CN111659394A - Copper-based catalyst and preparation method and application thereof - Google Patents
Copper-based catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 79
- 239000010949 copper Substances 0.000 title claims abstract description 47
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 15
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 150000001879 copper Chemical class 0.000 claims description 17
- 239000013110 organic ligand Substances 0.000 claims description 13
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000011593 sulfur Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 8
- 239000002041 carbon nanotube Substances 0.000 claims description 7
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 7
- 150000001450 anions Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 125000000129 anionic group Chemical group 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000004964 aerogel Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- -1 sulfide anion Chemical class 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 2
- IINNWAYUJNWZRM-UHFFFAOYSA-L erythrosin B Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(I)C(=O)C(I)=C2OC2=C(I)C([O-])=C(I)C=C21 IINNWAYUJNWZRM-UHFFFAOYSA-L 0.000 claims description 2
- 229940011411 erythrosine Drugs 0.000 claims description 2
- 235000012732 erythrosine Nutrition 0.000 claims description 2
- 239000004174 erythrosine Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 229930182817 methionine Natural products 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 12
- 238000005868 electrolysis reaction Methods 0.000 abstract description 10
- 239000002131 composite material Substances 0.000 abstract description 5
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 abstract description 3
- 230000003313 weakening effect Effects 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000008569 process Effects 0.000 description 12
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 10
- 235000019253 formic acid Nutrition 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000002048 multi walled nanotube Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- QIVBCDIJIAJPQS-VIFPVBQESA-N L-tryptophane Chemical compound C1=CC=C2C(C[C@H](N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-VIFPVBQESA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QIVBCDIJIAJPQS-UHFFFAOYSA-N Tryptophan Natural products C1=CC=C2C(CC(N)C(O)=O)=CNC2=C1 QIVBCDIJIAJPQS-UHFFFAOYSA-N 0.000 description 2
- CMPNPRUFRJFQIB-UHFFFAOYSA-N [N].[Cu] Chemical compound [N].[Cu] CMPNPRUFRJFQIB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000010813 internal standard method Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- NSBIQPJIWUJBBX-UHFFFAOYSA-N n-methoxyaniline Chemical compound CONC1=CC=CC=C1 NSBIQPJIWUJBBX-UHFFFAOYSA-N 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Images
Classifications
-
- B01J35/615—
-
- 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
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
-
- 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
- B01J23/72—Copper
-
- B01J35/33—
Abstract
The invention relates to the technical field of electrocatalysis, and discloses a copper-based catalyst, and a preparation method and application thereof. Forming an organic copper composite porous carrier, calcining to generate a copper-sulfur hybrid, oxidizing at low temperature to introduce an oxide layer, and finally reconstructing by utilizing an electroreduction induced morphology to generate a needle-shaped copper-based composite catalyst, wherein the specific surface area of the catalyst is 300-400 m2The catalyst has high catalytic activity and excellent electrocatalytic stability when being applied to electrocatalytic reduction of carbon dioxide, the electrolysis time reaches 20 hours, and the electrocatalytic performance is highWithout weakening.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a copper-based catalyst and a preparation method and application thereof.
Background
In accordance with the current trend, 2100 is expectedCO in the annual atmosphere2Concentrations will approach 600ppm and global warming is closely related to increased levels of carbon dioxide in the atmosphere. Therefore, the problem of reducing carbon dioxide emissions has attracted considerable attention. Electrochemical reduction of carbon dioxide is a process for the reduction of CO2The greenhouse gas is converted into valuable chemical substances, and CO is electrically reduced2The conversion technology can not only reduce the global cause CO2Environmental problems due to excessive emissions, and also to the potential use of converting them into high value added carbon-based chemicals and liquid fuels, such as CO, hydrocarbons, formic acid, and alcohols. The CO is used as a raw material of the synthesis gas, can be used for producing various chemical products, and can also be used for preparing oil fuels by utilizing an F-T reaction, so that carbon cycle is realized in a real sense.
