CN111229227A - Cobalt catalyst and preparation and application thereof - Google Patents
Cobalt catalyst and preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 35
- 239000010941 cobalt Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 230000003197 catalytic effect Effects 0.000 claims abstract description 18
- 238000009792 diffusion process Methods 0.000 claims abstract description 16
- 239000013114 Co-MOF-74 Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims abstract 2
- 239000000463 material Substances 0.000 claims description 25
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- 239000011259 mixed solution Substances 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 229910001868 water Inorganic materials 0.000 claims description 13
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 150000003863 ammonium salts Chemical class 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000000243 solution Substances 0.000 claims description 7
- 229920000557 Nafion® Polymers 0.000 claims description 6
- 150000001868 cobalt Chemical class 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003575 carbonaceous material Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 239000007769 metal material Substances 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 238000005457 optimization Methods 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 150000003460 sulfonic acids Chemical class 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000005695 Ammonium acetate Substances 0.000 claims description 2
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229940043376 ammonium acetate Drugs 0.000 claims description 2
- 235000019257 ammonium acetate Nutrition 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 14
- 239000001569 carbon dioxide Substances 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010170 biological method Methods 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- 229910020676 Co—N Inorganic materials 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000013460 polyoxometalate Substances 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/33—
-
- 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
Abstract
The invention relates to a preparation method and application of a cobalt catalyst. The cobalt catalyst is mainly applied to carbon dioxide electroreduction. The preparation method comprises the following steps: firstly, synthesizing Co-MOF-74 by a hydrothermal method; then obtaining a cobalt catalyst by a high-temperature carbonization method; finally, some particles are disposed of with acid. The cobalt catalyst prepared by the method has a structure mainly of a metal-nitrogen coordination structure, and is applied to a gas diffusion electrode of a carbon dioxide electrochemical reduction catalyst. The invention obviously improves the CO pair of the catalyst2The activity of electric reduction improves the catalytic stability, effectively inhibits the hydrogen evolution reaction and enhances the selectivity of the product CO.
Description
Technical Field
The invention relates to a preparation method and application of a metal catalyst, in particular to preparation and application of a cobalt metal related catalyst, and belongs to the field of electrochemistry.
Background
CO2Emission reduction is a major environmental problem to be solved urgently all over the world. Introducing CO2The conversion into useful chemicals not only can solve the environmental problem, but also can utilize abundant carbon resources of the chemicals to deeply affect the social energy structure. Current CO2The conversion method mainly focuses on a biological catalysis method and a photocatalysis methodMethods, high temperature high pressure catalytic hydrogenation and electrocatalysis methods. Wherein, the biological method has longer production period and is difficult to limit the application of the biological method on a large scale; the photocatalysis method mainly has the defects of unsatisfactory light energy utilization and CO2Low conversion rate and the like; the catalyst for high-temperature and high-pressure catalytic hydrogenation is easy to be poisoned at high temperature and high pressure, and the water generated in the reaction is easy to have negative influence on the reaction. Electrocatalysis methods are getting more and more attention from people because of their easy operation, controllable conversion, mild reaction conditions and large-scale production.
Carbon monoxide is an industrially useful raw material mainly for fischer-tropsch synthesis, but its production requires high-temperature methane reforming, is difficult to effectively dock with further fischer-tropsch synthesis, and causes huge energy loss. Electrochemical CO2The problem can be effectively solved by converting carbon monoxide, which is the most concerned CO at present2The catalysts for the electroreductive conversion to CO are gold, silver and related alloys. CN104846393A can generate nearly 90% of CO by using an Ag-containing electrode, but an ionic liquid needs to be added, so that the pollution is larger; CN104032324A takes polyoxometalate as catalyst, the catalyst preparation is difficult, and the product is complex. The whole catalyst has the problems of low activity, poor stability, high price and the like, so that the catalyst is difficult to apply to industrial production. In order to solve the above problems, it is necessary to develop a novel non-noble metal catalyst having high activity and stability. MOF compounds are structurally controllable and simple to synthesize, but their application is limited due to their relatively poor electrical conductivity. In recent years, researchers have found that carbonization can preserve the controlled structure and increase the conductivity of the structure. For this purpose, the invention is based on Co-MOF-74, introduces a carbon source and a nitrogen source, and can generate suitable CO after carbonization2Reacted Co-N structure. The catalyst can not only effectively inhibit hydrogen evolution reaction, but also effectively generate CO.
