Carbon dioxide catalytic decomposition material

Abstract

The invention discloses a carbon dioxide catalytic decomposition material which is characterized in that the main effective component of the carbon dioxide catalytic decomposition material is biomass activated carbon / Rh2O3 / NiO phase. The material provided by the invention can more efficiently and stably realize the treatment of decomposing and converting carbon dioxide into carbon monoxide, so that the material is more beneficial to large-scale production and preparation.

Description

[0001] The present application is a divisional application of the patent application No. 202411638327.1, filed on November 16, 2024, entitled "A catalytic conversion method for decomposing carbon dioxide into carbon monoxide". TECHNICAL FIELD

[0002] The present application relates to the technical field of contaminated gas decomposition treatment, in particular to a carbon dioxide catalytic decomposition material. BACKGROUND

[0003] Carbon dioxide is one of the main pollutants discharged in the processes of industrial production, building operation and human metabolism. It is necessary to further develop purification methods for carbon dioxide by means of adsorption capture, underground storage and other means. In addition, carbon dioxide can be catalytically converted into carbon monoxide gas with utilization value, realizing multiple recycling of carbon dioxide and producing the effect of turning waste into treasure.

[0004] CN117548144A has disclosed a metal-loaded mesoporous cerium-based MOFs, its preparation method and application; CN116083949A has disclosed an MXene-loaded Ag-ZnO electrocatalyst, its preparation method, application and testing method; CN116043258A has disclosed a preparation method and application of a self-supporting copper selenide nanosheet electrocatalyst; and CN114799197A has disclosed a preparation method of a copper-antimony single-atom alloy catalyst and its application in carbon dioxide reduction. The above-mentioned patent solutions can all realize the preparation process of decomposing and converting carbon dioxide into carbon monoxide. However, these existing catalysts for catalytically converting carbon dioxide and hydrogen into methane cannot meet the requirements of rapid and large-scale generation of carbon monoxide fuel because the liquid water generated during the reaction will isolate gaseous carbon dioxide from the surface of the solid catalyst, thereby seriously affecting the catalytic conversion efficiency of carbon dioxide.

[0005] Therefore, how to provide a catalytic conversion method for decomposing carbon dioxide into carbon monoxide, which is different from the prior art and can more efficiently and stably realize the decomposition of carbon dioxide into carbon monoxide, has become a problem to be considered and solved by those skilled in the art. SUMMARY

[0006] In view of the above-mentioned deficiencies of the prior art, the technical problem to be solved by the present application is: how to provide a catalytic conversion method for decomposing carbon dioxide into carbon monoxide and a carbon dioxide catalytic decomposition material, which can more efficiently and stably realize the decomposition and conversion treatment of carbon dioxide, so as to be more beneficial to large-scale production and preparation.

[0007] In order to solve the above-mentioned technical problems, the present application adopts the following technical solutions:

[0008] A catalytic conversion method for decomposing carbon dioxide into carbon monoxide, characterized in comprising the following steps:

[0009] In the first step, carbon dioxide molecules and added hydrogen molecules are adsorbed on the surface of a biomass activated carbon / Rh2O3 / NiO phase material to form an adsorbed state structure, the hydrogen molecules are decomposed into adsorbed hydrogen atoms, and the carbon dioxide reacts with part of the hydrogen atoms to form carboxyl groups; the reaction process includes the following reaction formula:

[0010]

[0011] In the second step, the generated adsorbed carboxyl groups react with the remaining hydrogen atoms to release a water molecule, forming an adsorbed carbon monoxide molecule, and the adsorbed carbon monoxide is desorbed into a free state to obtain carbon monoxide gas at a high reaction temperature; the reaction process includes the following reaction formula:

[0012]

[0013] As an optimization, the biomass activated carbon is a rice husk-based biomass activated carbon. It is easy to prepare and has better porosity, with an average specific surface area of >1500 m 2 / g.

[0014] Thus, the present application uses biomass activated carbon embedded with Rh2O3 and NiO as a catalytic conversion decomposition material for decomposing carbon dioxide, which can quickly and efficiently decompose and process carbon dioxide through the above reaction process. In this process, the biomass activated carbon has a large specific surface area (as mentioned above, the average specific surface area is >1500 m 2 / g), which can provide a large number of adsorption sites for carbon dioxide and hydrogen molecules; secondly, the functional components Rh2O3 and NiO embedded in the activated carbon can be used to catalyze the formation of carboxyl groups and water molecules, respectively, and the two can work together to greatly increase the efficiency of catalytic conversion of carbon dioxide into carbon monoxide.

