CN112791739A - Preparation and application of carbon dioxide electrochemical reduction catalyst - Google Patents
Preparation and application of carbon dioxide electrochemical reduction catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 35
- 230000009467 reduction Effects 0.000 title claims abstract description 25
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 67
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 90
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 28
- 238000006722 reduction reaction Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229920000557 Nafion® Polymers 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- -1 transition metal salt Chemical class 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 7
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 7
- 238000005507 spraying Methods 0.000 claims description 7
- 238000010306 acid treatment Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 150000001805 chlorine compounds Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000003837 high-temperature calcination Methods 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 7
- 238000003763 carbonization Methods 0.000 abstract description 6
- 238000005470 impregnation Methods 0.000 abstract description 6
- 239000007791 liquid phase Substances 0.000 abstract description 6
- 239000002243 precursor Substances 0.000 abstract description 5
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 13
- 229910021607 Silver chloride Inorganic materials 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
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- 238000011161 development Methods 0.000 description 2
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- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- HZUJFPFEXQTAEL-UHFFFAOYSA-N azanylidynenickel Chemical compound [N].[Ni] HZUJFPFEXQTAEL-UHFFFAOYSA-N 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect 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
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002815 nickel Chemical group 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 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
- 238000003860 storage Methods 0.000 description 1
Images
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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/615—
-
- B01J35/643—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
-
- 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
Abstract
The invention relates to a preparation method and application of a carbon dioxide electrochemical reduction catalyst. The preparation method of the catalyst takes carbon spheres rich in microporous structures as precursors, the microporous structures are utilized to confine and adsorb transition metal ions to the pore structure of the carbon spheres through a liquid-phase impregnation process, and a nitrogen source is introduced into high-temperature calcination carbonization treatment at a later stage, so that the carbon spheres generate rich in microporous structures at high temperatureThe nitrogen sheet structure further anchors the transition metal monoatomic atom. Thereby preparing a high-dispersion and high-load monatomic catalyst. The preparation method of the catalyst provided by the invention is simple and easy to control, and has excellent CO2The Faraday efficiency, catalytic activity and stability of the CO prepared by electrochemical reduction are expected to realize large-scale commercial production.
Description
Technical Field
The invention belongs to the technical field of carbon dioxide electrochemical reduction, and particularly relates to a preparation method and application of a carbon dioxide electrochemical reduction monatomic catalyst.
Background
Currently, the economy and society of China are in a high-speed development stage, the demand for energy is increasing day by day, and then the problem of serious carbon dioxide emission is brought. According to the latest report of International Energy Agency (IEA), the worldwide CO was estimated in 20172The emission reaches 410 hundred million tons, which is increased by 2 percent compared with 2016. Therefore, how to reduce CO2Effective utilization of CO2Has become a hot spot of research in recent years.
CO2The transformation and utilization of (1) mainly include the following four types, i.e., chemical transformation, biochemical transformation, photochemical transformation and electrochemical transformation. With other CO2Compared with the conversion technology, the electrochemical reduction of CO2The (ERC) technology has the outstanding advantages that water can be used as a hydrogen source for reaction, and CO can be realized at normal temperature and normal pressure2The energy consumption caused by hydrogen production, heating and pressurization required by the chemical conversion technology is not needed.
