CN110592606A - Preparation method and application of gold-iron nano alloy catalyst - Google Patents
Preparation method and application of gold-iron nano alloy catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- NPEWZDADCAZMNF-UHFFFAOYSA-N gold iron Chemical compound [Fe].[Au] NPEWZDADCAZMNF-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 81
- 239000000956 alloy Substances 0.000 title claims abstract description 81
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 238000013329 compounding Methods 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 25
- -1 gold salt compound Chemical class 0.000 claims description 24
- 239000007788 liquid Substances 0.000 claims description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 22
- 239000012265 solid product Substances 0.000 claims description 22
- 239000012300 argon atmosphere Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 239000000047 product Substances 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 239000002131 composite material Substances 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 12
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000003575 carbonaceous material Substances 0.000 claims description 10
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- OTCKNHQTLOBDDD-UHFFFAOYSA-K gold(3+);triacetate Chemical compound [Au+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OTCKNHQTLOBDDD-UHFFFAOYSA-K 0.000 claims description 8
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- GCFHZZWXZLABBL-UHFFFAOYSA-N ethanol;hexane Chemical compound CCO.CCCCCC GCFHZZWXZLABBL-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000002086 nanomaterial Substances 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 3
- NKJOXAZJBOMXID-UHFFFAOYSA-N 1,1'-Oxybisoctane Chemical group CCCCCCCCOCCCCCCCC NKJOXAZJBOMXID-UHFFFAOYSA-N 0.000 claims description 3
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical compound CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000523 polyvinylpolypyrrolidone Polymers 0.000 claims description 2
- 239000001253 polyvinylpolypyrrolidone Substances 0.000 claims description 2
- 235000013809 polyvinylpolypyrrolidone Nutrition 0.000 claims description 2
- 150000004685 tetrahydrates Chemical class 0.000 claims description 2
- 239000010931 gold Substances 0.000 abstract description 30
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052737 gold Inorganic materials 0.000 abstract description 24
- 230000009467 reduction Effects 0.000 abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910052709 silver Inorganic materials 0.000 abstract description 3
- 239000004332 silver Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 27
- 239000007789 gas Substances 0.000 description 18
- 238000010586 diagram Methods 0.000 description 16
- 238000006722 reduction reaction Methods 0.000 description 16
- 235000019441 ethanol Nutrition 0.000 description 14
- 229910017390 Au—Fe Inorganic materials 0.000 description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- 239000003792 electrolyte Substances 0.000 description 11
- 229910000640 Fe alloy Inorganic materials 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 239000002105 nanoparticle Substances 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 8
- 229910021397 glassy carbon Inorganic materials 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 241000282414 Homo sapiens Species 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 239000001569 carbon dioxide Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 241001481789 Rupicapra Species 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000004083 survival effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- B01J35/33—
-
- B01J35/60—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
Abstract
A preparation method and application of a gold-iron nano alloy catalyst relate to the electrocatalytic reduction of CO2A preparation method and application of a catalyst for preparing CO. The invention aims to solve the problem that the noble metals of gold and silver are used as CO2The catalytic material reduced to CO has a problem of high price. The preparation method comprises the following steps: firstly, preparing a surfactant solution; secondly, mixing;thirdly, carrying out hydrothermal reaction; fourthly, washing and dispersing; and fifthly, compounding to obtain the gold-iron nano alloy catalyst. Gold-iron nano alloy catalyst used as raw material for preparing working electrode for electrocatalytic reduction of CO2And (5) preparing CO. The advantages are that: the consumption of gold is reduced, and the cost of the gold-based catalyst in industrial application is greatly reduced.
Description
Technical Field
The invention relates to an electrocatalytic reduction method for CO2A preparation method and application of a catalyst for preparing CO.
Background
Human excessive dependenceThe natural resources consumed for the development of the human society are not sustainable, and the content of carbon dioxide in the atmosphere is rapidly increased, so that more and more environmental problems, such as greenhouse effect and the like, are caused, and the survival and the development of human beings are seriously threatened. More urgently, the demand for energy is increasing with the increase in population, the extension of human life, the development of new processes, and the like. Climate change and energy crisis gradually threaten the survival and the proliferation of human beings on the earth, and are scientific problems which must be solved by contemporary people. But CO2The speed of changing back to carbon-based energy materials is far behind the speed of human consumption of energy materials. The detection data of 2017 in month 2 show that the CO in the atmosphere2The concentration is as high as 406ppm, and far exceeds the safety upper limit of 350 ppm. With CO2The closed earth carbon circulation system is accelerated by reducing the carbon-based energy materials into resources by a chemical method, so that the energy is provided, and the CO is reduced2The content in the atmosphere is an effective way to solve the current increasingly worsening energy and environmental problems. Electrocatalytic reduction of CO2The advantages of mild reaction conditions, no need of high temperature and high pressure, flexible operation of the equipment, capability of obtaining higher energy utilization efficiency than other chemical conversion equipment and the like are considered to be CO2The transformation technology with the most development prospect for resource utilization.