[0015] Therefore, in the present application, a carbon dioxide catalytic decomposition material with a main effective component of biomass activated carbon / Rh2O3 / NiO phase is used to realize the catalytic decomposition and processing of carbon dioxide.

[0016] In the above carbon dioxide catalytic decomposition material, the biomass activated carbon serves as a substrate for loading effective components Rh2O3 and NiO and capturing and adsorbing carbon dioxide and hydrogen molecules, and as a catalyst reaction bed. The specific action process and principle of the reaction are as follows.

[0017] (a) The role of Rh2O3. For the step of carbon dioxide hydrogenation to form carboxyl group in the basic process of carbon dioxide catalytic conversion to carbon monoxide, it needs to break one bond in C=O double bond and then O atom bonds with adsorbed H atom. Since there is one active electron in the outer layer of Rh atom in Rh2O3, it can bond with one outer active electron in CO2, thus promoting the break of one single bond in the above C=O double bond. Meanwhile, the more basic role is that there are four unpaired electrons in the outer layer of Rh atom, which has a high probability and strength of attraction-bonding with adsorbed H atom, and can more easily form multiple state Rh(Rh2O3)-O(CO2) valence bond, further enhancing the partial break of C=O double bond. In addition, the supplementary promotion is that part of CO2 can be directly adsorbed on the O atom in Rh2O3, and then the C atom can directly bond with this O atom, thus reducing one C=O double bond to C-O single bond for subsequent bonding with adsorbed H atom.

[0018] (b) The role of NiO. For the step of carboxyl group hydrogenation and dehydration in the basic process of carbon dioxide catalytic conversion to carbon monoxide, it needs to break the C-O bond and combine with another adsorbed H atom. Since the outer layer of Ni atom in NiO has five active valence electrons, it can migrate on the whole surface through the delocalized π bond of the porous carbon surface, and when it migrates to the carboxyl group, it can combine with the O atom in -OH to form a free radical form, thus breaking the C-O bond and quickly combining with another adsorbed H atom. Meanwhile, the more basic role is that the H atoms formed after the decomposition of hydrogen molecules are more easily adsorbed on the O atoms in NiO, because there are still three valence electrons on the surface of NiO, which can form a Ni···H structure with H atoms, which can significantly fix free H atoms, attract and gather H atoms originally dispersed on different sites of the porous activated carbon surface to the surrounding of the NiO group, further increasing the reaction rate of carboxyl group hydrogenation and dehydration. It should be noted that the Rh2O3 group also has the function of combining with H atoms as described above for NiO, but since Rh in Rh2O3 only has one outer active valence electron, its ability to gather adsorbed H atoms is lower than that of NiO, and it is not the main functional component of the carboxyl group hydrogenation and dehydration step.

[0019] Therefore, the present application can be used for the industrialized production of carbon dioxide decomposition and conversion to carbon monoxide, which can quickly catalyze the decomposition of carbon dioxide and hydrogen into carbon monoxide and water under the action of the catalyst, reduce the harm of carbon dioxide emission to the environment, and turn waste into treasure; and can improve the efficiency of carbon dioxide catalytic decomposition. The applicant has verified that the Faraday efficiency of carbon monoxide generation can be increased from 80% to 95%+, and the Faraday efficiency loss after 6h of carbon dioxide catalytic conversion is less than 5%.

[0020] Further, the carbon dioxide catalytic decomposition material adopted by the present application comprises the following mass fraction of phase components: 0.01-0.15 parts of a biomass activated carbon phase, 0.01-0.08 parts of a Rh2O3 phase, 0.01-0.11 parts of a NiO phase, and 0.66-0.097 parts of a biomass activated carbon / Rh2O3 / NiO phase.

[0021] Further, the carbon dioxide catalytic decomposition material adopted by the present application comprises the following mass fraction of phase components: 0.01-0.15 parts of a biomass activated carbon phase, 0.01-0.08 parts of a Rh2O3 phase, 0.01-0.11 parts of a NiO phase, and 0.66-0.097 parts of a biomass activated carbon / Rh2O3 / NiO phase.

