WO2023029586A1 - δ-PHASE TUNGSTEN NITRIDE ELECTRODE MATERIAL, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF - Google Patents
δ-PHASE TUNGSTEN NITRIDE ELECTRODE MATERIAL, PREPARATION METHOD THEREFOR, AND APPLICATION THEREOF Download PDFInfo
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- WO2023029586A1 WO2023029586A1 PCT/CN2022/092834 CN2022092834W WO2023029586A1 WO 2023029586 A1 WO2023029586 A1 WO 2023029586A1 CN 2022092834 W CN2022092834 W CN 2022092834W WO 2023029586 A1 WO2023029586 A1 WO 2023029586A1
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- conductive substrate
- solution
- tungsten nitride
- acid
- electrode material
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- 229910052721 tungsten Inorganic materials 0.000 title claims abstract description 120
- 239000010937 tungsten Substances 0.000 title claims abstract description 120
- -1 TUNGSTEN NITRIDE Chemical class 0.000 title claims abstract description 109
- 239000007772 electrode material Substances 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 77
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 37
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 239000011148 porous material Substances 0.000 claims description 56
- 238000000034 method Methods 0.000 claims description 49
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 43
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 43
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 27
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 24
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 22
- 229910002804 graphite Inorganic materials 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000151 deposition Methods 0.000 claims description 16
- 230000008021 deposition Effects 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 229910033181 TiB2 Inorganic materials 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000004020 conductor Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000003085 diluting agent Substances 0.000 claims description 8
- 238000005868 electrolysis reaction Methods 0.000 claims description 8
- 229910052697 platinum Inorganic materials 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 235000006408 oxalic acid Nutrition 0.000 claims description 5
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- AAQNGTNRWPXMPB-UHFFFAOYSA-N dipotassium;dioxido(dioxo)tungsten Chemical compound [K+].[K+].[O-][W]([O-])(=O)=O AAQNGTNRWPXMPB-UHFFFAOYSA-N 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 238000002848 electrochemical method Methods 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 239000004332 silver Substances 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 102000016938 Catalase Human genes 0.000 claims description 2
- 108010053835 Catalase Proteins 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 2
- 238000009388 chemical precipitation Methods 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000002378 acidificating effect Effects 0.000 abstract description 10
- 239000000243 solution Substances 0.000 description 63
- 238000003756 stirring Methods 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- 239000005695 Ammonium acetate Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 235000019257 ammonium acetate Nutrition 0.000 description 2
- 229940043376 ammonium acetate Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
- 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
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Definitions
- the present disclosure relates to the technical field of hydrogen production by electrolysis of water, in particular to a ⁇ -phase tungsten nitride electrode material and its preparation method and application.
- Hydrogen is an important clean energy, and the energy production, storage and utilization system centered on hydrogen energy is considered to be an ideal way to replace the current energy system based on fossil fuels. Hydrogen production by electrolysis of water has attracted extensive attention because of its simple principle, high purity of hydrogen production, clean and pollution-free production process, and the ability to use renewable energy to abandon electricity. The research and development of hydrogen production electrode materials and their preparation methods It is of great significance to the development of hydrogen production technology by electrolysis of water.
- Transition metal compound-tungsten nitride is an economical and practical catalytic material that exhibits surface properties, adsorption characteristics, and catalytic activity similar to Pt, and can replace traditional noble metal catalysts for efficient hydrodesulfurization and hydrodesorption Nitrogen and other reactions.
- WN mainly has two crystal phases, cubic phase (ie, ⁇ phase) and hexagonal phase (ie, ⁇ phase).
- the ⁇ -phase WN ( ⁇ -WN) is relatively easy to obtain but its hydrogen production performance is limited; the ⁇ -phase WN ( ⁇ -WN) has excellent hydrogen production performance in a wide pH range (acidic and alkaline) electrolytic environment, but the current All tungsten nitrides are prepared under high temperature and high pressure conditions (as described in the patent US9624604B2 and the paper Inorg.Chem.2017, 56, 7, 3970-3975), and the obtained tungsten nitrides are mostly powder particles or film materials.
- This type of material is difficult to be directly used as a hydrogen production electrode material, and it needs to be further combined with a conductive material as a hydrogen production electrode material.
