5, greater than or equal to 2, greater than or equal to 4, greater than or equal to 5, or greater. In some embodiments in which the active component has an Fe metal content of Q at% (e.g., where 50 < Q < 94) and a Co metal content of Z at% (e.g., where 0 < Z < 40), the ratio (Q / Z) is less than or equal to 20, less than or equal to 15, less than or equal to 10, less than or equal to 6, or less. Combinations of these ranges are possible. For example, in some such embodiments, 1.5 < (Q / Z) < 20. As another example, in some such embodiments, 4 < (Q / Z) < 10.

[0115] In some embodiments, a catalyst for the synthesis of ammonia or other hydrogenation reactions comprising an active component comprising one or more base metals. The base metal(s) may be or comprise one or more inexpensive metals or metals having common abundance. For example, a base metal stands in contrast to a noble or precious metal, such as gold, silver, platinum, or ruthenium. Non-limiting examples of base metals include iron, cobalt,

[0116] #13981562vl nickel, manganese, copper, lead, aluminum, chromium, and / or zinc. Combinations of base metals are possible. The base metals may be present in the active component at a relatively high content (e.g., greater than or equal to 50 at%, greater than or equal to 60 at%, greater than or equal to 70 at%, greater than or equal to 75 at%, and / or up to 80 at%, up to 85 at%, up to 90 at%, up to 94 at%, or greater. In some embodiments, the base metal comprises Fe. In some embodiments, the base metals comprise Fe and Co.

[0117] The catalyst composition (e.g., containing a base metal catalyst) may exhibit at least one hydrogen desorption temperature peak at a relatively low temperature, according to some embodiments. It has been observed in the context of this disclosure that certain catalyst compositions, including some containing base metals, that exhibit a relatively low hydrogen desorption temperature peak may facilitate advantageous product yields and / or productivities (e.g., for ammonia synthesis). Hydrogen desorption temperature peaks may be measured by temperature programmed desorption (TPD), for example. In some embodiments, the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within a temperature range of greater than or equal to 125 degrees C, greater than or equal to 150 degrees C, greater than or equal to 175 degrees C, or greater. In some embodiments, the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within a temperature range of less than or equal to 200 degrees C, less than or equal to 175 degrees C, less than or equal to 150 degrees C, or less. Combinations of the above-recited ranges are possible (e.g., greater than or equal to 175 degrees C and less than or equal to 200 degrees C, greater than or equal to 150 degrees C and less than or equal to 200 degrees C, greater than or equal to 175 degrees C and less than or equal to 200 degrees C, greater than or equal to 150 degrees C and less than or equal to 175 degrees C, or greater than or equal to 125 degrees C and less than or equal to 150 degrees C).

[0118] In some embodiments, the active component may contain no more than trace amounts (e.g., <0.5 at%, < 1 at%) of lanthanides other than Ce measured as at% of total metal content. In some embodiments, the ratio of the mass of the active component to the total mass of the catalyst is in one or more of the following ranges: 0.5:1 to 1:1, 0.6:1 to 1:1, 0.7:1 to 1:1, 0.8:1 to 1:1, 0.9:1 to 1:1, and 0.95:1 to 1:1. In some embodiments, the ratio of the active component to a total mass of the catalyst may be between 0.5-1.

[0119] In some embodiments, the active component may contain 0.5-40 at% of Ni measured as at% of total metal content.

[0120] In some embodiments, at least a portion of the catalyst (in some instances, for example, some or all of the active component) has a stoichiometric formula selected from the group

[0121] #13981562vl consisting of CesFe76.8C015Cso.2Ox, Mg6Ce2Fe76.sC015Cso.2Ox, CesFe76.sC015Ko.2Ox, CesFe76.75C015Ko.25Ox, Ce25Fe55CoioKioOx, and Mg6Ce2Fe76.sC015Cso.1Ko.1Ox. In some embodiments, at least a portion of the catalyst (in some instances, for example, some or all of the active component) has a stoichiometric formula of CesFe76.8C015Cso.2Ox. In some embodiments, at least a portion of the catalyst (in some instances, for example, some or all of the active component) has a stoichiometric formula of Mg6Ce2Fe76.sC015Cso.2Ox. In some embodiments, at least a portion of the catalyst (in some instances, for example, some or all of the active component) has a stoichiometric formula of CesFe76.8C015Ko.2Ox. In some embodiments, at least a portion of the catalyst (in some instances, for example, some or all of the active component) has a stoichiometric formula of CesFe76.75C015Ko.25Ox. In some embodiments, at least a portion of the catalyst (in some instances, for example, some or all of the active component) has a stoichiometric formula of Ce25Fe55CoioKioOx. In some embodiments, at least a portion of the catalyst (in some instances, for example, some or all of the active component) has a stoichiometric formula of Mg6Ce2Fe76.sC015Cso.1Ko.1Ox.

[0122] The catalyst according to embodiments disclosed herein may have a BET surface area of 1-100 m2 / g. In other embodiments, the catalyst may have a BET surface area of 1-500 m2 / g, 1- 50 m2 / g, 1-20 m2 / g, 10-20 m2 / g, or 10-30 m2 / g. In some embodiments, the catalyst may have a BET surface area in the range of 1-100 m2 / g, 10-20 m2 / g, 1-20 m2 / g, 1-30 m2 / g, 10-20 m2 / g, 10- 30 m2 / g, 10-50 m2 / g, or 1-500 m2 / g. The density of the catalyst may fall between the ranges of 0.5-1 g / cc, between the ranges of 1-3 g / cc, and / or between the ranges of 3-5 g / cc.

[0123] The active component may be manufactured through one or more of the following catalyst manufacturing techniques: fusion, coprecipitation, incipient wetness impregnation, combustion synthesis, Pechini process, and / or pulsation reaction. The active component may be combined with an optional binder (e.g., passive binder) through one or more of the following catalyst formulation and shaping techniques: extrusion, pelletizing, tablet-moulding, spheronizing, or others to make different granules in shapes selected from the group comprising: rings, spheres, tablets, pellets, tripods, in both solid and hollowed forms. In some embodiments, the optional binder is an optional passive binder. In some embodiments, the catalyst may enable single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 H2:N2 ratio in excess of 3% at 400 °C, 50 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV). In some embodiments, yields may be in excess of 5%, in excess of 7%, in excess of 8%, in excess of 10%, in excess of 12%, in excess of 14%, or in excess of 15% at 400 °C, 50 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV). In some embodiments, the yields may be up to 20%, up to 25%, up to 30%, or greater at 400 °C, 50 bar

[0124] #13981562vl total pressure, and 15,000 h'1gas hourly space velocity (GHSV). In other embodiments, the catalyst may enable single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 H2:N2 ratio in excess of 3% at 365 °C, 90 bar total pressure, and 15,000 h’1gas hourly space velocity (GHSV). In some embodiments, yields may be in excess of 5%, in excess of 7%, in excess of 8%, in excess of 10%, in excess of 12%, in excess of 14%, or in excess of 15% at 365 °C, 90 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV). In some embodiments, the yields may be up to 20%, up to 25%, up to 30%, or greater at 365 °C, 90 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV). In some embodiments, yields may be in excess of 5%, in excess 8%, in excess of 10%, or in excess of 15%. In some embodiments, the yields may be up to 20%, up to 25%, up to 30%, or greater. The synthesis process for the catalyst may include one or more reduction steps under 1-100% hydrogen gas at 1-100 bar pressure at temperatures between 200-1200 °C for 3-96 hours total. For example, the synthesis process for the catalyst may include one or more reduction steps under 1-100% hydrogen gas at 1-100 bar pressure at temperatures between 200-1200 °C for 3-48 hours total. The catalyst may have an agglomerated particle size ranging from 25 pm to 10 mm as measured via mechanical sieving.

[0125] In some, but not necessarily all embodiments, at least a portion of the catalyst (e.g., some or all of the catalyst) comprises pores. In some embodiments, the pores have an average pore diameter is in a range of 2-4nm, 4-10nm, 10-20nm, 20-30nm, 30-40nm or 40-50nm. The pores may establish a pore volume. The pore volume may be in a range of 0.01-0.05 cc / g, 0.05- 0.1 cc / g, 0.1-0.15 cc / g, 0.15-0.2 cc / g, 0.2-0.3 cc / g and 0.3-0.5cc / g.

[0126] METHOD OF MAKING A HETEROGENEOUS CATALYST COMPOSITION

[0127] In another aspect, embodiments disclosed herein relate to a method of making the previously described heterogeneous catalyst. The method may include synthesis of different domains of the constituents like metals and metal oxides in varying degrees of proximity to each other via any of a variety of techniques, including but not limited to wet impregnation, sol-gel synthesis, colloidal deposition, or deposition-precipitation. For example, the method may include first making an oxide domain and then impregnating the domain with the metallic material via a wet impregnation technique. The oxide domain, for example, may be synthesized by calcining a mixture of the metal precursors along with a combustible organic dispersant and surfactant in a stepwise manner at progressively increasing temperatures in the range of 50-1500 °C. As another example, the oxide domain may be synthesized by coprecipitation in aqueous solvents or by thermal processing in a pulsation reactor between 250-1000 °C.

[0128] #13981562vl A non-limiting example of a suitable wet impregnation synthesis includes mixing one component (e.g., comprising ceria (CeC ), graphite, and / or ceramics with the perovskite crystal structure) with an aqueous solution including a soluble salt of two or more of the aforementioned metals. An example of such a suitable wet impregnation synthesis includes mixing the oxide powder with an aqueous solution including a soluble salt of one of the aforementioned metals. These salts may be nitrates, acetates, sulfates, halides, or oxides, for example. The metal salt may be included in an amount such that a ratio of the mass of the metal to the mass of the oxide is from about 1.0 to 40 wt%. The mixing of the oxide with the aqueous solution including a metal salt may be conducted using any known mixing methods in the art, and under ambient conditions. An example of a catalyst prepared by co-precipitation followed by wet impregnation is Ceo.74Feo.26Ox. Aqueous metal salts Ce nitrate and Fe nitrate are premixed at the desired stoichiometric ratio under heat, and co-precipitated by pH control, aged for 1-24 hours under stirring, and then cooled down to room temperature. The final catalyst is precipitated out and recovered, washed with deionized water and centrifuged multiple times with different wash cycles for purification. Finally, the material is dried and calcined in an oven to yield the support, which is impregnated to incipient wetness with the Fe nitrate salt solution, dried, calcined and reduced with forming gas to yield the final catalyst.

