CN110152735B - Carbon dioxide reduction catalyst, preparation method and reduction reaction method - Google Patents
Carbon dioxide reduction catalyst, preparation method and reduction reaction method Download PDFInfo
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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Abstract
The invention relates to a carbon dioxide reduction catalyst, a preparation method and a reduction reaction method, belongs to the technical field of carbon dioxide reduction, and solves the following problems in the prior art: the concentration of carbon dioxide on the surface of the catalyst is low, and the activity and the selectivity of the catalyst are low; the number of active sites available for the catalyst decreases. The catalyst comprises a metal organic framework and metal nanoparticles, wherein the metal nanoparticles are wrapped in the metal organic framework, the pore channel structure of the metal organic framework is ZIF-8 or UIO-66, and the metal nanoparticles are NixFey. The carbon dioxide reduction reaction method comprises the following steps: tabletting and granulating the carbon dioxide reduction catalyst, and filling the carbon dioxide reduction catalyst into an isothermal zone of a tubular fixed bed reactor; introducing hydrogen and carbon dioxide, and reacting the hydrogen and the carbon dioxide through an isothermal zone to generate CO and H2O; CO and H2O is output from the product outlet. The catalyst has the advantages of good catalytic performance, strong selectivity and good stability, and can effectively improve the yield of the synthesis gas of the reduction reaction.
Description
Technical Field
The invention relates to the technical field of carbon dioxide reduction, and particularly relates to a carbon dioxide reduction catalyst, a preparation method and a reduction reaction method.
Background
With the rapid development of modern industry, the problem of aggravated greenhouse effect makes environmental and economic sustainable development face a serious challenge. As a main greenhouse gas, several major effects of the greenhouse effect caused by carbon dioxide on the human living environment mainly include: firstly, extreme weather and climate phenomena frequently occur; secondly, the sea level rises due to the thawing of glaciers; thirdly, the number and the distribution of animal and plant populations are influenced; and fourthly, the global warming aggravates the problem of water resource shortage. Therefore, how to reduce the emission of carbon dioxide from the source, reduce the content of carbon dioxide in the atmosphere and create higher value for industrial production by using the greenhouse gas becomes a focus of attention of all countries. In recent years, the technology of carbon dioxide emission reduction and comprehensive utilization thereof is developed vigorously, and the research of laboratory theories is gradually developed to the industrialized popularization. China is used as a developing country, the energy consumption structure is mainly based on coal resources, the emission of carbon dioxide is the second place in the world, and the statistics result of related data shows that by 2050, China is expected to become a country with the highest global emission of carbon dioxide beyond the United states.
Currently, the world energy consumption still mainly comprises petrochemical energy, and increasing human activities not only accelerate the consumption of fossil fuels, but also increase the emission of carbon dioxide in the atmosphere and break the carbon balance in the nature. Since the end of the 19 th century, the concentration of carbon dioxide in the atmosphere has increased from 280ppm to the present 400 ppm. In this context, the search for effective techniques for reducing atmospheric carbon dioxide concentrations has become a major research direction for governments and scientists of various countries. Among the several possible strategies, the technology of reducing carbon dioxide by thermocatalytic, electrochemical or photochemical means and converting it into hydrocarbon fuels beneficial to humans is particularly competitive. The catalyst is the key of carbon dioxide conversion, determines the reaction efficiency and the product distribution, and has very important research significance.
The prior carbon dioxide reduction technical scheme usually adopts a supported metal catalyst, and the defects of the prior carbon dioxide reduction technical scheme are mainly reflected in two aspects: on one hand, the catalyst has low activity due to low concentration of a reactant on the surface of the catalyst, namely carbon dioxide, and meanwhile, products of reduction reaction are widely distributed, and the carbon dioxide reduction products contain small molecular substances such as synthesis gas, methane, methanol and the like, so that the problem of difficult separation is brought. On the other hand, the most commonly used catalyst in the carbon dioxide reduction technology is a supported metal catalyst, the common metal active components are Pd, Pt, Ni, Co, Cu and the like, and because carbon dioxide molecules are very stable, the activation of the carbon dioxide molecules usually needs high energy, namely the reaction temperature is high, and the active components of the supported metal catalyst are easy to agglomerate in the reaction process, so that the number of effective active sites is reduced, and the catalyst is inactivated.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a carbon dioxide reduction catalyst, a preparation method and a reduction reaction method. At least one of the following technical problems can be solved: (1) the concentration of carbon dioxide on the surface of the catalyst is low, and the activity of the catalyst is low; (2) products of the reduction reaction are widely distributed and difficult to separate; (3) the reaction temperature is high, and active components of the catalyst are easy to agglomerate in the reaction process, so that the number of effective active sites is reduced.