- the hydrogen production efficiency of tungsten nitride is impaired and the overall stability of the electrode material is insufficient. good.
- the purpose of the present disclosure is to provide a ⁇ -phase tungsten nitride electrode material and its preparation method and application.
- the ⁇ -phase tungsten nitride electrode material of the present disclosure can be used as an acidic or alkaline electrolyte hydrogen-producing electrode or electrode material, a catalyst and a conductive material.
- the materials are tightly bonded, have excellent hydrogen production performance and stability, and the preparation method of the ⁇ -phase tungsten nitride electrode material disclosed in the present disclosure has mild process conditions and low energy consumption.
- the first aspect of the present disclosure provides a ⁇ -phase tungsten nitride electrode material
- the ⁇ -phase tungsten nitride electrode material includes a conductive substrate with a slit structure and a ⁇ -phase tungsten nitride layer, at least part of the tungsten nitride electrode material
- the ⁇ -phase tungsten nitride layer is coated on the inner wall surface of the pore structure
- the slit structure includes holes extending inwardly on the surface of the conductive substrate and/or slits extending generally along the surface of the conductive substrate; the surface slits account for 5-70%, and the slit structure
- the size of the opening is 500nm-500 ⁇ m, and the depth of the slit structure is more than 1.5 times the size of the opening.
- the second aspect of the present disclosure provides a method for preparing a ⁇ -phase tungsten nitride electrode material, the method comprising: subjecting a conductive substrate containing tungsten oxide and/or tungstic acid to an ammoniation reaction in an ammonia gas atmosphere;
- the conductive substrate containing tungsten oxide and/or tungstic acid has a slit structure, and at least part of the tungsten oxide and/or tungstic acid is attached to the inner wall surface of the slit structure; the proportion of the surface slits is 5-70%, the opening size of the pore structure is 500nm-500 ⁇ m, and the depth of the pore structure is more than 1.5 times the opening size;
- the conditions of the ammoniation reaction include: the temperature is 900-1800°C, and the time is 30-240min.
- the third aspect of the present disclosure provides a ⁇ -phase tungsten nitride electrode material prepared by the method provided in the second aspect of the present disclosure.
- the fourth aspect of the present disclosure provides an application of the ⁇ -phase tungsten nitride electrode material provided in the first aspect and/or the third aspect of the present disclosure in hydrogen production by electrolysis of water.
- the ⁇ -phase tungsten nitride electrode material disclosed in the present disclosure can be used as an electrode or electrode material for hydrogen production in acidic or alkaline electrolytes, and has excellent hydrogen production in electrolytic environments with a wide pH range (acidic and alkaline) Performance:
- the preparation method of the ⁇ -phase tungsten nitride electrode material disclosed in the present disclosure has mild process conditions and low energy consumption.
- Figure 1 is the XRD spectrum of the ⁇ -phase tungsten nitride electrode material prepared in Example 1 of the present disclosure
- Example 2 is a scanning electron micrograph of the delta-phase tungsten nitride electrode material prepared in Example 1 of the present disclosure
- Fig. 3 is the hydrogen production polarization curve of the ⁇ -phase tungsten nitride electrode material prepared in Example 1 of the present disclosure and the ⁇ -phase tungsten nitride electrode material prepared in Comparative Example 1 in an acidic electrolyte;
- Example 4 is a graph showing the hydrogen production polarization curves of the ⁇ -phase tungsten nitride electrode material prepared in Example 1 of the present disclosure and the ⁇ -phase tungsten nitride electrode material prepared in Comparative Example 1 in an alkaline electrolyte;
- Fig. 5 is a time-current graph of hydrogen production of the ⁇ -phase tungsten nitride electrode material prepared in Example 1 of the present disclosure.
- the first aspect of the present disclosure provides a ⁇ -phase tungsten nitride electrode material
- the ⁇ -phase tungsten nitride electrode material includes a conductive substrate with a slit structure and a ⁇ -phase tungsten nitride layer, at least part of the ⁇ -phase tungsten nitride
- the tungsten layer is covered on the inner wall surface of the hole structure;
- the hole structure includes holes extending inwardly on the surface of the conductive substrate and/or slits extending generally along the surface of the conductive substrate; the surface hole
- the proportion is 5-70%, the opening size of the pore structure is 500nm-500 ⁇ m, and the depth of the pore structure is more than 1.5 times of the opening size.