[0129] Once sufficiently mixed, the mixture may be dried at a temperature ranging from about 100 °C to 150 °C for about a time ranging from 1 to 4 hours. The dried mixture may then be calcined at a temperature ranging from about 200 °C to 1200 °C for a time ranging from about 1 to 6 hours. For example, the calcination temperature may have a lower limit of any one of 200, 250, 300, 350, 400 and 600 °C, and / or an upper limit of any one of 350, 400, 450, 500, 600 and 1200 °C, where any lower may be paired with any upper limit. Further, the calcination time may have a lower limit of any one of 1, 2, 3, and 4 hours and an upper limit of any one of 3, 4, 5 and 6, hours, where any lower limit may be paired with any mathematically compatible upper limit. Then the metal salt may be reduced in a gas phase reduction in a gas mixture comprising 1-100 vol% H2 (e.g., 2-100 vol% H2) in an inert carrier like N2, at pressures ranging from 1-100 bar, with a flow rate sufficient to sweep out any moisture formed during the reduction. The gas phase reduction may be conducted at a temperature ranging from about 100 °C to 1200 °C for a time ranging from about 2 to 6 hours. During this reduction step, the metal salt is reduced to a metal domain. Once the reduction step is complete, the catalyst composition including the oxide and the metallic material has thereby been synthesized.

[0130] In some, but not necessarily all embodiments, the gas phase reduction is performed as follows. The metal salts are reduced to small metallic domains that could exist in different

[0131] #13981562vl scales ranging from sub-nanometer to a micron. If promoter materials are added, they may be added via similar wet impregnation steps at this time either before, after, or both before and after addition of metal salts. The promoter material may improve the performance of the catalyst and may be selected from materials including, but not limited to, cesium carbonate, barium nitrate, and / or potassium oxide. Then, a second reduction step, often key to the performance of the catalyst, may be performed in a hydrogen or hydrogen-containing atmosphere at temperatures between 200-1200 °C and total pressures between 1-100 bar for times between 3-48 hours. For example, the second reduction temperature may have a lower limit of any one of 200, 250, 300, 350, 400 and 600 °C, and / or an upper limit of any one of 350, 400, 450, 500, 600 and 1200 °C, where any lower may be paired with any upper limit. Further, the second reduction time may have a lower limit of any one of 3, 6, 12, and 24 hours and / or an upper limit of any one of 6, 12, 24 and 48 hours, where any lower limit may be paired with any mathematically compatible upper limit. Once the second reduction step is complete, the catalyst composition including the oxide domains and the metallic domains has thereby been synthesized.

[0132] Another technique that may be employed for forming metallic materials for the catalyst is physical deposition of small metal domains on other inorganic domains. In some embodiments, physical deposition of small metal domains comprises nanoparticle deposition of metal. In this technique, a single or multiple metal salts are mixed into a basic solution (e.g., pH of greater than 7, greater than or equal to 8, greater than or equal to 9, or greater) containing an organic molecule (e.g., an alcohol) and mixed for a set period of time. This solution may then be subjected to high temperature (e.g., greater than or equal to 100 °C) and optionally pressure (e.g., greater than 1 bar) for an extended period of time, for example, in an autoclave, to facilitate solvothermal synthesis of small metal domains. In some embodiments, small metal domains comprise nanoparticles. The metal domains may form a colloidal solution into which the oxide can be introduced. Metal deposition can be encouraged by centrifuging the mixture for an extended period of time, for example, hours to several days. In some embodiments, metal deposition comprises nanoparticle deposition. Centrifugation is followed by washing to remove excess salts, and the two steps are repeated multiple times until the desired level of deposition is met. Finally, the part of the catalyst comprising of inorganic domains may be dried in an oven over several hours to days. The catalyst can be weighed before and after the process to determine the exact % weight loading of the colloidal metallic domains. In some embodiments, the support material can be weighed before and after the process to determine the exact % weight loading of the colloidal nanoparticles.

[0133] #13981562vl Any of a variety of techniques may be employed to prepare different domains of the catalyst. In some embodiments, the domains of the catalysts comprise a support for the catalyst. However, in some embodiments, the catalyst composition does not comprise a support with which the active component is associated. For example, in some embodiments, one of the domains (e.g., oxide support such as ceria support) may be synthesized hydro thermally. This may involve calcining a mixture of the metal precursors along with a combustible organic dispersant and surfactant in a solution in a stepwise manner at progressively increasing temperatures in the range of, for example, 50-1500 °C. In some instances, an aging step is performed for several days following calcination to encourage the growth of crystallites. The size of the crystallites can be controlled by the length and temperature of the aging step, and a slow aging generally encourages better crystal structure. Finally, the crystals are recovered, washed and dried. In some embodiments, the crystals recovered are a support recovered. The organic molecules may be removed by calcination in air at sufficiently high temperatures such as 500-1500 °C and for a period of several hours to days, depending on the composition and amount present. A common example of a synthesis via the hydrothermal method is mesoporous silica materials (e.g., silica support material), which are synthesized by sol-gel method starting from tetraalkoxysilanes followed by hydrothermal treatment.

[0134] As noted above, a sol gel method may be employed to prepare part or all of the catalyst domains. In some embodiments, a specific sol gel technique called the Pecchini method is employed. In some such embodiments, a chelating agent is used to form a complex with the metal ions. The chelating agent may reduce or prevent the precipitation of insoluble metal salts and allows for the formation of a homogenous precursor solution. Carboxylic acids such as citric, malic, acetic, formic and other acids and molecules such as ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTP A), and / or hydroxyethylethylenediaminetriacetic acid (HEDTA) are possible chelating agents because they have a high complexing ability and can bind with metals in different oxidation states. The metal salt and chelating agent are dissolved in a solvent, such as water or ethanol, and the recipe may optionally also incorporate cross-linking molecules such as ethylene glycol. In some embodiments, the cross-linking molecule is butylene glycol. The solution is then heated to form a gel, which is dried and then calcined at high temperature (for example, 500-1500 °C) in a furnace to form the metal oxide. In some embodiments, a furnace may not be used. In some embodiments, this synthesis can produce relatively pure metal oxides, with controlled particle size and excellent thermal stability. This process can also be used to produce complex oxide systems, such as doped metal oxides (e.g., doped ceria) and / or mixed metal oxides.

[0135] #13981562vl Another technique that can be used to prepare the catalyst is flameless pyrolysis. Flameless pyrolysis can be used for the synthesis of inorganic materials, such as ceramic precursors, metal oxides, and other inorganic compounds. In some embodiments, the inorganic materials comprise nanoparticles. This process may involve the pyrolysis of a mixture of precursor materials (e.g. metallic salts including but not limited to citrates, oxalates and nitrates) in the absence of oxygen, leading to the formation of a solid inorganic material. The precursor material can be in the form of a liquid or a solid and may be heated to a high temperature in a controlled atmosphere to initiate the pyrolysis reaction. The reaction may take place in a flow reactor, including but not limited to a pulsation reactor, where the precursor is introduced into the reactor and heated to the desired temperature (e.g. 500 °C, 1000 °C, 1500 °C). In the absence of an open flame, and optionally in the presence of pulsation, the precursor material is broken down into its constituent elements or compounds, which then recombine to form the desired final inorganic product. The final product can be in the form of a powder, a coating, or a bulk material depending on the nature of the precursor and the reaction conditions.

[0136] After synthesis, the catalyst composition may be further processed via milling and sieving to achieve a desired particle size. The catalyst composition may then be processed with a binder to achieve an agglomerate / granule size as described above.

[0137] METHOD OF CATALYZING GAS PHASE REACTIONS

[0138] As noted above, the heterogeneous catalyst composition described herein may be used in methods of catalyzing various reactions (e.g., involving gaseous reactants and / or products). Examples of gas phase reactions that may be catalyzed by the catalyst described herein include but are not limited to ammonia synthesis and carbon-based sustainable fuel synthesis from CO2 and sustainable H2 feedstocks.

[0139] Thus, in another aspect, embodiments disclosed herein relate to a method of synthesizing ammonia using the previously described heterogeneous catalysis composition. The method may include contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases and then producing ammonia at a surface of the catalyst. In some embodiments, the method comprises contacting a catalyst with a single precursor gas stream comprising both nitrogen and hydrogen gases, while in other embodiments the nitrogen and hydrogen gases are provided to the catalyst as separate precursor streams.

[0140] Some embodiments disclosed relate to a method of synthesizing ammonia using the heterogeneous catalysis composition described herein. The method may include contacting a catalyst composition with one or more precursor gases (which may be feedstock gases). The

[0141] #13981562vl precursor gases may be in the form of a gas stream (e.g., comprising reactants such as nitrogen and hydrogen gases). The method may further comprises producing ammonia at a surface of the catalyst composition. The catalytic production of ammonia may be induced and / or accelerated via heating (e.g., heating the reaction environment at a temperature in a range described above and / or below). Alternatively or additionally, the catalytic production of ammonia may be induced and / or accelerated via application of pressure to the reaction mixture and / or catalyst (e.g., to a pressure in a range described above and / or below).

[0142] The catalyst may comprise an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), ICP-OES, or an equivalent method of elemental analysis, of: 50-94 at% Fe; 0.5-30 at% of one or more lanthanide metals; 0-40 at% of Co; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Cs, and / or Ba; 2-30 at% of Mg; and 0-0.5 at% additional elements (trace) (e.g., additional metal elements); and optionally, a binder (e.g., passive binder) comprising binding materials known in the heterogeneous catalyst art containing metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis.

[0143] In some embodiments, the catalyst may comprise an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), comprising: 25-94 at% Fe; 5-50 at% lanthanide metals; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, and / or Ba; and 0-1 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements including Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS.

[0144] In some embodiments, the catalyst may comprise an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), comprising: 50-94 at% Fe; 5-50 at% lanthanide metals; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, and / or Ba; and 0-1 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements including Al, Ti, Zr, Ce, Mg, and / or Ca as determined by

[0145] ICP-MS.

[0146] In some embodiments, the catalyst may comprise an active component, having metal

[0147] #13981562vl content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis, comprising: 50-94 at% Fe; 0.5-10 at% lanthanide metals; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 0.5-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, and / or Ba; and 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS or an equivalent method of elemental analysis.

[0148] In some embodiments, the at% of Fe in the active component is greater than or equal to 50%, greater than or equal to 55%, greater than or equal to 60%, greater than or equal to 65%, greater than or equal to 70%, greater than or equal to 72%, greater than or equal to 75%, greater than or equal to 80%, greater than or equal to 85%, greater than or equal to 90%, or greater than or equal to 94%. In some embodiments, the at% of Fe is less than or equal to 50%, less than or equal to 55%, less than or equal to 60%, less than or equal to 65%, less than or equal to 70%, less than or equal to 75%, less than or equal to 80%, less than or equal to 85%, less than or equal to 90%, or less than or equal to 94%.

[0149] In some embodiments, the catalyst may comprise an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis, comprising: 50-94 at% Co; 0.5-10 at% lanthanide metals; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Fe, Ni, and / or Cu; 0.5-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, and / or Ba; and 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements including but not limited to Ni, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS or an equivalent method of elemental analysis.

[0150] In some embodiments, the catalyst may include an active component and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art, which may contain metal elements including but not limited to Ni, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis. The active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), or an equivalent method of elemental analysis, comprising 50-94 at% Co; 5-50 at% lanthanide metals; and optionally, 0.5-40 at% of one or more of the following transition metals:

[0151] #13981562vl Fe, Ni, and / or Cu; 1-20 at% of one or more promoter metals: Ca, Al, Mg, K, Li, Na, and / or Ba; and 0-0.5 at% additional metal elements (trace).