Electrochemical reduction of CO2(ERC) technology is the use of electrical energy generated from renewable energy sources to convert CO2Reduction to chemicals to effect CO2A resource utilization technology. CO generation by electrochemical techniques2Directly with H2And O reacts to generate compounds with high added values, such as ethanol, methane, hydrocarbon compounds and the like, so that the conversion between electric energy and chemical energy is realized. Not only makes ERC technique more economic, but also can realize the storage of renewable energy sources and form a carbon and energy conversion cycle. Currently, ERC techniques are restrictedThe main factors of development include: (1) the reaction overpotential is high; (2) the conversion rate is low; (3) the product selectivity is poor. Therefore, the search for suitable catalysts to reduce reaction overpotentials, improve product selectivity and reactivity is the key to current research. At present, the research on the catalyst mainly focuses on noble metal catalysts such as gold and silver, and the like, although the catalysts have high selectivity and high price, the catalysts are not suitable for large-scale commercial production. However, the research on the non-metal catalyst is relatively less, and in recent years, the monoatomic metal-doped carbon-based material has attracted much attention, and the monoatomic catalyst has the following advantages: (1) the utilization rate of atoms is close to 100 percent, and (2) when the metal exists in the form of single atom, the metal has higher coordination unsaturation degree, and is favorable for adsorbing CO2And reaction intermediates are stabilized, so that the catalytic performance is higher. However, when a monatomic catalyst is synthesized by a general wet chemical method, there is a problem that metal atoms are agglomerated due to high-temperature calcination, thereby causing a great reduction in catalyst performance. Therefore, how to prepare the monatomic catalyst with high dispersion and high load becomes a problem which needs to be solved urgently at present.
Disclosure of Invention
Aiming at the problems, the prepared carbon sphere precursor rich in the microporous structure is subjected to liquid phase impregnation, the microporous structure is utilized to confine and adsorb transition metal ions into a pore structure of the carbon sphere precursor, a nitrogen source is introduced in the high-temperature calcination and carbonization treatment at the later stage, and a nitrogen-rich sheet structure is generated at high temperature to further anchor transition metal monoatomic atoms. Thereby preparing a high-dispersion and high-load monatomic catalyst. Preparing a transition metal monoatomic and nitrogen-doped porous hollow carbon sphere catalyst. The specific surface area of the carbon sphere precursor is as high as 300-500m2(ii) in terms of/g. The pore diameter is distributed about 0.5nm-1.5nm, the adsorbed transition metal ions (the diameter is about 0.15nm) are confined to the pore channel structure by utilizing the microporous structure in the liquid phase impregnation process, and a nitrogen source is introduced in the later high-temperature calcination carbonization treatment, and the nitrogen-rich lamellar structure is generated at high temperature to further anchor the transition metal atoms. Thereby preparing a high-dispersion and high-load monatomic catalyst. The single-atom nickel-doped carbon-based catalyst is prepared by simple liquid-phase impregnation and later-stage calcination carbonization treatment. Is realized inOver a wide potential range, not only the CO faradaic efficiency (97%) similar to that of noble metals, but also high catalytic activity. The method is simple, has good catalytic performance and is beneficial to large-scale commercial production.
The catalyst not only has high surface area (beneficial to exposing catalytic active sites), but also has monodispersed and high-loaded metal atoms, realizes wider potential range, has CO Faraday efficiency (97 percent) similar to that of noble metals, and has higher catalytic activity.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
the invention provides a preparation method of a single-atom carbon-based catalyst for electrochemical reduction of carbon dioxide, which comprises the following steps; firstly, preparing a carbon carrier, and then carrying out liquid phase impregnation and calcination treatment to obtain a transition metal and nitrogen co-doped carbon-based catalyst, wherein the method comprises the following steps:
1) adding tetraethoxysilane into ethanol, and stirring to obtain a solution A, wherein the volume ratio of tetraethoxysilane to ethanol in the solution A is 1-2: 30; adding ammonia water and water into ethanol, and stirring to obtain a solution B; the mass concentration of the ammonia water is 25-50%; in the solution B, ammonia: water: the volume ratio of the ethanol is 1-3:2-4: 8-12; mixing the solution A and the solution B, and stirring at 10-30 ℃ for 1-3h to obtain a solution C; pouring the solution C into a reaction kettle for hydrothermal treatment at 100-150 ℃, performing 12-24h, washing a product after the hydrothermal treatment, then performing drying treatment, calcining the dried sample, etching the calcined sample in a hydrofluoric acid solution for 24-48h, and performing drying treatment to obtain a hollow carbon sphere, wherein the concentration of the sample in the hydrofluoric acid solution is 40-80 g/l;
2) preparing a transition metal salt, a nitrogen source and the hollow carbon spheres into a solution D, stirring the solution D at 10-30 ℃ for 12-24h, evaporating the solvent in a water bath for 1-2 h, drying at 60-80 ℃ for 12-24h, calcining under an argon atmosphere, and then carrying out acid treatment to obtain the carbon-based catalyst; in the solution D, the concentrations of the hollow carbon spheres, the transition metal salt and the nitrogen source are respectively 5-10, 1-2.5 and 20-40 g/l.