- the slit extending substantially along the surface of the conductive base means that the main body of the slit is on the surface of the conductive base.
- the slit structure refers to regular or disordered elongated or channel-like slits.
- the opening size of the slit structure refers to the maximum width of the slit; when the slit structure In the case of channel-like slits, the opening size of the slit structure refers to the maximum diameter of the channel opening.
- the ⁇ -phase tungsten nitride electrode material disclosed in the present disclosure can be used as a hydrogen-producing electrode or electrode material for an acidic or alkaline electrolyte, and has excellent hydrogen-producing performance and stability in an electrolytic environment with a wide pH range (acidic and alkaline).
- the average thickness of the ⁇ -phase tungsten nitride layer in different regions of the slit structure in the ⁇ -phase tungsten nitride electrode material of the present application can be different.
- the average thickness of the ⁇ -phase tungsten nitride layer is 10 nm-20 ⁇ m, preferably 1-5 ⁇ m, and the average thickness of the ⁇ -phase tungsten nitride layer can be measured with a scanning electron microscope.
- the thickness of the delta-phase tungsten nitride layer within the above range is suitable, which is beneficial to the conductive contact and mass transfer of the outermost delta-phase tungsten nitride, and the delta-phase tungsten nitride electrode material has better hydrogen production performance.
- the second aspect of the present disclosure provides a method for preparing a ⁇ -phase tungsten nitride electrode material, the method comprising: subjecting a conductive substrate containing tungsten oxide and/or tungstic acid to an ammoniation reaction in an ammonia atmosphere; wherein, the The conductive substrate of tungsten oxide and/or tungstic acid has a pore structure, at least part of the tungsten oxide and/or tungstic acid is attached to the inner wall surface of the pore structure; the surface pore ratio is 5-70% , the opening size of the pore structure is 500nm-500 ⁇ m, and the depth of the pore structure is more than 1.5 times the opening size; the conditions of the ammoniation reaction include: the temperature is 900-1800°C, and the time is 30 -240min.
- the inventors of the present disclosure have found that based on the confinement effect of the pore structure, that is, under relatively mild reaction conditions, the special atmosphere (higher temperature, pressure or ammonia gas density) generated in the limited area where the substrate pore is located can Promotes the formation of delta-phase tungsten nitride (delta-WN).
- the process condition of the disclosed method is milder and the energy consumption is lower.
- the conditions of the ammoniation reaction include: the temperature is 950-1150°C, and the time is 60-180min; more preferably, the temperature is 1000-1100°C, and the time is 90- 120min.
- the ⁇ -phase tungsten nitride electrode material prepared under the above conditions has better hydrogen production performance when applied to the process of hydrogen production by electrolysis of water.
- the material of the conductive base is a conductive material with a porous structure and good high temperature stability.
- the material of the conductive substrate can be selected from one or more of graphite, titanium carbide and titanium diboride, and the above materials can be purchased from commercial sources or synthesized by oneself.
- the conductive substrate is subjected to surface treatment, such as potassium hydroxide activation treatment or surface etching treatment.
- surface treatment such as potassium hydroxide activation treatment or surface etching treatment.
- the present disclosure does not specifically limit the shape and size of the conductive substrate, which can be in any regular or irregular shape, such as flake, rod, circular column, block or powder, preferably flake or rod , circular columnar or massive.
- the prepared ⁇ -phase tungsten nitride electrode material does not need subsequent processing and molding, and can be directly used as a ⁇ -WN three-dimensional independent hydrogen production electrode, and the contact resistance is relatively small.
- the ⁇ -phase tungsten nitride electrode material is prepared as a small block or powder material, which can be used as an electrode after subsequent processing and molding, for example, the Small block materials and/or powder materials are made into membrane electrodes on the surface of glassy carbon electrodes as working electrodes.
- the opening size of the pore structure is 500nm-500 ⁇ m
- the depth of the pore structure is more than 1.5 times the width of the pore
- the proportion of the surface pores is 5-70%
- the surface pore ratio is 5-70%.