[0022] The biomass activated carbon / Rh2O3 / NiO phase in the above-mentioned carbon dioxide catalytic decomposition material is the main place for carbon dioxide catalytic decomposition reaction, so the proportion is large, the biomass activated carbon phase, the Rh2O3 phase and the NiO phase are also the co-reaction products and can be used to provide a reaction place and assist to enhance the carbon dioxide catalytic decomposition process, and the dynamic conversion and supplement effect between the phase components can better ensure the persistence of the treatment effect.

[0023] Further, the carbon dioxide catalytic decomposition material is prepared by the following steps:

[0024] Step 1: first obtain biomass activated carbon as a substrate;

[0025] Step 2: complete the generation and loading of rhodium trioxide and nickel oxide; pour 20 g of the above-mentioned biomass activated carbon into 500 ml of ultrapure water, and add 0.25 mol of rhodium nitrate dihydrate (Rh(NO3)3·2H2O) and 0.15 mol of nickel nitrate hexahydrate (Ni(NO3)2·6H2O) to form a mixed solution; then, the obtained mixed solution is stirred uniformly, dried and ground into a powder (as an optimization, the drying and grinding process is as follows: place in a magnetic stirrer for continuous stirring and mixing at 200 r / min and 50 ℃ for 2 h; then, place the mixed solution in an oven, evaporate all the water at 70 ℃ to obtain a lump, and grind the lump to a 200-mesh powder; in this way, the loading is first completed, which can better ensure the generation effect of the subsequent calcination reaction); then, the obtained powder is calcined to obtain a porous activated carbon loaded rhodium trioxide (Rh2O3) / nickel oxide (NiO) composite catalyst (as an optimization, the calcination process is as follows: place the above-mentioned 200-mesh powder in a muffle furnace, continuously calcine at 850 ℃ for 5 h (the temperature rising rate from room temperature to 500 ℃ is 50 ℃ / min), and then naturally ventilate and cool to room temperature to obtain a porous activated carbon loaded rhodium trioxide (Rh2O3) / nickel oxide (NiO) composite catalyst. In this way, the reaction generation effect is better ensured).

[0026] In the above steps, the ratio of each reaction component can be increased or decreased proportionally. During the preparation process, rhodium nitrate and nickel nitrate can decompose into rhodium sesquioxide and nickel oxide at high temperature, and the reaction equation is as follows: , . At the same time, Rh2O3 and NiO generated after decomposition can be embedded in activated carbon at high temperature to form a biomass activated carbon supported Rh2O3 / NiO composite catalyst, i.e. the carbon dioxide catalytic decomposition material, and the reaction equation is as follows: .

[0027] Therefore, the above reaction process can quickly and efficiently prepare a carbon dioxide catalytic decomposition material with a biomass activated carbon / Rh2O3 / NiO phase ratio of more than 50%, ensuring efficient catalytic decomposition of carbon dioxide after adsorption. The other phase components generated are uniformly mixed and doped together, which can assist in improving the decomposition reaction and better ensure the durability of the carbon dioxide catalytic treatment effect.

[0028] Further, the biomass carbon-based substrate is prepared by the following method: first, 50 g of rice husk-based biomass powder / blocks is weighed, dissolved in 500 ml of ultrapure water, and placed in a sealed reaction kettle, and heated at 150°C for 24 hours; then, the suspension after hydrothermal treatment is filtered through a 0.22 μm microporous filter membrane, and the obtained filter residue is washed with ultrapure water for 3 times, and dried in a drying oven at 50°C for 72 hours to obtain a cake, which is then ground to a 200 mesh powder; then, the obtained biomass powder is placed in a muffle furnace and calcined at 500°C for 3 hours under argon (Ar) protection (the heating rate from room temperature to 500°C is 25°C / min), and then naturally ventilated to cool to room temperature; the above calcined powder is immersed in 50 ml of sodium hydroxide solution (50 wt.%) for 1 hour to form a paste, and the paste is placed in a muffle furnace and calcined at 500°C for 6 hours under a normal air atmosphere (the heating rate from room temperature to 500°C is 20°C / min), and then naturally ventilated to cool to room temperature and ground to 200 mesh, to obtain a porous activated carbon substrate.