The purpose of the invention is mainly realized by the following technical scheme:
in one aspect, the invention provides a carbon dioxide reduction catalyst, which comprises a metal-organic framework and metal nanoparticles, wherein the metal nanoparticles are wrapped in the metal-organic framework, the metal center of the metal-organic framework is Zr or Cu,the pore structure of the metal organic framework is ZIF-8 or UIO-66, and the metal nanoparticles are NixFey。
Further, the specific surface area of the pore channel structure of the metal organic framework is 1000-1400m2/g。
Further, the particle size of the metal nanoparticles is 2.0-3.0 nm.
Further, the loading amount of the metal nanoparticles is 1.0-2.5% of the total mass of the metal organic framework and the metal nanoparticles.
On the other hand, the invention also provides a preparation method of the carbon dioxide reduction catalyst, which comprises the following steps:
the method comprises the following steps: preparing a metal organic framework;
step two: preparation of NixFeyA metal nanoparticle;
step three: mixing a metal organic skeleton with NixFeyAdding a solvent into the metal nano particles, stirring, dipping, washing and drying to obtain the metal organic framework coated NixFeyThe carbon dioxide reduction catalyst of (1).
Further, the metal organic framework in the step one is a ZIF-8 metal organic framework or a UIO-66 metal organic framework.
Further, in the second step, the specific preparation steps are as follows: with Ni (NO)3)2And Fe (NO)3)3Adding the precursor into a solvent for full dissolution, and preparing Ni by a liquid phase reduction method in the presence of a protective agent and a reducing agentxFeyMetal nanoparticles.
In another aspect, the present invention further provides a carbon dioxide reduction reaction method, including the following steps:
the method comprises the following steps: tabletting and granulating the carbon dioxide reduction catalyst, and filling the carbon dioxide reduction catalyst into an isothermal zone of a tubular fixed bed reactor;
step two: introducing hydrogen and carbon dioxide, and reacting the hydrogen and the carbon dioxide through an isothermal zone to generate CO and H2O；
Step three: CO and H2O is output from the product outlet.
Further, in the second step, the flow rate of the hydrogen is 120-180mL/h, and the flow rate of the carbon dioxide is 70-180 mL/h.
Further, in the second step, the reaction temperature is 500-600 ℃.
The invention has the following beneficial effects:
(1) the carbon dioxide reduction catalyst provided by the invention adopts Metal Organic Frameworks (MOFs) as functional carriers to wrap metal nano particles (NMPs) to synthesize the multifunctional catalyst with a sandwich structure, so that the high dispersion of active sites is realized, and the agglomeration is prevented. Aiming at the fact that the MOFs are made of ZIF-8 or UIO-66, small molecular gases such as hydrogen, carbon dioxide and the like can be trapped and stored under proper conditions, and therefore a local environment with high reactant concentration and optimal proportion can be formed on the surface of the catalyst; the metal organic framework has high specific surface area and can obviously improve the active site of the catalyst, namely NixFeyThe dispersion degree of the nano particles effectively improves the number of surface active sites; nixFeyThe nano particles form an alloy structure and are used as active sites of the carbon dioxide reduction reaction, so that the efficiency and the selectivity of the reaction for preparing the synthesis gas by the hydrogenation of the carbon dioxide can be obviously improved, and the performance of the catalyst is improved.
(2) The preparation method of the carbon dioxide reduction catalyst provided by the invention has the advantages that the prepared carbon dioxide reduction catalyst has good catalytic performance and strong selectivity by accurately controlling the types, concentrations and process parameters of chemical components in the preparation process, wherein the Ni coated by the UiO-661Fe3The catalyst can improve the selectivity of the synthesis gas to more than 99 percent.
(3) The carbon dioxide reduction catalyst provided by the invention is applied to a carbon dioxide reduction reaction system, and by utilizing the advantages of the multifunctional material such as respiration effect, gas selective adsorption, high dispersion active site and the like, the local concentration and reactant proportion which are beneficial to reaction are formed on the surface of the catalyst, so that the selectivity and the conversion rate of the reaction are obviously improved, and the yield of the synthesis gas is effectively improved.
