CN106807349A - A kind of nano metal simple substance modification transition metal hydroxide array catalyst and its preparation method and application - Google Patents
A kind of nano metal simple substance modification transition metal hydroxide array catalyst and its preparation method and application Download PDFInfo
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- CN106807349A CN106807349A CN201710060056.XA CN201710060056A CN106807349A CN 106807349 A CN106807349 A CN 106807349A CN 201710060056 A CN201710060056 A CN 201710060056A CN 106807349 A CN106807349 A CN 106807349A
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- transition metal
- metal hydroxide
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- nano
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 49
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 48
- 239000002184 metal Substances 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 239000000126 substance Substances 0.000 title claims abstract description 34
- 238000012986 modification Methods 0.000 title claims abstract description 23
- 230000004048 modification Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004070 electrodeposition Methods 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000012266 salt solution Substances 0.000 claims abstract description 15
- 239000003792 electrolyte Substances 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 38
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 239000011790 ferrous sulphate Substances 0.000 claims description 5
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 238000005234 chemical deposition Methods 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 20
- 239000001257 hydrogen Substances 0.000 abstract description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000007935 neutral effect Effects 0.000 abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 abstract description 7
- 238000003491 array Methods 0.000 description 25
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 17
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 17
- 229910052697 platinum Inorganic materials 0.000 description 10
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 9
- 230000010287 polarization Effects 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000004332 silver Substances 0.000 description 6
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002242 deionisation method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- -1 [J.Am.Chem.Soc.2013 Chemical compound 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000010742 number 1 fuel oil Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 230000001960 triggered effect Effects 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/4618—Devices therefor; Their operating or servicing for producing "ionised" acidic or basic water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
- C02F2001/46138—Electrodes comprising a substrate and a coating
- C02F2001/46142—Catalytic coating
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The present invention provides a kind of nano metal simple substance modification transition metal hydroxide array catalyst and its preparation method and application, belongs to alkalescence and Neutral Electrolysis water decomposes field.The catalyst first prepares transition metal hydroxide array, and be then respectively working electrode and electrolyte with above-mentioned transition metal hydroxide array and the second metal salt solution prepares nano metal simple substance modification transition metal hydroxide array by electro-deposition techniques.The present invention also provides the nano metal simple substance modification transition metal hydroxide array catalyst that above-mentioned preparation method is obtained.Preparation-obtained nano metal simple substance modification transition metal hydroxide array catalyst is applied in alkalescence and Neutral Electrolysis pond, with excellent electrocatalytic hydrogen evolution performance and full electrolysis water performance.
Description
Technical field
Field is decomposed the present invention relates to alkalescence and Neutral Electrolysis water, and in particular to a kind of nano metal simple substance modifies transition
Metal hydroxides array catalyst and its preparation method and application.
Background technology
Energy crisis and environmental pollution are 21 century two very severe problems facing of the whole world.In recent years, with stone
The increasingly exhaustion of the non-renewable fossil energy such as oil and coal, simultaneous carbon dioxide largely produces that is triggered " to imitate in greenhouse
Should " increasingly sharpen, countries in the world have all turned to the center of gravity of research the research and development of new energy.Persistence grinds in market
Study carefully company to claim, as national governments tend to more strict to the pay attention to day by day fuel specification of environmental protection, by gasoline in global range and
Diesel oil reduction sulfur content requirement drive, global hydrogen demand will increase by 27% before the year two thousand twenty, from 2013 when 255,300,000,000 cubes
Rice increases to 3248 billion cubic meters during the year two thousand twenty.Hydrogen is in oil refining, chemical industry, float glass, metal material and food production etc.
The consumption rapid growth in field.The nations of China and India will be promoted to implement stricter in road fuel field the need for clean air
Regulation, so as to make the Asian-Pacific area turn into the maximum hydrogen market in the whole world.In North America, road fuel specifies or will be further strict,
This will need to produce the gasoline and diesel oil of ultralow sulfur-bearing.Therefore, how to realize that preparation of industrialization hydrogen enjoys vast research work
The concern of person.