Based on the technical scheme, the mass concentration of the hydrofluoric acid solution in the step 1) is preferably 20-40%.
Based on the technical scheme, preferably, the drying in the step 1) is freeze drying or drying at 70-90 ℃ for 12-24 h; the calcination in the step 1) is 600-800 ℃ argon calcination for 3-5 h.
Based on the technical scheme, preferably, the transition metal in the transition metal salt in the step 2) is nickel, iron and cobalt; the transition metal salt is chloride, sulfate or nitrate of the metal; the nitrogen source is melamine, thiourea or dicyanodiamine.
Based on the technical scheme, preferably, the calcination in the step 2) is 900-1000 ℃ argon calcination for 1-3h, the acid treatment temperature is 60-80 ℃, and the acid treatment time is 3-5 h: the acid is hydrochloric acid or sulfuric acid; the concentration of the acid is 2-4M.
The invention also provides a carbon-based catalyst for electrochemical reduction of carbon dioxide, which is prepared by the preparation method, wherein the carbon carrier is a hollow carbon sphere with a microporous structure on the surface; in the carbon-based catalyst, the transition metal is dispersed in the microporous structure in a monoatomic form.
The invention also provides an electrode for electrochemical reduction of carbon dioxide, which comprises the carbon-based catalyst.
The invention also provides a preparation method of the electrode, which comprises the following steps: adding the carbon-based catalyst and 5-10 wt% of Nafion solution into ethanol solution, performing ultrasonic treatment for 0.5-2h to form mixed solution, and spraying the mixed solution on the surface of carbon paper to obtain the electrode for electrochemical reduction of carbon dioxide; in the mixed solution, the content of the catalyst is 0.005-0.015 g/ml; the Nafion content is 50-100ul/ml, and the catalyst loading on the carbon paper is 1-3mg/cm2。
The invention also provides an application of the electrode, and the electrode is used as a cathode for carbon dioxide electrochemical reduction reaction
Advantageous effects
(1) The invention uses the carbon sphere carrier with the surface rich in microporous structure (0.5nm-1.5nm) and the interior of hollow structure, which can effectively limit the single transition metal atom (about 0.15nm) to the pore channel structure and reduce the agglomeration of the transition metal atom at high temperature. And the hollow structure can effectively play the role of ion buffering.
(2) And in the later stage, a nitrogen source is introduced in the high-temperature calcination carbonization treatment, and a nitrogen-rich sheet structure is generated at high temperature to further anchor the transition metal monoatomic atoms in the pore canal and reduce the agglomeration of the transition metal atoms at high temperature, so that the high-dispersion and high-load monoatomic catalyst is prepared, the wide potential range is realized, the CO Faraday efficiency (97%) similar to that of noble metals is realized, and the catalyst has high catalytic activity. Thereby increasing CO2The conversion efficiency of (a);
(3) the method takes carbon spheres rich in a microporous structure as a precursor, the microporous structure of the carbon spheres is utilized to confine and adsorb transition metal ions into a pore structure of the carbon spheres through a liquid phase impregnation process, a nitrogen source is introduced into high-temperature calcination carbonization treatment at the later stage, and a nitrogen-rich sheet structure is generated at high temperature to further anchor transition metal monoatomic atoms, so that a high-dispersion and high-load monoatomic catalyst is prepared;
(4) the preparation method is simple, the production equipment is conventional, and the method is suitable for large-scale production.
Drawings
Fig. 1 is an SEM image of an electrode prepared in comparative example 1 of the present invention.
FIG. 2 is SEM (a) and TEM (b) images of electrodes prepared in comparative example 2 of the present invention.
FIG. 3 shows SEM (a), TEM (b) and STEM (c) images of the electrodes prepared in example 1 of the present invention.