However, due to CO2The high chemical stability of the molecule, the need to overcome significant energy barriers and the slow kinetics of electron and proton transfer in electrochemical reduction reactions, leads to high overpotentials. In addition, there is a competing reaction hydrogen evolution reaction, resulting in low selectivity of the target product. Therefore, it is crucial to develop an inexpensive and abundant catalyst with high selectivity and long stability. Researchers have also conducted a great deal of research in recent years on lower cost non-noble metal catalysts.
CN103566934A discloses a carbon dioxide electrochemical reduction catalyst, and preparation and application thereof, the catalyst comprises cuprous oxide nanowires synthesized by hydrothermal reaction, the synthesis raw materials comprise 0.05M copper acetate and 0.01-0.05M methoxyaniline in a volume ratio of 0.9: 0.1-0.1: 0.9, and the cuprous oxide nanostructures with special morphology are formed by hydrothermal synthesis, so that the specific surface area of the catalyst is increased, and the electrochemical reduction catalytic activity of the catalyst on carbon dioxide is increased.
CN108187713A discloses a copper-nitrogen CO-doped carbon nanotube catalyst and a preparation method thereof, the invention takes a carbon nanotube as a substrate, copper salt is added, the copper salt is stirred and dispersed and then roasted to obtain a copper-doped carbon nanotube, a nitrogen source is added in the hydrothermal reaction to obtain the copper-nitrogen CO-doped carbon nanotube, the preparation method is simple, and the obtained catalyst is subjected to CO CO-doping2The reduction activity is higher in the electrocatalysis process.
While the selectivity of the product depends mainly on the properties of the electrode material, in recent years, Transition Metal Chalcogenides (TMCs) have attracted the search of extensive researchers due to their low cost and abundant reserves, and have shown considerable application prospects in the fields of energy storage and water electrolysis. Secondly, the specific surface area of the catalyst can be increased and the current density of the reaction can be increased by means of proper carrier loading.
However, composite catalysts often exhibit poor stability in aqueous electrolytes, limiting their application. Therefore, it is important to find a suitable way to improve the stability and related performance of the catalyst, and secondly, a way to improve the performance intrinsically by forming the catalyst itself into a beneficial morphology by means of a simple electrochemical treatment has been reported.
Disclosure of Invention
The invention aims to solve the problems of poor stability and improved catalytic performance of an electrocatalytic material in the prior art, and provides a copper-based hybrid catalyst loaded on a porous carrier, wherein the catalyst has excellent stability and good catalytic performance in carbon dioxide electrocatalytic reduction.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a copper-based catalyst comprises the following steps:
(1) adding a porous carrier into a sulfur-containing anion organic ligand solution, stirring and mixing, adding a copper salt solution, and mixing to obtain a suspension;
(2) centrifuging, washing and drying the suspension liquid obtained in the step (1) to obtain a precipitate;
(3) calcining the precipitate obtained in the step (2) in a nitrogen atmosphere, and oxidizing in an air atmosphere;
(4) and taking the oxidized precipitate as a working electrode, and carrying out electrochemical treatment to obtain the copper-based catalyst.
According to the invention, a copper salt, a sulfur-containing anion organic ligand and a porous carrier are mixed to form a precursor of an organic copper composite porous carrier, the precursor is calcined to generate a copper-sulfur hybrid, then an oxide layer is introduced through low-temperature oxidation, and finally the morphology of the copper-sulfur hybrid is induced to reconstruct by utilizing electrical reduction to generate a needle-shaped copper-based composite catalyst.
In the step (2), the precipitate can be repeatedly washed by ethanol and deionized water to remove unreacted copper salt and sulfur-containing ligand, preferably, the washing times are 3-6 times; the drying temperature is 50-80 ℃ to remove water, and the preferable drying temperature is 50-60 ℃.
