CN112323094B - Preparation method and application of composite material - Google Patents
Preparation method and application of composite material Download PDFInfo
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- CN112323094B CN112323094B CN202011316164.7A CN202011316164A CN112323094B CN 112323094 B CN112323094 B CN 112323094B CN 202011316164 A CN202011316164 A CN 202011316164A CN 112323094 B CN112323094 B CN 112323094B
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- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 121
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 118
- 229910052802 copper Inorganic materials 0.000 claims abstract description 117
- 239000000956 alloy Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
- 230000009467 reduction Effects 0.000 claims abstract description 32
- 238000006722 reduction reaction Methods 0.000 claims description 43
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 239000003792 electrolyte Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000005238 degreasing Methods 0.000 claims description 13
- 238000004070 electrodeposition Methods 0.000 claims description 13
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000005498 polishing Methods 0.000 claims description 10
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000010335 hydrothermal treatment Methods 0.000 claims description 9
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 229910052573 porcelain Inorganic materials 0.000 claims description 8
- 239000002070 nanowire Substances 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract description 19
- 239000005977 Ethylene Substances 0.000 abstract description 19
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 12
- 239000000463 material Substances 0.000 abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- 229910021607 Silver chloride Inorganic materials 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract description 4
- 150000001879 copper Chemical class 0.000 abstract description 3
- 230000002035 prolonged effect Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 34
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 30
- 229910002091 carbon monoxide Inorganic materials 0.000 description 30
- 229910002092 carbon dioxide Inorganic materials 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 238000007254 oxidation reaction Methods 0.000 description 14
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000005751 Copper oxide Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 229910000431 copper oxide Inorganic materials 0.000 description 9
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910000570 Cupronickel Inorganic materials 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 244000137852 Petrea volubilis Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 239000013110 organic ligand Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910000881 Cu alloy Inorganic materials 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- -1 electrode type Chemical compound 0.000 description 4
- 235000019253 formic acid Nutrition 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000004073 vulcanization Methods 0.000 description 4
- 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 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910002056 binary alloy Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 229940116318 copper carbonate Drugs 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 2
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910017518 Cu Zn Inorganic materials 0.000 description 1
- 229910017755 Cu-Sn Inorganic materials 0.000 description 1
- 229910017752 Cu-Zn Inorganic materials 0.000 description 1
- 229910017927 Cu—Sn Inorganic materials 0.000 description 1
- 229910017943 Cu—Zn Inorganic materials 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- Catalysts (AREA)
Abstract
The invention provides a preparation method of a sulfur-modified copper-based composite material and application thereof in electrocatalytic reduction of CO2, wherein thorn-shaped copper is formed on the surface of the copper-based material in a hydrothermal mode, the specific surface area and active sites of an electrode material can be remarkably improved, the electrode is stable, and the obtained thorn-shaped copper is not easy to peel off and fall off; the service life of the copper-based alloy can be prolonged while the high ethylene conversion rate is ensured, the Faraday efficiency of an electrochemical conversion method is more than 72%, the ethylene selectivity is more than 60% under the electrolysis voltage of-1.8V vs Ag/AgCl, and the methane selectivity is obviously reduced.
Description
Technical Field
The invention belongs to the field of electrochemistry, and particularly relates to a preparation method of a high-service-life copper-based composite material, which is particularly suitable for application in the field of preparing ethylene by electrocatalytic reduction of carbon dioxide.
Technical Field
CO 2 Stable in chemical structure, and thus CO 2 Activation of the molecule is very difficult and thus difficult to participate in the reaction, which has been conventionally converted using severe reaction conditions such as high temperature and pressure. In general, researchers have employed chemical reforming, mineralization, enzymatic catalysis, photocatalysis, electrocatalysis, etc. to overcome the larger activation energy barrier of CO 2. In these methods, H is not required due to the mild electrochemical reduction reaction conditions 2 As a raw material, the reaction pH is close to neutral and excellent clean energy compatibility is attracting attention.
Electrochemical reduction is a means of reducing CO2 under relatively mild external conditions by applying an electric current such that CO2 is reduced at the cathode surface. Electrochemical reduction has the following advantages: the reduction product can be controlled by adjusting the electrolysis voltage, the electrolysis temperature and the electrolyte type; the electrolyte is convenient to recycle; the structure of the electrolytic cell is simple and convenient to manufacture, and the electrolytic cell is generally carried out at normal temperature; the electric energy for electrolysis can be generated by renewable energy sources such as solar energy, wind energy and geothermal energy; the electrochemical reaction system is compact, modularized and adjusted according to the needs, and is easy to be used in industrial factory building.