The method for commonly using natural gas pyrolysis reformation at present prepares hydrogen, thus inevitably a large amount of useizations
Stone fuel and emission greenhouse gas, it is impossible to realize real " green clean manufacturing ".And utilize renewable wind energy, solar energy etc.
Hydrogen prepared by the energy such as is subject to energy intermittence, is difficult to store and transport limited at the inferior position.And water electrolysis hydrogen production is to realize work
Industry, the cheap important means for preparing hydrogen.Recently, researcher is to based on the abundant and cheap metal sulfide of the earth
[Science 2007,317,100；Nat.Mater.2012,11,963；Nat.Mater.2013,12,850；Energy
Environ.Sci.2014,7,3519；Energy Environ.Sci.2013,6,3553], nitride [Angew.Chem.,
Int.Ed.2012,51,6131], boride [Angew.Chem., Int.Ed.2012,51,12703] and phosphide
The liberation of hydrogen such as [J.Am.Chem.Soc.2013,135,9267] catalyst has carried out numerous studies.However, exploitation design can be relatively low
With the new catalyst of high reaction rate liberation of hydrogen under overpotential, and further improve its long-time stability and realize extensive decomposition
Water hydrogen manufacturing is particularly important.
Recently, Xi'an Communications University Yang Bai human relations seminar reports low content platinum (5%) modification transition metal carbide and uses
The research [Chem.Commun.2016,52,369716] of Hydrogen Evolution Performance under its alkalescence condition is improved.The Dalian Chemistry and Physics Institute bag letter and
Seminar has delivered monoatomic metal modification molybdenum sulfide and can excite the paper of Hydrogen Evolution Performance under its acid condition, and the research is exploitation
Two-dimensional material catalyst opens a frontier [Energy Environ.Sci.2015,8,1594].Additionally, array is catalyzed
Agent has to be included good electric conductivity and structural stability is high, high surface contributes to active material efficient utilization and reduces to urge
Advantage [the J.Am.Chem.Soc.2014,136,10053 such as chemical property are improved while agent consumption；
Adv.Mater.2015,27,7051].Therefore, to improve catalyst catalytic performance and long-time stability, exploitation design is based on receiving
The high-performance liberation of hydrogen catalyst of rice metal simple-substance modification transition metal hydroxide array electrode has huge challenge.
The content of the invention
The present invention provides one kind and receives to solve low and stability relative mistake the technical problem of existing catalyst activity
Rice metal simple-substance modification transition metal hydroxide array catalyst and its preparation method and application.
The present invention provides the preparation method that a kind of nano metal simple substance modifies transition metal hydroxide array catalyst, should
Method includes：
Step one：Prepare transition metal hydroxide array；
Step 2：Work electricity is respectively with gained transition metal hydroxide array and the second metal salt solution in step one
Pole and electrolyte prepare nano metal simple substance and modify transition metal hydroxide array catalyst by electro-deposition techniques.
Preferably, described transition metal hydroxide array passes through hydro-thermal method, solvent-thermal method, chemical deposition or electricity
It is prepared by sedimentation.
Preferably, described electrodeposition process be using conductive substrates and the first metal salt solution as working electrode and
What electrolyte was prepared.
Preferably, the slaine in first metal salt solution is in nitrate, the chloride of iron, cobalt or nickel
Kind.
Preferably, described conductive substrates are carbon cloth, nickel screen, copper mesh, titanium net or titanium sheet.
Preferably, described electrodeposition temperature is 25 DEG C；Electrodeposition time is 2~60 minutes.
Preferably, the slaine in second metal salt solution be cobalt chloride, nickel nitrate, cobaltous sulfate, ferrous sulfate,
Nickel sulfate or chloroplatinic acid.
Preferably, the electrodeposition temperature of described step two is 25-30 DEG C；Electrodeposition time is 2~60 minutes.
The present invention also provides the nano metal simple substance modification transition metal hydroxide array that above-mentioned preparation method obtains and urges
Agent.