CO can be introduced by using different metal catalysts2Reduction to various products, currently in all CO2Among the reduction catalyst products, CO is considered to be the most desirable product in consideration of market price and the like, because CO is a raw material for the fischer-tropsch reaction and is used for the industrial production of methane. In all metal catalysts studied at present, the noble metals gold and silver are used as catalytic materials for CO2The reduction to CO has the highest selectivity and catalytic efficiency, wherein the gold-based catalyst reduces CO2The Faraday efficiency of CO can reach more than 90%. However, the noble metal gold is very rare in nature and high in price, and the industrial and large-scale use of the gold-based catalyst is severely limited. Because the nano material has high specific surface under a certain massThe current research focuses on developing novel noble metal nano materials, and the size, the morphology and the components of the materials are regulated to improve the catalytic performance and the quality activity of the noble metals, so that the consumption of the noble metals is further reduced.
The existing gold-based catalyst is mainly obtained by means of regulating and controlling the size, the surface appearance, the proportion of specific sites and the like of the catalyst. Although the catalytic activity is improved, the dosage of the noble metal gold is not obviously reduced, and the quality activity of the catalyst is not obviously improved. And the reaction condition for regulating and controlling the microscopic morphology of the nano material has extremely high requirement, the steps are complex, the preparation process has very high requirement, and the industrial actual production is difficult to meet.
Disclosure of Invention
The invention aims to solve the problem that the noble metals of gold and silver are used as CO2The catalytic material reduced to CO has the problem of high price, and provides a preparation method and application of the gold-iron nano alloy catalyst.
A preparation method of a gold-iron nano alloy catalyst comprises the following steps:
firstly, preparing a surfactant solution: adding a surfactant into a high-boiling-point organic solvent, and stirring until the surfactant is completely dissolved to obtain a surfactant solution; the volume ratio of the mass of the surfactant to the high-boiling-point organic solvent is (0.006-0.6) g (1-100) mL;
secondly, mixing: adding a gold salt compound, a ferric salt compound and a reducing agent into a surfactant solution, and stirring and uniformly mixing at the temperature of 30-80 ℃ in an argon atmosphere to obtain a mixture; the volume ratio of the mass of the gold salt compound to the volume of the surfactant solution is (0.0093-0.93) g, (1-100) mL; the volume ratio of the mass of the ferric salt compound to the surfactant solution is (0.0088-0.88) g (1-100) mL; the volume ratio of the mass of the reducing agent to the volume of the surfactant solution is (0.064-0.64) g (1-100) mL; the reducing agent is an alcohol compound;
thirdly, hydrothermal reaction: raising the temperature of the mixture to 250-290 ℃ under the argon atmosphere, preserving the heat for 0.5-3 h at the temperature of 250-290 ℃ under the argon atmosphere, cooling to room temperature to obtain a reaction product, adding ethanol into the reaction product, performing centrifugal separation, and removing supernatant to obtain a solid product; the volume ratio of the reaction product to the ethanol is 1: 1-3;
fourthly, washing and dispersing: cleaning the solid product for 2-5 times by using an ethanol-n-hexane mixed solution to obtain a washed product; dispersing the washed product in n-hexane to obtain a dispersion: the volume ratio of the mass of the washed product to the n-hexane is (0.0028-0.985) g, (5-500) mL;
fifthly, compounding: adding the nano carbon material into the dispersion liquid, ultrasonically mixing, then centrifugally separating, removing supernatant liquid to obtain a composite solid product, and drying the composite solid product in a vacuum drying oven to obtain a gold-iron nano alloy catalyst; the volume ratio of the mass of the nano carbon material to the dispersion liquid is (0.84-84) mg (1-100) mL.
Application of gold-iron nano alloy catalyst as raw material for preparing working electrode for electrocatalytic reduction of CO2And (5) preparing CO.
The principle and the advantages of the invention are as follows: the preparation method comprises the steps of preparing a gold-iron nano alloy catalyst by using a solvothermal synthesis method, wherein a gold salt compound and an iron salt compound are used as precursors, an alcohol compound is used as a reducing agent, a high-boiling-point organic solvent is used as a reaction solvent, a surfactant is used as a nano micelle, a nano carbon material is used as a carrier; not only has simple reaction operation and great flexibility, but also has excellent catalytic reduction of CO2Is a property of CO; secondly, the invention mixes noble metal gold and non-noble metal iron to prepare the gold-iron nano alloy catalyst for CO2The reduced CO has high selectivity and mass activity, the Faraday efficiency reaches 95 percent under the overpotential of-1.2V, the consumption of gold is reduced, and the cost of the industrial application of the gold-based catalyst is greatly reduced. Thirdly, the invention uses the nano carbon material as a carrier of the gold-iron alloy nano particles. Thus, the amount of the catalyst used per unit area of the electrode can be reduced, the conductivity of the catalyst can be increased, and the catalytic performance of the catalyst can be further improved. The gold-iron nano particles are tightly adsorbed on the surface of the carbon material and are uniformDispersing, preventing the nano particles from agglomerating and improving the stability of the catalyst.
