A metal oxide-supported active metal catalyst, a method for preparing the same, and use thereof

Abstract

The application provides a metal oxide supported active metal catalyst, a preparation method and application thereof. The metal oxide supported active metal catalyst comprises a metal oxide carrier and active metal particles supported on the metal oxide carrier; the loading amount of the active metal is 0.1wt%-5wt% based on 100% of the mass of the metal oxide carrier. It is tested that the hydrogenation reaction of carbonates to prepare formate by using the metal oxide supported active metal catalyst provided by the application as a hydrogen source or using gaseous carbon monoxide with different concentrations and water to provide in-situ hydrogen source for the water gas shift reaction realizes the hydrogenation reaction of carbonates to prepare formate, the yield of the obtained formate is high, the selectivity is above 99%, there is no attenuation after 6 cycles, and the metal oxide supported active metal catalyst has excellent bifunctional effect. In addition, the preparation method of the metal oxide supported active metal catalyst is simple, the operation condition is mild, and the cost is low, so that large-scale production can be realized.

Description

Technical Field

[0001] This invention belongs to the field of hydrogenation reaction catalysts, specifically relating to a metal oxide supported active metal catalyst, its preparation method, and its application. Background Technology

[0002] With the acceleration of global industrialization, the increasing depletion of fossil resources, and the rapid rise in energy consumption, carbon dioxide (CO2) emissions have continued to grow, and the greenhouse effect has become a serious challenge facing humanity. Therefore, how to efficiently capture and utilize CO2 is a current research hotspot in the fields of green chemistry and energy chemical engineering. Among numerous technical routes, using aqueous hydroxide solutions to capture CO2 to generate carbonates (or bicarbonates), and then selectively converting them into high-value-added chemicals (such as formates and methanol) through catalytic hydrogenation, has attracted widespread attention from scholars because it enables the closed-loop recycling of carbon resources.

[0003] Currently, research on the hydrogenation of carbonates to formate has made some progress, but existing technical routes still have significant limitations. Current carbonate hydrogenation technologies are mainly divided into homogeneous catalysis and heterogeneous catalysis. Homogeneous catalysis catalysts are usually soluble complexes, dissolving in water during the reaction, but they cannot be recycled. Heterogeneous catalysis catalysts are solid phases, insoluble in the reaction solvent, such as supported catalysts, and their advantage is that they can be recycled. While homogeneous catalysis routes (such as those using ruthenium and iridium complexes) have high activity, they face bottlenecks such as expensive ligands and difficulty in product separation. The most significant problem with existing heterogeneous catalysis routes is the singularity and limitation of the hydrogen source. Most existing reports strictly rely on high-pressure, high-purity hydrogen (H2) as the sole reducing agent. However, the preparation, storage, and transportation of high-purity hydrogen are costly and pose potential safety hazards. Meanwhile, in actual industrial production, large amounts of industrial waste gas (such as water gas, blast furnace gas, and syngas) are often rich in carbon monoxide (CO) or a mixture of CO and H2. Traditional precious metal catalysts (such as pure platinum catalysts) are highly susceptible to CO poisoning in CO-containing atmospheres, leading to the complete deactivation of active sites on the catalyst surface by dead adsorbed CO. Developing a highly compatible technology that can flexibly utilize CO (through in-situ hydrogen supply via water-gas shift reaction) or CO / H2 mixtures as a hydrogen source for reduction would greatly broaden raw material sources, reduce production costs, and improve atom economy. However, related technologies in this field are currently immature. The closest existing technology to this invention is conventional metal oxide-coated metal catalysts. While such technologies can provide limited CO tolerance through the coating layer, this often comes at the cost of sacrificing catalyst mass transfer efficiency and surface active sites, resulting in a decline in hydrogenation reactivity. Therefore, existing coating technologies still cannot truly be compatible with and efficiently utilize CO-containing industrial waste gas sources in practical applications. Summary of the Invention

[0004] Based on the aforementioned deficiencies in the existing technology, the first objective of this invention is to provide a metal oxide-supported active metal catalyst, which possesses anti-CO poisoning and in-situ hydrogen supply functions, while also exhibiting high activity, high selectivity, and high stability.

[0005] To achieve the above objectives, the present invention adopts the following technical solution: The present invention provides a metal oxide supported active metal catalyst, comprising a metal oxide support and active metal particles supported on the metal oxide support; Based on the mass of the metal oxide carrier being 100%, the loading of the active metal particles is 0.1wt%~5wt%.

[0006] As a further improvement of the present invention, the metal oxide support is any one or more selected from titanium oxide, cerium oxide, tungsten oxide and aluminum oxide; The active metal particles are spherical with an average particle size of 0.5 nm to 6.0 nm; the active metal in the active metal particles is any one or more selected from the noble metals platinum, ruthenium, rhodium, and palladium, and the non-noble metals nickel, cobalt, copper, and iron.

[0007] As a further improvement of the present invention, the metal oxide support is titanium dioxide (TiO2), which is prepared according to the following method: Tetrabutyl titanate was mixed with hydrofluoric acid, reacted in a high-pressure reactor, cooled to room temperature, centrifuged, and the centrifuged product was collected. The product was washed with NaOH solution to remove fluoride ions, centrifuged again, and the product was collected. Finally, the product was washed with water and alcohol and dried. This product was denoted as TiO2 support. The concentration of tetrabutyl titanate is 99 wt%, the concentration of hydrofluoric acid is 40 wt%, and the amount of tetrabutyl titanate to hydrofluoric acid is 20 mL to 30 mL and 2 mL to 5 mL, respectively; the concentration of the NaOH solution is 0.5 M to 1.5 M; the reaction temperature of the high-pressure reactor is 160 °C to 200 °C; and the reaction time is 12 h to 48 h. The centrifugation and re-centrifugation are performed at speeds of 6000 rpm to 12000 rpm for 2 min to 10 min, and at a drying temperature of 60℃ to 80℃.

[0008] As a further improvement of the present invention, the reaction temperature of the high-pressure reactor is 170℃~180℃; the reaction time is 24h~36h. The centrifugation and re-centrifugation are performed at speeds of 8000 rpm to 10000 rpm for 5 min to 8 min, and at a drying temperature of 65℃ to 75℃.

[0009] A second objective of this invention is to provide a method for preparing a metal oxide-supported active metal catalyst, comprising the following steps: A metal oxide support, an active metal salt, an alkaline substance, and a solvent are mixed, dried, and calcined to obtain a metal oxide-supported active metal catalyst. The ratio of the metal oxide carrier, active metal salt, alkaline substance and solvent is 100 mg:(0.1~5) mg:(20~200) μL:(25~50) mL.