Since there are many factors affecting the electrochemical reduction of CO2, such as electrode type, solvent type, electrolysis voltage, pressure, temperature, etc., the obtained products are also various, such as methanol, formic acid, methane, carbon monoxide, ethylene, etc., and various metals are classified into four major categories according to the product distribution rule thereof.
(I) First oneCopper (Cu) as a unique catalyst shows remarkable catalytic performance and can be used for preparing CO 2 Conversion to hydrocarbons and oxygenates is the only one that can convert CO with significant efficiency 2 Metal electrocatalysts for reduction to hydrocarbons or oxygenated hydrocarbons, such as methane, ethylene, ethanol, and propanol.
(II) the second category of metals, noble metals such as gold (Au), silver (Ag), zinc (Zn), palladium (Pd), and gallium (Ga), are selective to carbon monoxide (CO), and are produced primarily from CO.
(III) third class of metals tin (Sn), lead ((Pb), mercury (Hg), indium (In), cadmium (Cd), etc., which are mainly formate, are produced as formic acid (HCOOH) and formate ((HCOO) - ) Is a catalyst of the optimum type.
(N) a fourth metal such as nickel (Ni), iron (Fe), platinum (Pt) and titanium (Ti) and the like, and only generates hydrogen evolution reaction in a stable state to generate hydrogen (H) 2 ) Without CO 2 Is a reducing power of (a) to (b).
Among the various catalysts for electrochemical reduction of COZ, copper is considered to be the most promising catalyst for the production of hydrocarbons such as methane and ethylene. In recent years, high-selectivity copper-based electrocatalysts have attracted extensive attention from students at home and abroad because of their high energy density and ethylene as a chemical raw material.
CN202010628183 discloses a dendritic copper electrode with hydrophobic surface, a preparation method and application thereof. The copper electrode provided by the invention comprises a gas diffusion layer and a copper layer deposited on the surface of the gas diffusion layer; the microscopic morphology of the copper layer is dendritic. The surface of the copper electrode provided by the invention is composed of regular copper dendrites, shows good hydrophobicity, can effectively prevent excessive contact of electrolyte, avoids 'flooding' of the electrode, and improves the stability of the electrode; and dendrite-shaped copper can also efficiently enrich cations in the electrolyte to form a local high electric field, so that the carbon-carbon coupling rate is improved, and the electrode shows excellent electrocatalytic CO2 reduction activity.
CN201911278128 uses copper alloy material with amorphous structure as catalyst, and CO2 is subjected to electrochemical reaction to obtain carbon-containing compound. The invention adopts copper alloy material with amorphous structure as catalyst to directly prepare carbon-containing compounds such as alcohol, acid and ketone by electrocatalytic reduction of CO 2. The copper alloy material can be prepared into various macroscopic forms such as a block form, a powder form, a film form and the like, can be directly used as an electrocatalytic electrode material to be applied to a CO2 electrocatalytic reduction cell, and simultaneously improves the electrocatalytic activity and stability of the catalyst, thereby improving the performance and efficiency of the electrolytic cell. The synthesis method provided can effectively exert the synergistic catalytic performance among the catalysts by regulating and controlling the composition and the structure of the copper alloy material with the amorphous structure, further regulate and control the types of products, and selectively obtain different carbon-containing compounds such as alcohol, acid, ketone and the like.
CN201910713686 discloses a copper-based carbon dioxide electrocatalytic material and a preparation method thereof, wherein the method comprises the following steps: mixing an oxidant solution and an organic ligand solution to prepare a mixed solution; placing metal copper into the mixed solution, enabling the organic ligand to be adsorbed on part of specific crystal faces of the metal copper, and enabling the crystal faces of the metal copper which are not adsorbed by the organic ligand to undergo oxidation reaction; and (3) cleaning the metal copper after the oxidation reaction, removing the organic ligand adsorbed on the crystal face of the metal copper, and performing electrochemical reduction to obtain the OD-Cu carbon dioxide catalytic material with more specific crystal faces. According to the method, organic ligands with different types and concentrations are added in the oxidation process, so that on one hand, the regulation and control of different crystal forms of the OD-Cu material can be realized; on the other hand, the prepared OD-Cu material has the advantages of high surface roughness, high grain boundary density and the like, can preferentially expose crystal faces, and can remarkably improve the catalytic activity of the material on CO2 and the selectivity on a multi-carbon product.