[0029] In this way, the rice husk is used as a biomass carbon material, and the powder is washed, filtered and evaporated after hydrothermal treatment to remove non-carbonized components, and then carbonized by two times of grinding and calcination, so that the prepared pure bamboo-based biomass activated carbon can have higher adsorption efficiency. After hot water activation and high temperature calcination, the rice husk-based biomass powder / blocks is converted into a porous activated carbon (average pore size 5 nm, average specific surface area >1500 m 2 / g), and the reaction equation is as follows: C (inactive) → C (porous and active activated carbon). Therefore, it has the characteristics of low cost, easy preparation, good pore structure of the product, and large specific surface area.

[0030] Therefore, the present invention can achieve the decomposition of carbon dioxide into carbon monoxide more efficiently and stably, making it more suitable for large-scale production. Attached Figure Description

[0031] Figure 1 This is a schematic diagram illustrating the principle of the carbon dioxide catalytic decomposition material of the present invention for the catalytic decomposition of carbon dioxide.

[0032] Figure 2 This is a schematic diagram comparing the Faraday efficiency of the carbon dioxide catalytic decomposition material of the present invention with that of other types of carbon dioxide catalytic decomposition materials.

[0033] Figure 3 This is a schematic diagram comparing the Faraday efficiency loss of the carbon dioxide catalytic decomposition material of the present invention with that of other types of carbon dioxide catalytic decomposition materials. Detailed Implementation

[0034] The present invention will now be described in further detail with reference to specific embodiments.

[0035] Implementation method: A catalytic conversion method for the decomposition of carbon dioxide into carbon monoxide, characterized by comprising the following steps:

[0036] The first step involves adsorbing carbon dioxide molecules and added hydrogen molecules onto the surface of the biomass activated carbon / Rh2O3 / NiO phase material, forming an adsorbed structure. Hydrogen molecules decompose into adsorbed hydrogen atoms, and carbon dioxide reacts with some of the hydrogen atoms to generate carboxyl groups. The reaction process includes the following reaction equations:

[0037]

[0038] The second step involves the formation of an adsorbed carboxyl group reacting with the remaining hydrogen atoms to release a water molecule, forming an adsorbed carbon monoxide molecule. The adsorbed carbon monoxide then desorbs into a free state at the high reaction temperature to produce carbon monoxide gas. This process includes the following reaction equations:

[0039]

[0040] In practice, the biomass activated carbon used is rice husk-based biomass activated carbon. This is easier to prepare and has better porosity, with an average specific surface area >1500 m². 2 / g.

[0041] Thus, this invention employs biomass activated carbon embedded with Rh₂O₃ and NiO as a catalytic conversion and decomposition material for carbon dioxide decomposition. Through the aforementioned reaction process, carbon dioxide decomposition can be achieved rapidly and efficiently. In this process, the biomass activated carbon firstly possesses a large specific surface area (as mentioned above, the average specific surface area > 1500 m²). 2 / g), which can provide a large number of adsorption sites for the adsorption of carbon dioxide and hydrogen molecules; secondly, the functional components Rh2O3 and NiO embedded in activated carbon can be used to catalyze the formation of carboxyl groups and the formation of water molecules, respectively. The synergistic effect of the two can greatly increase the efficiency of carbon dioxide catalytic conversion to carbon monoxide.

[0042] In practice, a carbon dioxide catalytic decomposition material whose main effective component is biomass activated carbon / Rh2O3 / NiO phase is used to achieve the catalytic decomposition of carbon dioxide.

[0043] In the aforementioned carbon dioxide catalytic decomposition materials, biomass activated carbon serves as the substrate for the catalytic reaction, supporting the effective components Rh2O3 and NiO, as well as capturing and adsorbing carbon dioxide and hydrogen molecules. The specific working principle of the reaction is as follows.

[0044] (a) The role of Rh₂O₃. In the basic process of catalytic conversion of carbon dioxide to carbon monoxide, specifically the hydrogenation of carbon dioxide to form a carboxyl group, one bond in the C=O double bond needs to break, allowing the O atom to bond with the adsorbed H atom. Since the Rh atom in Rh₂O₃ has an active electron in its outer shell, it can combine with an active electron in the outer shell of the C atom in CO₂ to form a bond, thus promoting the breaking of one single bond in the C=O double bond. More fundamentally, the Rh atom has unpaired electrons in all four orbitals of its outer shell, resulting in a high probability and strength of attraction-bonding interactions with the adsorbed H atom. This facilitates the formation of a multiplying Rh(Rh₂O₃)-O(CO₂) valence bond, further enhancing the partial breaking of the C=O double bond. Furthermore, a supplementary promoting effect is that some CO₂ can be directly adsorbed onto the O atom in Rh₂O₃, allowing the C atom to directly bond with this O atom, thereby reducing one C=O double bond to a CO single bond, which is then used for subsequent bonding with the adsorbed H atom.