Drawings
FIG. 1 is a high-resolution TEM image of the Au-Fe nanoalloy catalyst prepared in example 1;
FIG. 2 is a HAADF-STEM diagram of the gold-iron nano-alloy catalyst prepared in example 1;
FIG. 3 is a Mapping diagram of Au elements in the A region of FIG. 2;
FIG. 4 is a Mapping diagram of the Fe element of the A region in FIG. 2;
FIG. 5 is an overlay of FIGS. 3 and 4;
FIG. 6 is an EDX elemental analysis chart of the gold-iron nano-alloy catalyst prepared in example 1;
FIG. 7 is an X-ray diffraction pattern in which a represents an X-ray diffraction pattern of the Au-Fe nano alloy catalyst prepared in example 1, b represents an X-ray diffraction pattern of the Au-Fe nano alloy catalyst prepared in example 2, c represents an X-ray diffraction pattern of the Au-Fe nano alloy catalyst prepared in example 3, pure Au represents a standard card of Au element, pure Fe represents a standard card of Fe element, and Fe represents a standard card of Fe element3O4Represents Fe3O4A standard card of the table;
FIG. 8 is a transmission electron microscope image of the gold-iron nano-alloy catalyst prepared in example 1;
FIG. 9 is a transmission electron microscope image of the gold-iron nano-alloy catalyst prepared in example 2;
FIG. 10 is a transmission electron microscope image of the gold-iron nano-alloy catalyst prepared in example 3;
FIG. 11 catalytic reduction of CO2In the graph, a tangle-solidup represents the catalytic reduction of CO by the gold-iron nano alloy catalyst of the example 62T. T.X represents the Faraday efficiency plot of CO for the catalytic reduction of CO by the gold-iron nano-alloy catalyst of example 72As a graph of the Faraday efficiency of CO,. diamond-solid.) represents the catalytic reduction of CO by the gold-iron nano-alloy catalyst of example 82● shows the catalytic reduction of CO by the Au-Fe nanoalloy catalyst of example 8, which is a graph of the Faraday efficiency of CO2Graph of Faraday efficiency for CO, ■Catalytic reduction of CO with the gold-iron nanoalloy catalyst representing example 102Graph of faradaic efficiency for CO;
FIG. 12 catalytic reduction of CO2The current density diagram of CO is shown, in the diagram, a-solidup part represents the catalytic reduction CO of the gold-iron nano alloy catalyst of the embodiment 62Is a current density graph of CO, t.t. represents the catalytic reduction of CO by the gold-iron nano-alloy catalyst of example 72Current density plot of CO,. diamond-solid.) represents the catalytic reduction of CO by the gold-iron nanoalloy catalyst of example 82● shows the current density plot of CO for the catalytic reduction of CO by the Au-Fe nanoalloy catalyst of example 82■ shows the current density diagram of CO in the catalytic reduction of CO by the Au-Fe nanoalloy catalyst of example 102The current density of CO is plotted.
Detailed Description
The first embodiment is as follows: the embodiment is a preparation method of a gold-iron nano alloy catalyst, which is specifically completed by the following steps:
firstly, preparing a surfactant solution: adding a surfactant into a high-boiling-point organic solvent, and stirring until the surfactant is completely dissolved to obtain a surfactant solution; the volume ratio of the mass of the surfactant to the high-boiling-point organic solvent is (0.006-0.6) g (1-100) mL;
secondly, mixing: adding a gold salt compound, a ferric salt compound and a reducing agent into a surfactant solution, and stirring and uniformly mixing at the temperature of 30-80 ℃ in an argon atmosphere to obtain a mixture; the volume ratio of the mass of the gold salt compound to the volume of the surfactant solution is (0.0093-0.93) g, (1-100) mL; the volume ratio of the mass of the ferric salt compound to the surfactant solution is (0.0088-0.88) g (1-100) mL; the volume ratio of the mass of the reducing agent to the volume of the surfactant solution is (0.064-0.64) g (1-100) mL; the reducing agent is an alcohol compound;
thirdly, hydrothermal reaction: raising the temperature of the mixture to 250-290 ℃ under the argon atmosphere, preserving the heat for 0.5-3 h at the temperature of 250-290 ℃ under the argon atmosphere, cooling to room temperature to obtain a reaction product, adding ethanol into the reaction product, performing centrifugal separation, and removing supernatant to obtain a solid product; the volume ratio of the reaction product to the ethanol is 1: 1-3;
fourthly, washing and dispersing: cleaning the solid product for 2-5 times by using an ethanol-n-hexane mixed solution to obtain a washed product; dispersing the washed product in n-hexane to obtain a dispersion: the volume ratio of the mass of the washed product to the n-hexane is (0.0028-0.985) g, (5-500) mL;
fifthly, compounding: adding the nano carbon material into the dispersion liquid, ultrasonically mixing, then centrifugally separating, removing supernatant liquid to obtain a composite solid product, and drying the composite solid product in a vacuum drying oven to obtain a gold-iron nano alloy catalyst; the volume ratio of the mass of the nano carbon material to the dispersion liquid is (0.84-84) mg (1-100) mL.