[0010] As a further improvement of the present invention, The metal oxide support is selected from any one or more of titanium oxide, cerium oxide, tungsten oxide, and aluminum oxide, and its morphology is selected from any one or more of flake, rod, and sphere. The active metal salt is selected from any one or more of the noble metal salts platinum salt, ruthenium salt, rhodium salt, palladium salt, and non-noble metal salts nickel salt, copper salt, cobalt salt, and iron salt, specifically including any one or more of chloroplatinic acid hexahydrate, ruthenium chloride, rhodium chloride, potassium chloropalladate, nickel chloride, copper chloride, cobalt chloride, and ferric chloride; The alkaline substance is selected from ammonia water; The solvent is selected from water; The ratio of the TiO2 support, active metal salt, alkaline substance and solvent is 100 mg:(0.3~0.8) mg:(50~150) μL:(30~45) mL; The mixing time is 10h~24h, and the mixing is carried out under stirring conditions at a stirring rate of 500r / min~1000r / min; the drying temperature is 80℃~120℃; the calcination is carried out in a reducing atmosphere, which is selected from a hydrogen-argon mixture or a hydrogen-nitrogen mixture; the calcination temperature is 300℃~450℃, and the time is 2h~6h.

[0011] A third objective of this invention is to provide the application of a metal oxide-supported active metal catalyst in the hydrogenation reaction of carbonates or bicarbonates with water, or with a mixture of aqueous hydroxide solution and CO2 gas, comprising the following steps: A hydrogenation reaction is carried out by mixing a metal oxide-supported active metal catalyst, a carbonate or bicarbonate, and water; or by mixing a metal oxide-supported active metal catalyst with a mixture of an aqueous hydroxide solution and CO2 gas, and then introducing a hydrogen-containing gas, a carbon monoxide-containing gas, or a mixture of hydrogen and carbon monoxide under a protective gas atmosphere.

[0012] As a further improvement of the present invention, the carbonate is any one or more selected from sodium carbonate, potassium carbonate and ammonium carbonate; The bicarbonate is selected from any one or more of sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate; The hydroxide in the aqueous hydroxide solution is any one or more selected from sodium hydroxide, potassium hydroxide, and ammonium hydroxide; The protective gas is argon and / or helium; The hydrogen-containing gas is pure hydrogen or a mixture containing hydrogen; the carbon monoxide-containing gas is pure carbon monoxide or a mixture containing carbon monoxide; the hydrogen and carbon monoxide mixture is a mixture of pure hydrogen and carbon monoxide or a mixture containing both hydrogen and carbon monoxide. The hydrogenation reaction is carried out at a pressure of 1 MPa to 5 MPa, a temperature of 100℃ to 500℃, and a time of 1 h to 5 h.

[0013] As a further improvement to the present invention, the following steps are also included: After the reaction is complete, the reaction vessel is opened and the product is taken out. It is then centrifuged and filtered for separation. The separated solid catalyst is washed and dried for reuse. The centrifugation speed is 6000 rpm to 12000 rpm and the time is 2 min to 10 min. The drying temperature is 60℃ to 80℃.

[0014] As a further improvement of the present invention, the centrifugation speed is 8000~10000 rpm; the time is 3 min~8 min; and the drying temperature is 65℃~75℃.

[0015] The technical challenge of this invention lies in how to weaken the strong adsorption of CO on the surface of an active metal while simultaneously triggering a water-gas shift reaction (WGSR) to achieve in-situ hydrogen production. To overcome this challenge, this invention cleverly employs a strategy of alkaline-assisted synthesis, which anchors the active metal to the support surface at a specific small size. This not only creates a unique coordination environment but also induces strong interactions (electron transfer) between the active metal and the metal oxide support, effectively reducing the adsorption energy of CO. Thus, it can produce hydrogen in situ while remaining resistant to CO poisoning.

[0016] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention provides a method for preparing a metal oxide-supported active metal catalyst. The method involves mixing a metal oxide support, an active metal salt, an alkaline substance, and a solvent, followed by drying and calcination to obtain the metal oxide-supported active metal catalyst. The presence of the alkaline substance generates hydroxyl radicals on the surface of the metal oxide support, thereby facilitating the electrostatic or chemical adsorption of inactive and active metals. The active metal grows into small particles and is loaded onto the support surface through coordination bonds between the active metal and oxygen. In this invention, the active metal particles are uniformly dispersed and do not readily aggregate. The catalyst, through its unique and stable coordination environment and the synergistic effect between the loaded active metal particles and the support, enables the catalyst to flexibly utilize carbon monoxide (through in-situ hydrogen supply via water-gas shift reaction) or a carbon monoxide-hydrogen mixture as a reducing hydrogen source in the selective catalytic hydrogenation reactions of carbonate, bicarbonate, or hydroxide aqueous solutions with CO2 gas. This technology offers advantages such as low production cost, high reactivity, good selectivity, and strong stability.

[0017] 2. The synergistic effect of this invention has been verified experimentally: Using either the active metal alone or the metal oxide support alone under the same CO atmosphere fails to yield the target product; however, in the reaction system, the catalyst of this invention utilizes the metal oxide support to activate water molecules and generate surface hydroxyl groups, while the active metal adsorbs CO. A synergistic reaction occurs at the interface between the two, generating an in-situ hydrogen source for further hydrogenation, thus achieving… Figure 4 Even after six cycles, it still maintains excellent results with over 99% selectivity and zero decay.

[0018] 3. Compared with other similar metal-supported catalysts in the prior art, the metal oxide-supported active metal catalyst provided by this invention achieves uniform dispersion of active metal particles on the metal oxide support through electrostatic adsorption, making them less prone to polymerization and exhibiting high reactivity. Due to its unique and stable coordination environment and the synergistic effect between the supported active metal particles and the support, the catalyst possesses advantages such as high activity, good selectivity, strong stability, and a broad-spectrum hydrogen source. In selective hydrogenation catalytic reactions, the metal oxide-supported active metal catalyst provided by this invention exhibits excellent catalytic performance.

[0019] 4. The preparation method of the metal oxide-supported active metal catalyst provided by this invention is simple, operates under mild conditions, and is inexpensive, which is conducive to large-scale production. Furthermore, this metal oxide-supported active metal catalyst not only possesses high activity, high selectivity, and high stability, but also exhibits excellent catalytic performance in selective hydrogenation reactions.

[0020] 5. Compared with existing technologies, the core difference of this invention lies in the efficient loading structure constructed by utilizing the electron-metal carrier interaction mechanism, achieving a coupling of high exposure of active sites and high CO tolerance. This not only solves the problems of mass transfer resistance and CO poisoning, but also ensures product yield, selectivity, and cycling stability in practical applications. Attached Figure Description

[0021] Figure 1 The image shows the X-ray diffraction pattern of the TiO2-based catalyst with platinum particles supported on it, prepared in Example 1.

[0022] Figure 2 Aberration-corrected transmission electron microscope images of TiO2-based catalysts with different sizes of supported platinum particles prepared in Example 1.