[0045] (b) The role of NiO. In the basic process of catalytic conversion of carbon dioxide to carbon monoxide, specifically the carboxyl group hydrogenation and dehydration step, the hydroxyl group needs to break from the carboxyl group and combine with another adsorbed H atom. This process involves the breaking of the CO bond. Since the Ni atom in NiO has five active valence electrons in its outer shell, it can migrate across the entire surface through delocalized π bonds on the porous carbon surface. When it migrates to the carboxyl group, it can combine with the O atom in the -OH group to form a free radical, thereby breaking the CO bond and rapidly combining with another adsorbed H atom. Simultaneously, and more fundamentally, the H atoms formed after the decomposition of hydrogen molecules are more easily adsorbed onto the O atoms in NiO. This is because the Ni surface in NiO still has three valence electrons, which can form a Ni···H structure with H atoms. This structure can significantly fix free H atoms, attracting and aggregating H atoms originally dispersed at different sites on the porous activated carbon surface to the vicinity of the NiO group, further increasing the rate of the carboxyl group hydrogenation and dehydration reaction. It should be noted that the Rh2O3 group also has the function of combining NiO and H atoms as mentioned above. However, since Rh in Rh2O3 only has one outer active valence electron, its ability to aggregate adsorbed H atoms is lower than that of NiO, and it is not the main functional component in the carboxyl hydrogenation dehydration step.

[0046] Therefore, this invention can be used for the industrial production of carbon dioxide decomposition into carbon monoxide. Under the action of a catalyst, carbon dioxide and hydrogen are rapidly catalytically decomposed into carbon monoxide and water, reducing the environmental harm caused by carbon dioxide emissions and turning waste into treasure; it can also improve the catalytic decomposition efficiency of carbon dioxide. The applicant has verified that this invention can increase the Faraday efficiency of carbon monoxide generation from 80% to 95%+; and that the Faraday efficiency loss after 6 hours of carbon dioxide catalytic conversion is less than 5%.

[0047] The carbon dioxide catalytic decomposition material used in this invention comprises the following phase components in the following mass proportions: 0.01-0.15 parts of biomass activated carbon phase, 0.01-0.08 parts of Rh2O3 phase, 0.01-0.11 parts of NiO phase, and 0.66-0.097 parts of biomass activated carbon / Rh2O3 / NiO phase.

[0048] The preferred mass ratio is: 0.02 parts biomass activated carbon phase, 0.08 parts Rh2O3 phase, 0.11 parts NiO phase, and 0.79 parts biomass activated carbon / Rh2O3 / NiO phase.

[0049] In the aforementioned carbon dioxide catalytic decomposition materials, the biomass activated carbon / Rh2O3 / NiO phase is the main site of the carbon dioxide catalytic decomposition reaction and therefore accounts for a large proportion. The biomass activated carbon phase, Rh2O3 phase, and NiO phase are common reaction products and can also be used to provide a reaction site and assist in enhancing the carbon dioxide catalytic decomposition process. Furthermore, the various phase components can play a certain dynamic conversion and replenishment role, which better ensures the durability of the treatment effect.

[0050] In practice, the carbon dioxide catalytic decomposition material is prepared using the following steps:

[0051] Step 1: First, obtain biomass activated carbon as a substrate;

[0052] Step 2: Complete the formation and loading of rhodium trioxide and nickel oxide; pour 20 g of the above-mentioned biomass activated carbon into 500 ml of ultrapure water, and add 0.25 mol of rhodium nitrate dihydrate. and 0.15 mol of nickel nitrate hexahydrate A mixed solution was formed; then, the resulting mixed solution was placed in a magnetic stirrer and continuously stirred at 200 r / min and 50 ℃ for 2 h; then, the mixed solution was placed in an oven and evaporated at 70 ℃ to obtain agglomerates, which were then ground into 200 mesh powder; subsequently, the above 200 mesh powder was placed in a muffle furnace and continuously calcined at 850 ℃ for 5 h (the heating rate from room temperature to 500 ℃ was 50 ℃ / min), and then naturally cooled to room temperature by ventilation to obtain a porous activated carbon-supported rhodium trioxide (Rh2O3) / nickel oxide (NiO) composite catalyst (i.e., " (”).