In addition to the catalyst, CO2The working electrode for electroreduction is another important factor affecting the reaction. Gas diffusion electrode (GDL) not only can increase CO2Electrochemical reduction current can also increase reaction selectivity. GDL can not only convert CO into reaction raw material2Effectively transferred to the surface of the catalyst, and can quickly diffuse the generated CO out of the electrode, increase the reaction rate and inhibit the hydrogen evolution reaction. Through optimization, the catalyst can efficiently and selectively reduce CO2CO is formed, and the Faraday efficiency is over 75 percent.
Disclosure of Invention
The purpose of the invention is to aim at CO2The cobalt catalyst prepared by the method is used as a gas diffusion electrode, can efficiently convert carbon dioxide into carbon monoxide, and is simple to prepare and low in cost.
The invention relates to an electroreduction method for CO2Catalytic material of said CO2The catalytic material is a cobalt catalytic material, and the preparation method of the catalyst is as follows:
1) dissolving 2, 5-dihydroxyterephthalic acid and cobalt salt into DMF, ethanol and H in a ratio of 1:1:12O in a mixed solution;
2) then placing the mixed solution in a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction in an oven, and washing and drying the obtained solid to obtain Co-MOF-74;
3) then mixing Co-MOF-74, carbon powder and ammonium salt and carbonizing at high temperature under the inert atmosphere of 800-;
4) and finally, placing the obtained crude cobalt catalyst under an acidic condition at a certain temperature for optimization.
Wherein the cobalt salt is cobalt nitrate, cobalt acetate, cobalt sulfate or cobalt hydrochloride; the ammonium salt is ammonium nitrate, ammonium chloride, ammonium sulfate or ammonium acetate; the Co-MOF-74: the mass ratio of the carbon powder is 1:1-1: 10; the mass ratio of the Co-MOF-74 to the ammonium salt is 1:1-1: 10.
Wherein the hydrothermal reaction temperature of the material is 80-200 ℃, and the hydrothermal reaction time is 1-48 h.
Particularly, the carbonization time of the material is 10min-10 h; the inert atmosphere is Ar gas, He gas or N2And (4) qi.
In particular, the optimized temperature is 50-100 ℃; the optimization time is 10min-10 h; the optimized acid is HCl and HNO3、H2SO4Or HClO4。
The invention relates to electro-reduction of CO2Use of catalytic materials for CO2Gas diffusion electrode for electroreduction of catalytic material, wherein the gas diffusion electrode is loaded with a metal/carbon material CO2Electro-reduction catalytic material, gas diffusion electrode size of 0.5 cm-10 cm, supported CO2The weight of the electro-reduction catalytic material is 0.1-10 mg/cm2(ii) a Wherein the gas diffusion electrode is carbon paper, carbon felt, carbon cloth or carbon fiber.
The CO is2The preparation method of the gas diffusion electrode of the electro-reduction catalytic material comprises the following steps: dispersing a metal/carbon material into a mixed solution of isopropanol and water, adding 1-10 wt% of perfluorinated sulfonic acid resin Nafion solution, stirring to obtain a mixed solution, coating the mixed solution on a gas diffusion electrode, and drying.
Isopropanol in the mixed solution of isopropanol and water: the water is 1:5-5: 1.
The ratio of the metal/carbon material to the mixed solution of isopropanol and water is 0.5-20 mg:1 mL.
The ratio of the 1-10 wt% perfluorinated sulfonic acid resin Nafion solution to the mixed solution of isopropanol and water is 1:100-1: 10.
The drying is vacuum drying at 60-120 ℃.
The cobalt catalyst prepared by the invention is used for electro-reduction of carbon dioxide and conversion of greenhouse gas carbon dioxide into synthesis gas CO and H2And the content of carbon dioxide in the atmosphere can be effectively reduced by utilizing the cyclic utilization of resources, and the environment is optimized. Meanwhile, the catalytic material has low cost, simple synthesis and remarkable catalytic effect, so that the catalyst can be applied to industrial production.
The cobalt catalyst prepared by the method has a structure mainly of a metal-nitrogen coordination structure, and is applied to a gas diffusion electrode of a carbon dioxide electrochemical reduction catalyst. The invention obviously improves the CO pair of the catalyst2The activity of electric reduction improves the catalytic stability, effectively inhibits the hydrogen evolution reaction and enhances the selectivity of the product CO.