The nanocarbon material in step five of the present embodiment is carbon black, carbon nanotubes, or graphite.
The second embodiment is as follows: the present embodiment differs from the first embodiment in that: in the first step, the surfactant is one or more of oleylamine, oleic acid or polyvinyl polypyrrolidone; the high-boiling-point organic solvent is octyl ether or octadecene. The rest is the same as the first embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: in the first step, the surfactant is added into the high boiling point organic solvent, and the mixture is stirred for 10 to 20min at the rotating speed of 300 to 800r/min, so as to obtain the surfactant solution. The others are the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: in the second step, the gold salt compound is gold acetate or chloroauric acid tetrahydrate; the ferric salt compound is ferric acetylacetonate or ferric chloride; the alcohol compound is 1, 2-hexadecanediol, ethylene glycol or glycerol. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: and in the second step, stirring for 30-120 min at a stirring speed of 500-1200 r/min at a temperature of 30-80 ℃ under an argon atmosphere. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and in the third step, the temperature of the mixture is increased to 250-290 ℃ at the heating rate of 3-6 ℃/min under the argon atmosphere. The rest is the same as the first to fourth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and in the third step, centrifugal separation is carried out for 1min to 5min at the speed of 8000r/min to 15000r/min, and supernatant is removed to obtain a solid product. The rest is the same as the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: and in the fourth step, the volume ratio of the ethanol to the n-hexane in the ethanol-n-hexane mixed solution is 1: 2. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: and fifthly, adding the nano carbon material into the dispersion liquid, carrying out ultrasonic mixing for 20-40 min, carrying out centrifugal separation at the centrifugal speed of 8000-15000 r/min, removing supernatant to obtain a composite solid product, placing the composite solid product into a vacuum drying oven, and drying at the temperature of 150-200 ℃ for 8-24 h to obtain the gold-iron nano alloy catalyst. The others are the same as the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is an application of a gold-iron nano alloy catalyst, and the gold-iron nano alloy catalyst is used as a raw material for preparing a working electrode for electro-catalytic reduction of CO2And (5) preparing CO.
The specific preparation method of the working electrode comprises the following steps:
firstly, adding a Nafion solution into absolute ethyl alcohol, uniformly mixing, adding a gold-iron nano alloy catalyst, and performing ultrasonic oscillation for 30-60 min to obtain an ink-like mixed solution;
polishing the glassy carbon electrode on chamois leather by using 500nm of aluminum oxide powder and 50nm of aluminum oxide powder in sequence until the mirror surface is smooth, ultrasonically cleaning the electrode for 1-3 times by using deionized water, ultrasonically cleaning the electrode for 1-3 times by using ethanol, and drying the electrode to obtain a clean glassy carbon electrode;
thirdly, according to the loading amount of the gold-iron nano alloy catalyst, the loading amount is 0.04mg/cm2～0.08mg/cm2And transferring the ink-like mixed liquid onto the clean glassy carbon electrode for a plurality of times by using a liquid transfer gun, wherein the single transfer amount of the liquid transfer gun is 2-3 mu L, and after the second dripping, performing the next transferring and dripping after naturally drying the ink-like mixed liquid on the surface of the clean glassy carbon electrode to obtain the working electrode.