[0152] In some embodiments, the catalyst may comprise an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis, of: 50-94 at% Fe; 5-50 at% of a single lanthanide metal; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, and / or Ba; and 0-0.5 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS or an equivalent method of elemental analysis.

[0153] In some embodiments, the active component may have metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP- MS), or an equivalent method of elemental analysis, of 50-94 at% Fe; 0.5-10 at% of a single lanthanide metal; and optionally, 0.5-40 at% of one or more of the following transition metals: Co, Ni, and / or Cu; 0.1-20 at% of one or more promoter metals: Ca, Al, K, and / or Ba; 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace).

[0154] In some embodiments, the catalyst may comprise an active component, having metal content (measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis, of: 50-94 at% Fe; 0.5-10 at% of a single lanthanide metal, which may be Ce or La in some embodiments of the present disclosure; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Cs, and / or Ba; and 2-30 at% of Mg; and 0-0.5 at% additional metal elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS or an equivalent method of elemental analysis.

[0155] In some embodiments, the catalyst may comprise an active component, having metal content(measured as at% of total metal content), as determined by inductively coupled plasma mass spectrometry (ICP-MS), or an equivalent method of elemental analysis, of: 50-94 at% Fe; 5-50 at% of a single lanthanide metal, which may be Ce or La in some embodiments of the present disclosure; optionally, 0.5-40 at% of one or more of transition metals selected from the group comprising: Co, Ni, and / or Cu; 0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and 0-0.5 at% additional metal

[0156] #13981562vl elements (trace); and optionally, a passive binder comprising binding materials known in the heterogeneous catalyst art containing metal elements such as Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS or an equivalent method of elemental analysis.

[0157] The catalyst also may include non-metal elements, as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis, comprising oxygen (O) and optionally one or more of the following elements: hydrogen (H), carbon (C), nitrogen (N), phosphorus (P), silicon (Si), and trace (e.g., <0.5 at%, <1 at%) amounts of other non-metal elements. In embodiments disclosed herein, the atomic ratio of H2:N2 in the feed gases during ammonia synthesis may be between 2-4: 1 at the point where the feedstocks make contact with the catalyst. The ammonia production volume may be less than 100 tons / day. In some embodiments, the production may be more than 500 tons / day, more than 750 tons / day, more than 1000 tons / day, or more. The catalyst may enable single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 H2:N2 ratio in excess of 3% at 400 °C, 50 bar total pressure, and 15000 h’1gas hourly space velocity (GHSV). In some embodiments, yields may be in excess of 5%, in excess 8%, in excess of 10%, or in excess of 15%. In some embodiments, the yields may be up to 20%, up to 25%, up to 30%, or greater. In other embodiments, the catalyst enables singlepass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 H2:N2 ratio in excess of 3% at 365 °C, 90 bar total pressure, and 15000 h'1gas hourly space velocity (GHSV). In some embodiments, yields may be in excess of 5%, in excess 8%, in excess of 10%, or in excess of 15%. In some embodiments, the yields may be up to 20%, up to 25%, up to 30%, or greater. In some embodiments, the catalyst may enable single-pass yields of hydrogen gas from an ammonia gas precursor in excess of 50 mmol H2 / g catalyst / min at 500 °C, 1 bar total pressure, and 30,000 mL / g catalyst / hour gas hourly space velocity (GHSV). In some embodiments, yields may be in excess of 5%, in excess 8%, in excess of 10%, or in excess of 15%. In some embodiments, the yields may be up to 20%, up to 25%, up to 30%, or greater.

[0158] In some embodiments, the distribution of the predominant metal elements in the catalyst composition (e.g., including in its active component) is relatively uniform compared to catalysts formed, for example, using different techniques which may result in significant domains lacking certain metals while having other domains containing the metals. In some embodiments, any metal element for which the metal content in the active component measured as at% of total metal content in the active component is greater than 0.5 at% is detectable in any square region of an active material surface of dimensions larger than 50 nm by 50 nm. In some embodiments, for any metal element present at greater than or equal to 0.5 at% in the active material, an integrated signal intensity for a detection method for that metal element in any 50 nm x 50 nm

[0159] #13981562vl square region of an active material surface is within 50%, within 25%, within 10%, within 5%, within 2%, or less of the average integrated signal intensity for that metal element across the entire active material surface.

[0160] Some aspects of this disclosure relate to reactors for gas phase catalysis. The reactor may comprise, for example, a reactor vessel. The vessel may comprise an enclosure establishing an interior volume that can be at least partially filled with reactants (e.g., precursor gases and / or catalysts). The vessel may be configured to contain the catalyst composition. For example, the catalyst composition may be present in the reactor vessel as or as part of a bed. In some embodiments, the reactor comprises one or more inlets for receiving one or more precursor gases (e.g., by being fluidically connected to a source of the one or more precursor gases). The one or more precursor gases may be supplied in a single stream (comprising multiple precursor gases) to a single inlet. For example, a single stream comprising both nitrogen gas and hydrogen gas may be supplied to an inlet of the reactor. Alternatively, the reactor may comprise two or more inlets, each of which may receive a portion but not all of the precursor gases. For example, the reactor may comprises a first inlet that receives nitrogen gas and a second inlet that receives hydrogen gas. The reactor vessel may be configured to receive the one or more precursor gases (e.g., from the one or more inlets). For example, one or more inlets may be fluidically to the vessel.

[0161] FIG. 1 shows a schematic cross-sectional diagram of reactor 200, according to some embodiments. Reactor 200 may comprise reactor vessel 201 fluidically connected to inlet 202, which is in turn fluidically connected to source 203 of precursor gas stream 204 (e.g., via a conduit). Reactor vessel 201 contains bed 205 comprising catalyst composition 100, which may be any of the catalyst compositions described in this disclosure. In some embodiments, the reactor further comprises an outlet, which may be configured to output a product gas (e.g., as a product gas stream). The product gas may comprise, for example, ammonia gas (NH3). As an example, in FIG. 1, reactor 200 may further comprise outlet 206 fluidically connected to vessel 201 and configured to output product gas 207.

[0162] Commercial ammonia reaction conditions are as follows. The ammonia synthesis may be conducted in any commercial reactor known in the art. However, it should be understood that the ammonia synthesis (or any of other gas phase catalytic reaction described in this disclosure) need not be limited to commercial reactors. In particular, the reactor may be selected from the group consisting of a batch reactor, a semibatch reactor, a continuous stirred tank reactor, a plug-flow reactor, a trickle -bed reactor, a fixed bed reactor, a moving bed

[0163] #13981562vl reactor, a rotating bed reactor, a slurry reactor, a tubular reactor, a radial and axial packed bed reactor, a membrane reactor, and a fluidized bed reactor. These reactions may be used for contacting and / or producing steps in embodiments of the present disclosure.

[0164] Non-limiting examples of hydrogenation reactions that the catalyst composition may, in some instances, be capable of catalyzing include olefin and / or alkyne hydrogenation, carbon monoxide to methanol and / or methane, carbon dioxide to carbon monoxide, methanol, and / or methane, aldehydes to alcohols, ketones to alcohols, esters to alcohols, carboxylic acids to alcohols, and nitro groups to anilines.

[0165] The ammonia synthesis may be conducted at standard temperatures and pressures for ammonia production. However, advantageously, the catalyst described herein may allow for lower temperatures and pressures to be utilized. For example, the temperature during ammonia production may range from 0 °C to 450-500 °C. The temperature may have a lower limit of any one of 0 °C, 5 °C, 10 °C, 20 °C, 50 °C, 100 °C, and 200 °C and an upper limit of any one of 150 °C, 200 °C, 300 °C, 400 °C, 450 °C, and 500 °C where any lower limit may be paired with any mathematically compatible upper limit. The pressure during ammonia production may range from 1 bar to 200 bar. For example, the pressure may have a lower limit of any one of 1, 2, 5, 10, 20, 30, 50 and 75 bar and an upper limit of any one of 75, 100, 125, 150, and 200 bar, where any lower limit may be paired with any mathematically compatible upper limit.

[0166] The catalyst described herein does not require an electric field. However, an electric field may be used to improve catalyst efficiency. As such, in some embodiments, the contacting and producing steps of the method of producing ammonia are conducted in the absence of an electric field applied to the catalyst composition. In some embodiments, the contacting and producing steps of the method of producing hydrogen gas and nitrogen gas are conducted in the absence of an electric field applied to the catalyst composition. In other embodiments, the contacting and producing steps are conducted with an electric field applied to the catalyst composition. The contacting and producing steps may be conducted with either a DC or AC electric field or electromagnetic radiation, including, but not limited to, microwave or visible light applied to the catalyst composition.

[0167] The method herein may be performed such that the product (e.g., ammonia) is generated with a single-pass productivity of greater than or equal to 0.01 millimoles of product per gram of catalyst per hour (mmol / g / h), greater than or equal to 0.1 mmol / g / h, greater than or equal to 0.2 mmol / g / h, greater than or equal to 0.5 mmol / g / h, greater than or equal to 1 mmol / g / h, greater than or equal to 2 mmol / g / h, greater than or equal to 3 mmol / g / h, greater than or equal to 5 mmol / g / h, and / or up to 8 mmol / g / h, up to 10 mmol / g / h, up to 20 mmol / g / h, up to 50

[0168] #13981562vl mmol / g / h, up to 100 mmol / g / h, up to 1000 mmol / g / h, or more under the conditions with which the method is performed (e.g., at any of the temperature, pressure, feedstock mixtures, and flow rates described in this disclosure).

[0169] The catalyst may achieve a suitable rate of ammonia production for standard commercial processes. Specifically, the catalyst may achieve a rate of ammonia production of at least 1 mmol product / gram catalyst / hour for a single pass over a single bed under standard commercial reactor space velocities. The rate of ammonia production may be at least 2, or at least 5, or at least 10, or at least 20, or at least 50, or at least 100, or at least 120, or at least 300, or at least 500 or at least 1000 mmol product / gram catalyst / hour for a single pass over a single bed under standard commercial reactor space velocities at conditions of 200-500 °C, 1-200 bar total pressure, and 5,000-100,000 h'1GHSV.

[0170] After the ammonia has been produced, the method may further include separating ammonia from the precursor gas stream via a technique selected from the group consisting of condensation, pressure swing adsorption, temperature swing adsorption, microwave swing adsorption, vacuum swing adsorption, and combinations thereof.

[0171] In some embodiments, the method further comprises generating hydrogen gas to be used as a precursor gas in the ammonia production process. The hydrogen gas may be produced via electrolysis or from fossil fuels. When electrolysis is used, suitable methods include but are not limited to alkali electrolysis, polymer electrolyte membrane (PEM) electrolysis, and / or solid oxide electrolyzer cell (SOEC) electrolysis. When hydrogen is produced from fossil fuels, suitable production methods include but are not limited to the steam methane reforming (SMR) process, the water-gas shift (WGS) process, and the coal-gasification process. These processes may or may not be integrated into the ammonia synthesis production process.

[0172] In some embodiments, the method further comprises generating the nitrogen gas to be used as a precursor gas in the ammonia production process. Nitrogen may be produced via air using conventional air separation processes. These processes may or may not be integrated into the ammonia synthesis production process.