In the invention, the technical schemes can be combined with each other to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention, wherein like reference numerals are used to designate like parts throughout.
Fig. 1 is a schematic structural diagram of a carbon dioxide reduction catalyst according to an embodiment of the present invention.
Reference numerals:
1-a metal organic framework; 2-metal nanoparticles.
Detailed Description
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate preferred embodiments of the invention and together with the description, serve to explain the principles of the invention and not to limit the scope of the invention.
Example 1
One specific embodiment of the invention discloses a carbon dioxide reduction catalyst, as shown in fig. 1, the catalyst comprises a metal organic framework 1 and metal nanoparticles 2, the metal nanoparticles are wrapped in the metal organic framework, the metal center of the Metal Organic Framework (MOFs) is Zr or Cu, the pore channel structure of the Metal Organic Framework (MOFs) is ZIF-8 or UIO-66, and the metal nanoparticles are NixFey。
In the prior art, a metal organic framework material is adopted as a carbon dioxide reduction catalyst, but the effect is poor, for example, the activation capability of unsaturated sites of the metal organic framework to carbon dioxide is extremely weak, so that the activity of the catalyst is too low; when the Pd or Pt metal nanoparticles are selected for coating, the synergistic effect of the framework and the active sites is weak, and the partial reduction of carbon dioxide is not facilitated, so that the selectivity of the catalyst is not ideal.
Compared with the prior artCompared with the prior art, the carbon dioxide reduction catalyst of the embodiment adopts a proper Metal Organic Frameworks (MOFs) as a functional carrier to wrap metal Nanoparticles (NMPs), and has a remarkable synergistic effect and selective effect on the reaction of preparing synthesis gas by carbon dioxide hydrogenation; the metal center of the Metal Organic Frameworks (MOFs) is Zr or Cu, the pore channel structure of the Metal Organic Frameworks (MOFs) is ZIF-8 or UIO-66, the metal organic frameworks adopted by the invention have the characteristics of large specific surface area, ordered and stable pore channel structure, unsaturated metal sites, respiratory effect, gas selective adsorption and the like, the MOFs can be used as a functional carrier to wrap metal Nanoparticles (NMPs), the high dispersion of the active sites and the agglomeration prevention are realized, and each pore cage can be used as a mimicry microreactor; on the other hand, the MOFs adopted by the invention has good adsorbability on hydrogen and carbon dioxide, can collect and store small molecular gases such as hydrogen, carbon dioxide and the like under proper conditions, can improve local reaction concentration, can form a local environment with high reactant concentration and optimal proportion on the surface of the catalyst, is beneficial to improving the efficiency and selectivity of the reaction for preparing the synthesis gas by hydrogenating the carbon dioxide, and has low metal cost. The metal organic framework has high specific surface area, can obviously improve the dispersion degree of metal nano particles, effectively improves the number of surface active sites and is beneficial to improving the reaction conversion ratexFeyIs a metal active site to catalyze the carbon dioxide reduction reaction method. NixFeyThe nanoparticles exhibit excellent catalytic performance for the above carbon dioxide reduction reaction method. Firstly, an Ni-Fe surface alloy structure can be obtained by selecting a proper raw material proportion and proper catalyst preparation conditions, and the alloy structure is favorable for dissociation of hydrogen and adsorption reaction of carbon dioxide, so that the catalyst has high activity; meanwhile, the carbon dioxide is mainly adsorbed on the Ni-Fe alloy structure in a bridge mode, and the adsorption effect of the carbon monoxide on the Ni-Fe alloy structure is weaker, so that the process is favorable for desorption of products from the surface of the catalyst, the products are prevented from being further hydrogenated to prepare methanol or methane, and carbon deposition inactivation of the catalyst can be reduced, so that the selectivity and the stability of the catalyst can be improved.
Specifically, x is 1-5, and y is 1-5.
Particularly, ZIF-8 or UIO-66 is easier to capture hydrogen and carbon dioxide, and can improve local reaction concentration; secondly, the matching degree of the pore size of the ZIF-8 or UIO-66 and the size of the metal nano-particles is good, so that a synergistic effect can be formed between a metal active site of the catalyst and an unsaturated site of a metal organic framework, and the pseudo-homogenization degree of the heterogeneous catalyst can be improved; thirdly, the goodness of fit between the pore size of the ZIF-8 or UIO-66 and the kinetic diameter size of the reaction molecule is high, which is beneficial to promoting the adsorption of reactants and the desorption of products.