The electrocatalytic reduction of CO2The specific process for preparing CO is as follows:
firstly, assembling a reactor: an H-shaped three-electrode electrolytic cell is adopted, a cathode cell and an anode cell of the H-shaped three-electrode electrolytic cell are separated by a Nafion 117 proton ion exchange membrane, and KHCO with the concentration of 0.5mol/L is adopted3Pouring electrolyte into an H-shaped three-electrode electrolytic cell by taking an aqueous solution as the electrolyte until a channel between an anode pool and a cathode pool of the H-shaped three-electrode electrolytic cell is filled with the electrolyte, taking a platinum sheet as a counter electrode, placing the counter electrode in the anode pool of the H-shaped three-electrode electrolytic cell, placing a working electrode and a reference electrode in a cathode pool of the H-shaped three-electrode electrolytic cell, wherein the reference electrode is a saturated KCl Ag/AgCl electrode, arranging a cathode area air inlet and a cathode area air outlet in the cathode pool, and arranging CO and CO in the cathode pool2The air inlet pipe extends to the position below the liquid level of the electrolyte through the air inlet of the cathode area, the air outlet of the cathode area is communicated with the gas collecting device, 1 magnetic stirring rotor is placed in the cathode pool, the cathode pool is sealed by adopting a sealing piece, and the contact positions of the working electrode and the reference electrode with the sealing piece are sealed to obtain the electro-catalytic reduction CO2A CO production device;
secondly, electrocatalytic reduction: passing CO at a gas flow rate of 20mL/min2Introducing carbon dioxide gas into the electrolyte of the cathode pool through the gas inlet pipe, starting the power supply and the magnetic stirrer after the introduction time is 30min, wherein the rotating speed of the magnetic stirrer is 500-1200 r/min, and the carbon dioxide gas is introduced into the electrolyte of the cathode pool through the gas inlet pipe when CO is present2The gas flow is 1mL/min to 30mL/min, the magnetic stirring rotating speed is 500r/min to 1200r/min, and the potential of the working electrode is-1.0V to-2.4V (vs Ag/AgCl)2Electrocatalytic reduction of gasThe gas generated by the reaction in the cathode pool is collected by the body collecting device through the gas outlet of the cathode area, namely the electrocatalytic reduction of CO is completed2And (5) preparing CO.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The following tests were carried out to confirm the effects of the present invention
Example 1: a preparation method of a gold-iron nano alloy catalyst comprises the following steps:
firstly, preparing a surfactant solution: 0.03344g of oleylamine and 0.03231g of oleic acid are added into 10mL of octyl ether, and stirred for 15min at the rotating speed of 500r/min to obtain a surfactant solution;
secondly, mixing: adding 0.14g of gold acetate, ferric acetylacetonate and 0.6461g of 1, 2-hexadecanediol into the surfactant solution obtained in the step one, and stirring at the temperature of 50 ℃ and the stirring speed of 800r/min for 60min under the argon atmosphere to obtain a mixture; the molar ratio of the gold element in the gold acetate to the iron element in the iron acetylacetonate is 3: 1;
thirdly, hydrothermal reaction: raising the temperature of the mixture to 280 ℃ at a heating rate of 5 ℃/min under the argon atmosphere, preserving the heat for 1h at the temperature of 280 ℃ under the argon atmosphere, cooling to room temperature to obtain a reaction product, adding 20mL of ethanol into the reaction product, performing centrifugal separation for 3min at a speed of 12000r/min, and removing supernatant to obtain a solid product;
fourthly, washing and dispersing: cleaning the solid product for 3 times by using a mixed solution of ethanol and n-hexane to obtain a washed product; dispersing the washed product in 50mL of n-hexane to obtain a dispersion liquid: the volume ratio of the ethanol to the n-hexane in the ethanol-n-hexane mixed solution is 1: 2;
fifthly, compounding: adding 8.5mg of carbon black into 10mL of dispersion liquid, carrying out ultrasonic mixing for 30min, carrying out centrifugal separation at the centrifugal speed of 12000r/min, removing supernatant liquid to obtain a composite solid product, placing the composite solid product into a vacuum drying oven, and drying for 24h at the temperature of 180 ℃ to obtain the gold-iron nano alloy catalyst.
The gold-iron nano-alloy catalyst prepared in example 1 was observed by using a high-resolution transmission electron microscope, as shown in fig. 1, fig. 1 is a high-resolution transmission electron microscope photograph of the gold-iron nano-alloy catalyst prepared in example 1, and it can be seen from fig. 1 that the lattice spacing of the gold-iron alloy nanoparticles having a darker color was 0.23nm and the gold-iron alloy nanoparticles were closely bonded to carbon black having a lattice spacing of 0.34nm, indicating that the gold-iron alloy nanoparticles and the carbon black substrate were bonded together by ultrasonic mixing and the particle size of the gold-iron alloy nanoparticles was about 5 nm.
FIG. 2 is a HAADF-STEM image of the gold-iron nano-alloy catalyst prepared in example 1, with the gold-iron alloy nano-particles appearing off-white and the carbon black and background black under the HAADF-STEM; performing Mapping surface scanning on the region A in FIG. 2, as shown in FIGS. 3-5, wherein FIG. 3 is a Mapping diagram of the Au element in the region A in FIG. 2, FIG. 4 is a Mapping diagram of the Fe element in the region A in FIG. 2, and FIG. 5 is a superimposed diagram of FIGS. 3 and 4; as can be seen from fig. 3 to 5, the element distribution diagram of the gold element and the element distribution diagram of the iron element are superimposed, and the graphic outlines thereof are completely overlapped, so that the gold element and the iron element are uniformly mixed in the selected area, and the gold-iron nano-alloy catalyst prepared in example 1 is an alloy with uniformly distributed elements of gold and iron.