[0023] Figure 3 The formate NMR spectrum of the catalytic product of the TiO2-based catalyst with supported platinum particles prepared in Example 1 is shown in the figure.

[0024] Figure 4 The graphs show the yield and selectivity of sodium formate, the target product, which was repeatedly used in the sodium carbonate hydrogenation reaction of the TiO2-based catalyst with platinum particles supported by the catalyst prepared in Example 1. Detailed Implementation

[0025] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] To address the problems of existing technologies in the direct conversion of carbonates to formates, such as complex preparation, high cost, harsh reaction conditions, difficulty in recovery, low efficiency, single hydrogen source, and poor selectivity and stability, this invention provides a metal oxide-supported active metal catalyst (hereinafter referred to as: M). NPs / M X O Y It includes a metal oxide support and active metal particles loaded on the metal oxide support (where "M" represents a specific active metal element (Metal), "NPs" represents nanoparticles, "M" represents a specific active metal element (Metal), and "NPs" represents nanoparticles (Nanoparticles). X O Y "Represents metal oxides".

[0027] In this invention, the metal oxide support is selected from any one or more of titanium oxide, cerium oxide, tungsten oxide, and aluminum oxide, preferably TiO2. Furthermore, the metal oxide support is sheet-like, providing more metal growth binding sites, making it easier to form active metal sites subsequently.

[0028] In this invention, the active metal in the active metal particles is selected from any one or more of noble metal salts such as platinum, ruthenium, rhodium, and palladium, and non-noble metal salts such as nickel, copper, cobalt, and iron, preferably platinum, because platinum has extremely high hydrogen dissociation and activation capabilities. Under the special coordination environment of this invention, the d-band center of platinum shifts, effectively weakening the poisoning adsorption of CO, enabling high-frequency catalytic conversion under extremely mild conditions. Simultaneously, the active metal particles are spherical, with an average particle size of 0.5 nm to 6.0 nm, preferably 1.8 nm to 2 nm. This size exposes a sufficient number of catalytically active edge sites while maintaining a moderate metal-support interaction on the support surface, avoiding the defects of easy agglomeration of single atoms and low specific surface area of ​​ultra-large particles.

[0029] Excessive loading of active metals can lead to over-aggregation, reducing the effective catalytic area and hindering subsequent practical applications. Therefore, in this invention, with the TiO2 support as 100% by mass, the loading of the active metal particles is 0.1wt%~5wt%. Within this loading range, the active metals can achieve near-limited highly uniform dispersion on the support surface. Values ​​below this range result in insufficient overall catalytic active sites; values ​​above this range easily lead to agglomeration and growth of metal particles during calcination, resulting in a decrease in effective catalytic area and wasted costs. The preferred loading of the active metal particles is 0.3wt%~0.8wt%. This preferred range ensures that the number of active sites meets catalytic requirements while preventing the aggregation of active metal particles, maintaining a good dispersion state, and avoiding a decrease in catalytic performance.

[0030] In this invention, the aforementioned active metal particles can be uniformly dispersed and are not easily aggregated. The catalyst, through its special and stable coordination environment and the synergistic effect between the active metal and the support, enables it to exhibit high reactivity, good selectivity, strong stability, and the ability to utilize hydrogen, carbon monoxide (through in-situ hydrogen supply via water-gas shift reaction), or a carbon monoxide / hydrogen mixture as a reducing hydrogen source in the selective catalytic hydrogenation reaction of mixtures of carbonates or bicarbonates with water, or mixtures of hydroxide aqueous solution and CO2 gas. This technology will greatly broaden the sources of raw materials and reduce production costs.

[0031] In this invention, there are no particular limitations on the preparation of the above-mentioned metal oxide support, and it can be prepared according to preparation methods well known to those skilled in the art.

[0032] For example, the TiO2 support is prepared according to the following method: Tetrabutyl titanate was mixed with hydrofluoric acid, reacted in a high-pressure reactor, cooled to room temperature, centrifuged, and the product was collected. The product was washed with NaOH solution to remove fluoride ions, centrifuged again, and the product was collected. Finally, the product was washed with water and alcohol and dried. This product was denoted as TiO2 support.

[0033] The tetrabutyl titanate concentration is 99 wt%, the hydrofluoric acid concentration is 40 wt%, and the dosage of tetrabutyl titanate to hydrofluoric acid is 20 mL to 30 mL and 2 mL to 5 mL, respectively; the concentration of the NaOH solution is 0.5 M to 1.5 M. The reaction temperature in the high-pressure reactor is 160℃ to 200℃, preferably 170℃ to 180℃; the reaction time is 12 h to 48 h, preferably 24 h to 36 h. Its advantage is that under these hydrothermal temperature, pressure, and time conditions, tetrabutyl titanate can be completely hydrolyzed and crystallized to form anatase TiO2 with suitable crystallinity and abundant surface oxygen vacancy defects. Too low a temperature or too short a time will lead to incomplete crystallization, while too high a temperature or too long a time will cause excessive grain growth, reducing the specific surface area. The centrifugation speed is 6000 rpm to 12000 rpm, preferably 8000 rpm to 10000 rpm; the time is 2 min to 10 min, preferably 5 min to 8 min. The advantage of this preferred range is that it can efficiently separate nanoscale solid supports while avoiding irreversible hard agglomeration of the wet gel due to excessive centrifugal force. The drying temperature is 60℃ to 80℃, preferably 65℃ to 75℃. The advantage of this preferred range is that this mild drying condition can effectively remove physically adsorbed water while maximally retaining the hydroxyl groups on the support surface, which are key sites for subsequent anchoring of active metal precursors. In the above method, raw materials such as tetrabutyl titanate, hydrofluoric acid, and NaOH solution can also be replaced with other substances commonly used in the preparation of TiO2 supports in this field.

[0034] The present invention provides a method for preparing a metal oxide-supported active metal catalyst, comprising the following steps: A metal oxide support, an active metal salt, an alkaline substance, and a solvent are mixed, dried, and calcined to obtain a metal oxide-supported active metal catalyst.

[0035] In this invention, the alkaline substance is preferably selected from ammonia water, which is used to generate hydroxyl radicals on the surface of TiO2 support. At the same time, it can decompose into gas during the subsequent heating process, so as not to introduce other impurities.

[0036] In this invention, the solvent is selected from water, preferably deionized water, in order to eliminate the influence of impurities in the water.

[0037] In this invention, the mass ratio of TiO2 support to active metal salt and the amount of alkaline substance added affect the loading, dispersion and coordination environment of the active metal, thereby affecting the hydrogenation catalytic activity.

[0038] In this invention, the ratio of the TiO2 support, active metal salt, alkaline substance, and solvent is 100 mg:(0.1~1) mg:(20~200) μL:(25~50) mL, preferably 100 mg:(0.3~0.8) mg:(50~150) μL:(30~45) mL. Within this preferred range, a structurally complete supported catalyst can be successfully synthesized. Simultaneously, uniform loading of the active metal on the TiO2 support surface is effectively achieved, and particle agglomeration is suppressed, resulting in well-dispersed nanoparticles. If this ratio is exceeded, it is difficult to simultaneously achieve both uniform loading and dispersion.