Considering the adsorptivity of the pore channels to reactants, namely hydrogen and carbon dioxide and the dispersion effect of metal active sites, the specific surface area of the pore channel structure is 1000-1400m2The specific surface area can ensure that the catalyst has sufficient functionalized space, and guarantee is provided for selective adsorption and desorption of reactants and products; meanwhile, the dispersity of the metal nanoparticles can be improved, so that the conversion frequency of a single active site is improved. The specific surface area of the pore channel structure is less than 1000m2The selective adsorption performance of the catalyst and the dispersion degree of the metal nano particles can not be ensured when per gram, and the specific surface area of the pore channel structure is more than 1400m2At the time of/g, the synthesis difficulty and purification cost are too high, and the economical efficiency is poor.
Considering that the number of the surface effective metal active sites is reduced and the catalytic efficiency is reduced when the particle size of the metal nano-particles is too large, the particle size of the metal nano-particles is 2.0-3.0nm, so that the number of the surface effective metal active sites is increased and the catalytic efficiency is improved by 15-35%.
Specifically, the loading capacity of the selected metal nanoparticles is 1.0-2.5% of the total mass of NMPs-MOFs. When the loading capacity of the metal nanoparticles is lower than 1.0%, the number of metal active sites is too small, so that the requirement of catalytic reaction is difficult to meet; when the loading amount of the metal nano particles is higher than 2.5%, the size of the metal nano particles is difficult to control, and the cost of the catalyst is greatly improved.
The organic ligand of the MOFs in the application is one of terephthalic acid and dimethyl imidazole.
Example 2
Another embodiment of the present invention discloses a method for preparing the carbon dioxide reduction catalyst of embodiment 1, comprising the steps of:
the method comprises the following steps: preparing ZIF-8 metal organic framework by using an autogenous method, and reacting Zn (NO)3)2Dissolving (12mmol) and 2-methylimidazole (25mmol) in methanol (250mL) to prepare a ZIF-8 precursor solution;
step two: adding Zn (NO)3)2(12mmol) is dissolved in deionized water (250mL) to prepare zinc nitrate aqueous solution;
step three: taking an equal amount of ZIF-8 precursor solution, fully mixing with a zinc nitrate aqueous solution, soaking for 80min at room temperature, washing with methanol, and drying with nitrogen to obtain a ZIF-8 material;
step four: metallic nanoparticle NixFeyPrepared with Ni (NO)3)2And Fe (NO)3)3Accurately weighing the precursor according to the mass ratio of 1:5-5:1, adding the precursor into a solvent for full dissolution, and preparing Ni by using a liquid phase reduction method in the presence of a protective agent and a reducing agentxFeyA metal nanoparticle;
step five: mixing ZIF-8 material and NixFeyAdding a solvent into the metal nano particles, stirring at room temperature, dipping, washing and drying to obtain a metal organic framework ZIF-8 wrapped NixFeyThe NiFe @ ZIF-8 carbon dioxide reduction catalyst.
Specifically, in the step one, the cost of the catalyst can be reduced by selecting non-noble metal central atoms for the metal organic framework, and a perfect framework topological structure can be ensured by selecting a proper amount of organic ligands.
Specifically, the solvent in the fourth step is one or two of deionized water or methanol, and the reducing agent is one of sodium borohydride or a mixture of glucose and thiourea dioxide.
Example 3
Another embodiment of the present invention discloses a method for preparing a carbon dioxide reduction catalyst, comprising the steps of:
step 1: weighing a zirconium metal salt precursor and an organic ligand according to a ratio by a hydrothermal method, adding the zirconium metal salt precursor and the organic ligand into a solvent, mixing, and performing ultrasonic treatment at room temperature for 10-45min to completely dissolve the zirconium metal salt precursor and the organic ligand in the solvent to obtain a mixed liquid;
step 2: transferring the mixed solution obtained in the step 1 to a stainless steel reaction kettle with a polytetrafluoroethylene lining for reaction, and carrying out hydrothermal reaction for 8-36h at the temperature of 150 ℃ and 250 ℃ to generate a reactant;
and step 3: centrifuging, washing and drying the reactant obtained in the step 2 to obtain a UiO-66 material;
and 4, step 4: metallic nanoparticle NixFeyPrepared with Ni (NO)3)2And Fe (NO)3)3Accurately weighing the precursor according to the mass ratio of 1:5-5:1, adding the precursor into a solvent for full dissolution, and preparing Ni by a liquid phase reduction method in the presence of a protective agent and a reducing agentxFeyA metal nanoparticle;
and 5: metal organic framework UiO-66 wrapped NixFeyPreparation of the catalyst: mixing UiO-66 with NixFeyAdding a solvent into the metal nano particles, stirring, dipping, washing and drying at room temperature to obtain a metal organic framework UiO-66 wrapped NixFeyThe NiFe @ UiO-66 carbon dioxide reduction catalyst.