The EDX of the au-fe nano alloy catalyst prepared in example 1 was subjected to energy spectrum analysis, as shown in fig. 6 and table 1, and fig. 6 is an EDX elemental analysis diagram of the au-fe nano alloy catalyst prepared in example 1, and it can be seen from fig. 6 and table 1 that the atomic ratio of au element to fe element is 1.02:0.33 and approximately 3:1, indicating that it is possible to perform experiments by controlling the element ratio of au-fe alloy according to the charge ratio.
TABLE 1
| Element(s) | Mass% | Atomic number% |
| Fe | 1.02 | 0.33 |
| Au | 11.18 | 1.02 |
Example 2: the present embodiment is different from embodiment 1 in that: and in the second step, the molar ratio of the gold element in the gold acetate to the iron element in the ferric acetylacetonate is 1: 1. The rest is the same as in example 1.
Example 3: the present embodiment is different from embodiment 1 in that: and in the second step, the molar ratio of the gold element in the gold acetate to the iron element in the ferric acetylacetonate is 1: 3. The rest is the same as in example 1.
Example 4: the present embodiment is different from embodiment 1 in that: and in the second step, the molar ratio of the gold element in the gold acetate to the iron element in the ferric acetylacetonate is 6: 1. The rest is the same as in example 1.
Example 5: the present embodiment is different from embodiment 1 in that: and in the second step, the molar ratio of the gold element in the gold acetate to the iron element in the ferric acetylacetonate is 9: 1. Otherwise the same as in example 1
X-ray diffraction analysis was performed on the gold-iron nano-alloy catalysts prepared in examples 1 to 3, and as shown in FIG. 7, FIG. 7 is an X-ray diffraction pattern in which a represents an X-ray diffraction pattern of the gold-iron nano-alloy catalyst prepared in example 1, b represents an X-ray diffraction pattern of the gold-iron nano-alloy catalyst prepared in example 2, c represents an X-ray diffraction pattern of the gold-iron nano-alloy catalyst prepared in example 3, pure Au represents a standard card of gold element, pure Fe represents a standard card of iron element, and Fe represents a standard card of iron element3O4Represents Fe3O4A standard card of the table; as can be seen from fig. 7, the four characteristic peaks of the gold-iron nano-alloy catalyst prepared in example 1 are respectively located at 38.144.3 degrees, 64.5 degrees and 77.6 degrees respectively correspond to the (111) plane, the (200) plane, the (220) plane and the (311) plane of the gold face-centered cubic lattice, and the characteristic peaks at 44.3 degrees and 64.5 degrees correspond to the (110) plane and the (200) plane of the iron body-centered cubic lattice, further illustrating that the invention successfully prepares the gold-iron nano alloy catalyst.
Fig. 8 is a transmission electron microscope image of the gold-iron nano-alloy catalyst prepared in example 1, fig. 9 is a transmission electron microscope image of the gold-iron nano-alloy catalyst prepared in example 2, fig. 10 is a transmission electron microscope image of the gold-iron nano-alloy catalyst prepared in example 3, and fig. 8-10 show that the gold-iron alloy nanoparticles having the same morphology and particle size as those of the gold-iron nano-alloy catalyst are successfully prepared by changing the charge ratio and are uniformly loaded on carbon black, thereby illustrating that the method is stable and reliable.
Example 6: application of gold-iron nano alloy catalyst as raw material for preparing working electrode for electrocatalytic reduction of CO2And (5) preparing CO.
The specific preparation method of the working electrode comprises the following steps: firstly, adding a Nafion solution into absolute ethyl alcohol, uniformly mixing, adding a gold-iron nano alloy catalyst, and performing ultrasonic oscillation for 45min to obtain an ink-like mixed solution; the gold-iron nano-alloy catalyst was prepared from example 1; polishing the glassy carbon electrode on chamois leather by using 500nm of aluminum oxide powder and 50nm of aluminum oxide powder in sequence until the mirror surface is smooth, ultrasonically cleaning the electrode for 3 times by using deionized water, ultrasonically cleaning the electrode for 3 times by using ethanol, and drying the electrode to obtain a clean glassy carbon electrode; thirdly, according to the loading amount of the gold-iron nano alloy catalyst, the loading amount is 0.05mg/cm2And transferring the ink-like mixed liquid onto the clean glassy carbon electrode for a plurality of times by using a liquid transfer gun, wherein the single transfer amount of the liquid transfer gun is 2-3 mu L, and after the second dripping, performing the next transferring and dripping after naturally drying the ink-like mixed liquid on the surface of the clean glassy carbon electrode to obtain the working electrode.