The sulfur-containing anionic organic ligand comprises one or more of erythrosine, thiourea and methionine, and other sulfur-containing anionic organic ligands can also be adopted.
The porous carrier has a common carrier with large specific surface area, good conductivity and the like, and comprises carbon nanotubes, graphene aerogel, activated carbon fibers or mesoporous carbon and the like.
Preferably, the carbon nanotube is a multi-walled carbon nanotube (MWCNT) which has an ultrahigh specific surface area, a plurality of catalytic sites, good electrical and thermal conductivity and high mechanical strength.
The copper salt is soluble copper salt, including but not limited to one or more of copper nitrate, copper chloride and copper sulfate.
The concentration of the sulfur-containing anion organic ligand in the sulfur-containing anion organic ligand solution is 1-6 mol/L; the concentration of copper salt in the copper salt solution is 1-6 mol/L; the molar ratio of the sulfur-containing anionic organic ligand to the copper salt is 1: 0.8-1.2.
The solvent in the sulfur-containing anion organic ligand solution and the copper salt solution is water, ethanol, methanol or other common organic solvents.
The molar ratio of the mass of the porous carrier to the copper salt is 2-10 g: 1 mol.
In the step (2), the calcining temperature is 600-800 ℃, and the calcining time is 2-5 h. The calcination temperature has a large influence on the catalytic activity, the higher the temperature and the longer the time are, the larger the catalyst particle size is, and the catalyst can be caused by the overhigh temperatureSintering is not favorable to CO2And (4) carrying out reduction reaction. At this temperature range, a copper-based catalyst having the most excellent performance can be obtained.
Preferably, the calcining temperature is 600-700 ℃.
In the calcining process, the nitrogen flow rate is controlled to be 100-200 mL min-1The temperature rising speed is 2-5 ℃/min;
in the step (3), the temperature of oxidation is 180-220 ℃, and the oxidation time is 3-5 h; the higher the temperature and the longer the time, the deeper the oxidation degree, and the oxidized copper oxide is helpful for the shape reconstruction of copper in the electrochemical treatment process. Preferably, the temperature of the oxidation is 190-210 ℃.
In the oxidation process, the air flow rate is controlled to be 60-200 mL min-1The temperature rising speed is 2-5 ℃/min;
in the step (4), the precipitate oxidized in the step (3), a perfluorosulfonic acid polymer solution (Nafion) and ethanol are mixed into a suspension, and the suspension is dropped on carbon paper to be dried to be used as a working electrode.
In the step (4), the potential of the electrochemical treatment is-0.57 to-0.87V (relative to a standard reversible hydrogen electrode), and the time of the electrochemical treatment is not less than 1 h. The copper-based material can generate shape reconstruction in the process of electroreduction, and the needle-shaped nano structure can enable the metal-based electrode to have ordered porosity and increase the specific surface area, so that the metal-based electrode has more active surface sites, thereby remarkably improving the electrochemical catalytic performance and showing excellent stability.
The invention also provides the copper-based catalyst prepared by the preparation method, and the specific surface area of the copper-based catalyst is 300-400 m2/g。
The invention also provides application of the copper-based catalyst prepared by the preparation method in electrocatalytic reduction of carbon dioxide. In the application process, the catalyst provided by the invention has excellent catalytic activity and stability, the electrolysis time is 20 hours, and the electrocatalytic performance is not weakened. As the electrolysis reaction continues, product selectivity and current density also increase to some extent.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, a porous material is used as a carrier, an oxide layer is introduced by low-temperature oxidation, and the catalyst is subjected to shape reconstruction through a simple electrochemical treatment mode to finally prepare the needle-shaped electrocatalyst, so that the intrinsic catalytic activity of the catalyst is improved, the good carbon dioxide electrocatalytic reduction capability is shown, and the current density and the Faraday efficiency are increased; the catalyst shows excellent stability, the electrolysis time is 20 hours, and the electrocatalytic performance is not weakened.