FIG. 4 is a graph showing electrochemical properties of an electrode prepared in example 1 of the present invention.
FIG. 5 is a diagram of the distribution of STEM (a), C (b), Ni (c), O (d) and N (e) elements of the product of example 1.
FIG. 6 is a graph of X-ray photoelectron spectroscopy analysis of the product of example 1 of the present invention.
FIG. 7 is a graph showing electrochemical properties of an electrode prepared in comparative example 1 of the present invention.
FIG. 8 is a graph showing electrochemical properties of an electrode prepared in comparative example 2 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.
The electrode thus produced was used as a cathode for carbon dioxide reduction. And electrochemical testing was performed by a three-electrode system:
the working electrode is the prepared electrode; the counter electrode is Pt wire, and the reference electrode is Ag/AgCl. The distance between WE and RE is 0.5cm, and a salt bridge is adopted to reduce the liquid junction potential. The electrolyte of cathode and anode is 0.5MKHCO3Sol, catholyte volume 160ml, anolyte volume 80 ml. CO 22The flow rate is controlled by a mass flow meter, and the flow rate is 25 ml/min.
Example 1
1) Mixing the solution A: 2.55ml of ethyl orthosilicate is added into 45ml of ethanol and stirred; and (3) mixing the solution B: 6ml of 25% ammonia water and 9ml of water are added to 30ml of ethanol and stirred. Adding the solution A into the solution B, and stirring for 1 h; pouring the solution B into a reaction kettle, carrying out hydrothermal treatment for 24 hours at 100 ℃, washing the hydrothermal product with distilled water for more than three times, then carrying out drying treatment for 8 hours at 70 ℃, carrying out high-temperature calcination for the dried sample with argon gas at 600 ℃ for 3 hours, and raising the temperature at the speed of 2 ℃/min. And 3g of calcined product is added into 40ml (20%) of hydrofluoric acid solution for etching for 24h, and finally the hollow carbon sphere carrier rich in the microporous structure is obtained.
2) Adding 0.1g of hollow carbon sphere carrier, 50mg of nickel chloride and 0.6g of melamine into 20ml of ethanol solution, stirring for 12h at 25 ℃, evaporating to dryness in a water bath at 80 ℃, and then drying for 12 h;
3) calcining the dried sample in argon at 1000 ℃ for 1h, raising the temperature at the speed of 2 ℃/min, and then treating the sample with 2M sulfuric acid at 80 ℃ for 5h to obtain a catalyst;
4) adding the prepared catalyst and 5 wt% Nafion solution into ethanol solution, ultrasonic treating for 0.5 hr to obtain ethanol solution with catalyst content of 20mg and Nafion content of 100ul, and spraying onto 12cm2And (3) carbon paper surface. And drying to obtain the electrode. The preparation method provided by the invention is simple/easy to control, and the prepared electrode has controllable structure and excellent CO2Electrochemical reductionSelectivity for producing CO. Such electrodes have excellent ERC stability. The prepared electrode is taken as a working electrode, the counter electrode is Pt wire, the reference electrode is Ag/AgCl, and the cathode and anode electrolyte is 0.5MKHCO3and aq, constant potential electrolysis is carried out at a potential of-0.4V to-1.0V. The faradaic efficiency of CO is more than 90% under-0.6-1.0V potential. The Faraday efficiency of CO reaches 97% at-0.8V, and the current density is 12mA/cm2. It can be seen from fig. 7 that the faraday efficiency is improved by 27% and the current density is improved by 6 times as compared with that of comparative example 1. The introduction of the monatomic Ni on the basis of N doping to form the N/Ni co-doped catalyst is illustrated, and the catalytic performance is greatly improved; it can be seen from fig. 8 that the faraday efficiency is improved by 7% and the current density is improved by 1.5 times as compared with comparative example 2. Table 1 shows a comparison of the nickel content in the catalysts of example 1 and comparative example 2 according to the invention (ICP test results). It can be seen from table 1 that the nickel loading of example 1 of the present invention is 2.5 times higher than that of comparative example 2, which shows that the loading and dispersion of monatomic nickel can be further improved by increasing the calcination temperature, thereby improving the catalytic selectivity and activity of the material. In comparative example 3, the catalyst is doped with nickel only, and lacks of the anchoring effect of nitrogen on metal atoms at high temperature, so that the metal is greatly agglomerated, and the catalytic performance is greatly reduced.