[0173] In some embodiments, the method may further comprise supplying the energy needed to drive the ammonia synthesis processes. The energy may be provided via renewable energy processes or by using waste heat from the ammonia production process to further reduce the overall carbon footprint of the ammonia synthesis. For example, electricity generated via renewable energy generation techniques such as solar power, wind power, and nuclear power. Additionally, waste heat may be recovered from the steam methane reforming (SMR) process,

[0174] #13981562vl the water-gas shift (WGS) process, and the coal-gasification process. These processes may or may not be integrated into the ammonia synthesis production process.

[0175] METHODS FOR PRODUCTION OF AMMONIA

[0176] In some embodiments, low-carbon ammonia may be produced using an advanced catalyst that is differentiated from commercial catalysts in several ways, for example: (i) >2wt% lanthanide with respect to total metals, (ii) structurally higher porosity and surface area, (iii) morphologically controlled to promote small size constituent domains in close proximity to each other. In some embodiments, the advanced catalyst comprises an advanced base-metal catalyst. The catalyst has higher yield compared to commercial catalysts (i.e., wustite, magnetite) under mild reactor conditions.

[0177] In certain embodiments, the process for producing ammonia (e.g., low-carbon ammonia) may include (a) producing hydrogen (e.g., low-carbon hydrogen) at >99% purity by, but not limited to, one of the following means combined with dehydration / purification steps: (i) Steam Methane Reforming (SMR) coupled with carbon capture, (ii) water electrolysis, (iii) methane pyrolysis with or without carbon sequestration (iv) biomass gasification with or without carbon capture or (v) use of naturally occurring geological hydrogen; (b) compression of H2 to 1-20, 20- 50 bar, 50-100 bar, 100-150 bar, or 150-250 bar via electrically powered compressors that use low-carbon or renewable electricity; (c) production of nitrogen of >99% purity by cryogenic separation of air, pressure swing adsorption (PSA), separation of air, vacuum pressure swing adsorption (VPSA), temperature swing adsorption (TSA) or a combination thereof; (d) compression of N2 to 1-20, 20-50 bar, 50-100 bar, 100-150 bar, or 150-250 bar via electrically powered compressors that use low carbon or renewable electricity; (e) combining H2 and N2 in a reactor at elevated temperatures and pressures in the range of 250-350 °C, 350-380 °C, or 380- 400 °C and 10-20 bar, 20-50 bar, 50-90 bar, 90-150 bar, and 150-250 bar, a H2 / N2 molar ratio of 2-4:1, using a catalyst (e.g., supported catalyst or unsupported catalyst) that produces NH3 yields in the range of 1-5%, 5-10%, 10-15%, 15-20%, 20-25%, at the ammonia converter outlet; (f) separating NH3 in the reactor effluent via condensation, PSA, VPSA, TSA or a combination thereof; and (g) compressing and recycling the unreacted H2 and N2 back into the reactor, with an option to purge to avoid inert buildup. In some embodiments, no precious metals may be used in the catalyst. There may be other embodiments where there may be 0.1-1 wt%, 1-2 wt%, 2-3 wt%, or 3-5 wt% precious metals in the catalyst.

[0178] In some embodiments, a reactor is provided. According to some embodiments, the reactor has a reactor vessel. The reactor vessel may be loaded with multiple layers of catalysts

[0179] #13981562vl across the bed height, with different levels of yield in each layer spanning 5-10%, 10-15%, 15- 20% or 20-25% at the end of each layer. The reactor vessel may also be capable of adsorptive or absorptive separation of NH3 and may be loaded with multiple layers of catalysts and adsorbents or absorbents across the bed height with different levels of yield in each catalyst layer spanning 5-10%, 10-15%, 15-20%, 20-25%, or 25-50% at the end of each layer. The reactor system can exist as a single or a series of vessels, in a variety of possible configurations including batch reactor, a semibatch reactor, a continuous stirred tank reactor, a plug-flow reactor, a trickle-bed reactor, a fixed bed reactor, a moving bed reactor, a rotating bed reactor, a slurry reactor, a tubular reactor, a radial and axial packed bed reactor, a membrane reactor, and a fluidized bed reactor, with the option of inter- vessel or intra- vessel cooling.

[0180] The process according to embodiments described herein may have a gas hourly space velocity (GHSV) of 5,000-100,000 h’1. Recycle may be completely eliminated, and unreacted components may be integrated into other parts of the ammonia or other co-located process like chemicals or steel production in some embodiments. In some embodiments, the reactor feed compressor may be completely eliminated. High-pressure electrolyzers may produce H2 at 20- 40 bar, 40-60 bar, or 60-100 bar. An ammonia production volume may be less than 1-10, 10- 100, or 100-600 tons / day. In some embodiments, an ammonia production volume is less than 600-6000 tons / day. An ammonia production volume may be in the range of 1-10, 10-100, 100- 600, or 600-6000 tons / day.

[0181] The contacting and producing steps may be conducted in the absence of an applied electric field applied to the catalyst composition in some embodiments. In other embodiments, the contacting and producing steps may be conducted with either a DC or AC electric field or electromagnetic radiation, including but not limited to either microwaves or visible light applied to the catalyst.

[0182] It should be appreciated that an ammonia plant may be co-located with a urea plant for the production of fertilizer, and excess energy from the SMR may be used by the urea plant. Excess energy from the SMR may be used for carbon capture on one or more CCE-containing effluent or flue gas streams. Excess energy from the SMR may be used for cogeneration of electricity. Ammonia production is programmable and controllable to be “load-following” (i.e. it can follow cycles in renewable energy production).

[0183] In some embodiments, a non-limiting example of a process for the synthesis of a catalyst with stochiometric composition Ce25Fe65KioOx. This process uses an organic acid as the organic component. Metal precursors in the form of metal salts are mixed with an organic acid like acetic, oxalic, citric acid, and the like to form a final gel, which is dried stepwise in

[0184] #13981562vl progressively increasing temperatures from room temperature at optimized amounts of time per step to give the final catalyst.

[0185] In some embodiments, a non-limiting example of a process for the synthesis of a catalyst with stoichiometric composition Ce23Fe65Co2KioOx. This process uses alcohols or other organic cross linkers like butylene glycol (BG) in place of organic acid as the organic component / cross- linker, in an adjusted organics: metal ratio. Metal precursors are used in the process. The organics, and K and Ce salts are mixed in stoichiometric proportion to create a slurry which is pH controlled. This makes a clear solution to which Co and Fe salts are added stepwise to create another clear solution. The resulting gel is dried stepwise in progressively increasing temperatures from room temperature at refined amounts of time per step to give the final catalyst.

[0186] In some embodiments, a non-limiting example of a process for the synthesis of a catalyst with stoichiometric composition Mg6Ce2Fe76.8C015Cso.2Ox, is described. The Mg, Ce and K salt precursors are mixed in stoichiometric proportion to create a slurry which is pH controlled. This makes a clear solution to which Co and Fe salts are added stepwise to create another clear solution. The resulting gel is dried stepwise in progressively increasing temperatures from room temperature at optimized amounts of time per step to give the final catalyst.

[0187] In some embodiments, a non-limiting example of process for the synthesis of a catalyst with stoichiometric composition Ce23Fe6sCo2KioOx. This process uses alcohols or other organic cross linkers like butylene glycol (BG) in place of organic acid as the organic component / cross- linker, in an adjusted organics: metal ratio. The resulting gel is dried stepwise in progressively increasing temperatures from room temperature at optimized amounts of time per step and the organic component is removed by combustion to give the final catalyst.

[0188] In some embodiments, a non-limiting example of process for the synthesis of a catalyst with stoichiometric composition CesFe76.8C015Cso.2Ox is described. The Ce salt precursors and Cs salts are mixed in stoichiometric proportion to create a slurry which is pH controlled. This makes a clear solution to which Co and Fe salts are added stepwise to create another clear solution. The resulting gel is dried stepwise in progressively increasing temperatures from room temperature at optimized amounts of time per step and the organic component is removed by combustion to give the final catalyst.

[0189] In some embodiments, a non-limiting example of process for the synthesis of a catalyst with stochiometric composition Ce25Fe65KioOx. This process uses an organic acid as the organic component. Metal salts are mixed in stoichiometric proportion with the organic acid solution to

[0190] #13981562vl create a final solution volume of 50 mL. The resulting gel is dried at 85°C for 12 hours in a convection oven and calcined stepwise to give an isolated yield of 2.36 g catalyst.

[0191] In some embodiments, a non-limiting example of process for the synthesis of a catalyst with stoichiometric composition Ce23Fe6sCo2KioOx. This process uses butylene glycol (BG) and aminopolycarboxylic acid (DTPA) as the organic component / cross-linker, DTPA, BG, and K and Ce salts are mixed in stoichiometric proportion to create a slurry which is pH controlled. This makes a clear solution to which Co and Fe salts are added stepwise to create another clear solution. The resulting gel is dried in a convection oven and calcined stepwise to give an isolated yield of 1g catalyst.

[0192] The following are incorporated herein by reference in their entireties for all purposes: U.S. Provisional Patent Application No. 63 / 652,225, filed May 28, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 681,253, filed August 9, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 684,469, filed August 19, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 684,474, filed August 19, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 686,806, filed August 25, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 686,809, filed August 25, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 699,368, filed September 26, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 699,392, filed September 26, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 715,134, filed November 1, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 715,139, filed November 1, 2024, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” U.S. Provisional Patent Application No. 63 / 756,402, filed February 10 , 2025, and entitled “Compositions, Methods of Manufacture, and Uses for Catalysts,” and U.S. Provisional Patent Application No. 63 / 756,406, filed February 10, 2025.

[0193] Example General Synthetic Protocol

[0194] The following Example General Synthetic Protocol is a non-limiting example of a synthetic protocol for producing a catalyst composition comprising some or all of the elements

[0195] #13981562vl Ce, Fe, K, Mg, Co, and / or Cs, in accordance with some embodiments. The precursors include an organic component comprising (i) one or more organic acids such as acetic acid, citric acid, oxalic acid, malic acid, diethylenetriaminepentaacetic acid (DTP A), ethylenediaminetetraacetic acid (EDTA), and / or hydroxyethylethylenediaminetriacetic acid (HEDTA); (ii) an inorganic component comprising metal salts of Fe, Ce, K, Mg, Co, and / or Cs in the form of acetates, hydroxides, carbonates, nitrates, malates, oxalates, and / or citrates; and, optionally, (iii) alcohols or other organic crosslinkers including butylene glycol (BG) and / or ethylene glycol (EG). The inorganic components are measured out in stoichiometric proportions, and the organic components are added in a specific ratio, where the molar ratio of organics inorganics ranges from 0.1-10:1. The solutions are mixed, which is sometimes done in a stepwise manner with an ordered addition of the inorganics to the organic components and is sometimes pH controlled. The mixture is then dried stepwise between room temperature and 150 °C under progressively increasing temperatures for between 2- 48 hours, then calcined stepwise at temperatures ranging from 300-1500 °C for periods ranging from 2-48 hours, then reduced under a series of concentrations of hydrogen ranging from 0-100% at progressively elevated temperatures ranging from 20-900 °C for l-48h, and then passivated under passivation gas (5% O2 in N2) for l-48h to yield the active catalyst material in powder form.