CN201810661930 discloses a preparation method of flower-shaped copper oxide, which comprises the following steps: a) Mixing an oxidant, a morphology control agent, a hydrophilic group surfactant and an alkaline compound in water to obtain an initial solution; the morphology control agent is selected from sodium tungstate, potassium tungstate, sodium molybdate, urea or ethylenediamine; b) Immersing the cleaned copper into the initial solution for hydrothermal reaction to obtain flower-like copper oxide. The application also provides a method for photoelectrocatalytic reduction of CO2 by using the flower-like copper oxide as an electrode. The invention provides a method for preparing flower-like copper oxide by taking elemental copper as a copper source, and the flower-like copper oxide prepared by the method can be directly used as an electrode for photoelectrocatalytic reduction of CO2 without additional molding treatment.
CN201310254758 discloses a flower-like copper oxide/iron oxide nanotube catalyst and a preparation method thereof, firstly volcanic-like iron oxide nanotubes are grown on an iron substrate in situ by an electrochemical anodic oxidation method, then copper oxide with a flower-like structure is deposited on the iron oxide substrate by a pulse electrodeposition method, and the flower-like copper oxide/iron oxide nanotube catalyst is obtained after calcination. The catalyst has good photoelectrocatalysis performance, realizes the coupling of two reactions of water splitting and CO2 reduction, reduces CO2 photoelectrocatalytically, and is subjected to gas chromatography detection analysis, and the products are methanol and ethanol.
The following problems are evident from the above patents: (1) As the most excellent ethylene selective catalyst, there are few research directions aimed at improving ethylene selectivity, and ethylene is the most important energy hydrogenation raw material in chemical production; (2) life of electrocatalytic electrodes was not investigated; (3) the catalytic activity is to be improved.
Disclosure of Invention
Based on the problems, the key problem to be solved by the invention is to provide a preparation method of a sulfur-modified copper-based composite material and application thereof in electrocatalytic reduction of CO 2 An electrode structure and a preparation technology capable of improving the service life of ethylene while ensuring high ethylene conversion rate.
The method comprises the following steps:
(1) Pretreating the copper-based alloy;
(2) The copper-containing solution is used as electrolyte, copper-based material is used as cathode, and electrochemical deposition reduction is carried out under extremely high negative bias.
(3) Chemically reducing copper nanowire seed crystals at a high temperature;
(4) Hydro-thermal treatment to obtain thorn-shaped copper-based composite material
(5) And (5) oxidizing.
Wherein the pretreatment in the step (1) is polishing and inorganic degreasing;
wherein the copper-containing electrolyte in the step (2) comprises copper sulfate, sulfuric acid, chloride ions and a surfactant, and the anode is an inert electrode or pure copper;
wherein the solution used in the high-temperature chemical reduction in the step (3) is a mixed solution of copper acetate and glycerol;
wherein the solution used by the water heating in the step (4) is consistent with the solution in the step (3), and is in a closed state,
wherein the oxidizing solution used in the step (5) is a mixed solution of ammonia water and copper carbonate.
The Faraday efficiency of the electrochemical conversion method of the copper-based alloy is more than 60% and the ethylene selectivity is more than or equal to 40% under the electrolysis voltage of-1.8V vs Ag/AgCl.
Further, the copper-based alloy is copper-nickel-white copper alloy, and the shape is bar-shaped or plate-shaped.
Further, the sanding is sequentially carried out by using 200# sand paper, 600# sand paper and 1200# sand paper.
Further, the degreasing is 15g/L Na 2 CO 3 、 10g/L Na 3 PO 4 . 12H 2 O、10 g/L Na 2 SiO 3 At a temperature of 50 o C, time 2min.
Further, the copper-containing electrolyte: 140-150g/L CuSO 4 . 5H 2 O；30-35g/L H 2 SO 4 ；40-45g/L Cl - The method comprises the steps of carrying out a first treatment on the surface of the 0.5-1g/L APEO; temperature of 25-30 DEG C o C, performing operation; direct current constant voltage-13V for 5s-10s.
Further, the solution used in the high temperature chemical reduction of step (3): 3-5M anhydrous copper acetate glycerol solution at 300-350 o C, in a non-sealing state, the time is 15-20min.
Further, the hydrothermal temperature in the step (4) is 110-120 DEG C o C, the time is 12-24h.
Furthermore, the reaction kettles in the step (3) and the step (4) are stainless steel lining-free hydrothermal reaction kettles, and before the step (4), nitrogen is used for exhausting air in the reaction kettles in the step (3).