- Ratio means the ratio of the area occupied by pores on the surface of the substrate to the surface area of the substrate.
- the proportion of pores on the surface can be obtained by taking electron micrographs of the material with a scanning electron microscope, and then importing the electron micrographs into IMAGE G software for analysis.
- the opening size of the pore structure is 5-200 ⁇ m
- the depth of the pore structure is 2-10 times the width of the pore
- the proportion of surface pores is 30-60%.
- the method also includes: preparing the conductive substrate containing tungsten trioxide and/or tungstic acid in situ by a chemical synthesis method; the chemical synthesis method is selected from hydrothermal method, electrochemical method, co-precipitation method and One or more of the chemical precipitation methods.
- the conductive substrate containing tungsten oxide and/or tungstic acid is prepared in situ by a hydrothermal method comprising the following steps: S1, mixing and adjusting the first tungsten source, strong acid and solvent The pH value is 1-2, and the first solution is obtained; S2, the first solution is mixed with a weak acid to obtain a tungstic acid precursor; S3, the tungstic acid precursor and the first conductive substrate are placed in a heat-resistant airtight container The hydrothermal reaction is carried out to obtain the conductive substrate containing tungsten oxide and/or tungstic acid.
- the product obtained by the hydrothermal reaction is cleaned and dried.
- the solution used for cleaning is conventionally used by those skilled in the art, such as ethanol, deionized water, etc., and the drying temperature can be 50-150°C , the time is 8-48 hours.
- step S3 may include: performing a hydrothermal reaction on the tungstic acid precursor, capping agent, surfactant, template agent and the first conductive substrate in a heat-resistant airtight container.
- Capping agent can be well known to those skilled in the art, for example can be selected from one or more in ammonium sulfate, sodium sulfate, sodium lauryl sulfate and citric acid;
- Surfactant and templating agent can be independently One or more selected from n-butanol, cyclohexane and cetyltrimethylammonium bromide.
- the molar ratio of the first solution to the amount of the weak acid can be changed within a wide range, for example, it can be 1:(2-3), preferably 1:(2-2.5 ), the first solution is based on the first tungsten source.
- the hydrothermal reaction is well known to those skilled in the art, and can be carried out in a heat-resistant airtight container, for example, it can be carried out in a polytetrafluoroethylene-lined hydrothermal kettle.
- the conditions of the hydrothermal reaction It may include: the temperature is 120-220°C, and the time is 6-48 hours; preferably, the temperature is 160-200°C, and the time is 12-24 hours.
- the first tungsten source can be selected from one or more of sodium tungstate, potassium tungstate, zinc tungstate, ammonium metatungstate and tungsten chloride;
- the strong acid can be selected from hydrochloric acid, nitric acid and dilute sulfuric acid One or more of them, the concentration of the strong acid can vary within a relatively large range, preferably 1-5mol/L;
- the solvent can be selected from deionized water, ethanol, ethylene glycol, isopropanol, N , one or more of N-dimethylformamide and acetonitrile;
- the weak acid can be selected from one or more of oxalic acid, formic acid, acetic acid and carbonic acid;
- the material of the first conductive substrate has holes
- the conductor material with seam structure and good high temperature stability is preferably one or more of graphite, titanium carbide and titanium diboride.
- the electrochemical method comprising the following steps is used to prepare the conductive substrate containing tungsten oxide and/or tungstic acid: (1), making the second tungsten source contact with hydrogen peroxide solution After the reaction, optionally remove the hydrogen peroxide contained in the reacted solution to obtain a second solution; (2), dilute the second solution with a diluent to obtain an electrolyte; (3), use the second
- the conductive substrate is a working electrode, and it is placed in the electrolyte, and tungsten oxide and/or tungstic acid are deposited on the second conductive substrate by a constant potential method to obtain a conductive substrate containing tungsten oxide and/or tungstic acid .
- the removal of hydrogen peroxide contained in the reacted solution includes: contacting the catalyst with the reacted solution to obtain a second solution; or, removing the reacted solution Heating at 50-90°C to obtain a second solution; wherein, the catalyst is one or more of platinum, silver, chromium, manganese dioxide, ferric chloride, copper oxide and catalase, when the When the ratio of the volume of the second solution to the volume of the hydrogen peroxide solution initially added in step (1) is 0.75-0.85, take out the catalyst or stop the heating.