Specifically, in step 1, the zirconium metal salt is preferably zirconium nitrate, the organic ligand is preferably one of terephthalic acid, amino-group or sulfonic-group modified terephthalic acid, and the solvent is preferably N-N dimethylformamide; the adoption of the raw materials can reduce the use of solvents, simplify the steps of washing, separation and purification, is beneficial to reducing the synthesis cost of the catalyst and is also beneficial to generating a UIO-66 framework structure.
Specifically, stainless steel reation kettle has the polytetrafluoroethylene inside lining, and the polytetrafluoroethylene inside lining can improve stainless steel reation kettle's anticorrosion and prevent the performance, improves stainless steel reation kettle's resistance to deformation.
Specifically, in step 3, the centrifugation speed is 4500-5500rmp, such as 5000rmp, each time for 1-3min, such as 1 min; the solvent used in the washing process is one or more of deionized water, methanol, ethanol, acetone and N-N-dimethylformamide, the dosage of the solvent is 100-300mL/g of catalyst, and the washing times are 3-5 times.
Specifically, in step 4, the solvent is one or two of deionized water or methanol, and the reducing agent is one of sodium borohydride or a mixture of glucose and thiourea dioxide.
Specifically, in step 5, NixFeyThe mass of the metal nano particles is 1.0-2.5% of the total mass of NMPs-MOFs; the solvent is one or two of deionized water or methanol, and the dosage of the solvent is 50-100mL/g of the catalyst; the immersion time was 24-72 hours and the stirring rate was 200-800 rmp.
Example 4
Another embodiment of the present invention discloses a carbon dioxide reduction reaction method, comprising the steps of:
the method comprises the following steps: tabletting and granulating 0.05-5.0g of carbon dioxide reduction catalyst to obtain particles with the particle size of 60-80 meshes, and filling the particles into an isothermal zone of a tubular fixed bed reactor;
step two: introducing high-purity hydrogen into the hydrogen inlet, introducing high-purity carbon dioxide into the carbon dioxide inlet, and reacting the hydrogen and the carbon dioxide through an isothermal zone to generate CO and H2O；
Step three: CO and H2O is output from the product outlet.
Specifically, in the step one, a tubular furnace is adopted to realize the temperature rise and heat preservation of the reactor, a thermocouple is adopted to detect the temperature of the reaction isothermal zone, and an outlet back pressure valve is adopted to adjust and control the pressure of the reactor.
Specifically, in the second step, the mass flow meter is adopted to control the flow rates of the carbon dioxide and the hydrogen, the flow rate of the hydrogen is controlled to be 180mL/h, the flow rate of the carbon dioxide is controlled to be 70-180mL/h, the over-high flow rates of the hydrogen and the carbon dioxide are not beneficial to complete reaction conversion, and the over-low flow rate is easy to cause the over-hydrogenation of the carbon dioxide to generate byproducts.
Specifically, the reaction temperature in the second step is controlled to be 500-.
Specifically, the reaction pressure in the second step is controlled to be 0.5-1.0 MPa; too high reaction pressure is easy to increase the operation cost, and too low reaction pressure is not favorable for improving the yield of the synthesis gas.
Specifically, in the second step, the reaction product is quantitatively analyzed by adopting gas chromatography.
Example 5
Another embodiment of the present invention discloses a carbon dioxide reduction reaction process, using, for example, the steps of embodiment 4, with the catalyst being ZIF-8 wrapped Ni1Fe3The catalyst loading amount is 0.5g, high-purity hydrogen is introduced into a hydrogen inlet at a rate of 160mL/h, carbon dioxide is introduced into a carbon dioxide inlet at a rate of 160mL/h, the reaction temperature is 500 ℃, the reaction pressure is 0.5MPa, and the yield of the synthesis gas is 95% after the reaction is stable for 4 hours.