The present invention also provide above-mentioned nano metal simple substance modification transition metal hydroxide array catalyst alkalescence and in
Application in terms of property electrolytic cell.
Beneficial effects of the present invention
The present invention provides a kind of nano metal simple substance modification transition metal hydroxide array catalyst and preparation method thereof
And application, the catalyst is first to prepare transition metal hydroxide array；Then by gained transition metal hydroxide array and
Second metal salt solution is respectively working electrode and electrolyte and prepares nano metal simple substance modification transition gold by electro-deposition techniques
Category hydroxide array catalyst.Above-mentioned preparation method is simple, can be mass-produced, preparation-obtained array catalyst application
In alkalescence and Neutral Electrolysis pond, with excellent electrocatalytic hydrogen evolution and full electrolysis water performance.
Brief description of the drawings
Fig. 1 is the surface sweeping electromicroscopic photograph figure that the platinum that embodiment 1 is prepared modifies cobalt hydroxide nano-chip arrays；
Fig. 2 is the transmission electron microscope picture that the platinum that embodiment 1 is prepared modifies cobalt hydroxide nano-chip arrays；
Fig. 3 is that the platinum that embodiment 1 is prepared modifies cobalt hydroxide nano-chip arrays polarization curve in the basic conditions
Figure；
Fig. 4 is that the platinum that embodiment 1 is prepared modifies cobalt hydroxide nano-chip arrays polarization curve in neutral conditions
Figure；
Fig. 5 is the stereoscan photograph figure that the nickel that embodiment 2 is prepared modifies nickel hydroxide nano chip arrays；
Fig. 6 is that the nickel that embodiment 2 is prepared modifies nickel hydroxide nano chip arrays polarization curve in the basic conditions
Figure；
Fig. 7 is that the nickel that embodiment 2 is prepared modifies nickel hydroxide nano chip arrays in two electrode system neutral and alkali conditions
Under polarization curve.
Specific embodiment
The present invention provides the preparation method that a kind of nano metal simple substance modifies transition metal hydroxide array catalyst, should
Method includes：
Step one：Prepare transition metal hydroxide array；
Step 2：Work electricity is respectively with gained transition metal hydroxide array and the second metal salt solution in step one
Pole and electrolyte prepare nano metal simple substance and modify transition metal hydroxide array catalyst by electro-deposition techniques.
According to the present invention, transition metal hydroxide array is first prepared, the system of described transition metal hydroxide array
Preparation Method is not particularly limited, using hydro-thermal method well known to those skilled in the art, solvent-thermal method, chemical deposition or electro-deposition
Method, preferably hydro-thermal method or electrodeposition process.
First metal salt solution is preferably dissolved in solvent and fully dissolved by described hydro-thermal method in a kettle., then by conduction
Substrate cleans the intercalation reaction kettle that retreads with watery hydrochloric acid, ethanol, deionization；It is put into after sealed reactor in convection oven in 100-
8 hours are reacted at 180 DEG C；Transition metal hydroxide is obtained after being rinsed repeatedly with ethanol and deionized water after natural cooling
Array.Slaine in the first described metal salt solution is preferably the one kind in the nitrate of iron, cobalt or nickel, chloride, more
Preferably cobalt nitrate, nickel nitrate, ferrous sulfate or nickel sulfate；Solvent is preferably hexamethylenetetramine；Described conductive substrates are excellent
Elect the substrates such as carbon cloth, nickel screen, copper mesh, titanium net or titanium sheet as.
Described electro-deposition method is preferably with conductive substrates as working electrode, graphite flake is to be to electrode, silver/silver chlorate
Electro-deposition is carried out using CHI660E types electrochemical workstation in the three-electrode system of reference electrode, electrolyte is the first slaine
Solution is molten, and electrodeposition temperature is preferably 25 DEG C, and sedimentation time is 2~60 minutes, more preferably 5~15 minutes, will be post-depositional
Sample can obtain transition metal hydroxide array after being washed with deionized water and ethanol.The first described slaine is molten
Slaine in liquid is preferably the one kind in the nitrate of iron, cobalt or nickel, chloride, more preferably cobalt nitrate, ferrous sulfate or
Nickel sulfate；Described conductive substrates are preferably the substrates such as carbon cloth, nickel screen, copper mesh, titanium net or titanium sheet.