Drawings
FIG. 1 is a SEM image of the structural characterization of the material of example 4.
Figure 2 is a structural characterization graph X-ray diffraction XRD of the material in example 4.
FIG. 3 represents the KHCO contents of the materials of example 4 respectively3One of the performance maps in the electrolyte
FIG. 4 represents the KHCO of the material of example 43A second performance diagram in the electrolyte.
Wherein Carbon represents the synthetic raw material Carbon powder mentioned in example 2, Co-MOF-74 represents the synthetic product in example 1, Co-C represents the material synthesized without adding ammonium nitrate in example 2, and Co-N-C represents the synthetic material in example 4), and the used instrument is an electrochemical workstation manufactured by Shanghai Chenghua company and having a model number of CHI660 e. Test conditions, the performances referred to in FIGS. 3 and 4 were tested in an H-cell, with an electrolyte of 0.5M KHCO3The working electrode is the gas diffusion electrode prepared in the invention, the counter electrode is a platinum sheet electrode, and the reference electrode is a saturated calomel electrode.
Fig. 5 is a schematic structural view of a material.
Detailed Description
For better understanding of the present invention, the technical solutions of the present invention are described in detail below with reference to examples, but it should be understood that the examples do not limit the scope of the present invention.
Example 1
Preparation of Co-MOF-74
1) 2, 5-Dihydroxyterephthalic acid (0.2216g, 1.12mmol) and cobalt nitrate (1.077g, 3.70mmol) were dissolved in 1:1:1 DMF, ethanol, H2O in 75mL of mixed solution;
2) stirring for 1h at room temperature to fully dissolve and mix the mixture;
3) transferring the mixed solution into a stainless steel reaction kettle with a 100mL polytetrafluoroethylene lining, and heating for 24h at 120 ℃;
4) and after the reaction is finished, the solid generated in the reaction is centrifuged, washed by DMF and dried in vacuum to obtain Co-MOF-74.
Example 2
Preparation of cobalt catalyst precursor
Taking 0.5g of Co-MOF-74, 3g of carbon powder and 3g of ammonium nitrate in example 1, putting the mixture into a ball milling tank, then carrying out ball milling on the mixture in a ball mill at the ball milling rotation speed of 100rpm/min for 2h, and fully mixing to obtain a catalyst precursor.
Example 3
Preparation of cobalt catalyst
And (2) transferring the precursor in the embodiment 2 into a zirconium oxide boat, then placing the zirconium oxide boat in a tube furnace, introducing Ar gas at the flow rate of 25mL/min, heating to 150 ℃ at the speed of 3 ℃/min and keeping for 1h, then heating to 900 ℃ at the speed of 1.5 ℃/min and keeping for 1h, finally naturally cooling, and taking out to obtain the crude cobalt catalyst.
Example 4
The crude cobalt catalyst obtained in example 3 was placed in 100mL of 1M HCl, stirred in an oil bath at 80 ℃ for 24h, filtered, washed with deionized water, vacuum dried, finally placed in a zirconia boat, heated to 800 ℃ at 3 ℃/min in a tube furnace, held for 1h, and naturally cooled to obtain the optimized cobalt catalyst.
Example 5
Dispersing the cobalt catalyst 10mg in the example 4 in the mixed solution of 480. mu.L of ultrapure water and 480. mu.L of isopropanol, adding 40. mu.L of 5 wt% Nafion solution, ultrasonically mixing, taking 120. mu.L of the obtained mixed solution, coating the mixed solution on carbon paper, and drying in vacuum at 60 ℃ for 2h to obtain the load electro-reduction CO2Carbon paper of catalytic material, wherein the carbon paper has a size of 1cm x 1cm and is loaded with electro-reduced CO2The weight of the catalytic material is 1mg, and the electro-reduction CO is prepared2A catalytic electrode.
Example 6
Dispersing the cobalt catalyst 10mg in the example 4 in the mixed solution of 480. mu.L of ultrapure water and 480. mu.L of isopropanol, adding 40. mu.L of 5 wt% Nafion solution, ultrasonically mixing, taking 120. mu.L of the obtained mixed solution, coating the mixed solution on carbon cloth, and drying in vacuum at 60 ℃ for 2h to obtain the load electro-reduction CO2Carbon cloth of catalytic material, wherein the size of the carbon cloth is 1cm x 1cm, and electro-reduction CO is loaded on the carbon cloth2The weight of the catalytic material is 1mg, and the electro-reduction CO is prepared2A catalytic electrode.