(2) The preparation method of the catalyst is simple to operate, excellent in performance, wide in applicability and wide in prospect. Provides a new effective mode for improving the stability and catalytic activity of the catalyst.
Drawings
FIG. 1 is an SEM image of a copper-based catalyst prepared in example 1.
Fig. 2 is an SEM image of the copper-based catalyst prepared in comparative example 1.
FIG. 3 is a graph showing the relationship between the current density of formic acid and the electrolytic potential when the catalyst of example 1 was used.
FIG. 4 is a graph showing the relationship between the faradaic efficiency of formic acid and the electrolytic potential when the catalyst of example 1 was used.
FIG. 5 is a graph showing the current density and the formic acid Faraday efficiency as a function of the electrolysis time in application example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. Those skilled in the art should understand that they can make modifications and equivalents without departing from the spirit and scope of the present invention, and all such modifications and equivalents are intended to be included within the scope of the present invention.
Example 1
(1) To a 50mL ethanol solution were added 0.05mol of tryptophan (RA) followed by 0.1g of MWCNT, and the mixture was stirred well. Then 50mL of Cu (NO) containing 0.05mol of copper nitrate is added dropwise under the condition of uniform stirring3)2·3H2An aqueous solution of O. Stirring the mixed solution at room temperature for 24h at a constant speed to form uniform suspension;
(2) removing the solvent by centrifugation, collecting gelatinous precipitate, alternately washing with ethanol and deionized water for 3 times, and drying the obtained precipitate in an oven at 50 ℃ for 8 hours to obtain a dried precipitate CuRA @ MWCNT;
(3) placing the CuRA @ MWCNT dried in the step (2) in a quartz boat, placing the quartz boat in a tube furnace for calcination, and keeping the nitrogen flow rate at 100mL min-1Heating to 600 ℃ at a heating rate of 3 ℃/min, preserving heat for 2h, and obtaining Cu after calcination1.81S @ MWCNT-600 samples.
Mixing Cu1.81S @ MWCNT-600 is placed in a quartz boat and placed in a tube furnace for calcination, and the air flow rate is 60mL min-1Heating to 200 ℃ at a heating rate of 3 ℃/min, and keeping the temperature for 3 h. Obtaining Cu after calcining1.81S @ MWCNT-600-OD samples.
(4) Taking 5mg of Cu1.81The S @ MWCNT-600-OD sample was sonicated with 30. mu.L Nafion solution (5 wt%) and 970. mu.L ethanol solution to form a uniform suspension (ink). Dripping 10 μ L ink with pipette each time, coating on glassy carbon electrode (diameter is 8mm), dripping 6 times respectively, and drying to obtain working electrode. Hg/HgO was used as a reference electrode, a platinum sheet was used as a counter electrode, and 0.5M KHCO was used3As an electrolyte, the catalyst is electrolyzed for 1h under the given potential of-0.67V (vs RHE) to obtain the copper-based catalyst taking the multi-walled carbon nano-tube as a carrier. The specific surface area of the catalyst was 362m2/g。
Comparative example 1
Cu obtained in step (3) of example 11.81The S @ MWCNT-600-OD sample was used as the catalyst of comparative example 1, which was not subjected to the electrochemical treatment process of step (4). The specific surface area of the catalyst was 218m2/g。
The surface morphology of the catalysts prepared in example 1 and comparative example 1 is observed by a Scanning Electron Microscope (SEM), and as a result, as shown in fig. 1 and fig. 2, it can be seen that the surface of the copper-based catalyst prepared in example 1 (fig. 1) has a distinct needle-like nanostructure, and such a structure illustrates that the preparation method of example 1 can greatly increase the specific surface area of the metal-based electrode, so that the metal-based electrode has more active surface sites.
In contrast, in the copper-based catalyst (fig. 2) of comparative example 1, in which the electrochemical treatment process was not performed, the supported copper sulfide was agglomerated, no needle-like structure was observed, and the specific surface area was inferior to that of the copper-based catalyst prepared in example 1.