[0196] The active material powder is, in some instances, formed into a shaped catalyst product using a binder comprising binding materials including one or more of the following: carbon black, graphite, stearic acid, acrylic glass (poly(methyl methacrylate)), fumed silica, glucose, hydroxyethyl cellulose, formaldehyde, alumina (e.g., boehmite), silica (e.g., silanes, tetraethyl orthosilicate (TEOS), bentonite), alite (3CaO SiO2), belite (2CaO SiO2), tricalcium aluminate or celite (3CaO- AI2O3), brownmillerite (4CaO- A12O3-Fe2O3), water-soluble alumina-silica dispersions (e.g., DISPAL®, SIRAL), titania (metatitanic acid, titanium tetraethoxide (TEOT)), zirconia (zirconyl acetate), calcium aluminate (cement), magnesium aluminate (hydrotalcite), and / or aluminum phosphates, and combinations thereof. The ratio of the active component to the total mass of the catalyst is between 0.5-1: 1. A method of combining the active component with the optional binder involves one or more of the following catalyst formulation and shaping techniques: extrusion, pelletizing, tablet- moulding, and / or spheronization to make different granules in shapes selected from the group comprising (in both solid and hollow forms): rings, spheres, tablets, pellets, and / or tripods.

[0197] #13981562vl The following examples are intended to illustrate certain embodiments of the present invention, but do not exemplify the full scope of the invention.

[0198] EXAMPLE 1

[0199] This Example describes the synthesis of a catalyst with stoichiometric composition Ce25Fe65KioOx. This process was consistent with the Example General Synthetic Protocol described above. The inorganic precursors - salts of Ce, Fe, and K - were mixed with an organic acid to form a mixture, which was dried stepwise in progressively increasing temperatures starting from room temperature at optimized amounts of time per step, calcined stepwise under progressively increasing temperatures, reduced stepwise under different H2 concentrations at progressively increasing temperatures, and finally passivated with passivation gas to give the active material in powder form. The active material was shaped into both pellets and tablets using a binder.

[0200] EXAMPLE 2

[0201] This Example describes the synthesis of a catalyst with stoichiometric composition Ce23Fe65Co2KioOx. This process was consistent with the Example General Synthetic Protocol described above. This process used EG and / or BG as cross-linker and an organic acid in an adjusted organics: inorganics ratio with respect to salts of Ce, Fe, Co and K. The organics, potassium and Ce salts were mixed in stoichiometric proportion to create a slurry which was pH controlled. This made a clear solution to which Co and Fe salts were added stepwise to create another clear solution. The resulting mixture was dried stepwise at progressively increasing temperatures starting from room temperature at optimized amounts of time per step, calcined under progressively increasing temperatures, reduced stepwise under different H2 concentrations at progressively increasing temperatures, and finally passivated with passivation gas to give the active material in powder form. The active material was shaped into both pellets and tablets using a binder.

[0202] EXAMPLE 3

[0203] This Example describes the synthesis of a catalyst with stoichiometric composition Mg6Ce2Fe76.8C015Cso.2Ox. This process was consistent with the Example General Synthetic Protocol described above. The stoichiometric Mg, and Ce and K salt precursors were mixed with an organic acid to create a mixture that was pH controlled. This resulted in a clear solution to which stoichiometric Co and Fe salts were added stepwise to create another clear solution. The

[0204] #13981562vl resulting mixture was dried stepwise in progressively increasing temperatures starting from room temperature, calcined under progressively increasing temperatures, reduced stepwise under different H2 concentrations at progressively increasing temperatures, and finally passivated with passivation gas to give the active material in powder form. The active material was shaped into both pellets and tablets using a binder.

[0205] EXAMPLE 4

[0206] This Example describes the synthesis of a catalyst with stoichiometric composition CesFe76.8C015Cso.2Ox. This process was consistent with the Example General Synthetic Protocol described above. The Ce and Cs salt precursors were mixed with an organic acid to create a mixture which was pH controlled. This resulted in a clear solution to which Co and Fe salts were added stepwise to create another clear solution. The resulting mixture was dried stepwise at progressively increasing temperatures starting from room temperature at optimized amounts of time per step, calcined at progressively increasing temperatures, reduced stepwise under different H2 concentrations at progressively increasing temperatures, and finally passivated with passivation gas to give the active material in powder form. The active material was shaped into both pellets and tablets using a binder.

[0207] EXAMPLE 5

[0208] This Example describes the synthesis of a catalyst with stoichiometric composition Mg6Ce2Fe76.8C015Cso.1Ko.1Ox. This process was consistent with the Example General Synthetic Protocol described above. The Mg, Ce, Cs and K salt precursors were mixed with an organic acid to create a slurry which was pH controlled. This resulted in a clear solution to which Co and Fe salts were added stepwise to create another clear solution. The resulting mixture was dried stepwise in progressively increasing temperatures starting from room temperature, calcined under progressively increasing temperatures, reduced stepwise under different H2 concentrations at progressively increasing temperatures, and finally passivated with passivation gas to give the active material in powder form. The active material was shaped into both pellets and tablets using a binder.

[0209] EXAMPLE 6

[0210] This Example describes the ammonia yield percentage of catalysts, including examples of advanced catalysts. FIG. 2 shows a plot of ammonia yield percentage against temperature (in Celsius) at 50 bar and 15,000 h'1GHSV, with a 3:1 H2:N2 feed, comparing wustite, magnetite,

[0211] #13981562vl and the advanced catalyst according to embodiments described herein. The inventive catalysts tested were produced by a process consistent with the Example General Synthetic Protocol described above. The plot in FIG. 2 is associated with several example embodiments of the catalyst, such as those having a stoichiometric composition of Mg6Ce2Fe76.8C015Cso.2Ox, Ce25Fe5sCoioKioOx, and Ce2sFe65KioOx. however, it should be appreciated that other advanced catalysts described herein in other embodiments may produce similar plots. The variation of the metal ratio as described in the present disclosure and the addition of other elements may also lead to high-performing catalysts. Another example of such a catalyst is CesFe76.8C015Cso.2Ox, which is also described herein. Another example of such a catalyst is Ce23Fe65Co2KioOx, which is also described herein. The data below compares the performance of the advanced catalysts like Mg6Ce2Fe76.8C015Cso.2Ox, CesFe76.8C015Cso.2Ox, and Ce23Fe65Co2KioOxwith other catalysts with similar elements that fall outside certain stoichiometric ranges described in this disclosure and / or different domain sizes of the inorganic components, thereby demonstrating the importance of these attributes to performance. Despite the lower pressure (50 vs. 85 bar) and higher space velocity (15,000 vs. 10,000 h'1GHSV) at which performance of the advanced catalyst in TABEE 2 below was measured, it beats the yields of the other catalysts of similar composition shown in TABEE 1 below.

[0212] TABEE 1. Commercial and tier 1 catalyst compositions and their respective ammonia yield.

[0213] #13981562vl TABLE 2. Tier 2 catalyst compositions and their respective ammonia yield

[0214] EXAMPLE 7

[0215] The catalyst, such as the advanced catalyst described in Example 6, is also differentiated, in some embodiments, from other catalysts by the small domain sizes of the different elements and metal oxides, which may not exceed 50 nm x 50 nm. The TEM images in FIG. 3 and 4 show a regular catalyst (large elemental domains) and an advanced catalyst (small elemental domains), respectively. The advanced catalyst tested was produced by a process consistent with the Example General Synthetic Protocol described above.

[0216] EXAMPLE 8

[0217] Catalyst productivity (mmol NEL / gcat / h) was analyzed under different conditions and ratios of Fe:Co. TABLE 3 and FIG. 5 summarize catalyst productivity at a variety of Fe:Co ratios and at two different sets of conditions. The inventive catalysts tested were produced by a process consistent with the Example General Synthetic Protocol described above. A ratio of Fe:Co was identified at approximately 5:1 to lead, in some instances, to impressive catalyst performance.

[0218] TABLE 3. Catalyst productivity (mmol NHa / gcat / h) for catalyst compositions.

[0219] #13981562vl EXAMPLE 9

[0220] Testing also was conducted to evaluate how the presence of Ce in the catalyst composition may affect FPR performance / catalyst productivity. TABLE 4 summarizes catalyst

[0221] 5 productivity for various catalyst compositions containing Ce at different conditions and Ce mol percentages. The inventive catalysts tested were produced by a process consistent with the Example General Synthetic Protocol described above. As reflected herein, higher levels of Ce may improve catalyst performance dramatically between 0-10% with the impact plateauing beyond 20%. 0

[0222] TABLE 4. Catalyst productivity for catalyst compositions.

[0223] EXAMPLE 10

[0224] Testing also was performed to evaluate the impact of inclusion of a promoter metal at 5 certain percentages in the catalyst composition on catalyst productivity. More specifically, TABLE 5 reflects use of K as the promoter metal and the importance of K mol% for catalyst performance at two different conditions at two different levels for Ce mol%. The inventive catalysts tested were produced by a process consistent with the Example General Synthetic

[0225] Protocol described above. In each sample, the Fe:Co ratio is approximately 16: 1. An 0 impressive performance was observed at K=0.25%.

[0226] TABLE 5. Catalyst productivity for catalyst compositions.

[0227] #13981562vl EXAMPLE 11

[0228] Evaluation of additional metals, particularly Mg, in the catalyst composition also was performed to evaluate catalyst productivity. The inventive catalysts tested were produced by a process consistent with the Example General Synthetic Protocol described above. As depicted in TABLE 6, the catalyst performance at two different conditions depends on the mol% of Mg. The Fe:Co ratio was approximately 5:1 for each composition, and K=2 mol%. An impressive performance was observed at Mg = 6 mol% at a 3:1 Mg:Ce molar ratio.

[0229] TABLE 6. Catalyst productivity for catalyst compositions.

[0230] EXAMPLE 12

[0231] FIGS. 6A-6K show a range of Samples showcasing certain representative catalysts covering different stoichiometric compositions, form factors (i.e., powders, pellets and tablets), along with their respective densities, surface areas, and performance at two different process conditions. The inventive catalysts tested were produced by a process consistent with the Example General Synthetic Protocol described above. The commercial magnetite and 4wt% Ru / graphite are commercial references shown here for benchmarking purposes only.

[0232] EXAMPLE 13

[0233] The following Example describes temperature programmed desorption (TPD) measurements for different catalysts and related parameters. The catalysts tested were produced by a process consistent with the Example General Synthetic Protocol described above. As shown in Table 7, various catalysts showed at least one hydrogen desorption temperature peak in certain temperature ranges, as measured via TPD, while other materials did not. It was observed that other comparative materials tested, such as commercial materials or materials lacking certain components, performed poorly as catalysts while also not having a hydrogen desorption temperature peak in any of the indicated ranges.

[0234] #13981562vl TABLE 7. Temperature programmed desorption data for catalysts and materials tested.