TABLE 1
| Comparison of experiments | Amount of Ni (ICP) |
| Comparative example 2 | 0.44％ |
| Example 1 | 1.03％ |
From the electron micrographs of fig. 3a and 3b, it can be seen that the catalyst is a hollow carbon sphere having a diameter of about 200nm, and in fig. 3c, it is seen that the nickel atom is supported on the carbon sphere support in a monoatomic form. The Faraday efficiency of the prepared electrode is as high as 97 percent as can be seen from figure 4; it can be seen from fig. 5c and 5e that nickel and nitrogen are uniformly distributed on the carbon spheres. From fig. 6, it is known that N and Ni are successfully incorporated into the carbon spheres.
Example 2
1) Mixing the solution A: 2.55ml of ethyl orthosilicate is added into 45ml of ethanol and stirred; and (3) mixing the solution B: 6ml of 25% ammonia water and 9ml of water are added to 30ml of ethanol and stirred. Adding the solution A into the solution B, and stirring for 1 h; pouring the solution B into a reaction kettle, carrying out hydrothermal treatment for 24 hours at 100 ℃, washing the hydrothermal product with distilled water for more than three times, then carrying out drying treatment for 8 hours at 70 ℃, carrying out high-temperature calcination for the dried sample with argon gas at 600 ℃ for 3 hours, and raising the temperature at the speed of 2 ℃/min. And 3g of calcined product is added into 40ml (20%) of hydrofluoric acid solution for etching for 24h, and finally the hollow carbon sphere carrier rich in the microporous structure is obtained.
2) Adding 0.1g of hollow carbon sphere carrier, 50mg of nickel chloride and 0.6g of melamine into 20ml of ethanol solution, stirring for 12h at 25 ℃, evaporating to dryness in a water bath at 80 ℃, and then drying for 12 h;
3) calcining the dried sample in argon at 900 ℃ for 1h, raising the temperature at the speed of 2 ℃/min, and then treating the sample with 2M sulfuric acid at 80 ℃ for 5h to obtain a catalyst;
4) adding the prepared catalyst and 5 wt% Nafion solution into ethanol solution, ultrasonic treating for 0.5 hr to obtain ethanol solution with catalyst content of 20mg and Nafion content of 100ul, and spraying onto 12cm2And (3) carbon paper surface. And drying to obtain the electrode. The preparation method provided by the invention is simple/easy to control, and the prepared electrode has controllable structure and excellent CO2Selectivity of electrochemical reduction to CO. Such electrodes have excellent ERC stability. The prepared electrode is taken as a working electrode, the counter electrode is Pt wire, the reference electrode is Ag/AgCl, and the cathode and anode electrolyte is 0.5MKHCO3and aq, the faradaic efficiency of CO is more than 90% under-0.6 to-1.0V potential of the obtained catalyst. The Faraday efficiency of CO reaches 95% at-0.8V, and the current density is 11mA/cm2. It is shown that the catalyst still achieves catalytic performances similar to those of example 1, with a suitable reduction in the temperature of calcination.
Example 3
1) Mixing the solution A: 2.55ml of ethyl orthosilicate is added into 45ml of ethanol and stirred; and (3) mixing the solution B: 6ml of 25% ammonia water and 9ml of water are added to 30ml of ethanol and stirred. Adding the solution A into the solution B, and stirring for 1 h; pouring the solution B into a reaction kettle, carrying out hydrothermal treatment for 24 hours at 100 ℃, washing the hydrothermal product with distilled water for more than three times, then carrying out drying treatment for 8 hours at 70 ℃, carrying out high-temperature calcination for the dried sample with argon gas at 600 ℃ for 3 hours, and raising the temperature at the speed of 2 ℃/min. And 3g of calcined product is added into 40ml (20%) of hydrofluoric acid solution for etching for 24h, and finally the hollow carbon sphere carrier rich in the microporous structure is obtained.