According to the present invention, by above-mentioned gained transition metal hydroxide array be working electrode, graphite flake be to electrode,
To carry out electro-deposition using CHI660E types electrochemical workstation in the three-electrode system of reference electrode, electrolyte is silver/silver chlorate
Second metal salt solution, electrodeposition temperature is preferably 25-30 DEG C, and sedimentation time is 2~60 minutes, more preferably 5~15 minutes,
The method of described electro-deposition is preferably cyclic voltammetry, and electricity volt is preferably -0.2~-1.4 volts, post-depositional sample is passed through
Nano metal simple substance modification transition metal hydroxide array catalyst is can obtain after being washed with deionized water and ethanol.It is described
Slaine in second metal salt solution is preferably cobalt chloride, nickel nitrate, cobaltous sulfate, ferrous sulfate, nickel sulfate or chloroplatinic acid.
The present invention nano metal simple substance modification transition metal hydroxide array that also the offer above method is prepared is urged
Agent.
The present invention also provide above-mentioned nano metal simple substance modification transition metal hydroxide array catalyst alkalescence and in
Property electrolytic cell in terms of application, using above-mentioned nano metal simple substance modify transition metal hydroxide array as negative electrode, anode or
Battery is helped in negative and positive level assembling, using CHI660E type electrochemical workstations test its electrocatalytic hydrogen evolution in alkaline electrolyte,
Analysis oxygen performance.
With reference to embodiment, the present invention will be further described in detail, and the raw material being related in embodiment is commercially available
Obtain.
Embodiment 1
1.45 grams of cobalt nitrates are weighed respectively and 1.4 grams of hexamethylenetetramines are dissolved in 35 ml deionized waters, treat that it fills
50 milliliters of reactors are transferred to after dividing dissolving；Carbon cloth is cleaned into the intercalation reaction kettle that retreads with watery hydrochloric acid, ethanol, deionization；Sealing
It is put into after reactor in convection oven and reacts 8 hours at 100 DEG C；After being rinsed repeatedly with ethanol and deionized water after natural cooling
Obtain cobalt hydroxide nano-chip arrays.
It is to use pole CHI660E type electrochemistry using above-mentioned cobalt hydroxide nano-chip arrays as working electrode, graphite flake
Work station carries out platinum electro-deposition, and electrolyte is the mixing of 1 mmoles chloroplatinic acid, 0.5 mmoles sodium hypophosphite and 0.2 mmoles sodium citrate
Solution, 3.5 are adjusted to using NaOH by pH, then with 0.25 milliampere/centimetre2Current density electro-deposition 15 at 30 DEG C
Minute, platinum modification cobalt hydroxide nano-chip arrays are obtained after being rinsed repeatedly using ethanol and deionized water.
Fig. 1 is the surface sweeping electromicroscopic photograph figure that the platinum that embodiment 1 is prepared modifies cobalt hydroxide nano-chip arrays, wherein scheming
A is the stereoscan photograph under 5 microns of scales, and figure b is the stereoscan photograph under 500 m-ns, the figure illustrates carbon cloth
It is completely covered by nano-chip arrays, its length is about 0.5~2 micron, and thickness is 10~30 nanometers.Fig. 2 is prepared into for embodiment 1
The platinum for arriving modifies the transmission electron microscope photo figure of cobalt hydroxide nano-chip arrays, wherein figure a is the transmission electron microscope under 200 m-ns
Photo, figure b is the transmission electron microscope photo under 5 m-ns, and the figure shows can just see diameter about 2~4 only in high-resolution
The Pt nanoparticle (Fig. 2 b) of nanometer.Fig. 3 shows the catalyst (1 rub potassium hydroxide, pH=14) pole in the basic conditions
Change curve map.With compare cobalt hydroxide array compared with, increased considerably by catalytic performance after platinum electrodeposition, and with and business
Change platinum carbon equally close to zero take-off potential, it is only necessary to 32 and 122 millivolts of overpotentials can drive 10 and 100 milliamperes/centimetre2Electricity
Current density.Fig. 4 shows the catalyst (1 rub phosphate buffer, pH=7) polarization curve in neutral conditions.With it is right
Compared according to cobalt hydroxide array, the catalyst equally illustrates excellent catalytic performance in neutral conditions.