Example 2
According to the process of the embodiment 1, the calcination temperature in the nitrogen atmosphere in the step (3) is changed to 700 ℃, and the copper-based catalyst taking the multi-walled carbon nanotube as the carrier is obtained. The specific surface area of the catalyst is 325m2/g。
Example 3
According to the process of the example 1, the tryptophan in the step (1) is changed into thiourea, the multi-walled carbon nano tube is changed into graphene aerogel, other steps are not changed, the copper-based catalyst taking the graphene aerogel as the carrier is obtained, and the specific surface area of the catalyst is tested to be 377m2/g。
Application example 1
The catalysts prepared in examples 1 and 2 and comparative example 1 were used as working electrodes, Hg/HgO as reference electrode, platinum sheet as counter electrode, H-type electrolytic cell was used, the volume of cathode and anode chambers was 30mL, and they were separated by Nafion 117 membrane, and 0.5M KHCO was selected3The solution is an electrolyte. Carrying out CO2When in electrochemical characterization, the gas velocity is controlled to be 15mL min-1. Respectively in a potential interval of-0.5V to-0.9V (vs RHE), and the electrolysis duration is 1 h. The gas product was detected by gas chromatography equipped with a Flame Ionization Detector (FID) and a Thermal Conductivity Detector (TCD). For liquid-phase products1H nuclear magnetic detection, and DMSO is adopted for calibration by an internal standard method.
The current density of the catalysts prepared in examples 1 and 2 and comparative example 1 is plotted against the electrolytic potential in application as shown in fig. 3, and it can be seen that the current density of formic acid component of the copper-based catalysts prepared in examples 1 and 2 is significantly higher than that of the catalyst of the comparative example which is not electrochemically treated, indicating that the electrochemical treatment process can significantly improve the electrocatalytic activity of the product. The formic acid partial current density of the copper-based catalyst of example 1 is slightly higher than that of the copper-based catalyst of example 2 when the copper-based catalyst is applied, because the particle size of the catalyst is increased and the specific surface area is reduced due to the increase of the calcination temperature, and the catalytic activity is further reduced.
Similarly, the results of observing the faradaic efficiencies of the three catalysts are shown in fig. 4, which shows that the faradaic efficiencies of formic acid of examples 1 and 2 are better than that of comparative example 1, the faradaic efficiency of formic acid of the catalyst of example 1 is higher than that of the catalyst of example 2, and the selectivity of the product can be remarkably improved by the needle-shaped catalysts prepared in examples 1-2.
Application example 2
The catalyst prepared in example 1 was used as a working electrode, an electrochemical experiment was carried out according to application example 1, electrolysis was carried out for 20 hours at an electrolysis potential of 0.67v (vs rhe), and a liquid phase sample was taken every 1 hour to measure the faradaic efficiency of formic acid, and as a result, as shown in fig. 5, it was found that the catalyst had excellent catalytic stability, and the current density and the faradaic efficiency of formic acid remained stable even after electrolysis for 20 hours, and not only did not decrease but also slightly increased.
Claims (10)
1. The preparation method of the copper-based catalyst is characterized by comprising the following steps of:
(1) adding a porous carrier into a sulfur-containing anion organic ligand solution, stirring and mixing, adding a copper salt solution, and mixing to obtain a suspension;
(2) centrifuging, washing and drying the suspension liquid obtained in the step (1) to obtain a precipitate;
(3) calcining the precipitate obtained in the step (2) in a nitrogen atmosphere, and oxidizing in an air atmosphere;
(4) and (4) taking the precipitate oxidized in the step (3) as a working electrode, and carrying out electrochemical treatment to obtain the copper-based catalyst.
2. The process for preparing copper-based catalysts according to claim 1, characterized in that the sulfur-containing anionic organic ligands comprise one or more of erythrosine, thiourea, methionine.