Claims (10)
1. A preparation method of a cobalt catalyst is characterized by comprising the following steps:
1) dissolving 2, 5-dihydroxyterephthalic acid and cobalt salt in DMF, ethanol and H2O, and the volume ratio of DMF: ethanol is 1:3-3:1, DMF: h2O is 1:3-3: 1;
2) then placing the mixed solution in a polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction in an oven, and washing and drying the obtained solid to obtain Co-MOF-74;
3) then mixing Co-MOF-74, carbon powder and ammonium salt and carbonizing at high temperature under the inert atmosphere of 800-;
4) and finally, washing the obtained crude cobalt catalyst under an acid condition, and carbonizing the crude cobalt catalyst for 10min-10h at the high temperature of 700-900 ℃ in an inert atmosphere to obtain the cobalt catalyst.
2. The method for preparing a cobalt catalyst according to claim 1, wherein: the cobalt salt is one or more of cobalt nitrate, cobalt acetate, cobalt sulfate or cobalt hydrochloride; the ammonium salt is one or more of ammonium nitrate, ammonium chloride, ammonium sulfate and ammonium acetate;
the mass ratio of the 2, 5-dihydroxyterephthalic acid to the cobalt salt is 1:4-4:1 (preferably 2:1) Co-MOF-74: the mass ratio of the carbon powder is 1:1-1:10 (preferably 1: 5); the mass ratio of the Co-MOF-74 to the ammonium salt is 1:1-1:10 (preferably 1: 5).
3. The cobalt catalyst of claim 1, wherein: the hydrothermal reaction temperature of the material is 80-200 ℃ (preferably 120 ℃), and the hydrothermal reaction time is 1-48 h.
4. The cobalt catalyst of claim 1, wherein: the carbonization time of the material is 10min-10 h; the inert atmosphere is Ar gas, He gas or N2One or more of the following gases.
5. Cobalt catalyst according to claim 1An agent characterized by: the optimized temperature is 50-100 ℃ (preferably 80 ℃); the optimization time is 10min-10h (preferably 5 h); the optimized acid is HCl and HNO3、H2SO4Or HClO4And the molar concentration is 0.5M-5M.
6. A method for preparing a cobalt catalyst according to any one of claims 1 to 5, characterized in that: firstly, 2, 5-dihydroxy terephthalic acid and cobalt salt are dissolved in DMF, ethanol and H2Performing hydrothermal synthesis on Co-MOF-74 in the mixed solution consisting of O; then mixing the cobalt powder with carbon powder and ammonium salt and carrying out high-temperature carbonization to obtain a crude cobalt catalyst; finally, some particles are removed by acid treatment to optimize and obtain the cobalt catalyst.
7. A cobalt catalyst prepared by the preparation method of claims 1-6.
8. Use of a cobalt catalyst according to claim 7, wherein: the material can be used for electroreduction of CO2In the catalytic reaction of (1).
9. Use according to claim 8, characterized in that: application to electroreduction of CO2Loaded with CO for catalytic reactions2The gas diffusion electrode of the electro-reduction catalytic material is characterized in that a cobalt catalyst is loaded on the gas diffusion electrode, and the loaded weight is 0.1-10 mg/cm2(ii) a Wherein the gas diffusion electrode is carbon paper, carbon felt, carbon cloth or carbon fiber.
10. Use according to claim 9, characterized in that: the preparation method of the gas diffusion electrode of the cobalt catalyst comprises the following steps: dispersing a cobalt catalyst into a mixed solution of isopropanol and water, adding 1-10 wt% of perfluorinated sulfonic acid resin Nafion solution, stirring to obtain a mixed solution, coating the mixed solution on a gas diffusion electrode, and drying;
isopropanol in the mixed solution of isopropanol and water: the volume ratio of water is 1:5-5: 1;
the ratio of the metal/carbon material to the mixed solution of isopropanol and water is 1 mg-20 mg:1 mL;
the volume ratio of the 1-10 wt% perfluorinated sulfonic acid resin Nafion solution to the mixed solution of isopropanol and water is 1:100-1: 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811449044.7A CN111229227A (en) | 2018-11-29 | 2018-11-29 | Cobalt catalyst and preparation and application thereof |
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