[0039] Specifically, in some embodiments of the present invention, the amount of TiO2 carrier is 100 mg, the amount of ammonia water is 20 μL to 200 μL, the amount of active metal salt is 0.1 to 5 wt.% (compared to the amount of TiO2 carrier), and the amount of water is 25 mL to 50 mL.

[0040] In this invention, the mixing is preferably carried out under stirring conditions, with a stirring rate of 500 r / min to 1000 r / min, preferably 600 r / min to 800 r / min; and a stirring time of 10 h to 24 h, preferably 12 h to 20 h. The stirring process affects the active metal loading, dispersion, and coordination environment, thereby influencing the hydrogenation catalytic activity. Its advantages include ensuring uniform diffusion of the active metal precursor in the liquid phase system and deep penetration into the internal pores of the porous support, achieving sufficient adsorption-desorption equilibrium and guaranteeing the uniformity of the final loading.

[0041] In some embodiments of the present invention, it is preferable to disperse the TiO2 support in an aqueous solution, and then add an alkaline substance and an aqueous solution containing an active metal salt, and stir at room temperature. The advantage of this method is that it can promote the formation of hydroxyl radicals in the system, so that the active metal precursor can undergo uniform electrostatic adsorption on the surface of the TiO2 support, thereby improving the uniformity of the active component loading and the consistency of material preparation.

[0042] In this invention, the room temperature is "10℃~30℃", preferably "15℃~25℃", which has the advantage of not requiring an additional heat source.

[0043] In this invention, the drying temperature is 80℃~120℃, preferably 90℃~110℃. The advantage of the preferred range is that it can rapidly vaporize the solvent and prevent the metal precursor from migrating and accumulating on the outer surface due to the capillary force of the solvent during the slow evaporation process.

[0044] In this invention, the calcination treatment is carried out in a reducing atmosphere, which is selected from a hydrogen-argon mixture or a hydrogen-nitrogen mixture. During this calcination process, the active metal grows into small particles on the surface of the TiO2 support. The calcination temperature is 300℃~450℃, preferably 320℃~400℃; the time is 2h~6h, preferably 3h~4h. The calcination treatment affects the loading, dispersion, and coordination environment of the active metal, thereby affecting the hydrogenation catalytic activity. The advantage of the preferred range is that the energy provided by this heat treatment condition is just sufficient to reduce the metal precursor to a catalytically active metal phase and induce strong metal-support interactions, thereby achieving electron transfer; at the same time, it effectively avoids Oswald ripening and agglomeration of metal nanoparticles caused by excessively high temperatures.

[0045] In summary, in some embodiments of the present invention, the preparation method of the metal oxide-supported active metal catalyst includes the following steps: Step (1): Tetrabutyl titanate and hydrofluoric acid are mixed, placed in a high-pressure reactor for reaction, cooled to room temperature, centrifuged and the centrifuged product is collected. The product is washed with NaOH solution to remove fluoride ions, centrifuged again and the product is collected. Finally, the product is washed with water and alcohol and dried to obtain the product, which is denoted as metal oxide TiO2. Step (2): Disperse the TiO2 metal oxide prepared in step (1) into an aqueous solution, then add ammonia and an aqueous solution containing a metal salt. After stirring at room temperature, dry and calcinate to reduce and obtain a loaded active metal particle (M). NPs The product of ) is denoted as M. NPs / TiO2.

[0046] In this invention, the active metal particles can be uniformly dispersed on the metal oxide support, making them less prone to aggregation. Through their special and stable coordination environment, as well as the synergistic effect between the supported active metal particles and the support, the metal oxide-supported active metal catalyst can flexibly utilize carbon monoxide (through in-situ hydrogen supply via water-gas shift reaction) or a carbon monoxide-hydrogen mixture as a reducing hydrogen source in the selective catalytic hydrogenation reaction of mixtures of carbonate, bicarbonate, or hydroxide aqueous solutions with CO2 gas. This technology has advantages such as low production cost, high reactivity, good selectivity, and strong stability.

[0047] Based on this, the present invention also provides an application of the above-mentioned metal oxide supported active metal catalyst in a hydrogenation reaction in a mixture of carbonate, bicarbonate or hydroxide aqueous solution and CO2 gas, under a protective gas atmosphere, by introducing hydrogen or carbon monoxide or a mixture of hydrogen and carbon monoxide.

[0048] In this invention, the pressure of the hydrogenation reaction is 1 MPa to 5 MPa, preferably 2 MPa to 4 MPa; the temperature is 100℃ to 500℃, preferably 200℃ to 400℃; and the time is 1 h to 5 h, preferably 2 h to 4 h. The advantage of the preferred range is that these conditions thermodynamically greatly promote the occurrence of the water-gas shift reaction (in-situ hydrogen production) and the subsequent positive shift in the equilibrium for the hydrogenation conversion to formate, while kinetically ensuring a high reaction rate. If the temperature and pressure are too high, it will increase equipment costs and operational risks, and may also trigger side reactions that reduce selectivity.

[0049] In some specific embodiments of the present invention, preferably, a metal oxide-supported active metal catalyst, carbonate or bicarbonate, and water, or a metal oxide-supported active metal catalyst and CO2 gas dissolved in water, are added to a high-pressure reactor. A protective gas is introduced to purge the reactor, followed by the introduction of hydrogen, carbon monoxide, or a mixture of hydrogen and carbon monoxide. The reactor is then sealed, and the reaction temperature and time are set. After the reaction is complete, the reactor is cooled to room temperature. The product is then removed from the reactor and centrifuged and filtered. The separated solid catalyst is washed, dried, and reused. The separated liquid product is analyzed. The centrifugation speed is 6000 rpm to 12000 rpm, preferably 8000 rpm to 10000 rpm; the centrifugation time is 2 min to 10 min, preferably 3 min to 8 min. The drying temperature is 60℃ to 80℃, preferably 65℃ to 75℃. The above-mentioned preferred conditions enable rapid and non-destructive efficient separation of the catalyst from the liquid phase products. The gentle drying process prevents the collapse of catalyst channels and passivation of surface active sites, ensuring the excellent stability of the catalyst in multiple cycles.

[0050] Specifically, when the metal oxide used to prepare the metal oxide supported active metal catalyst is TiO2 and the active metal salt is platinum salt, a TiO2-based catalyst with platinum particles is obtained. It can withstand CO poisoning and undergo water-gas shift reaction to supply hydrogen in situ under reaction temperature of 200℃ and 1MPa CO conditions, using sodium carbonate as the reaction substrate. This produces sodium formate with high activity and selectivity greater than 99%, and its performance does not decline after 6 cycles.