Embodiment 2
With carbon cloth as working electrode, graphite flake be three electrodes to electrode and silver/silver chlorate (3M KCl) as reference electrode
Electro-deposition is carried out in system.Electrolyte rubs nickel nitrate solution for 0.1.Using CHI660E types electrochemical workstation with relative to full
Deposited 7 minutes at 25 DEG C with the constant potential that calomel electrode (SCE) is 1 volt, hydrogen-oxygen is can obtain after second alcohol and water is cleaned
Change nickel nano film array.
With nickel hydroxide nano chip arrays as working electrode, silver/silver chlorate is as reference electrode and 0.1 rubs nickel sulfate to be electrolysed
Liquid, is deposited 15 minutes using cyclic voltammetry between -0.2~-1.4 volts, and elemental nickel is can obtain after second alcohol and water is cleaned
The nickel hydroxide nano chip arrays of modification.
Fig. 5 is the surface sweeping electromicroscopic photograph figure that the nickel that embodiment 2 is prepared modifies nickel hydroxide nano chip arrays, wherein scheming
A is the stereoscan photograph under 5 microns of scales, and figure b is the stereoscan photograph under 500 m-ns, the figure illustrates carbon cloth
It is completely covered by nano-chip arrays, its length is about 30~100 nanometers, and thickness is 5~20 nanometers.Fig. 6 shows the catalyst
(1 rub potassium hydroxide, pH=14) polarization curve in the basic conditions.Compared with nickel hydroxide array is compareed, electric deposition nickel
Rear catalyst catalytic performance is significantly improved, and with the take-off potential as commercialization platinum carbon close to zero, needs 68 and 190 millivolts of mistakes
Current potential can drive 10 and 100 milliamperes/centimetre2Current density.Fig. 7 is the nickel modification nickel hydroxide that embodiment 2 is prepared
Polarization curve of the nano-chip arrays under the conditions of two electrode system neutral and alkalis, when current density is 10 milliamperes/centimetre2When nickel repair
Current potential when decorations nickel hydroxide nano chip arrays catalyst electrode is relative to standard hydrogen electrode is 1.58 volts.
Embodiment 3
Cobalt hydroxide nano-chip arrays will be obtained in embodiment 1 for working electrode, graphite flake are to be to pole, silver/silver chlorate
Reference electrode and 0.1 rubs nickel nitrate solution for electrolyte, is deposited 10 minutes between -0.2~-1.4 volts using cyclic voltammetry, leads to
The cobalt hydroxide nano-chip arrays that elemental nickel is modified are can obtain after crossing the cleaning of second alcohol and water.
The nickel modification cobalt hydroxide nano-chip arrays that embodiment 3 is obtained carry out alkaline Hydrogen Evolution Performance test, need 163 millivolts
Overpotential can drive 10 milliamperes/centimetre2Current density.
Embodiment 4
Cobalt hydroxide nano-chip arrays will be obtained in embodiment 1 for working electrode, graphite flake are to be to pole, silver/silver chlorate
Reference electrode and 0.1 rubs copperas solution for electrolyte, is deposited 5 minutes between -0.2~-1.4 volts using cyclic voltammetry,
The cobalt hydroxide nano-chip arrays that fe is modified are can obtain after second alcohol and water is cleaned.
The iron modification cobalt hydroxide nano-chip arrays that embodiment 4 is obtained carry out alkaline Hydrogen Evolution Performance test, need 215 millivolts
Overpotential can drive 10 milliamperes/centimetre2Current density.