- the concentration of the hydrogen peroxide solution can vary within a relatively large range, and the preferred mass fraction is 25-35%.
- the volume ratio of the second solution to the amount of the diluent can vary within a relatively large range, preferably 1: (9-29); the diluent contains water , isopropanol, ethanol, ethylene glycol, acetone, acetonitrile and one or more of N, N-dimethylformamide, preferably, the diluent contains water and isopropanol, and the water and The volume ratio of isopropanol is 1:(0.4-1).
- the deposition conditions include: the deposition potential is from -0.4V to -5V, and the deposition time is 1-60min; preferably, the deposition potential is from -1V to -3V, and the deposition time is 5 min. -30min.
- the second conductive substrate is immersed in the electrolyte solution for 5-15 hours, and then tungsten oxide and/or tungstic acid are deposited on the second conductive substrate by a constant potential method.
- the second tungsten source can be selected from one or more of metal tungsten powder, tungsten wire and tungsten sheet, more preferably tungsten powder; the material of the second conductive substrate has a slit structure and The conductor material with good high temperature stability is preferably one or more of graphite, titanium carbide and titanium diboride.
- the ammoniation reaction can be carried out in a muffle furnace, a tube furnace or a fluidized bed.
- a sealed reaction furnace such as a muffle furnace or a tube furnace
- the ammonia atmosphere The volume concentration of ammonia can be 10-100%; when the ammoniation reaction is carried out in a fluidized bed, the flow of ammonia can be any flow, preferably 10-100mL/min.
- the ammonia gas atmosphere can be obtained by directly feeding ammonia gas, or by decomposing compounds that are easy to decompose to generate ammonia gas (such as urea, melamine, ammonium acetate, etc.) during the heating process.
- the third aspect of the present disclosure provides a ⁇ -phase tungsten nitride electrode material prepared by the method provided in the second aspect of the present disclosure.
- the ⁇ -phase tungsten nitride electrode material of the present disclosure is an efficient and economical hydrogen-producing electrode material that meets the requirements of different types of electrolytic cells, is applicable to a wide pH range.
- the fourth aspect of the present disclosure provides an application of the ⁇ -phase tungsten nitride electrode material provided in the first aspect and/or the third aspect of the present disclosure in hydrogen production by electrolysis of water.
- the ⁇ -phase tungsten nitride electrode material is used as a hydrogen-producing electrolytic material in an electrolytic cell.
- the following examples and comparative examples use XRD to detect the phase state of tungsten nitride contained in the electrode material, and use a scanning electron microscope to measure the thickness of the tungsten nitride layer.
- the raw materials in the following examples are all commercially available.
- the graphite rod (WO 3 /GR) with dark blue tungsten oxide (WO 3 ) was taken out, rinsed with ethanol and water for 5-7 times, and dried in an oven at 80°C to obtain A conductive substrate containing tungsten oxide, tungsten oxide is grown in the pore structure of the conductive substrate;
- the body is the particle of the ⁇ -phase tungsten nitride electrode material of the substrate (the thickness of the ⁇ -phase tungsten nitride layer is 1-5 ⁇ m), and the ⁇ -phase tungsten nitride electrode material is dispersed in isopropanol containing a certain amount of Nafion membrane solution , drop-coated on the surface of the glassy carbon electrode to make a membrane electrode for testing.
- the graphite sheet (the surface pores account for about 40%, and the opening size of the pore structure is 100 to 250 ⁇ m, The depth is 3-10 times of the width of the hole) soaked in the electrolyte for 10 hours.
- Set the deposition potential to -1.0V, and deposit at a constant potential on the graphite sheet for 30 min.
- the material is taken out, rinsed with deionized water for 3 to 5 times, and dried in an oven at 60°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
- the titanium carbide sheet (surface slits account for about 60%, and the opening size of the slit structure is 50 ⁇ 200 ⁇ m, the depth is 3-10 times the width of the hole) soaked in the electrolyte for 10 hours.
- Set the deposition potential to -3.0V, and deposit at a constant potential for 5 minutes.