Further, the concentration of the ammonia water in the step (5) is 100-120ml/L of an ammonia water solution with the mass fraction of 25 wt%, 40g/L of copper carbonate is 3-5min, and the temperature is 15-20 o C。
Further, the Gao Shoutong-based composite material is produced by CO 2 Electrocatalytic reduction electrodes.
(1) Regarding the selection of the substrate: the copper-based alloy is copper-nickel-white copper alloy and is copper-nickel binary alloy, wherein the nickel content is 5-10wt.%, the binary alloy has better corrosion resistance under the premise of meeting the mechanical strength, and the nickel in the binary alloy is in CO 2 No catalytic reduction of CO in electrocatalytic processes 2 I.e. nickel does not cause any side reactions, does not affect the conversion of ethylene with high selectivity according to the invention, if brass (Cu-Zn) or bronze (Cu-Sn) alloys are chosen, zn will be electrocatalytically CO-produced, and tin will be electrocatalytically formic acid, which is detrimental to the object of the invention.
(2) Pretreatment of a substrate: including polishing and degreasing, wherein polish: the 200# sand paper, the 600# sand paper and the 1200# sand paper are sequentially used for sanding, so that the surface of the abrasive paper is smooth, the purpose of the abrasive paper is to reduce roughness, remove macroscopic defects such as scratches, oxide layers, corrosion marks, rust spots and the like on the surface, improve the surface smoothness, enable the surface to reach enough smoothness, and the degreasing is 15g/L Na 2 CO 3 、 10g/L Na 3 PO 4 . 12H 2 O、10 g/L Na 2 SiO 3 At a temperature of 50 o C, for 2min, the degreasing fluid used in the invention does not contain strong alkaline sodium hydroxide, mainly because Cu+NaOH+O2 can form Na2CuO 2 While Na2CuO 2 Can be decomposed into CuO proper oxide film in water, is unfavorable for robbing the surface, and comprises a hot water washing step, a cold water washing step, the surface of a piece to be plated is washed by deionized water heated to at least 45-50 ℃, the residual alkali liquor is removed, and then the piece to be plated is washed by cold deionized water.
(3) Electrochemical deposition reduction is carried out with extremely high negative bias: in the copper-containing solution as electrolyte, copper-base alloy is used as cathode, inert or pure copper electricityThe cathode is extremely anode, direct current is conducted, copper ions are reduced at the cathode, but because extremely high negative bias is applied to the copper-based alloy plate, severe hydrogen evolution reaction is caused, hydrogen exists in the form of bubbles at the cathode, no metal ions exist at the place where the hydrogen bubbles appear, namely, no copper ion deposition reaction occurs, so that the reaction of electrodeposited copper to form a compact structure at the cathode is consistent, thus forming cavities, as shown in fig. 1, fig. 2, fig. 3 and fig. 4, holes with different densities are formed on the surface of the copper-based alloy with the increase of time, the density of the holes is closely related to voltage and time, the specific surface area of the cathode material is obviously increased in the cathode deposition process, and the specific surface area of the polished copper-based alloy is approximately equal to 0m 2 /g; after 10s of cathodic deposition, the specific surface rises to 9m 2 Per g, if the time is increased, a cathode current density of more than 100m can be obtained by reasonably adjusting 2 Three-dimensional porous copper material per gram, which, however, is high in specific surface area by the abovementioned process, is also active for electrocatalytic reduction of CO 2 But the catalytic activity conversion, ethylene selectivity and Faraday efficiency are low, and the preparation method can be referred to in the prior art.
The invention has the main purpose of obtaining a porous copper layer in a short time of 5s-10s, and aims at digging pits, facilitating the subsequent seed crystal attachment, and finally obtaining the CO2 electrocatalytic material with high strength, bonding strength and long service life through subsequent hydrothermal reaction pit burying.
The copper-containing electrolyte of the present invention: 140-150g/L CuSO 4 . 5H 2 O；30-35g/L H 2 SO 4 ；40-45g/L Cl - The method comprises the steps of carrying out a first treatment on the surface of the 0.5-1g/L APEO, where the theoretical CuSO 4 . 5H 2 O may be about 230g/L, but the CuSO is reduced in consideration of the solubility to cause precipitation of copper sulfate 4 . 5H 2 O is 140-150g/L; the sulfuric acid can obviously reduce the resistance of the plating solution in the plating solution, can prevent the hydrolysis of the copper sulfate to form copper hydroxide sediment, has the concentration lower than that of actual copper plating, is generally more than 40g/L in industry and is favorable for forming a flat plating layer, and when the concentration of the sulfuric acid is higherWhen the coating is low, a rough coating is easy to form, and the coating is required by the invention; APEO surfactant is added in the application, mainly to improve the surface tension of the plating solution and avoid excessive overflow of hydrogen bubbles.