[0235] EXAMPLE 14

[0236] TABLE 8-11 contains a selection of catalysts on which ICP analysis was performed. The inventive catalysts tested were produced by a process consistent with the Example General Synthetic Protocol described above. The stoichiometric compositions were observed to be reasonably consistent with the precursor recipe for the catalyst composition, with maximum errors within 20%. Accordingly, the catalyst formulas described herein were confirmed.

[0237] #13981562vl TABLE 8. Weight ratio of catalyst samples.

[0238] TABLE 9. Expected molar ratio of catalyst samples based on precursor composition.

[0239] #13981562vl

[0240] TABLE 10. Actual molar ratio of catalyst samples.

[0241] #13981562vl TABLE 11. Percentage of error of actual vs expected molar ratio of catalyst samples.

[0242] While several embodiments of the present invention have been described and illustrated herein, those of ordinary skill in the art will readily envision a variety of other means and / or structures for performing the functions and / or obtaining the results and / or one or more of the advantages described herein, and each of such variations and / or modifications is deemed to be within the scope of the present invention. More generally, those skilled in the art will readily appreciate that all parameters, dimensions, materials, and configurations described herein are meant to be exemplary and that the actual parameters, dimensions, materials, and / or configurations will depend upon the specific application or applications for which the teachings of the present invention is / are used. Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to the specific embodiments of the invention described herein. It is, therefore, to be understood that the foregoing embodiments are presented by way of example only and that, within the scope of the appended claims and equivalents thereto, the invention may be practiced otherwise than as specifically described and claimed. The present invention is directed to each individual feature, system, article, material, and / or method described herein. In addition, any combination of two

[0243] #13981562vl or more such features, systems, articles, materials, and / or methods, if such features, systems, articles, materials, and / or methods are not mutually inconsistent, is included within the scope of the present invention.

[0244] The indefinite articles “a” and “an,” as used herein in the specification and in the claims, unless clearly indicated to the contrary, should be understood to mean “at least one.”

[0245] The phrase “and / or,” as used herein in the specification and in the claims, should be understood to mean “either or both” of the elements so conjoined, i.e., elements that are conjunctively present in some cases and disjunctively present in other cases. Other elements may optionally be present other than the elements specifically identified by the “and / or” clause, whether related or unrelated to those elements specifically identified unless clearly indicated to the contrary. Thus, as a non-limiting example, a reference to “A and / or B,” when used in conjunction with open-ended language such as “comprising” can refer, in one embodiment, to A without B (optionally including elements other than B); in another embodiment, to B without A (optionally including elements other than A); in yet another embodiment, to both A and B (optionally including other elements); etc.

[0246] As used herein in the specification and in the claims, “or” should be understood to have the same meaning as “and / or” as defined above. For example, when separating items in a list, “or” or “and / or” shall be interpreted as being inclusive, i.e., the inclusion of at least one, but also including more than one, of a number or list of elements, and, optionally, additional unlisted items. Only terms clearly indicated to the contrary, such as “only one of’ or “exactly one of,” or, when used in the claims, “consisting of,” will refer to the inclusion of exactly one element of a number or list of elements. In general, the term “or” as used herein shall only be interpreted as indicating exclusive alternatives (i.e. “one or the other but not both”) when preceded by terms of exclusivity, such as “either,” “one of,” “only one of,” or “exactly one of.” “Consisting essentially of,” when used in the claims, shall have its ordinary meaning as used in the field of patent law.

[0247] As used herein in the specification and in the claims, the phrase “at least one,” in reference to a list of one or more elements, should be understood to mean at least one element selected from any one or more of the elements in the list of elements, but not necessarily including at least one of each and every element specifically listed within the list of elements and not excluding any combinations of elements in the list of elements. This definition also allows that elements may optionally be present other than the elements specifically identified within the list of elements to which the phrase “at least one” refers, whether related or unrelated to those elements specifically identified. Thus, as a non-limiting example, “at least one of A and

[0248] #13981562vl B” (or, equivalently, “at least one of A or B,” or, equivalently “at least one of A and / or B”) can refer, in one embodiment, to at least one, optionally including more than one, A, with no B present (and optionally including elements other than B); in another embodiment, to at least one, optionally including more than one, B, with no A present (and optionally including elements other than A); in yet another embodiment, to at least one, optionally including more than one, A, and at least one, optionally including more than one, B (and optionally including other elements); etc.

[0249] As used herein, “wt%” is an abbreviation of weight percentage. As used herein, “at%” is an abbreviation of atomic percentage.

[0250] Some embodiments may be embodied as a method, of which various examples have been described. The acts performed as part of the methods may be ordered in any suitable way. Accordingly, embodiments may be constructed in which acts are performed in an order different than illustrated, which may include different (e.g., more or less) acts than those that are described, and / or that may involve performing some acts simultaneously, even though the acts are shown as being performed sequentially in the embodiments specifically described above.

[0251] Use of ordinal terms such as “first,” “second,” “third,” etc., in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but are used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements.

[0252] In the claims, as well as in the specification above, all transitional phrases such as “comprising,” “including,” “carrying,” “having,” “containing,” “involving,” “holding,” and the like are to be understood to be open-ended, i.e., to mean including but not limited to. Only the transitional phrases “consisting of’ and “consisting essentially of’ shall be closed or semi-closed transitional phrases, respectively, as set forth in the United States Patent Office Manual of Patent Examining Procedures, Section 2111

[0253] #13981562vl

Claims

CLAIMSWhat is claimed is:

1. A catalyst for the synthesis of ammonia or other hydrogenation reactions, comprising: an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;0.5-30 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba;2-30 at% of Mg; and0-0.5 at% additional metal elements (trace).

2. The catalyst of claim 1, wherein the active component has metal content (measured as at% of total metal content in the active component) in its finished form, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;0.5-30 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba;2-30 at% of Mg; and0-0.5 at% additional metal elements (trace).

3. The catalyst of claim 1, wherein the active component has metal content (measured as at% of total metal content in the active component) as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP- OES, or an equivalent method of elemental analysis, comprising:#13981562vl50-94 at% Fe;0.5-30 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba;2-30 at% of Mg; and0-0.5 at% additional metal elements (trace).

4. The catalyst of any one of claims 1-3, wherein the one or more promoter metals are selected from the group comprising: Ca, Al, K, Cs, and / or Ba.

5. A catalyst for the synthesis of ammonia or other hydrogenation reactions comprising: an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;5-50 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace).

6. The catalyst of claim 5, wherein the active component has metal content (measured as at% of total metal content in the active component) in its finished form, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;5-50 at% of one or more lanthanide metals;0-40 at% of Co;#13981562vl0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace).

7. The catalyst of claim 5, wherein the active component has metal content (measured as at% of total metal content in the active component) as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP- OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;5-50 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace).

8. A catalyst for the synthesis of ammonia or other hydrogenation reactions, comprising: an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;X at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba;0-0.5 at% additional metal elements (trace); andJ at% of Mg; and wherein:X > 0;J > 0;5 < (X + J) < 50; and2.5 < (J / X) < 3.5 when J > 0.#13981562vl9. The catalyst of claim 8, wherein 6 < (X + J) < 12.

10. The catalyst of claim 8, wherein 7.5 < (X + J) < 8.5.

11. The catalyst of any one of claims 8-10, wherein 2.8 < (J / X) < 3.2 when J > 0.

12. The catalyst of any one of claims 8-11, wherein the one or more promoter metals are selected from the group comprising: Ca, Al, K, Cs, and / or Ba.

13. A catalyst for the synthesis of ammonia or other hydrogenation reactions comprising an active component comprising a base metal, wherein the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within the temperature range of greater than or equal to 125 degrees C and less than or equal to 200 degrees C.

14. A catalyst for the synthesis of ammonia or other hydrogenation reactions comprising: an active component capable of catalyzing the synthesis of ammonia or other hydrogenation reactions having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:Q at% Fe;0.5-50 at% of one or more lanthanide metals;Z at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace); wherein:50 < Q < 94;0 < Z < 40; and1.5 < (Q / Z) < 20.#13981562vl15. The catalyst of any one of claims 1-14, wherein the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within the temperature range of greater than or equal to 125 degrees C and less than or equal to 200 degrees C.

16. The catalyst of any one of claims 13 and 14, wherein the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within the temperature range of greater than or equal to 125 degrees C and less than or equal to 200 degrees C, greater than or equal to 150 degrees C and less than or equal to 200 degrees C, greater than or equal to 175 degrees C and less than or equal to 200 degrees C, greater than or equal to 150 degrees C and less than or equal to 175 degrees C, or greater than or equal to 125 degrees C and less than or equal to 150 degrees C.

17. The catalyst of any one of claims 1-16, further comprising a binder.

18. The catalyst of claim 17, wherein the binder comprises binding materials well known in the heterogeneous catalyst art containing metal elements including but not limited to Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis.

19. The catalyst of any one of claims 14-18, wherein the one or more promoter metals are selected from the group comprising: Ca, Al, K, Cs, and / or Ba.

20. The catalyst of any one of claims 1-19, wherein the at% of Fe is in one or more of the following ranges: 55-94, 60-94, 65-94, 70-94, and 75-94.

21. The catalyst of any one of claims 1-20, wherein the metal content of the one or more lanthanide metals is in one or more of the following ranges: 0.5-1 at%, 0.5-2 at%, 0.5-3 at%, 0.5- 4 at%, 0.5-5 at%, 0.5-6 at%, 0.5-7 at%, 0.5-8 at%, 0.5-9 at%, 0.5-10 at%, 1-2 at%, 1-3 at%, 1-4 at%, 1-5, at%, 1-6 at%, 1-7 at%, 1-8 at%, 1-9 at%, 1-10 at%, 2-3 at%, 2-4 at%, 2-5 at%, 2-6 at%, 2-7 at%, 2-8 at%, 2-9 at%, 2-10 at%, 3-4 at%, 3-5 at%, 3-6 at%, 3-7 at%, 3-8 at%, 3-9 at%, 3-10 at%, 4-5 at%, 4-6 at%, 4-7 at%, 4-8 at%, 4-9 at%, 4-10 at%, 5-6 at%, 5-7 at%, 5-8 at%, 5-9 at%,#13981562vl5-10 at%, 6-7 at%, 6-8 at%, 6-9 at%, 6-10 at%, 7-8 at%, 7-9 at%, 7-10 at%, 8-9 at%, 8-10 at%, 9-10 at%, 0.5-15 at%, 0.5-20 at%, 0.5-25 at%, 5-15 at%, 10-20 at%, 10-25 at%, and 0.5-30 at%.

22. The catalyst of claim 21, wherein the content of the one or more lanthanide metals is 1-10 at%.

23. The catalyst of any one of claims 1-22, further comprising: non-metal elements, as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis, comprising oxygen (O) and optionally one or more of the following elements: hydrogen (H), carbon (C), nitrogen (N), phosphorus (P), silicon (Si), and trace (<0.5 at%) amounts of other non-metal elements.

24. The catalyst of any one of claims 1-23, wherein the active component contains no more than trace amounts of lanthanides other than Ce or Pr measured as at% of total metal content.