- the material is taken out, rinsed with deionized water for 3 to 5 times, and dried in an oven at 60°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
- the titanium diboride sheet (the surface slits account for about 50%, and the openings of the slit structure
- the size is 50-150 ⁇ m, and the depth is 5-10 times of the width of the hole) soaked in the electrolyte for 10 hours, set the deposition potential to -0.8V, and deposited at a constant potential for 25 minutes.
- the material is taken out, rinsed with deionized water for 3 to 5 times, and dried in an oven at 70°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
- the titanium diboride rod (the surface pores account for about 70%, and the opening size of the pore structure is 50-200 ⁇ m, the depth is 2-8 times the width of the hole) soak in the electrolyte for 10 hours, set the deposition potential to -0.7V, and deposit at a constant potential for 25 minutes.
- the material is taken out, rinsed with deionized water for 3 to 5 times, and dried in an oven at 70°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
- the ⁇ -phase tungsten nitride electrode material was prepared by the same method as in Example 1, except that in step S4, the temperature was raised to 1050°C at 2°C/min and kept at this temperature for 120min, and the obtained ⁇ -phase tungsten nitride
- the thickness of the layer is from 100 nm to 5 ⁇ m.
- the ⁇ -phase tungsten nitride electrode material was prepared by the same method as in Example 1, except that in step S4, the temperature was raised to 900°C at 2°C/min and kept at this temperature for 120min, and the ⁇ -phase tungsten nitride layer The thickness is 100nm-2 ⁇ m.
- step S3 Adopt the same method as Example 1 to prepare ⁇ -phase tungsten nitride electrode materials, the only difference is that in step S3, take 40mL of tungstic acid precursor, add 2g of ammonium sulfate as a capping agent, and then transfer the solution to Graphite rods with a ⁇ 3mm ⁇ 50mm surface and a slit structure are placed in advance (the proportion of surface slits is about 30%, the opening size of the slit structure is 300-500 ⁇ m, and the depth is 3-10 times the width of the slits)
- the hydrothermal reaction is carried out at 200° C. for 12 hours in a hydrothermal kettle lined with polytetrafluoroethylene, and the thickness of the delta-phase tungsten nitride layer is 5-10 ⁇ m.
- the ⁇ -phase tungsten nitride electrode material was prepared by the same method as in Example 1, except that in step S2, the temperature of the hydrothermal reaction was 140° C., and the time was 16 hours.
- the thickness of the obtained ⁇ -phase tungsten nitride layer was 500nm-3 ⁇ m.
- the tungsten nitride electrode material was prepared by the same method as in Example 1, except that in step S4, the temperature was raised to 800° C. at 6° C./min and kept at this temperature for 120 minutes. According to XRD detection, the tungsten nitride electrode material prepared in this comparative example is a ⁇ -phase tungsten nitride electrode material.
- step S3 The same method as in Example 1 was used to prepare the tungsten nitride electrode material, the only difference being that in step S3, 40mL of tungstic acid precursor was taken, 2g of ammonium sulfate was added as a capping agent, and then the solution was transferred to a pre-placed A solid graphite rod ( ⁇ 3mm ⁇ 50mm) lined with polytetrafluoroethylene, which accounts for 3% of the surface pores, the opening size of the pore structure is 2-5 ⁇ m, and the depth of the pore structure is 3-5 times the opening size. In a hydrothermal kettle, the hydrothermal reaction was carried out at 180°C for 16 hours, and most of the surface was grown as ⁇ -phase tungsten nitride electrode material.
- Example 1 of US9624604B2 using WCl 6 and NaN 3 (ratio 3:2) as precursors, NaCl+10wt% ZrO 2 as filler, reacting at 1400 ° C and 7.7 GPa, the resulting product was washed with water , centrifugation, and drying to obtain ⁇ -phase tungsten nitride powder.
- the ⁇ -phase tungsten nitride material is dispersed in isopropanol containing a certain amount of Nafion membrane solution, and dropped on the surface of a glassy carbon electrode to form a membrane electrode for testing.
- the electrode material or membrane electrode prepared in the above examples and comparative examples is used as the working electrode, the common graphite rod is used as the counter electrode, and silver/silver chloride is used as the reference electrode.