Finally, the process should be optimally placed in a stationary state without any stirring assistance.
(4) Regarding high temperature chemical reduction copper nanowire seed: the process uses glycerol solution of 3-5M anhydrous copper acetate, wherein glycerol has a certain reducibility at normal temperature, but has no capability of reducing copper sulfate, and the temperature is 300-350 ℃ at high temperature o Under the condition C, the glycerol has extremely strong reducing capability, copper sulfate can be reduced into copper polyhedral particles through no electrochemistry, the particles can be adsorbed into pits in the step (2) to serve as crystal seeds, a reaction kettle is not sealed in the process, but evaporation loss of a solution is required to be reduced as much as possible, and the main density of the process is that seed crystals are formed.
(5) The spiny copper-based composite material is obtained by hydro-thermal treatment, and the hydro-thermal temperature in the process is 110-120 DEG C o C, the time is 12-24 hours, before the step (4), nitrogen is used for exhausting the air in the reaction kettle in the step (3), the nano copper can be shaped and grown by a hydrothermal method, the nano wire is obtained, and then the copper-based electrode material with high specific surface area is obtained.
To further illustrate the above process, an extremely fine copper nickel wire was used as the substrate, as shown in FIG. 5; electrochemical deposition reduction is carried out by extremely high negative bias to form a porous copper layer on the surface of the copper layer, as shown in figure 6; then forming copper crystals in the pore channels through high-temperature electrochemical-free reduction, as shown in figure 7; the spiny copper-based composite material obtained by the hydro-thermal treatment is shown in fig. 8, and the spiny copper on the surface of the copper material can be more clearly seen from fig. 9.
(6) Regarding oxidation: the purpose of the oxidation is to form CuO X The layer, the oxidation state metal has abundant crystal boundary on the catalyst surface, and the specific crystal surface shows stronger catalytic activity and selectivity, under the condition of CO2 electrocatalysis, the oxidation layer can be electrochemically reduced into a metal layer, the process activates the metal catalyst, specific low coordination active sites are formed on the catalyst surface,meanwhile, the reaction site of competing Hydrogen Evolution Reaction (HER) is blocked, the selectivity of the product is improved, the reduction activity of the copper-based electrode has strong dependence on the initial thickness of the copper oxide layer, which shows that the oxidation state of the metal has positive significance on the electrocatalytic performance, and the oxidation is carried out by partial oxidation before sulfur modification, wherein the oxidation atmosphere is 5vol.% O 2 /N 2 At 5 o C/min,5min up to 50 o About C, sulfur powder does not volatilize during the process, but is partially oxidized, so that the content of oxidation loss should be considered during the sulfur modification process.
(7) Regarding vulcanization: in the preparation and constitution of the electrode material of the same-day series application of the inventor, although the copper-based composite material has good catalytic performance, the selectivity of the copper-based composite material still needs to be improved, and the main reason of lower selectivity is the existence of methane competition reaction, but the methanation reaction of CO2 in the electro-reduction process can be obviously inhibited by using sulfur to carry out vulcanization modification on the copper-based composite material, as shown in figure 10, the thickness of the thorn-shaped structure is obviously increased after vulcanization, and the surface of each thorn-shaped structure has obvious fold structure.
The beneficial technical effects are as follows:
(1) The electrode is stable, and the obtained thorn-shaped copper is not easy to peel off and fall off.
(2) The thorn-shaped copper material obviously improves the contact specific surface area of the reactant and the electrode, and provides rich sites for catalytic reduction of CO 2.
（3）CuO X The layer effectively inhibits hydrogen evolution reaction, and oxidation state is preferentially combined with H ions for reduction, so that the combination reaction of H and H is avoided.
(4) Further improves the selectivity of ethylene, has high conversion rate and Faraday efficiency.
(5) CO inhibition 2 Methanation reaction.
Drawings
FIG. 1 is a 2s SEM image of electrochemical deposition at a streamer constant voltage of-13V according to the invention.
FIG. 2 is a 5s SEM image of electrochemical deposition at a streamer constant voltage of-13V according to the invention.