25. The catalyst of any one of claims 1-24, wherein the one or more lanthanide metals comprises Ce and / or Pr.

26. The catalyst of any one of claims 1-25, wherein the one or more lanthanide metals comprises Ce and Pr.

27. The catalyst of any one of claims 1-26, wherein the one or more lanthanide metals consists of Ce and Pr.

28. The catalyst of any one of claims 1-27, wherein the one or more lanthanide metals comprises Ce in an amount of at least 95 at% relative to the total amount of the one or more lanthanide metals.

29. The catalyst of any one of claims 1-25, wherein the one or more lanthanide metals consists of Ce.

30. The catalyst of any one of claims 24-29, wherein the one or more promoter metals is K,Cs, or a combination thereof.#13981562vl31. The catalyst of any one of claims 1-24, wherein the one or more lanthanide metals consists of Pr.

32. The catalyst of claim 31, wherein the one or more promoter metals is K, Cs, or a combination thereof.

33. The catalyst of any one of claims 1-32, wherein the at% of Co is in one or more of the following ranges: 0-40, 0-20, 0-30, 5-40, 5-20, 5-30, 10-20, 10-30, 10-40, 15-20, 15-30, and 15- 40.

34. The catalyst of any one of claims 1-33, wherein the ratio of the mass of the active component to the total mass of the catalyst is in one or more of the following ranges: 0.5:1 to 1:1, 0.6:1 to 1:1, 0.7:1 to 1:1, 0.8:1 to 1:1, 0.9:1 to 1:1, and 0.95:1 to 1:1.

35. The catalyst of any one of claims 1-34, the at% of the one or more promoter metals is in one or more of the following ranges: 0.1-20, 0.2-20, 0.1-10, 0.2-10, 0.1-5, and 0.2-5.

36. The catalyst of any one of claims 1-35, wherein the at% of Mg is in one or more of the following ranges: 2-30, 2-25, 2-20, 2-10, 3-30, 3-25, 3-20, 3-15, 3-10, 4-30, 4-25, 4-20, 4-10, 5- 30, 5-25, 5-20, 5-15, 5-10, 6-30, 6-25, 6-20, 6-15, and 6-10.

37. The catalyst of any one of claims 1-36, wherein any metal element in the active component that is present at concentrations greater than 0.5% (measured as at% of total metal content) as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis is detectable in any square region of an active material surface of dimensions larger than 50 nm by 50 nm as determined by Energy Dispersive X-ray Spectrometry (EDXS) or an equivalent technique.

38. The catalyst of any one of claims 1-37, wherein the catalyst has a BET surface area of 1- 100 m2 / g.#13981562vl39. The catalyst of any one of claims 1-37, wherein the catalyst has a BET surface area in the range of 1-100 m2 / g, 10-20 m2 / g, 1-20 m2 / g, 1-30 m2 / g, 10-20 m2 / g, 10-30 m2 / g, 10-50 m2 / g, or 1-500 m2 / g.

40. The catalyst of any one of claims 1-39, wherein a density falls between the ranges of 0.5- 1 g / cc.

41. The catalyst of any one of claims 1-39, wherein a density falls between the ranges of 1-3 g / cc.

42. The catalyst of any one of claims 1-39, wherein a density falls between the ranges of 3-5 g / cc.

43. The catalyst of any one of claims 1-42, where the catalyst enables lowering of reactor inlet temperature by 5-10 °C, 10-20 °C, 20-30 °C, 30-40 °C, 40-50 °C, 50-70 °C, 70-100 °C, or 100-150 °C and maintains reactor outlet temperatures.

44. The catalyst of any one of claims 1-43, wherein average pore diameter is in a range of 2- 4nm, 4-10nm, 10-20nm, 20-30nm, 30-40nm or 40-50nm.

45. The catalyst of any one of claims 1-44, where pore volume is in a range of 0.01-0.05 cc / g, 0.05-0.1 cc / g, 0.1-0.15 cc / g, 0.15-0.2 cc / g, 0.2-0.3 cc / g and 0.3-0.5cc / g.

46. The catalyst of any one of claims 1-45, wherein the catalyst enables single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 th:N2 ratio in excess of 3%, in excess of 5%, in excess of 7%, in excess of 10%, in excess of 12%, or in excess of 15% at 400 °C, 50 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV).

47. The catalyst of any one of claims 1-46, wherein the catalyst enables single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 th:N2 ratio in excess of 3%, in excess of 5%, in excess of 7%, in excess of 10%, in excess of 12%, or in excess of 15% at 365 °C, 90 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV).#13981562vl48. The catalyst of any one of claims 1-47, wherein the synthesis process of the catalyst includes one or more reduction steps under 1-100% hydrogen gas at 1-100 bar pressure at temperatures between 200-1200 °C for 3-48 hours total.

49. The catalyst of any one of claims 1-48, wherein the catalyst has an agglomerated particle size ranging from 25 pm to 10 mm as measured via mechanical sieving.

50. The catalyst of any one of claims 1-49, wherein at least a portion of the catalyst has a stoichiometric formula selected from the group consisting of CesFe76.8C015Cso.2Ox, Mg6Ce2Fe76.sC015Cso.2Ox, CesFe76.8C015Ko.2Ox, CesFe76.75C015Ko.25Ox, Ce25Fe55CoioKioOx, and Mg6Ce2Fe76sC015Cso 1Ko1Ox.

51. A catalyst for the synthesis of ammonia or other hydrogenation reactions comprising: an active component, having metal content (measured as at% of total metal content) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;0.5-30 at% of Ce and / or Pr;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace); and optionally, a binder comprising binding materials well known in the heterogeneous catalyst art containing metal elements including but not limited to Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis.

52. The catalyst of claim 51, wherein the metal content of the active component further comprises 2-30 at% of Mg.#13981562vl53. A method of manufacturing of the active component of the catalyst in any one of claims 1-52, wherein the method involves one or more of the following catalyst manufacturing techniques: fusion, coprecipitation, incipient wetness impregnation, combustion synthesis, Pechini process, and / or pulsation reaction.

54. A method of combining the active component with the optional binder of any one of claims 17-52, wherein the method involves one or more of the following catalyst formulation and shaping techniques: extrusion, pelletizing, tablet-moulding, spheronizing, or others to make different granules in shapes selected from the group comprising: rings, spheres, tablets, pellets, tripods, in both solid and hollowed forms.

55. A method of producing ammonia, the method comprising: contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising: an active component capable of catalyzing the production of ammonia having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis comprising:50-94 at% Fe;0.5-30 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba;2-30 at% of Mg; and0-0.5 at% additional metal elements (trace).

56. The method of claim 55, wherein the active component has metal content in its finished form, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;#13981562vl0.5-30 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba;2-30 at% of Mg; and0-0.5 at% additional metal elements (trace).

57. The method of claim 55, wherein the active component has metal content as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;0.5-30 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba;2-30 at% of Mg; and0-0.5 at% additional metal elements (trace).

58. The method of any one of claims 55-57, wherein the one or more promoter metals are selected from the group comprising: Ca, Al, K, Cs, and / or Ba.

59. A method of producing ammonia, the method comprising: contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising: an active component capable of catalyzing the production of ammonia having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;5-50 at% of one or more lanthanide metals;0-40 at% of Co;#13981562vl0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace).

60. The method of claim 59, wherein the active component has metal content in its finished form, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;5-50 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace).

61. The method of claim 59, wherein the active component has metal content as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis, comprising:50-94 at% Fe;5-50 at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace).

62. A method of producing ammonia, the method comprising: contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising: an active component capable of catalyzing the production of ammonia having metal content (measured as at% of total metal content in the active component) in either its finished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis comprising:50-94 at% Fe;#13981562vlX at% of one or more lanthanide metals;0-40 at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, K, Li, Na, Cs, and / or Ba;0-0.5 at% additional metal elements (trace); andJ at% of Mg; wherein:X > 0;J > 0;5 < (X + J) < 50; and2.5 < (J / X) < 3.5 when J > 0.

63. The method of claim 62, wherein 6 < (X + J) < 12.

64. The method of claim 62, wherein 7.5 < (X + J) < 8.5.

65. The method of any one of claims 62-64, wherein 2.8 < (J / X) < 3.2 when J > 0.

66. The method of any one of claims 62-65, wherein the one or more promoter metals are selected from the group comprising: Ca, Al, K, Cs, and / or Ba.

67. A method of producing ammonia, the method comprising: contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising an active component comprising a base metal, wherein the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within the temperature range of greater than or equal to 125 degrees C and less than or equal to 200 degrees C.

68. A method of producing ammonia, the method comprising: contacting a catalyst with a precursor gas stream comprising nitrogen and hydrogen gases, the catalyst comprising: an active component capable of catalyzing the production of ammonia having metal content (measured as at% of total metal content in the active component) in either its#13981562vlfinished form or as a sum of the metal content of its precursors, as determined by inductively coupled plasma mass spectrometry (ICP-MS), ICP-OES, or an equivalent method of elemental analysis comprising:Q at% Fe;0.5-50 at% of one or more lanthanide metals;Z at% of Co;0.1-20 at% of one or more promoter metals selected from the group comprising: Ca, Al, Mg, K, Li, Na, Cs, and / or Ba; and0-0.5 at% additional metal elements (trace); wherein:50 < Q < 94;0 < Z < 40; and1.5 < (Q / Z) < 20.

69. The method of any one of claims 55-68, wherein the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within the temperature range of greater than or equal to 125 degrees C and less than or equal to 200 degrees C.

70. The method of any one of claims 67 and 68, wherein the catalyst exhibits at least one hydrogen desorption temperature peak (as measured by temperature programmed desorption) within the temperature range of greater than or equal to 125 degrees C and less than or equal to 200 degrees C, greater than or equal to 150 degrees C and less than or equal to 200 degrees C, greater than or equal to 175 degrees C and less than or equal to 200 degrees C, greater than or equal to 150 degrees C and less than or equal to 175 degrees C, or greater than or equal to 125 degrees C and less than or equal to 150 degrees C.

71. The method of any one of claims 55-70, wherein the catalyst further comprises a binder.

72. The method of claim 71, wherein the binder comprises binding materials well known in the heterogeneous catalyst art containing metal elements including but not limited to Fe, Al, Ti, Zr, Ce, Mg, and / or Ca as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis.#13981562vl73. The method of any one of claims 68-72, wherein the one or more promoter metals are selected from the group comprising: Ca, Al, K, Cs, and / or Ba.

74. The method of producing ammonia of any one of claims 55-73, wherein the at% of Fe is in one of the following ranges: 55-94, 60-94, 65-94, 70-94, and 75-94.