2) Adding 0.1g of hollow carbon sphere carrier, 25mg of nickel chloride and 0.6g of melamine into 20ml of ethanol solution, stirring for 12h at 25 ℃, evaporating to dryness in a water bath at 80 ℃, and then drying for 12 h;
3) calcining the dried sample in argon at 1000 ℃ for 1h, raising the temperature at the speed of 2 ℃/min, and then treating the sample with 2M sulfuric acid at 80 ℃ for 5h to obtain a catalyst;
4) adding the prepared catalyst and 5 wt% Nafion solution into ethanol solution, ultrasonic treating for 0.5 hr to obtain ethanol solution with catalyst content of 20mg and Nafion content of 100ul, and spraying onto 12cm2And (3) carbon paper surface. And drying to obtain the electrode. The preparation method provided by the invention is simple/easy to control, and the prepared electrode has controllable structure and excellent CO2Selectivity of electrochemical reduction to CO. Such electrodes have excellent ERC stability. The prepared electrode is taken as a working electrode, the counter electrode is Pt wire, the reference electrode is Ag/AgCl, and the cathode and anode electrolyte is 0.5MKHCO3and aq, the faradaic efficiency of CO is more than 90% under-0.6 to-1.0V potential of the obtained catalyst. The Faraday efficiency of CO reaches 97 percent at-0.8V, and the current density is 12mA/cm2. It is shown that the catalyst still achieves catalytic performance similar to that of example 1 by properly reducing the addition amount of the metal salt.
Comparative example 1
1. Nitrogen-doped porous carbon spheres
1) Mixing the solution A: 2.55ml of ethyl orthosilicate is added into 45ml of ethanol and stirred; and (3) mixing the solution B: 6ml of 25% ammonia water and 9ml of water are added to 30ml of ethanol and stirred. Adding the solution A into the solution B, and stirring for 1 h; pouring the solution B into a reaction kettle, carrying out hydrothermal treatment for 24 hours at 100 ℃, washing the hydrothermal product with distilled water for more than three times, then carrying out drying treatment for 8 hours at 70 ℃, carrying out high-temperature calcination for the dried sample with argon gas at 600 ℃ for 3 hours, and raising the temperature at the speed of 2 ℃/min. And 3g of calcined product is added into 40ml (20%) of hydrofluoric acid solution for etching for 24h, and finally the hollow carbon sphere carrier rich in the microporous structure is obtained.
2) Adding 0.1g of hollow carbon sphere carrier and 0.6g of melamine into 20ml of ethanol solution, stirring for 12h at 25 ℃, evaporating to dryness at 80 ℃ in a water bath, and then drying for 12 h;
3) calcining the dried sample in argon at 1000 ℃ for 1h, and heating at the speed of 2 ℃/min to obtain a catalyst;
4) adding the prepared catalyst and 5 wt% Nafion solution into ethanol solution, performing ultrasonic treatment for 0.5 hr to obtain catalyst content of 20mg and Nafion content of 100ul/ml, and spraying onto 12cm2And (3) carbon paper surface. Drying to obtain the electrode. The counter electrode is Pt wire, and the reference electrode is Ag/AgCl. The distance between WE and RE is 0.5cm, and a salt bridge is adopted to reduce the liquid junction potential. The electrolyte of the cathode and the anode is 0.5M KHCO3Sol, catholyte volume 160ml, anolyte volume 80 ml. CO 22The flow rate is controlled by a mass flow meter, and the flow rate is 25 ml/min. At a potential of-0.8V, CO2The reduction was carried out in the presence of 40% of CO Faraday efficiency and 2mA/cm of current density2。
As can be seen from the electron micrograph of FIG. 1, the catalyst is a hollow carbon sphere having a diameter of about 200 nm.