FIG. 3 is a 7s SEM image of electrochemical deposition at a streamer constant voltage of-13V according to the invention.
FIG. 4 is a 10s SEM image of electrochemical deposition at a streamer constant voltage of-13V according to the invention.
Fig. 5 is a TEM image of the invention on a copper wire.
FIG. 6 is a 10s TEM image of electrochemical deposition at a streamer constant voltage of-13V according to the invention.
Fig. 7 is a TEM image of the invention without electrochemical reduction at high temperature.
Fig. 8 is a TEM image of the hydrothermal process of the present invention.
Fig. 9 is an SEM image of a spiny copper-based composite obtained by the hydrothermal treatment of the present invention.
FIG. 10 is an SEM image of a copper matrix composite of the present invention obtained by the curing process.
FIG. 11 is an SEM partial enlarged view of a copper-matrix composite of the present invention obtained by the vulcanization treatment.
Description of the embodiments
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
Copper-based composite material for electrocatalytic reduction of CO 2 The copper-based composite material is prepared by the following steps:
(1) Pretreating the copper-based alloy; the copper-based alloy is copper-nickel-white copper alloy.
Wherein the pretreatment in the step (1) comprises polishing and inorganic degreasing: polishing is as follows: sanding was performed using 200#, 600#, 1200# sandpaper in sequence.
Degreasing to 15g/L Na 2 CO 3 、 10g/L Na 3 PO 4 . 12H 2 O、10 g/L Na 2 SiO 3 At a temperature of 50 o C, time 2min.
(2) And taking the copper-containing solution as electrolyte, taking the copper-based alloy as a cathode, and carrying out electrochemical deposition reduction under extremely high negative bias.
Wherein the steps are as followsThe copper-containing electrolyte in the step (2) comprises copper sulfate, sulfuric acid, chloride ions and a surfactant, wherein the anode is an inert electrode or pure copper, and the copper-containing electrolyte comprises: 140g/L CuSO 4 . 5H 2 O；30g/L H 2 SO 4 ；40g/L Cl - The method comprises the steps of carrying out a first treatment on the surface of the 0.5g/L APEO; temperature 25 o C, performing operation; direct current constant voltage-13V for 5s.
(3) High temperature chemical reduction copper nanowire seed.
Wherein the solution used in the high-temperature chemical reduction in the step (3) is a mixed solution of copper acetate and glycerol, and the temperature of the glycerol solution of 3M anhydrous copper acetate is 300 o And C, in a non-sealing state, the time is 15min.
(4) And performing hydrothermal treatment to obtain the thorn-shaped copper-based composite material.
The solution used by the water heating in the step (4) is consistent with the solution in the step (3), and the air in the reaction kettle in the step (3) is exhausted by using nitrogen before the step (4) in a closed state.
The hydrothermal temperature in the step (4) is 110 o C, time is 12h.
(5) Vulcanizing: placing the copper-based alloy porcelain boat treated in the step (4) in the central position of a furnace chamber of a vacuum quartz tube furnace; the porcelain boat filled with sulfur powder is placed in a position close to an air inlet in a vacuum quartz tube furnace, two ends of the vacuum quartz tube furnace are plugged by furnace plugs to ensure uniform temperature, the mass of the sulfur powder is 5wt.% of the mass of the copper-based alloy, and the temperature is 150 o C, a temperature programming step: room temperature to 150 DEG C o Rate of temperature rise of C5 o C/min, holding for 30min, naturally cooling, heating for 5min, and introducing 5vol.% O 2 /N 2 Then switching the gas path to pure nitrogen.
Example 2
Copper-based composite material for electrocatalytic reduction of CO 2 The copper-based composite material is prepared by the following steps:
(1) Pretreating the copper-based alloy; the copper-based alloy is copper-nickel-white copper alloy.
Wherein the pretreatment in the step (1) comprises polishing and inorganic degreasing: polishing is as follows: sanding was performed using 200#, 600#, 1200# sandpaper in sequence.
Degreasing to 15g/L Na 2 CO 3 、 10g/L Na 3 PO 4 . 12H 2 O、10 g/L Na 2 SiO 3 At a temperature of 50 o C, time 2min.
(2) And taking the copper-containing solution as electrolyte, taking the copper-based alloy as a cathode, and carrying out electrochemical deposition reduction under extremely high negative bias.