Claims (10)
1. a kind of nano metal simple substance modifies the preparation method of transition metal hydroxide array catalyst, it is characterised in that should
Method includes：
Step one：Prepare transition metal hydroxide array；
Step 2：With in step one gained transition metal hydroxide array and the second metal salt solution be respectively working electrode and
Electrolyte prepares nano metal simple substance and modifies transition metal hydroxide array catalyst by electro-deposition techniques.
2. a kind of nano metal simple substance according to claim 1 modifies the preparation of transition metal hydroxide array catalyst
Method, it is characterised in that described transition metal hydroxide array passes through hydro-thermal method, solvent-thermal method, chemical deposition or electricity
It is prepared by sedimentation.
3. a kind of nano metal simple substance according to claim 2 modifies the preparation of transition metal hydroxide array catalyst
Method, it is characterised in that described electrodeposition process be using conductive substrates and the first metal salt solution as working electrode and
What electrolyte was prepared.
4. a kind of nano metal simple substance according to claim 3 modifies the preparation of transition metal hydroxide array catalyst
Method, it is characterised in that the slaine in first metal salt solution is in nitrate, the chloride of iron, cobalt or nickel
Kind.
5. a kind of nano metal simple substance according to claim 3 modifies the preparation of transition metal hydroxide array catalyst
Method, it is characterised in that described conductive substrates are carbon cloth, nickel screen, copper mesh, titanium net or titanium sheet.
6. a kind of nano metal simple substance according to claim 2 modifies the preparation of transition metal hydroxide array catalyst
Method, it is characterised in that described electrodeposition temperature is 25 DEG C；Electrodeposition time is 2~60 minutes.
7. a kind of nano metal simple substance according to claim 1 modifies the preparation of transition metal hydroxide array catalyst
Method, it is characterised in that slaine in second metal salt solution is cobalt chloride, nickel nitrate, cobaltous sulfate, ferrous sulfate,
Nickel sulfate or chloroplatinic acid.
8. a kind of nano metal simple substance according to claim 1 modifies the preparation of transition metal hydroxide array catalyst
Method, it is characterised in that the electrodeposition temperature of described step two is 25-30 DEG C；Electrodeposition time is 2~60 minutes.
9. the nano metal simple substance modification transition metal hydroxide that the preparation method described in claim 1-8 any one is obtained
Array catalyst.
10. the nano metal simple substance modification transition metal hydroxide array catalyst described in claim 9 is in alkalescence and neutrality
Application in terms of electrolytic cell.
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| CN107308958A (en) * | 2017-06-12 | 2017-11-03 | 首都师范大学 | A kind of oxygen evolution reaction electrochemical catalyst and its preparation and application |
| CN107630227A (en) * | 2017-08-04 | 2018-01-26 | 天津理工大学 | A kind of method that three-D nano-porous copper mesh elctro-catalyst is prepared based on metal net |
| CN109628952A (en) * | 2018-12-31 | 2019-04-16 | 武汉工程大学 | A kind of Ni-based double-metal hydroxide electrocatalytic hydrogen evolution catalyst of foamed nickel supported Ag doping and preparation method thereof |
| CN110965076A (en) * | 2019-12-06 | 2020-04-07 | 吉林大学 | Preparation method of electrolytic water electrode with double-function three-dimensional layered core-shell structure |
| CN111962099A (en) * | 2020-08-20 | 2020-11-20 | 中国科学院宁波材料技术与工程研究所 | Electrode for electrocatalytic production of hydrogen peroxide, preparation method and application thereof |
| WO2021143151A1 (en) * | 2020-01-16 | 2021-07-22 | 厦门大学 | Catalyst, preparation method therefor, and process for electrocatalytic decomposition of water into hydrogen |
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| CN113943950A (en) * | 2021-11-18 | 2022-01-18 | 西安工业大学 | Multi-metal hydroxide pre-catalyst and preparation method and application thereof |
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| CN111962099A (en) * | 2020-08-20 | 2020-11-20 | 中国科学院宁波材料技术与工程研究所 | Electrode for electrocatalytic production of hydrogen peroxide, preparation method and application thereof |
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