[0051] The catalytic reaction performance testing process and method of the present invention are as follows: A high-pressure reactor was used as the reaction equipment. A metal oxide-supported active metal catalyst, the reaction substrate, and water were added to the reactor. After purging the reactor with a protective gas, a reaction gas (carbon monoxide, hydrogen, or a mixture thereof) was introduced to the set pressure, and the reaction was carried out under constant temperature and stirring. After the reaction, the mixture was cooled to room temperature, and solid-liquid separation was performed by centrifugation or filtration. The separated solid catalyst was washed and dried before being used for cycle life testing. The separated liquid product was subjected to qualitative and quantitative analysis using liquid chromatography and nuclear magnetic resonance spectroscopy. The test results showed that the formate yield obtained by hydrogenation reaction using the catalyst provided by this invention was high, with a selectivity of over 99%. The catalytic performance showed no decline after six consecutive cycles, exhibiting excellent anti-poisoning and in-situ hydrogen donation dual functions. The reaction substrate was a carbonate or bicarbonate, or a mixture of aqueous hydroxide solution and carbon dioxide.

[0052] To further illustrate the present invention, the following embodiments provide a detailed description. The experimental materials used in the following embodiments of the present invention are all commercially available products.

[0053] Example 1 The TiO2-based catalyst with platinum particles supported in this embodiment is prepared by the following steps: S1: Mix 25 mL of 99 wt% Ti(OBu)4 with 3 mL of 40 wt% HF, place in a high-pressure reactor at 180℃ for 24 h, cool to room temperature, centrifuge at 10000 rpm for 5 min, then wash the product with 1 M NaOH solution to remove fluoride ions, and finally wash with water and alcohol, and dry at 70℃ to obtain the product, which is denoted as TiO2, for later use; S2: Disperse 100 mg TiO2 in 25 mL of aqueous solution, add 100 μL of ammonia and 1.09 mg of chloroplatinic acid hexahydrate, and stir at room temperature for 24 h at a speed of 500 r / min; dry at 100 °C, and finally calcine the intermediate mixture in a tube furnace at 350 °C for 3 h in a 10 vt% hydrogen-argon mixed atmosphere (H2:Ar=10:90, volume ratio (vt%)) at a heating rate of 2 °C / min, and then cool to room temperature to obtain the TiO2-based product loaded with platinum particles, denoted as Pt. NPs / TiO2.

[0054] Specifically, during the implementation of Embodiment 1 of the present invention, the following detection results were obtained: (1) The TiO2-based catalyst supported on platinum particles was characterized by X-ray diffraction, thus obtaining the following results: Figure 1The X-ray diffraction pattern shown is illustrated, where the horizontal axis 2Theta (degree) represents the diffraction angle, with Cu Kα radiation, commonly used in X-ray diffraction testing, as the reference system; and the vertical axis Intensity (au) represents the diffraction peak intensity. Figure 1 It can be seen that the obvious diffraction peak positions of the catalyst prepared in Example 1 of the present invention are basically consistent with the characteristic diffraction peaks of anatase TiO2, and there are no obvious characteristic diffraction peaks of active metals (such as Pt). This indicates that the active metals do not exist as bulk crystals, but are highly dispersed on the surface of the metal oxide support in extremely small nanoscales, without serious agglomeration.

[0055] (2) The TiO2-based catalyst with supported platinum particles was observed using a high-resolution transmission electron microscope, thus obtaining the following results: Figure 2 The transmission electron microscope images shown; in which, Figure 2 The image on the right is a magnified view of the left. Due to technical requirements, the high-resolution imaging modes differ. The left image is a bright-field image, where the darker black particles are Pt grains; the right image is a dark-field image, where the lighter white particles are Pt. Figure 2 It can be seen that the metal particles are regular spherical with an average particle size of about 2 nm, and are densely and uniformly anchored on the TiO2 support surface, which confirms that the preparation method can effectively control the particle size.

[0056] (3) The TiO2-based catalyst supported on platinum particles was used as a catalyst for the hydrogenation reaction of sodium carbonate and its performance was tested. The specific process is as follows: In the hydrogenation process, 1 mmol of sodium carbonate, 10 mg of the TiO2-based catalyst with platinum particles supported as prepared in Example 1, and 6 mL of water were added to a high-pressure reactor. Nitrogen gas was introduced to 1 MPa, and this operation was repeated three times to purge the gas from the reactor. Carbon monoxide was then introduced to 1 MPa, the reactor was sealed, and the reaction temperature was set to 200 °C for 1 h. After the reaction was completed, the reactor was cooled to room temperature. The product was then removed from the reactor and separated by centrifugation and filtration. The centrifugation speed was 6000 rpm to 12000 rpm, preferably 8000 rpm to 10000 rpm; the centrifugation time was 2 min to 10 min, preferably 5 min to 8 min. The advantage of the preferred range is that it can efficiently separate the nanoscale solid catalyst from the reaction solution. The separated solid catalyst was washed and dried, and the reaction was repeated 6 times. The separated liquid product was analyzed by liquid chromatography using an Aminex HPX-87H column with a mobile phase of 5 mM H2SO4 aqueous solution and a flow rate of 0.6 mL / min. -1 Detection was performed using a UV detector (detection wavelength 210 nm) and nuclear magnetic resonance spectroscopy. Tests were conducted on a 400 MHz NMR spectrometer, using D₂O as the deuterated solvent and DMSO as the internal standard. Figure 3 It can be seen that a distinct formate-characteristic proton NMR peak appeared at a specific chemical shift, with a flat baseline and no other byproduct peaks, demonstrating the extremely high hydrogenation selectivity (>99%) of this catalyst. Figure 4 As can be seen, after six consecutive cycles of reaction, the yield and selectivity of the target product, sodium formate (both above 99%), exhibited a flat linear trend without any decline, fully demonstrating the catalyst's excellent resistance to CO poisoning and structural stability. The yield (mol) HCOOM mol Pt -1 h -1 Selectivity (%) = (Molar amount of product formate / (Molar amount of Pt in catalyst × Reaction time)). Selectivity (%) = (Molar amount of product formate / Sum of molar amounts of all carbon-containing products) × 100%. Figure 4 It can be seen that the TiO2-based catalyst with platinum particles supported by Example 1 of the present invention has strong sodium carbonate hydrogenation performance. Under the conditions of reaction temperature of 200℃ and carbon monoxide pressure of 1MPa, sodium carbonate is used as the reaction substrate. It is resistant to CO poisoning and undergoes water-gas shift reaction to produce sodium formate with high activity and selectivity greater than 99% in situ. Moreover, there is no decay after 6 cycles.