Wherein the copper-containing electrolyte in the step (2) comprises copper sulfate, sulfuric acid, chloride ions and a surfactant, the anode is an inert electrode or pure copper, and the copper-containing electrolyte comprises: 145g/L CuSO 4 . 5H 2 O；32.5g/L H 2 SO 4 ；42.5g/L Cl - The method comprises the steps of carrying out a first treatment on the surface of the 0.75g/L APEO; temperature 27 o C, performing operation; DC constant voltage-13V, time 8s.
(3) High temperature chemical reduction copper nanowire seed.
Wherein the solution used in the high-temperature chemical reduction in the step (3) is a mixed solution of copper acetate and glycerol, and the temperature of the glycerol solution of 4M anhydrous copper acetate is 320 DEG C o And C, in a non-sealing state, the time is 17.5min.
(4) And performing hydrothermal treatment to obtain the thorn-shaped copper-based composite material.
The solution used by the water heating in the step (4) is consistent with the solution in the step (3), and the air in the reaction kettle in the step (3) is exhausted by using nitrogen before the step (4) in a closed state.
The hydrothermal temperature in the step (4) is 115 o C, time is 18h.
(5) Vulcanizing: placing the copper-based alloy porcelain boat treated in the step (4) in the central position of a furnace chamber of a vacuum quartz tube furnace; the porcelain boat filled with sulfur powder is placed in a position close to an air inlet in a vacuum quartz tube furnace, two ends of the vacuum quartz tube furnace are plugged by furnace plugs to ensure uniform temperature, the mass of the sulfur powder is 7.5wt.% of the mass of the copper-based alloy, and the temperature is 150 o C, a temperature programming step: room temperature to 150 DEG C o Rate of temperature rise of C5 o C/min, holding time for 30min, naturally cooling, and heating5vol.% O is introduced for the first 5min 2 /N 2 Then switching the gas path to pure nitrogen.
Example 3
Copper-based composite material for electrocatalytic reduction of CO 2 The copper-based composite material is prepared by the following steps:
(1) Pretreating the copper-based alloy; the copper-based alloy is copper-nickel-white copper alloy.
Wherein the pretreatment in the step (1) comprises polishing and inorganic degreasing: polishing is as follows: sanding was performed using 200#, 600#, 1200# sandpaper in sequence.
Degreasing to 15g/L Na 2 CO 3 、 10g/L Na 3 PO 4 . 12H 2 O、10 g/L Na 2 SiO 3 At a temperature of 50 o C, time 2min.
(2) And taking the copper-containing solution as electrolyte, taking the copper-based alloy as a cathode, and carrying out electrochemical deposition reduction under extremely high negative bias.
Wherein the copper-containing electrolyte in the step (2) comprises copper sulfate, sulfuric acid, chloride ions and a surfactant, the anode is an inert electrode or pure copper, and the copper-containing electrolyte comprises: 150g/L CuSO 4 . 5H 2 O； 35g/L H 2 SO 4 ；45g/L Cl - The method comprises the steps of carrying out a first treatment on the surface of the 1g/L APEO; temperature 30 o C, performing operation; DC constant voltage-13V, time 10s.
(3) High temperature chemical reduction copper nanowire seed.
Wherein the solution used in the high-temperature chemical reduction in the step (3) is a mixed solution of copper acetate and glycerol, and the temperature of the 5M anhydrous copper acetate glycerol solution is 350 DEG C o And C, in a non-sealing state, the time is 20min.
(4) And performing hydrothermal treatment to obtain the thorn-shaped copper-based composite material.
The solution used by the water heating in the step (4) is consistent with the solution in the step (3), and the air in the reaction kettle in the step (3) is exhausted by using nitrogen before the step (4) in a closed state.
The hydrothermal temperature in the step (4) is 120 o And C, the time is 24h.
(5) Vulcanizing: placing the copper-based alloy porcelain boat treated in the step (4) in the central position of a furnace chamber of a vacuum quartz tube furnace; the porcelain boat filled with sulfur powder is placed in a position close to an air inlet in a vacuum quartz tube furnace, two ends of the vacuum quartz tube furnace are plugged by furnace plugs to ensure uniform temperature, the mass of the sulfur powder is 10wt.% of the mass of the copper-based alloy, and the temperature is 150 o C, a temperature programming step: room temperature to 150 DEG C o Rate of temperature rise of C5 o C/min, holding for 30min, naturally cooling, heating for 5min, and introducing 5vol.% O 2 /N 2 Then switching the gas path to pure nitrogen.
Designated as S-3 sample.
And (5) testing the performance of electrocatalytic reduction CO 2.