3. The method for preparing the copper-based catalyst according to claim 1, wherein the porous carrier comprises one or more of carbon nanotubes, graphene aerogel, activated carbon fibers and mesoporous carbon.
4. The method for preparing a copper-based catalyst according to claim 1, wherein the concentration of the sulfide anion organic ligand in the sulfide anion organic ligand solution is 1 to 6 mol/L; the concentration of copper salt in the copper salt solution is 1-6 mol/L; the molar ratio of the sulfur-containing anionic organic ligand to the copper salt is 1: 0.8-1.2.
5. The method for preparing the copper-based catalyst according to claim 1, wherein the molar ratio of the mass of the porous carrier to the copper salt is 2-10 g: 1 mol.
6. The method for preparing the copper-based catalyst according to claim 1, wherein in the step (2), the calcining temperature is 600-800 ℃ and the calcining time is 2-5 h.
7. The method for preparing the copper-based catalyst according to claim 1, wherein in the step (3), the temperature of the oxidation is 180-220 ℃ and the oxidation time is 3-5 h.
8. The method for preparing a copper-based catalyst according to claim 1, wherein in the step (4), the potential of the electrochemical treatment is-0.57 to-0.87V, and the time of the electrochemical treatment is not less than 1 h.
9. The copper-based catalyst prepared by the preparation method according to any one of claims 1 to 8, wherein the specific surface area of the copper-based catalyst is 300-400 m2/g。
10. The application of the copper-based catalyst prepared by the preparation method according to any one of claims 1 to 8 in electrocatalytic reduction of carbon dioxide.
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| CN112899709A (en) * | 2021-01-19 | 2021-06-04 | 北京化工大学 | Copper-based compound/copper nano electrode with interface synergistic effect and preparation and application thereof |
| CN114108026A (en) * | 2021-11-25 | 2022-03-01 | 南京航空航天大学 | Carbon-supported mercapto-coated silver nanoparticle catalyst and preparation method and application thereof |
| CN114855206A (en) * | 2022-04-19 | 2022-08-05 | 厦门大学 | Preparation of 3D printing monolithic electrocatalyst and application thereof in electrocatalytic reaction |
| CN115852485A (en) * | 2023-02-07 | 2023-03-28 | 南开大学 | Graded tip cuprous oxide single crystal material and preparation method and application thereof |
| CN116273180A (en) * | 2022-09-09 | 2023-06-23 | 浙江大学 | Catalyst of organic zinc complex and molybdenum sulfide heterostructure, preparation method and application |
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| CN110841606A (en) * | 2019-11-21 | 2020-02-28 | 浙江大学 | Composite material for capturing carbon dioxide and preparation method and application thereof |
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| CN110841606A (en) * | 2019-11-21 | 2020-02-28 | 浙江大学 | Composite material for capturing carbon dioxide and preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112899709A (en) * | 2021-01-19 | 2021-06-04 | 北京化工大学 | Copper-based compound/copper nano electrode with interface synergistic effect and preparation and application thereof |
| CN114108026A (en) * | 2021-11-25 | 2022-03-01 | 南京航空航天大学 | Carbon-supported mercapto-coated silver nanoparticle catalyst and preparation method and application thereof |
| CN114855206A (en) * | 2022-04-19 | 2022-08-05 | 厦门大学 | Preparation of 3D printing monolithic electrocatalyst and application thereof in electrocatalytic reaction |
| CN114855206B (en) * | 2022-04-19 | 2023-12-12 | 厦门大学 | Preparation of 3D printing integral electrocatalyst and application thereof in electrocatalytic reaction |
| CN116273180A (en) * | 2022-09-09 | 2023-06-23 | 浙江大学 | Catalyst of organic zinc complex and molybdenum sulfide heterostructure, preparation method and application |
| CN115852485A (en) * | 2023-02-07 | 2023-03-28 | 南开大学 | Graded tip cuprous oxide single crystal material and preparation method and application thereof |
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