[0057] Example 2 Compared to Example 1, the difference lies in the preparation of the TiO2 support. 20 mL of 99 wt% Ti(OBu)4 was mixed with 2 mL of 40 wt% HF. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0058] Example 3 Compared to Example 1, the difference lies in the preparation of the TiO2 support. 30 mL of 99 wt% Ti(OBu)4 was mixed with 5 mL of 40 wt% HF. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance was tested in the same manner as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0059] Example 4 Compared to Example 1, the difference lies in the use of a high-pressure reaction at 160°C in the preparation of the TiO2 support. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0060] Example 5 Compared to Example 1, the difference lies in the use of a high-pressure reaction at 170°C in the preparation of the TiO2 support. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0061] Example 6 Compared to Example 1, the difference lies in the use of a 200°C high-pressure reaction in the preparation of the TiO2 support. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0062] Example 7 Compared to Example 1, the difference lies in the centrifugation speed used in the preparation of the TiO2 support, which is 6000 rpm for 10 min. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0063] Example 8 Compared to Example 1, the difference lies in the preparation of the TiO2 support, where a centrifugal speed of 8000 rpm and a time of 7 min were used. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0064] Example 9 Compared to Example 1, the difference lies in the centrifugation speed used in the preparation of the TiO2 support, which was 12,000 rpm for 2 minutes. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0065] Example 10 Compared to Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on platinum particles. In this example, 0.5M NaOH was used to wash the centrifuged product. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance was tested in the same manner as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0066] Example 11 Compared to Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on platinum particles. In this example, 1.5M NaOH was used to wash the centrifuged product. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance was tested in the same manner as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0067] Example 12 Compared to Example 1, the difference lies in the use of CeO2 as the oxide support in the preparation of the CeO2-based catalyst supported on platinum particles. All other parameters and steps remain the same as in Example 1, resulting in a CeO2-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0068] Example 13 Compared to Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on platinum particles. 100 mg of TiO2 was dispersed in 25 mL of aqueous solution, and 20 μL of ammonia was added. All other parameters and steps remained the same as in Example 1. The reaction performance test was the same as in Example 1; the sodium carbonate hydrogenation reaction exhibited high activity and a selectivity greater than 99%.

[0069] Example 14 Compared with Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on platinum particles. 100 mg of TiO2 was dispersed in 50 mL of aqueous solution, and 200 μL of ammonia was added. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0070] Example 15 Compared to Example 1, the difference lies in the use of 1.87 mg of potassium chloropalladate as the active metal salt in the preparation of the TiO2-based catalyst with supported palladium particles, resulting in a TiO2-based catalyst with supported palladium particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0071] Example 16 Compared to Example 1, the difference lies in the use of 1.10 mg of nickel chloride as the active metal salt in the preparation of the TiO2-based catalyst supported on platinum particles. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on nickel particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0072] Example 17 Compared to Example 1, the difference lies in the use of 40 mL of water to disperse TiO2 in the preparation of the TiO2-based catalyst supported on platinum particles. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0073] Example 18 Compared to Example 1, the difference lies in the stirring speed at 1000 r / min for 10 hours during the preparation of the TiO2-based catalyst supported on platinum particles. All other parameters and steps remain the same as in Example 1, and the resulting material is a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0074] Example 19 Compared to Example 1, the difference lies in the stirring speed at 500 r / min for 24 hours during the preparation of the TiO2-based catalyst supported on platinum particles. All other parameters and steps remain the same as in Example 1, and the resulting material is a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0075] Example 20 Compared to Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on platinum particles. After stirring and centrifugation, the drying temperature was set to 80°C. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0076] Example 21 Compared to Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on platinum particles. After stirring and centrifugation, the drying temperature was set to 120°C. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0077] Example 22 Compared to Example 1, the difference lies in the use of a 10 wt% hydrogen-helium mixed atmosphere as the calcination reducing atmosphere in the preparation of the TiO2-based catalyst supported on platinum particles. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0078] Example 23 Compared with Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on platinum particles, where calcination at 300°C for 6 hours was used. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0079] Example 24 Compared with Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on platinum particles, where calcination at 450 °C for 2 hours was used for reduction. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0080] Example 25 Compared to Example 1, the difference lies in the replacement of sodium carbonate with sodium bicarbonate in the preparation of the TiO2-based catalyst supported on platinum particles. Testing showed that the hydrogenation reaction of sodium bicarbonate exhibited high activity and a selectivity greater than 99%.

[0081] Example 26 Compared to Example 1, the difference lies in the replacement of sodium carbonate with potassium carbonate as the reaction substrate in the preparation of the TiO2-based catalyst supported on platinum particles. Testing showed that the potassium carbonate hydrogenation reaction exhibited high activity and a selectivity greater than 99%.

[0082] Example 27 Compared to Example 1, the difference lies in the replacement of sodium carbonate with ammonium carbonate as the reaction substrate in the preparation of the TiO2-based catalyst supported on platinum particles. Testing showed that the hydrogenation reaction of ammonium carbonate exhibited high activity and a selectivity greater than 99%.

[0083] Example 28 Compared to Example 1, the difference lies in the fact that in the hydrogenation reaction, carbon monoxide is replaced with hydrogen gas. The reaction performance tests are the same as in Example 1; the sodium carbonate hydrogenation reaction exhibits high activity and a selectivity greater than 99%.

[0084] Example 29 Compared to Example 1, the difference lies in that, in the hydrogenation reaction, the reactant gas carbon monoxide is replaced with a 50 vt% mixture of carbon monoxide and hydrogen. The reaction performance tests were the same as in Example 1; the sodium carbonate hydrogenation reaction exhibited high activity and a selectivity greater than 99%.