Comparative example 2
1. Preparation of nickel-nitrogen co-doped carbon spheres
1) Mixing the solution A: 2.55ml of ethyl orthosilicate is added into 45ml of ethanol and stirred; and (3) mixing the solution B: 6ml of 25% ammonia water and 9ml of water are added to 30ml of ethanol and stirred. Adding the solution A into the solution B, and stirring for 1 h; pouring the solution B into a reaction kettle, carrying out hydrothermal treatment for 24 hours at 100 ℃, washing the hydrothermal product with distilled water for more than three times, then carrying out drying treatment for 8 hours at 70 ℃, carrying out high-temperature calcination for the dried sample with argon gas at 600 ℃ for 3 hours, and raising the temperature at the speed of 2 ℃/min. And 3g of calcined product is added into 40ml (20%) of hydrofluoric acid solution for etching for 24h, and finally the hollow carbon sphere carrier rich in the microporous structure is obtained.
2) Adding 0.1g of hollow carbon sphere carrier, 50mg of nickel chloride and 0.6g of melamine into 20ml of ethanol solution, stirring for 12h at 25 ℃, evaporating to dryness in a water bath at 80 ℃, and then drying for 12 h;
3) calcining the dried sample in argon at 800 ℃ for 1h, raising the temperature at the speed of 2 ℃/min, and then treating the sample with 2M sulfuric acid at 80 ℃ for 5h to obtain a catalyst;
4) adding the prepared catalyst and 5 wt% Nafion solution into ethanol solution, performing ultrasonic treatment for 0.5 hr to obtain catalyst content of 20mg and Nafion content of 100ul/ml, and spraying onto 12cm2And (3) carbon paper surface. And drying to obtain the electrode. The counter electrode is Pt wire, and the reference electrode is Ag/AgCl. The distance between WE and RE is 0.5cm, and a salt bridge is adopted to reduce the liquid junction potential. The electrolyte of the cathode and the anode is 0.5M KHCO3Sol, catholyte volume 160ml, anolyte volume 80 ml. CO 22The flow rate is controlled by a mass flow meter, and the flow rate is 25 ml/min. At a potential of-0.8V, CO2The Faraday efficiency of the reduction to CO is 90 percent, and the current density is 8mA/cm2。
Comparative example 3
1. Nickel-doped porous carbon spheres
1) Mixing the solution A: 2.55ml of ethyl orthosilicate is added into 45ml of ethanol and stirred; and (3) mixing the solution B: 6ml of 25% ammonia water and 9ml of water are added to 30ml of ethanol and stirred. Adding the solution A into the solution B, and stirring for 1 h; pouring the solution B into a reaction kettle, carrying out hydrothermal treatment for 24 hours at 100 ℃, washing the hydrothermal product with distilled water for more than three times, then carrying out drying treatment for 8 hours at 70 ℃, carrying out high-temperature calcination for the dried sample with argon gas at 600 ℃ for 3 hours, and raising the temperature at the speed of 2 ℃/min. And 3g of calcined product is added into 40ml (20%) of hydrofluoric acid solution for etching for 24h, and finally the hollow carbon sphere carrier rich in the microporous structure is obtained.