Example 6
Another embodiment of the present invention discloses a carbon dioxide reduction process using, for example, the steps of example 4, the catalyst being Ni encapsulated by UIO-661Fe3The catalyst loading amount is 0.5g, high-purity hydrogen is introduced into a hydrogen inlet at a rate of 160mL/h, carbon dioxide is introduced into a carbon dioxide inlet at a rate of 160mL/h, the reaction temperature is 500 ℃, the reaction pressure is 0.5MPa, and the yield of the synthesis gas is 100% after the reaction is stable for 4 hours.
Comparative example 1
The comparative example of the invention, using the traditional Ni-based catalyst, yields of synthesis gas from carbon dioxide were only 75%.
In conclusion, the carbon dioxide reduction catalyst provided by the invention is applied to a reaction system for preparing synthesis gas by carbon dioxide hydrogenation, can capture and store hydrogen, carbon dioxide and other small molecule gases under appropriate conditions, can form a local environment with high reactant concentration and optimal proportion on the surface of the catalyst, can obviously improve the selectivity and the conversion rate of the reaction, and can reach the synthesis gas yield of 95-100%,
the above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (7)
1. The carbon dioxide reduction catalyst is characterized by comprising a metal organic framework and metal nanoparticles, wherein the metal nanoparticles are wrapped in the metal organic framework, the metal organic framework is ZIF-8 or UIO-66, and the metal nanoparticles are NixFeyX is 1-5, y is 1-5; the specific surface area of the metal organic framework is 1000-1400m2/g；
The preparation method of the carbon dioxide reduction catalyst comprises the following steps:
the method comprises the following steps: preparing a metal organic framework;
step two: preparation of NixFeyA metal nanoparticle;
step three: mixing a metal organic skeleton with NixFeyAdding a solvent into the metal nano particles, stirring, dipping, washing and drying to obtain the metal organic framework coated NixFeyA carbon dioxide reduction catalyst of (a);
in the second step, the preparation steps are as follows: with Ni (NO)3)2And Fe (NO)3)3Adding the precursor into a solvent for full dissolution, and preparing Ni by a liquid phase reduction method in the presence of a protective agent and a reducing agentxFeyMetal nanoparticles.
2. The carbon dioxide reduction catalyst according to claim 1, wherein the metal nanoparticles have a particle size of 2.0 to 3.0 nm.
3. The carbon dioxide reduction catalyst according to claim 2, wherein the loading of the metal nanoparticles is 1.0 to 2.5% of the total mass of the metal-organic framework and the metal nanoparticles.
4. A method for producing a carbon dioxide reduction catalyst, for producing the carbon dioxide reduction catalyst according to any one of claims 1 to 3, comprising the steps of:
the method comprises the following steps: preparing a metal organic framework, wherein the metal organic framework is a ZIF-8 metal organic framework or a UIO-66 metal organic framework;
step two: preparation of NixFeyA metal nanoparticle;
step three: mixing a metal organic skeleton with NixFeyAdding a solvent into the metal nano particles, stirring, dipping, washing and drying to obtain the metal organic framework coated NixFeyA carbon dioxide reduction catalyst of (a);
wherein in the second step, the concrete preparation steps are as follows: with Ni (NO)3)2And Fe (NO)3)3Adding the precursor into a solvent for full dissolution, and preparing Ni by a liquid phase reduction method in the presence of a protective agent and a reducing agentxFeyMetal nanoparticles.
5. A carbon dioxide reduction reaction method using the carbon dioxide reduction catalyst according to any one of claims 1 to 3, comprising the steps of:
the method comprises the following steps: tabletting and granulating the carbon dioxide reduction catalyst, and filling the carbon dioxide reduction catalyst into an isothermal zone of a tubular fixed bed reactor;
step two: introducing hydrogen and carbon dioxide, and reacting the hydrogen and the carbon dioxide through an isothermal zone to generate CO and H2O；
Step three: CO and H2O is output from the product outlet.
6. The carbon dioxide reduction reaction method as claimed in claim 5, wherein in the second step, the flow rate of hydrogen is 120-180mL/h, and the flow rate of carbon dioxide is 70-180 mL/h.
7. The carbon dioxide reduction reaction method as set forth in claim 5 or 6, wherein the reaction temperature in the second step is 500-600 ℃.
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