[0085] Example 30 Compared to Example 1, the difference lies in the use of 1.03 mg of ruthenium chloride as the active metal salt in the preparation of the TiO2-based catalyst supported on ruthenium particles. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on ruthenium particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0086] Example 31 Compared with Example 1, the difference lies in the use of 1.02 mg of rhodium chloride as the active metal salt in the preparation of the rhodium-supported TiO2-based catalyst. All other parameters and steps remain the same as in Example 1, and the resulting material is a rhodium-supported TiO2-based catalyst. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0087] Example 32 Compared with Example 1, the difference lies in the use of 1.06 mg of copper chloride as the active metal salt in the preparation of the TiO2-based catalyst supported on copper particles. All other parameters and steps remain the same as in Example 1, and the resulting material is a TiO2-based catalyst supported on copper particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0088] Example 33 Compared to Example 1, the difference lies in the use of 1.45 mg of ferric chloride as the active metal salt in the preparation of the TiO2-based catalyst with supported iron particles. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst with supported iron particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0089] Example 34 (Load value verification: 0.1 wt%) Compared to Example 1, the difference lies in the use of 0.27 mg of chloroplatinic acid hexahydrate as the active metal salt in the preparation of the TiO2-based catalyst supported on platinum particles (chloroplatinic acid hexahydrate feed amount = (molecular weight of chloroplatinic acid hexahydrate / atomic weight of platinum) × loading amount × support mass). All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0090] Example 35 (Load value verification: 5.0 wt%) Compared to Example 1, the difference lies in the use of 13.5 mg of chloroplatinic acid hexahydrate as the active metal salt in the preparation of the TiO2-based catalyst supported on platinum particles (chloroplatinic acid hexahydrate feed amount = (chloroplatinic acid hexahydrate molecular weight / platinum atomic weight) × loading amount × support mass). All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0091] Example 36 (Verification of intermediate load value: 2.5 wt%) Compared to Example 1, the difference lies in the use of 6.75 mg of chloroplatinic acid hexahydrate as the active metal salt in the preparation of the TiO2-based catalyst supported on platinum particles (chloroplatinic acid hexahydrate feed amount = (chloroplatinic acid hexahydrate molecular weight / platinum atomic weight) × loading amount × support mass). All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0092] Example 37 Compared to Example 1, the difference lies in the preparation of the WO3-based catalyst supported on platinum particles, where the support is replaced with an equal mass of tungsten oxide (WO3). All other parameters and steps remain the same as in Example 1, resulting in a WO3-based catalyst supported on platinum particles. Reaction performance testing was conducted in the same manner as in Example 1, demonstrating high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0093] Example 38 Compared to Example 1, the difference lies in the preparation of the Al2O3-based catalyst supported on platinum particles, where the support is replaced with an equal mass of alumina (Al2O3). All other parameters and steps remain the same as in Example 1, resulting in an Al2O3-based catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0094] Example 39 Compared to Example 1, the difference lies in the preparation of the platinum-supported metal oxide catalyst. The metal oxide support is replaced with a physical mixture of 25 mg TiO2, 25 mg CeO2, 25 mg WO3, and 25 mg Al2O3 (total amount 100 mg). All other parameters and steps remain the same as in Example 1, resulting in a composite catalyst supported on platinum particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0095] Example 40 Compared to Example 1, the difference lies in the use of 1.05 mg of cobalt chloride as the active metal salt in the preparation of the TiO2-based catalyst supported on active metal particles. All other parameters and steps remain the same as in Example 1, resulting in a TiO2-based catalyst supported on cobalt particles. The reaction performance test was the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0096] Example 41 Compared to Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on active metal particles. The active metal salt was replaced with a mixture of 0.36 mg chloroplatinic acid hexahydrate, 0.62 mg potassium chloropalladate, and 0.37 mg nickel chloride. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum-palladium-nickel multimetal particles. The reaction performance tests were the same as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0097] Example 42 Compared to Example 1, the difference lies in the preparation of the TiO2-based catalyst supported on active metal particles. The active metal salt was replaced with a mixture of 0.36 mg chloroplatinic acid hexahydrate, 0.37 mg nickel chloride, and 0.35 mg cobalt chloride. All other parameters and steps remained the same as in Example 1, resulting in a TiO2-based catalyst supported on platinum-nickel-cobalt multimetallic particles. The reaction performance was tested in the same manner as in Example 1, showing high activity and a selectivity greater than 99% in the sodium carbonate hydrogenation reaction.

[0098] Example 43 Compared to Example 1, the difference lies in that, in the hydrogenation reaction, 1 mmol of sodium carbonate was replaced with a mixture of 0.5 mmol of sodium carbonate and 0.5 mmol of potassium carbonate. Testing showed that the hydrogenation reaction of the mixed carbonate exhibited high activity, with a total formate selectivity greater than 99%.

[0099] Example 44 Compared to Example 1, the difference lies in replacing the sodium carbonate substrate with 1 mmol of potassium bicarbonate in the hydrogenation reaction. Testing showed that the potassium bicarbonate hydrogenation reaction exhibited high activity and a selectivity greater than 99%.

[0100] Example 45 Compared to Example 1, the difference lies in replacing the sodium carbonate substrate with 1 mmol of ammonium bicarbonate in the hydrogenation reaction. Testing showed that the ammonium bicarbonate hydrogenation reaction exhibited high activity and a selectivity greater than 99%.

[0101] Example 46 Compared to Example 1, the difference lies in replacing the sodium carbonate substrate with 1 mmol of sodium hydroxide in the hydrogenation reaction. Testing showed that the sodium hydroxide hydrogenation reaction exhibited high activity and a selectivity greater than 99%.

[0102] Example 47 Compared to Example 1, the difference lies in replacing the sodium carbonate substrate with 1 mmol of potassium hydroxide in the hydrogenation reaction. Testing showed that the potassium hydroxide hydrogenation reaction exhibited high activity and a selectivity greater than 99%.

[0103] Example 48 Compared to Example 1, the difference lies in replacing the sodium carbonate substrate with 1 mmol of ammonium hydroxide in the hydrogenation reaction. Testing showed that the ammonium hydroxide hydrogenation reaction exhibited high reactivity and a selectivity greater than 99%.

[0104] Example 49 Compared to Example 1, the difference lies in that, in the hydrogenation reaction, the sodium carbonate substrate was replaced with a mixture of 0.5 mmol sodium carbonate and 0.5 mmol potassium carbonate. Testing showed that this mixed substrate exhibited high activity in the hydrogenation reaction, with a selectivity greater than 99%.

[0105] Example 50 Compared to Example 1, the difference lies in that, in the hydrogenation reaction, the sodium carbonate substrate was replaced with a mixture of 0.5 mmol sodium bicarbonate and 0.5 mmol ammonium bicarbonate. Testing showed that this mixed substrate hydrogenation reaction exhibited high activity and a selectivity greater than 99%.

[0106] Example 51 Compared to Example 1, the difference lies in that, in the hydrogenation reaction, the sodium carbonate substrate was replaced with 0.5 mmol of sodium hydroxide and 0.5 mmol of potassium hydroxide. Testing showed that the hydrogenation reaction of this mixed substrate exhibited high activity and a selectivity greater than 99%.

[0107] Example 52 Compared to Example 1, the difference lies in that, in the hydrogenation reaction, the sodium carbonate substrate was replaced with 0.5 mmol of sodium carbonate and 0.5 mmol of potassium bicarbonate. Testing showed that the hydrogenation reaction of this mixed substrate exhibited high activity and a selectivity greater than 99%.

[0108] Example 53 Compared to Example 1, the difference lies in that, in the hydrogenation reaction, the sodium carbonate substrate was replaced with 0.5 mmol of sodium carbonate and 0.5 mmol of sodium hydroxide. Testing showed that the hydrogenation reaction of this mixed substrate exhibited high activity and a selectivity greater than 99%.

[0109] Example 54 The specific reaction process and detection method are the same as in Example 1, except that in the hydrogenation reaction, the sodium carbonate substrate is replaced with 0.33 mmol sodium carbonate, 0.33 mmol potassium bicarbonate, and 0.33 mmol ammonium hydroxide. The hydrogenation reaction of this mixed substrate was found to have high activity and a selectivity greater than 99%.