An H-type double-air-chamber electrochemical cell is selected in the carbon dioxide reduction reactor device, a copper-based composite material is used as a working electrode, a Pt sheet is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, a three-electrode system is formed, a Nafion membrane is used as a diaphragm between the working electrode and the counter electrode/reference electrode, only protons are allowed to pass through, gas communication is blocked, the reaction temperature is normal temperature and normal pressure, and CO is carried out 2 Before the reduction reaction, CO with high purity (99.99%) is used 2 Continuously bubbling and cleaning the electrolyte for 30 minutes at the flow rate of 20ml/min to remove other gases in the electrolyte so as to reach CO 2 The product was analyzed at different moles of potassium bromide at a saturation, electrolysis voltage of-1.8V vs Ag/AgCl, electrolysis time of 40min, as shown in Table 1 below.
Table 1, product distribution and selectivity at 2.5MKBr concentration.
From the above table 1, it can be obtained that the sulfur-modified copper-based composite material of the present invention has significantly improved selectivity to ethylene, and the faraday efficiency of methane is significantly reduced, with the faraday efficiency of ethylene being 72.3%.
Table 2 table of faraday efficiencies of copper-based composites at different voltages.
The Faraday efficiency of S-3 ethylene was tested at different voltage ratings of 2.5MKBr, as shown in Table 2, with increasing voltage, FE increased slowly and then decreased rapidly, reaching a peak at-1.8V with an FE value of 72.3%.
Table 3 table CO conversion of copper matrix composites at different times.
As can be seen from the table above, the conversion rate of the copper-based composite material is obviously improved along with time, namely the copper-based composite material has excellent stability and carbon deposition resistance.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (5)
1. A preparation method of a composite material is characterized in that the composite material is prepared by the following steps:
(1) Pretreating the copper-based alloy;
(2) Taking copper-containing solution as electrolyte, taking copper-based alloy as cathode, and carrying out electrochemical deposition reduction under extremely high negative bias;
(3) Chemically reducing copper nanowire seed crystals at a high temperature;
(4) Carrying out hydrothermal treatment to obtain a thorn-shaped copper metal composite material;
(5) Sulfur modification;
wherein the pretreatment in the step (1) is polishing and inorganic degreasing;
wherein the copper-containing solution in the step (2) comprises copper sulfate, sulfuric acid, chloride ions and a surfactant, the anode is an inert electrode or pure copper, and the copper-containing solution is 140-150g/L CuSO 4 . 5H 2 O；30-35g/L H 2 SO 4 ；40-45g/L Cl - The method comprises the steps of carrying out a first treatment on the surface of the 0.5-1g/L APEO; the temperature is 25-30 ℃; direct current constant voltage-13V for 5s-10s;
wherein the solution used in the high-temperature chemical reduction in the step (3) is 3-5M glycerol solution of anhydrous copper acetate, the temperature is 300-350 ℃, and the time is 15-20min in a non-closed state;
wherein the solution used by the water heating in the step (4) is consistent with the solution in the step (3), and is in a closed state,
wherein the sulfur modification process in the step (5) comprises the following steps: placing a porcelain boat filled with the copper metal composite material treated in the step (4) in the central position of a furnace chamber of a vacuum quartz tube furnace; placing a porcelain boat filled with sulfur powder in a position close to an air inlet in a vacuum quartz tube furnace, plugging two ends of the vacuum quartz tube furnace by using furnace plugs to ensure uniform temperature, wherein the mass of the sulfur powder is 5-10wt.% of that of a copper-based alloy, the temperature is 150 ℃, and the temperature programming step is as follows: heating up at a rate of 5 ℃/min from room temperature to 150 ℃, preserving heat for 30min, naturally cooling, and introducing 5vol.% O5 min before heating up 2 /N 2 Then switching the gas path to pure nitrogen.
2. A method of preparing a composite material according to claim 1, wherein the polishing is: sanding was performed using 200#, 600#, 1200# sandpaper in sequence.
3. The method of claim 1, wherein the degreasing is 15g/L Na 2 CO 3 、 10g/L Na 3 PO 4 . 12H 2 O and 10 g/L Na 2 SiO 3 The temperature was 50℃for 2min.
4. The method of claim 1, wherein the hydrothermal treatment temperature in step (4) is 110-120 ℃ for 12-24 hours.
5. The method for preparing a composite material according to claim 1, wherein the reaction kettles in the step (3) and the step (4) are stainless steel lining-free hydrothermal reaction kettles, and nitrogen is used for exhausting air in the reaction kettles in the step (3) before the step (4).
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