[0053] In the above steps, the proportions of each reactant can be increased or decreased proportionally. During the preparation process, rhodium nitrate and nickel nitrate decompose at high temperatures into rhodium trioxide and nickel oxide, as shown in the following reaction equation: , Simultaneously, the Rh2O3 and NiO produced after decomposition will embed into the activated carbon at high temperature, forming a biomass activated carbon-supported Rh2O3 / NiO composite catalyst, i.e., the carbon dioxide catalytic decomposition material. The reaction equation is: .

[0054] Therefore, the above reaction process can rapidly and efficiently produce a carbon dioxide catalytic decomposition material with a main effective component of biomass activated carbon / Rh2O3 / NiO phase accounting for more than 50%, ensuring a highly efficient catalytic decomposition effect after carbon dioxide adsorption. Simultaneously, the other phase components generated are uniformly mixed and incorporated together, which can further enhance the decomposition reaction and better guarantee the durability of the carbon dioxide catalytic treatment effect.

[0055] In practice, the biomass carbon-based substrate was prepared using the following method: First, 50 g of rice husk-based biomass powder / lumps were weighed, dissolved in 500 ml of ultrapure water, and placed in a sealed reactor. The solution was continuously heated at 150 °C for 24 h. Next, the hydrothermally treated suspension was filtered through a 0.22 μm microporous membrane. The resulting filter residue was rinsed three times with ultrapure water and dried continuously at 50 °C for 72 h in a drying oven to obtain agglomerates. These agglomerates were then ground to a 200-mesh powder. The resulting biomass powder was then calcined in a muffle furnace at 500 °C for 3 h under argon (Ar) protection (heating rate from room temperature to 500 °C was 25 °C / min), followed by natural ventilation cooling to room temperature. The calcined powder was then immersed in 50 ml of sodium hydroxide solution (50 wt.%) for 1 h to form a paste. This paste was then placed in a muffle furnace and calcined at 500 °C for 6 h under normal air conditions. After being cooled to room temperature by natural ventilation for h (the heating rate from room temperature to 500 °C is 20 °C / min), it is ground to 200 mesh to obtain a porous activated carbon substrate.

[0056] This method utilizes rice husks as the material for biomass carbon preparation. The powder is initially removed by hydrothermal treatment followed by washing, filtration, and evaporation to remove non-carbonized components. Carbonization is then achieved through two grinding and calcination processes, resulting in pure bamboo-based biomass activated carbon with higher adsorption efficiency. Rice husk-based biomass powder / blocks are transformed into porous activated carbon (average pore size 5 nm, average specific surface area >1500 m²) after hot water activation and high-temperature calcination. 2 / g), the reaction equation is: C (inactive) → C (porous activated carbon). Therefore, it has the characteristics of low cost, easy preparation, good porosity, and large specific surface area of ​​the product.

[0057] To better verify the effectiveness of the present invention, the applicant conducted comparative experiments. The carbon dioxide catalytic decomposition material obtained in the above-described specific embodiments was used as the experimental group, while other carbon dioxide catalytic decomposition materials were used as the control group. Comparative experiments on catalytic conversion efficiency and the degree of conversion efficiency loss were conducted. The experimental results are detailed below. Figure 2 and Figure 3 .

[0058] for Figure 2Under environmental conditions of 300 ℃ / 3.5 MPa / 0% relative humidity, Pd-supported Ag, AuCu, AuCuB, and NiMn were used as control catalysts, with the molar contents of hydrogen (reactant gas) and nitrogen (carrier gas) set at 76% and 5%, respectively. A comparative experiment was conducted on the catalytic conversion efficiency of carbon dioxide (19% molar content) to carbon monoxide via hydrogenation. The experimental results show that the carbon monoxide conversion efficiency of the control catalysts is lower than that of the rice husk-based activated carbon-supported Rh2O3 / NiO catalyst. In particular, the carbon monoxide conversion efficiency of rice husk-based activated carbon-supported Rh2O3 / NiO is significantly higher than that of AuCu, indicating that the coexistence of Rh2O3 and NiO can produce a synergistic effect on the surface of rice husk-based activated carbon for carbon dioxide catalysis, greatly enhancing the catalytic conversion ability of this type of composite catalyst.