The electrocatalytic reduction of CO2The specific process for preparing CO is as follows:
firstly, assembling a reactor: an H-shaped three-electrode electrolytic cell is adopted, and a cathode cell and an anode of the H-shaped three-electrode electrolytic cell are respectively connected by a Nafion 117 proton ion exchange membraneSeparating the tanks by using KHCO with the concentration of 0.5mol/L3Pouring electrolyte into an H-shaped three-electrode electrolytic cell by taking an aqueous solution as the electrolyte until a channel between an anode pool and a cathode pool of the H-shaped three-electrode electrolytic cell is filled with the electrolyte, taking a platinum sheet as a counter electrode, placing the counter electrode in the anode pool of the H-shaped three-electrode electrolytic cell, placing a working electrode and a reference electrode in a cathode pool of the H-shaped three-electrode electrolytic cell, wherein the reference electrode is a saturated KCl Ag/AgCl electrode, arranging a cathode area air inlet and a cathode area air outlet in the cathode pool, and arranging CO and CO in the cathode pool2The air inlet pipe extends to the position below the liquid level of the electrolyte through the air inlet of the cathode area, the air outlet of the cathode area is communicated with the gas collecting device, 1 magnetic stirring rotor is placed in the cathode pool, the cathode pool is sealed by adopting a sealing piece, and the contact positions of the working electrode and the reference electrode with the sealing piece are sealed to obtain the electro-catalytic reduction CO2A CO production device;
secondly, electrocatalytic reduction: passing CO at a gas flow rate of 20mL/min2Introducing carbon dioxide gas into the electrolyte of the cathode pool through the gas inlet pipe, starting the power supply and the magnetic stirrer after the introduction time is 30min, wherein the rotating speed of the magnetic stirrer is 800r/min, and the carbon dioxide gas is introduced into CO2The gas flow is 1mL/min to 30mL/min, the magnetic stirring rotating speed is 800r/min, and the potential of the working electrode is-1.0V to-2.4V (vs Ag/AgCl)2The gas collecting device collects the gas generated by the reaction in the cathode pool through the gas outlet of the cathode area, namely the electrocatalytic reduction of CO is completed2And (5) preparing CO.
Example 7: the present embodiment is different from embodiment 6 in that: the gold-iron nano-alloy catalyst prepared in example 2 was used instead of the gold-iron nano-alloy catalyst prepared in example 1. The rest is the same as in example 6.
Example 8: the present embodiment is different from embodiment 6 in that: the gold-iron nano-alloy catalyst prepared in example 3 was used instead of the gold-iron nano-alloy catalyst prepared in example 1. The rest is the same as in example 6.
Example 9: the present embodiment is different from embodiment 6 in that: the gold-iron nano-alloy catalyst prepared in example 4 was used instead of the gold-iron nano-alloy catalyst prepared in example 1. The rest is the same as in example 6.
Example 10: the present embodiment is different from embodiment 6 in that: the gold-iron nano-alloy catalyst prepared in example 5 was used instead of the gold-iron nano-alloy catalyst prepared in example 1. The rest is the same as in example 6.
FIG. 11 catalytic reduction of CO2In the graph, a tangle-solidup represents the catalytic reduction of CO by the gold-iron nano alloy catalyst of the example 62T. T.X represents the Faraday efficiency plot of CO for the catalytic reduction of CO by the gold-iron nano-alloy catalyst of example 72As a graph of the Faraday efficiency of CO,. diamond-solid.) represents the catalytic reduction of CO by the gold-iron nano-alloy catalyst of example 82● shows the catalytic reduction of CO by the Au-Fe nanoalloy catalyst of example 8, which is a graph of the Faraday efficiency of CO2■ shows the catalytic reduction of CO by the Au-Fe nanoalloy catalyst of example 10, which is a graph showing the Faraday efficiency of CO2For the Faraday efficiency plot of CO, it can be seen from FIG. 11 that the gold-iron alloy nanocatalysts exhibit excellent reduced CO over the range of operating potentials2For the performance of CO, the performance of samples obtained from different feed ratios is different, and the gold-iron nano alloy catalyst prepared in example 1 is used as a raw material to prepare a working electrode for electrocatalytic reduction of CO2When CO is prepared, the Faraday efficiency is as high as 95 percent under-1.2V.
FIG. 12 catalytic reduction of CO2The current density diagram of CO is shown, in the diagram, a-solidup part represents the catalytic reduction CO of the gold-iron nano alloy catalyst of the embodiment 62Is a current density graph of CO, t.t. represents the catalytic reduction of CO by the gold-iron nano-alloy catalyst of example 72Current density plot of CO,. diamond-solid.) represents the catalytic reduction of CO by the gold-iron nanoalloy catalyst of example 82● shows the current density plot of CO for the catalytic reduction of CO by the Au-Fe nanoalloy catalyst of example 82■ shows the current density diagram of CO in the catalytic reduction of CO by the Au-Fe nanoalloy catalyst of example 102The current density diagram of CO shows that the gold-iron alloy nano-catalyst with different charge ratios realizes larger reduction of CO within the working potential range through the graph 122For the current density of CO, the gold prepared by the inventionThe iron nano-alloy catalyst has excellent CO production capacity.