75. The method of producing ammonia of any one of claims 55-74, wherein the metal content of the one or more lanthanide metals is in one or more of the following ranges: 0.5-1 at%, 0.5-2 at%, 0.5-3 at%, 0.5-4 at%, 0.5-5 at%, 0.5-6 at%, 0.5-7 at%, 0.5-8 at%, 0.5-9 at%, 0.5-10 at%, 1-2 at%, 1-3 at%, 1-4 at%, 1-5, at%, 1-6 at%, 1-7 at%, 1-8 at%, 1-9 at%, 1-10 at%, 2-3 at%, 2-4 at%, 2-5 at%, 2-6 at%, 2-7 at%, 2-8 at%, 2-9 at%, 2-10 at%, 3-4 at%, 3-5 at%, 3-6 at%, 3-7 at%, 3-8 at%, 3-9 at%, 3-10 at%, 4-5 at%, 4-6 at%, 4-7 at%, 4-8 at%, 4-9 at%, 4-10 at%, 5-6 at%, 5-7 at%, 5-8 at%, 5-9 at%, 5-10 at%, 6-7 at%, 6-8 at%, 6-9 at%, 6-10 at%, 7-8 at%, 7-9 at%, 7-10 at%, 8-9 at%, 8-10 at%, 9-10 at%, 0.5-15 at%, 0.5-20 at%, 0.5-25 at%, 5-15 at%, 10-20 at%, 10- 25 at%, and 0.5-30 at%.

76. The method of claim 75, wherein the metal content of the one or more lanthanide metals is 1-10 at%.

77. The method of producing ammonia of any one of claims 55-76, wherein the active component contains no more than trace amounts of lanthanides other than Ce or Pr measured as at% of total metal content.

78. The method of any one of claims 55-77, wherein the one or more lanthanide metals comprises Ce and / or Pr.

79. The method of any one of claims 55-78, wherein the one or more lanthanide metals comprises Ce and Pr.

80. The method of producing ammonia of any one of claims 55-79, wherein the one or more lanthanide metals consists of Ce and Pr.#13981562vl81. The method of any one of claims 55-80, wherein the one or more lanthanide metals comprises Ce in an amount of at least 95 at% relative to the total amount of the one or more lanthanide metals.

82. The method of producing ammonia of any one of claims 55-77, wherein the one or more lanthanide metals consists of Ce.

83. The method of producing ammonia of any one of claims 55-77, wherein the one or more lanthanide metals consists of Pr.

84. The method of any one of claims 55-83, wherein the one or more promoter metals is K, Cs, or a combination thereof.

85. The method of producing ammonia of any one of claims 55-84, wherein the ratio of the mass of the active component to the total mass of the catalyst is in one or more of the following ranges: 0.5: 1 to 1: 1, 0.6: 1 to 1: 1, 0.7: 1 to 1: 1, 0.8: 1 to 1: 1, 0.9: 1 to 1: 1, and 0.95: 1 to 1: 1.

86. The method of producing ammonia of any one of claims 55-85, the catalyst further comprising: non-metal elements, as determined by ICP-MS, ICP-OES, or an equivalent method of elemental analysis, comprising oxygen (O) and optionally one or more of the following elements: hydrogen (H), carbon (C), nitrogen (N), phosphorus (P), silicon (Si), and trace (<0.5 at%) amounts of other non-metal elements.

87. The method of any one of claims 55-86, wherein at least a portion of the catalyst has a stoichiometric formula selected from the group consisting of CesFe76.8C015Cso.2Ox, Mg6Ce2Fe76.8C015Cso.2Ox, CesFe76.8C015Ko.2Ox, CesFe76.75C015Ko.25Ox, Ce25Fe55CoioKioOx, and Mg6Ce2Fe76.8Co isCso.1 Ko.1 Ox.

88. The method of producing ammonia of any one of claims 55-87, whereby the atomic ratio of H2:N2 is between 2-4: 1 at the point where the feedstocks make contact with the catalyst.#13981562vl89. The method of any one of claims 55-88, wherein the ammonia production volume is more than 500 tons / day.

90. The method of producing ammonia of any one of claims 55-89, wherein the catalyst enables single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 th:N2 ratio in excess of 3%, in excess of 5%, in excess of 7%, in excess of 10%, in excess of 12%, or in excess of 15% at 400 °C, 50 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV).

91. The method of producing ammonia of any one of claims 55-90, wherein the catalyst enables single-pass yields of ammonia synthesized from hydrogen gas and nitrogen gas precursors at a 3:1 th:N2 ratio in excess of 3% in excess of 5%, in excess of 7%, in excess of 10%, in excess of 12%, or in excess of 15% at 365 °C, 90 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV).

92. The method of any one of claims 55-91, wherein the contacting and producing steps are conducted at a temperature ranging from 0 °C to 500 °C.

93. The method of any one of claims 55-92, wherein the contacting and producing steps are conducted at an initial contact temperature ranging from 0 °C to 750 °C, 280 °C to 300 °C, 300 °C to 320 °C, 320 °C to 350 °C, or 350 °C to 380 °C.

94. The method of any one of claims 55-92, wherein the contacting and producing steps are conducted at a temperature ranging from 0 °C to 450 °C.

95. The method of any one of claims 55-94, wherein the contacting and producing steps are conducted at a pressure ranging from 1 bar to 200 bar.

96. The method of any one of claims 55-95, wherein the contacting and producing steps are conducted in the absence of an electric field applied to the catalyst.

97. The method of any one of claims 55-96, wherein the contacting and producing steps are conducted with an electric field applied to the catalyst.#13981562vl98. The method of any one of claims 55-97, wherein the contacting and producing steps are conducted with either a DC or AC electric field or electromagnetic radiation, including but not limited to either microwaves or visible light applied to the catalyst.

99. The method of any one of claims 55-98, wherein the producing step produces ammonia at a rate of at least 1 mmol product / gram catalyst / hour for a single pass over a single bed under standard commercial reactor space velocities, conditions of 200-500 °C, 280°C -300 °C, 300°C - 320 °C, 320°C -350 °C, or 350°C -380 °C, and 1-200 bar total pressure, 1-20 bar total pressure, 20-50 bar total pressure, 50-100 bar total pressure, 100-150 bar total pressure, or 150-250 bar total pressure, and 5,000-100,000 h'1GHSV.

100. The method of any one of claims 55-99, further comprising: separating ammonia from the precursor gas stream via a technique selected from the group comprising: condensation, pressure swing adsorption, temperature swing adsorption, microwave swing adsorption, vacuum swing adsorption, and combinations thereof.

101. The method of any one of claims 55-100, wherein the contacting and producing steps are conducted in a reactor selected from the group comprising: a batch reactor, a semibatch reactor, a continuous stirred tank reactor, a plug-flow reactor, a trickle-bed reactor, a fixed bed reactor, a moving bed reactor, a rotating bed reactor, a slurry reactor, a tubular reactor, a radial and axial packed bed reactor, a membrane reactor, and a fluidized bed reactor.

102. A method for production of ammonia using an advanced base-metal catalyst with higher yield compared to commercial catalysts comprising:(a) producing hydrogen at >99% purity by one of the following means combined with dehydration / purification steps: (i) Steam Methane Reformer (SMR) coupled with carbon capture, (ii) water electrolyzation, (iii) methane pyrolysis with or without carbon sequestration (iv) biomass gasification with or without carbon capture or (v) use of naturally occurring geological hydrogen;(b) compression of th to 1-20, 20-50 bar, 50-100 bar, 100-150 bar, or 150-250 bar via#13981562vlelectrically powered compressors that use renewable electricity;(c) production of nitrogen of >99% purity by cryogenic separation of air, pressure swing adsorption (PSA), separation of air, vacuum pressure swing adsorption (VPSA), temperature swing adsorption (TSA) or a combination thereof;(d) compression of N2 to 1-20, 20-50 bar, 50-100 bar, 100-150 bar, or 150-250 bar via electrically powered compressors that use low-carbon or renewable electricity;(e) combining H2 and N2 in a reactor at elevated temperatures and pressures in the range of 250-350 °C, 350-380 °C, or 380-400 °C and 10-20 bar, 20-50 bar, 50-90 bar, 90-150 bar, and 150-250 bar, a H2 / N2 molar ratio of 2-4:1, using a catalyst that produces NH3 yields in the range of 1-5%, 5-10%, 10-15%, 15-20%, 20-25%, at an ammonia converter outlet;(f) separating NH3 in the reactor effluent via condensation, PSA, VPSA, TSA or a combination thereof; and(g) compressing and recycling the unreacted H2 and N2 back into the reactor, with an option to purge to avoid inert buildup, wherein the advanced catalyst enables single-pass ammonia yields in excess of 3% under process conditions comprising 3:1 H2:N2 ratio at 350 °C, 50 bar total pressure, and 15,000 h'1gas hourly space velocity (GHSV).

103. The method of claim 102, wherein no precious metals are used in the catalyst.

104. The method of any one of claims 102-103, wherein the catalyst includes 0.1-1 wt%, 1-2 wt%, 2-3 wt%, or 3-5 wt% precious metals.

105. The method of any one of claims 102-104, wherein a reactor vessel is loaded with multiple layers of catalysts across the bed height, with different levels of yield in each layer spanning 5-10%, 10-15%, 15-20% or 20-25% at the end of each layer.

106. The method of any one of claims 102-105, wherein the reactor vessel is capable of adsorptive or absorptive separation of NH3 and is capable of being loaded with multiple layers of catalysts and adsorbents or absorbents across the bed height with different levels of yield in each catalyst layer spanning 5-10%, 10-15%, 15-20%, 20-25%, or 25-50% at the end of each layer.

107. The method of any one of claims 102-106, wherein a reactor system exists as a single or a#13981562vlseries of reactor vessels.

108. The method of claim 107, wherein the reactor system is in one of the following configurations: batch reactor, a semibatch reactor, a continuous stirred tank reactor, a plug-flow reactor, a trickle-bed reactor, a fixed bed reactor, a moving bed reactor, a rotating bed reactor, a slurry reactor, a tubular reactor, a radial and axial packed bed reactor, a membrane reactor, and a fluidized bed reactor, with the option of inter- vessel or intra- vessel cooling.

109. The method of any one of claims 102-108, wherein the method has a gas hourly space velocity (GHSV) of 5,000-100,000 h’1.

110. The method of any one of claims 102-109, wherein recycle is completely eliminated, and unreacted components are integrated into other parts of the ammonia production process or another co-located process.

111. The method of any one of claims 102- 110, wherein no reactor feed compressor is needed.

112. The method of any one of claims 102-111, wherein high-pressure electrolyzers produce th at 20-40 bar, 40-60 bar, or 60-100 bar.

113. The method of any one of claims 102-112, wherein ammonia production volume is less than 1-10, 10-100, 100-600, or is 600-6000 tons / day.

114. The method of any one of claims 102-113, wherein the method is conducted in the absence of an applied electric field applied to the catalyst.

115. The method of any one of claims 102-114, wherein the method is conducted with either a DC or AC electric field or electromagnetic radiation.

116. The method of any one of claims 102-115, wherein a plant for production of ammonia is co-located with a urea plant for the production of fertilizer, and excess energy from the production of hydrogen step is used by the urea plant.#13981562vl117. The method of any one of claims 102-116, wherein excess energy from the production of hydrogen step is used for carbon capture on one or more CCT-containing effluent or flue gas streams.

118. The method of any one of claims 102-117, wherein excess energy from the production of hydrogen step is used for cogeneration of electricity.

119. The method of any one of claims 102-118, wherein the method is programmable and controllable to be “load-following”.#13981562vl

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