[0059] for Figure 3 Under environmental conditions of 300 ℃ / 3.5 MPa / 0% relative humidity, Pd-supported Ag and AuCu were used as control catalysts, with the molar contents of hydrogen (reactant gas) and nitrogen (carrier gas) set at 76% and 5%, respectively. A comparative experiment was conducted on the 6-hour conversion efficiency loss of carbon dioxide hydrogenation to carbon monoxide with a molar content of 19%. The experimental results show that the 6-hour conversion efficiency loss of the Pd-supported Ag catalyst is higher than that of the rice husk-based activated carbon-supported Rh2O3 / NiO catalyst. This indicates that the coexistence of Rh2O3 and NiO can induce a synergistic effect on the surface of rice husk-based activated carbon for carbon dioxide catalysis, significantly reducing the loss of catalytic conversion capacity of this type of composite catalyst.

Claims

1. A material for catalytic decomposition of carbon dioxide, characterized by, The main effective component is a biomass activated carbon / Rh2O3 / NiO phase.

2. The carbon dioxide catalytic decomposition material of claim 1, wherein, The biomass activated carbon is used as a matrix for loading effective components Rh2O3 and NiO.

3. The carbon dioxide catalytic decomposition material of claim 1, wherein, The phase components include the following mass proportions: 0.01-0.15 parts of a biomass activated carbon phase, 0.01-0.08 parts of a Rh2O3 phase, 0.01-0.11 parts of a NiO phase, and 0.66-0.097 parts of a biomass activated carbon / Rh2O3 / NiO phase.

4. The carbon dioxide catalytic decomposition material of claim 1, wherein, The phase components include the following mass proportions: 0.02 parts of a biomass activated carbon phase, 0.08 parts of a Rh2O3 phase, 0.11 parts of a NiO phase, and 0.79 parts of a biomass activated carbon / Rh2O3 / NiO phase.

5. The carbon dioxide catalytic decomposition material of claim 1, wherein, The carbon dioxide catalytic decomposition material is prepared by the following steps: Step 1: first obtain biomass activated carbon as a substrate; Step 2: complete the generation and loading of Rh2O3 and NiO; pour 20 g of the biomass activated carbon into 500 ml of ultrapure water, and add 0.25 mol of Rh(NO3)3·2H2O and 0.15 mol of Ni(NO3)2·6H2O to form a mixed solution; then, the mixed solution is stirred uniformly, dried, and ground into a powder; subsequently, the obtained powder is calcined to obtain a porous activated carbon loaded Rh2O3 / NiO composite catalyst.

6. The carbon dioxide catalytic decomposition material of claim 5, wherein, The drying and grinding process is as follows: place in a magnetic stirrer and continuously stir at 200 r / min and 50 ℃ for 2 h; then, place the mixed solution in an oven and evaporate all the water at 70 ℃ to obtain a lump, which is ground into a 200-mesh powder.

7. The carbon dioxide catalytic decomposition material of claim 5, wherein, The calcination process is as follows: place the 200-mesh powder in a muffle furnace and continuously calcine at 850 ℃ for 5 h, with a temperature rising rate of 50 ℃ / min from room temperature to 500 ℃, and then naturally air-cool to room temperature to obtain a porous activated carbon loaded Rh2O3 / NiO composite catalyst.

8. The carbon dioxide catalytic decomposition material of claim 5, wherein, The biomass carbon substrate was prepared by the following method: first, 50 g of proportioned rice husk-based biomass powder / lumps was dissolved in 500 ml of proportioned ultrapure water and placed in a sealed reaction kettle, and continuously heated at 150 °C for 24 h; then, the hydrothermal treated suspension was filtered through a 0.22 μm microporous filter membrane, the obtained residue was continuously washed 3 times with ultrapure water, and dried in a drying oven at 50 °C for 72 h to obtain a lump, which was then ground to a 200 mesh powder; then, the obtained biomass powder was placed in a muffle furnace and calcined at 500 °C for 3 h under argon protection, the temperature rising rate from room temperature to 500 °C was 25 °C / min, and then naturally ventilated to cool to room temperature; the above calcined powder was immersed in 50 ml of sodium hydroxide solution (50 wt.%) for 1 h to form a paste, and the paste was placed in a muffle furnace and calcined at 500 °C for 6 h under a conventional air atmosphere, the temperature rising rate from room temperature to 500 °C was 20 °C / min, and after natural ventilation to cool to room temperature, it was ground to 200 mesh, to obtain a porous activated carbon substrate.

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