Claims (10)
1. The preparation method of the gold-iron nano alloy catalyst is characterized by comprising the following steps of:
firstly, preparing a surfactant solution: adding a surfactant into a high-boiling-point organic solvent, and stirring until the surfactant is completely dissolved to obtain a surfactant solution; the volume ratio of the mass of the surfactant to the high-boiling-point organic solvent is (0.006-0.6) g (1-100) mL;
secondly, mixing: adding a gold salt compound, a ferric salt compound and a reducing agent into a surfactant solution, and stirring and uniformly mixing at the temperature of 30-80 ℃ in an argon atmosphere to obtain a mixture; the volume ratio of the mass of the gold salt compound to the volume of the surfactant solution is (0.0093-0.93) g, (1-100) mL; the volume ratio of the mass of the ferric salt compound to the surfactant solution is (0.0088-0.88) g (1-100) mL; the volume ratio of the mass of the reducing agent to the volume of the surfactant solution is (0.064-0.64) g (1-100) mL; the reducing agent is an alcohol compound;
thirdly, hydrothermal reaction: raising the temperature of the mixture to 250-290 ℃ under the argon atmosphere, preserving the heat for 0.5-3 h at the temperature of 250-290 ℃ under the argon atmosphere, cooling to room temperature to obtain a reaction product, adding ethanol into the reaction product, performing centrifugal separation, and removing supernatant to obtain a solid product; the volume ratio of the reaction product to the ethanol is 1: 1-3;
fourthly, washing and dispersing: cleaning the solid product for 2-5 times by using an ethanol-n-hexane mixed solution to obtain a washed product; dispersing the washed product in n-hexane to obtain a dispersion: the volume ratio of the mass of the washed product to the n-hexane is (0.0028-0.985) g, (5-500) mL;
fifthly, compounding: adding the nano carbon material into the dispersion liquid, ultrasonically mixing, then centrifugally separating, removing supernatant liquid to obtain a composite solid product, and drying the composite solid product in a vacuum drying oven to obtain a gold-iron nano alloy catalyst; the volume ratio of the mass of the nano carbon material to the dispersion liquid is (0.84-84) mg (1-100) mL.
2. The method for preparing a gold-iron nano alloy catalyst according to claim 1, wherein the surfactant in the first step is one or more of oleylamine, oleic acid or polyvinyl polypyrrolidone; the high-boiling-point organic solvent is octyl ether or octadecene.
3. The method for preparing a gold-iron nano alloy catalyst according to claim 1, wherein in the step one, the surfactant is added into the high boiling point organic solvent, and the mixture is stirred at a rotation speed of 300r/min to 800r/min for 10min to 20min to obtain a surfactant solution.
4. The method according to claim 1, wherein the gold salt compound in the second step is gold acetate or chloroauric acid tetrahydrate; the ferric salt compound is ferric acetylacetonate or ferric chloride; the alcohol compound is 1, 2-hexadecanediol, ethylene glycol or glycerol.
5. The method for preparing a gold-iron nano alloy catalyst according to claim 1, wherein in the second step, the mixture is stirred at a stirring speed of 500r/min to 1200r/min for 30min to 120min at a temperature of 30 ℃ to 80 ℃ under an argon atmosphere.
6. The method for preparing a gold-iron nano-alloy catalyst according to claim 1, wherein the temperature of the mixture is raised to 250 to 290 ℃ at a heating rate of 3 to 6 ℃/min under an argon atmosphere in the third step.
7. The method for preparing a gold-iron nano-alloy catalyst according to claim 6, characterized in that the centrifugal separation is performed at 8000 r/min-15000 r/min for 1 min-5 min in the third step, and the supernatant is removed to obtain a solid product.
8. The method for preparing a gold-iron nano alloy catalyst according to claim 1, wherein the volume ratio of ethanol to n-hexane in the ethanol-n-hexane mixed solution in the fourth step is 1: 2.
9. The method for preparing a gold-iron nano alloy catalyst according to claim 1, wherein the carbon nano material is added into the dispersion liquid in the fifth step, the ultrasonic mixing is performed for 20min to 40min, then the centrifugal separation is performed at a centrifugal speed of 8000r/min to 15000r/min, the supernatant is removed to obtain a composite solid product, and the composite solid product is placed in a vacuum drying oven and dried at a temperature of 150 ℃ to 200 ℃ for 8h to 24h to obtain the gold-iron nano alloy catalyst.
10. The application of the gold-iron nano alloy catalyst is characterized in that the gold-iron nano alloy catalyst is used as a raw material for preparing a working electrode for electro-catalytic reduction of CO2And (5) preparing CO.
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