2) Adding 0.1g of hollow carbon sphere carrier and 50mg of nickel chloride into 20ml of ethanol solution, stirring for 12h at 25 ℃, evaporating to dryness in a water bath at 80 ℃, and then drying for 12 h;
3) calcining the dried sample in argon at 1000 ℃ for 1h, raising the temperature at the speed of 2 ℃/min, and then treating the sample with 2M sulfuric acid at 80 ℃ for 5h to obtain a catalyst;
4) the prepared catalyst and 5 wt% Nafion solution were added to an ethanol solution with a catalyst content of 20mg and a Nafion content of 100ul/ml, sonicated for 0.5h, and then sprayed onto a 12cm2 carbon paper surface. Drying to obtain the electrode. The counter electrode is Pt wire, and the reference electrode is Ag/AgCl. The distance between WE and RE is 0.5cm, and a salt bridge is adopted to reduce the liquid junction potential. The electrolyte of the cathode and the anode is 0.5M KHCO3Sol, catholyte volume 160ml, anolyte volume 80 ml. CO 22The flow rate is controlled by a mass flow meter, and the flow rate is 25 ml/min. At a potential of-0.8V, CO2The reduction is that the Faraday efficiency of CO is 50 percent and the current density is 5mA/cm2。
Claims (10)
1. A preparation method of a carbon-based catalyst for electrochemical reduction of carbon dioxide is characterized by comprising the following steps:
1) adding tetraethoxysilane into ethanol, and stirring to obtain a solution A, wherein the volume ratio of tetraethoxysilane to ethanol in the solution A is 1-2: 30; adding ammonia water and water into ethanol, and stirring to obtain a solution B; the mass concentration of the ammonia water is 25-50%; in the solution B, the volume ratio of ammonia water to ethanol is 1-3:2-4: 8-12; mixing the solution A and the solution B, and stirring at 10-30 ℃ for 1-3h to obtain a solution C; pouring the solution C into a reaction kettle for hydrothermal treatment at 100-150 ℃, performing 12-24h, washing a product after the hydrothermal treatment, then performing drying treatment, calcining the dried sample, etching the calcined sample in a hydrofluoric acid solution for 24-48h, and performing drying treatment to obtain a hollow carbon sphere, wherein the concentration of the sample in the hydrofluoric acid solution is 40-80 g/l;
2) preparing a transition metal salt, a nitrogen source and the hollow carbon spheres into a solution D, stirring the solution D at 10-30 ℃ for 12-24h, evaporating the solvent in a water bath for 1-2 h, drying at 60-80 ℃ for 12-24h, calcining under an argon atmosphere, and then carrying out acid treatment to obtain the carbon-based catalyst; in the solution D, the concentrations of the hollow carbon spheres, the transition metal salt and the nitrogen source are respectively 5-10g/l, 1-2.5g/l and 20-40 g/l; the solvent of the solution D is water or alcohol.
2. The method according to claim 1, wherein the hydrofluoric acid solution of step 1) has a mass concentration of 20 to 40%.
3. The method of claim 1, wherein: the drying in the step 1) is freeze drying or drying at 70-90 ℃ for 12-24 h; the calcination in the step 1) is 600-800 ℃ argon calcination for 3-5 h.
4. The method of claim 1, wherein: transition metals in the transition metal salt in the step 2) are nickel, iron and cobalt; the transition metal salt is chloride, sulfate or nitrate of the metal; the nitrogen source is melamine, thiourea or dicyanodiamine.
5. The method of claim 1, wherein: the calcination in the step 2) is 900-1000 ℃ argon calcination for 1-3h, the acid treatment temperature is 60-80 ℃, and the acid treatment time is 3-5 h: the acid is hydrochloric acid or sulfuric acid; the concentration of the acid is 2-4M.
6. The method according to claim 1, wherein the alcohol in step 2) is ethanol.
7. The carbon-based catalyst for electrochemical reduction of carbon dioxide obtained by the preparation method of any one of claims 1 to 6, wherein the carbon support is a hollow carbon sphere having a microporous structure on the surface; in the carbon-based catalyst, the transition metal is dispersed in the microporous structure in a monoatomic form.
8. An electrode for electrochemical reduction of carbon dioxide, comprising the carbon-based catalyst for electrochemical reduction of carbon dioxide according to claim 6.
9. An apparatus as claimed in claim 8A method of making a pole, comprising the steps of: adding the carbon-based catalyst and 5-10 wt% of Nafion solution into ethanol solution, performing ultrasonic treatment for 0.5-2h to form mixed solution, and spraying the mixed solution on the surface of carbon paper to obtain the electrode for electrochemical reduction of carbon dioxide; in the mixed solution, the content of the catalyst is 0.005-0.015 g/ml; the Nafion content is 50-100ul/ml, and the catalyst loading on the carbon paper is 1-3mg/cm2。
10. Use of an electrode according to claim 8, wherein: the electrode serves as a cathode for the electrochemical reduction reaction of carbon dioxide.
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