[0110] It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of protection of the invention. Furthermore, it should be understood that after reading the technical description of this invention, those skilled in the art can make various modifications, alterations, and / or variations to the invention, and all such equivalent forms also fall within the scope of protection defined by the appended claims. As is known from common technical knowledge, the invention can be implemented through other embodiments that do not depart from its spirit or essential characteristics. Therefore, the embodiments disclosed above are merely illustrative in all respects and are not exhaustive. All changes within or equivalent to the scope of this invention are included in this invention.

Claims

1. A metal oxide supported active metal catalyst characterized in that This includes metal oxide supports and active metal particles supported on metal oxide supports; Based on the mass of the metal oxide carrier being 100%, the loading of the active metal particles is 0.1wt%~5wt%.

2. The metal oxide supported active metal catalyst of claim 1, wherein, The metal oxide support is selected from any one or more of titanium oxide, cerium oxide, tungsten oxide, and aluminum oxide; The active metal particles are spherical with an average particle size of 0.5 nm to 6.0 nm; the active metal in the active metal particles is any one or more selected from the noble metals platinum, ruthenium, rhodium, and palladium, and the non-noble metals nickel, cobalt, copper, and iron.

3. The metal oxide-supported active metal catalyst according to claim 1, characterized in that, The metal oxide support is titanium dioxide (TiO2), which is prepared according to the following method: Tetrabutyl titanate was mixed with hydrofluoric acid, reacted in a high-pressure reactor, cooled to room temperature, centrifuged, and the centrifuged product was collected. The product was washed with NaOH solution to remove fluoride ions, centrifuged again, and the product was collected. Finally, the product was washed with water and alcohol and dried. This product was denoted as TiO2 support. The concentration of tetrabutyl titanate is 99 wt%, the concentration of hydrofluoric acid is 40 wt%, and the amount of tetrabutyl titanate to hydrofluoric acid is 20 mL to 30 mL and 2 mL to 5 mL, respectively; the concentration of the NaOH solution is 0.5 M to 1.5 M; the reaction temperature of the high-pressure reactor is 160 °C to 200 °C; and the reaction time is 12 h to 48 h. The centrifugation and re-centrifugation are performed at speeds of 6000 rpm to 12000 rpm for 2 min to 10 min, and at a drying temperature of 60℃ to 80℃.

4. The metal oxide-supported active metal catalyst according to claim 3, characterized in that, The reaction temperature in the high-pressure reactor is 170℃~180℃; the reaction time is 24h~36h. The centrifugation and re-centrifugation are performed at speeds of 8000 rpm to 10000 rpm for 5 min to 8 min, and at a drying temperature of 65℃ to 75℃.

5. A method for preparing a metal oxide-supported active metal catalyst according to any one of claims 1-4, characterized in that... Includes the following steps: A metal oxide support, an active metal salt, an alkaline substance, and a solvent are mixed, dried, and calcined to obtain a metal oxide-supported active metal catalyst. The ratio of the metal oxide carrier, active metal salt, alkaline substance and solvent is 100 mg:(0.1~5) mg:(20~200) μL:(25~50) mL.

6. The method for preparing a metal oxide-supported active metal catalyst according to claim 5, characterized in that, The metal oxide support is selected from any one or more of titanium oxide, cerium oxide, tungsten oxide, and aluminum oxide, and its morphology is selected from any one or more of flake, rod, and sphere. The active metal salt is selected from any one or more of the noble metal salts platinum salt, ruthenium salt, rhodium salt, palladium salt, and non-noble metal salts nickel salt, copper salt, cobalt salt, and iron salt, specifically including any one or more of chloroplatinic acid hexahydrate, ruthenium chloride, rhodium chloride, potassium chloropalladate, nickel chloride, copper chloride, cobalt chloride, and ferric chloride; The alkaline substance is selected from ammonia water; The solvent is selected from water; The ratio of the TiO2 support, active metal salt, alkaline substance and solvent is 100 mg:(0.3~0.8) mg:(50~150) μL:(30~45) mL; The mixing time is 10h~24h, and the mixing is carried out under stirring conditions at a stirring rate of 500r / min~1000r / min; the drying temperature is 80℃~120℃; the calcination is carried out in a reducing atmosphere, which is selected from a hydrogen-argon mixture or a hydrogen-nitrogen mixture; the calcination temperature is 300℃~450℃, and the time is 2h~6h.

7. The use of the metal oxide-supported active metal catalyst according to any one of claims 1 to 4 in the hydrogenation reaction of carbonates or bicarbonates with water, or with a mixture of aqueous hydroxide and CO2 gas, characterized in that... Includes the following steps: A hydrogenation reaction is carried out by mixing a metal oxide-supported active metal catalyst, a carbonate or bicarbonate, and water; or by mixing a metal oxide-supported active metal catalyst with a mixture of an aqueous hydroxide solution and CO2 gas, and then introducing a hydrogen-containing gas, a carbon monoxide-containing gas, or a mixture of hydrogen and carbon monoxide under a protective gas atmosphere.

8. The application of the metal oxide-supported active metal catalyst according to claim 7 in the hydrogenation reaction of carbonates or bicarbonates with water, or with a mixture of aqueous hydroxide solution and CO2 gas, characterized in that, The carbonate is selected from any one or more of sodium carbonate, potassium carbonate, and ammonium carbonate; The bicarbonate is selected from any one or more of sodium bicarbonate, potassium bicarbonate and ammonium bicarbonate; The hydroxide in the aqueous hydroxide solution is any one or more selected from sodium hydroxide, potassium hydroxide, and ammonium hydroxide; The protective gas is argon and / or helium; The hydrogen-containing gas is pure hydrogen or a mixture containing hydrogen; the carbon monoxide-containing gas is pure carbon monoxide or a mixture containing carbon monoxide; the hydrogen and carbon monoxide mixture is a mixture of pure hydrogen and carbon monoxide or a mixture containing both hydrogen and carbon monoxide. The hydrogenation reaction is carried out at a pressure of 1 MPa to 5 MPa, a temperature of 100°C to 500°C, and a time of 1 h to 5 h.

9. The application of the metal oxide-supported active metal catalyst according to claim 7 in the hydrogenation reaction of carbonates or bicarbonates with water, or with a mixture of aqueous hydroxide solution and CO2 gas, characterized in that... It also includes the following steps: After the reaction is complete, the reaction vessel is opened and the product is taken out. It is then centrifuged and filtered for separation. The separated solid catalyst is washed and dried for reuse. The centrifugation speed is 6000 rpm to 12000 rpm and the time is 2 min to 10 min. The drying temperature is 60℃ to 80℃.

10. The application of the metal oxide-supported active metal catalyst according to claim 9 in the hydrogenation reaction of carbonates or bicarbonates with water, or with a mixture of aqueous hydroxide solution and CO2 gas, characterized in that, The centrifugation speed is 8000~10000 rpm; the time is 3min~8min; and the drying temperature is 65℃~75℃.

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