- the overpotential required for hydrogen production by electrolysis of water to achieve a current density of 10mA/cm -2 is shown in Table 1, and the hydrogen production polarization curves of the electrodes prepared in Example 1 and Comparative Example 1 are shown in Figure 3 .
- the electrode materials prepared in the examples and comparative examples were subjected to a 15-hour continuous hydrogen production reaction by electrolyzing water at a constant overpotential, and the change of the current density over time was detected. , the hydrogen production time-current density curve of the electrode prepared in Example 1 is shown in FIG. 5 .
- the current density refers to the current per unit electrode area obtained under a certain voltage.
- the method of the present disclosure has mild process conditions and low energy consumption, and can prepare ⁇ -phase tungsten nitride electrode materials, and the ⁇ -phase tungsten nitride electrode materials prepared by the method of the present disclosure can be used as acidic or alkaline electrolytes to produce hydrogen Electrodes or electrode materials have better hydrogen production activity and stability.
- the temperature of the ammoniation reaction is 1000-1100° C. and the time is 90-120 minutes, the prepared ⁇ -phase tungsten nitride electrode material has better hydrogen production activity and stability.
- the prepared The ⁇ -phase tungsten nitride electrode material has better hydrogen production activity and stability.
- the hydrothermal temperature is 160-200°C and the hydrothermal time is 12-24 hours, the prepared delta-phase tungsten nitride electrode material has better hydrogen production activity and stability.
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Abstract
The present disclosure relates to a δ-phase tungsten nitride electrode material, a preparation method therefor, and an application thereof. The δ-phase tungsten nitride electrode material comprises a conductive substrate having an aperture-slit structure and a δ-phase tungsten nitride layer, and at least part of the δ-phase tungsten nitride layer covers the inner wall surface of the aperture-slit structure; the aperture-slit structure comprises an aperture extending inwards on the surface of the conductive substrate and/or a slit extending substantially along the surface of the conductive substrate; and the surface aperture-slit accounts for 5-70%, the opening size of the aperture-slit structure is 500 nm to 500 μm, and the depth of the aperture-slit structure is 1.5 times or more of the opening size. The δ-phase tungsten nitride electrode material of the present disclosure can be used as an acidic or alkaline electrolyte hydrogen production electrode or electrode material, and has excellent hydrogen production performance and stability.
Description
相关申请的交叉引用Cross References to Related Applications
本公开要求在2021年9月6日提交中国专利局、申请号为202111040477.9、名称为“一种δ相氮化钨电极材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。This disclosure claims the priority of the Chinese patent application with the application number 202111040477.9 and the title "a delta-phase tungsten nitride electrode material and its preparation method and application" submitted to the China Patent Office on September 6, 2021, the entire content of which Incorporated by reference in this disclosure.
本公开涉及电解水制氢技术领域，具体地，涉及一种δ相氮化钨电极材料及其制备方法和应用。The present disclosure relates to the technical field of hydrogen production by electrolysis of water, in particular to a δ-phase tungsten nitride electrode material and its preparation method and application.
氢气是重要的清洁能源，以氢能为核心的能源生产、储存与利用***被认为是替代当前基于化石燃料能源体系的理想方式。电解水制氢技术因其原理简单、制氢纯度高、生产过程清洁无污染、能够利用可再生能源弃电等优点，受到了广泛的关注，而产氢电极材料及其制备方法的研究和开发对电解水制氢技术的发展具有重要意义。Hydrogen is an important clean energy, and the energy production, storage and utilization system centered on hydrogen energy is considered to be an ideal way to replace the current energy system based on fossil fuels. Hydrogen production by electrolysis of water has attracted extensive attention because of its simple principle, high purity of hydrogen production, clean and pollution-free production process, and the ability to use renewable energy to abandon electricity. The research and development of hydrogen production electrode materials and their preparation methods It is of great significance to the development of hydrogen production technology by electrolysis of water.
过渡金属化合物——氮化钨(WN)是一种经济实用的催化材料，表现出类似于Pt的表面性质、吸附特性和催化活性，可替代传统贵金属催化剂用于高效加氢脱硫和加氢脱氮等反应。WN主要有立方相(即β相)和六方相(即δ相)两种晶相。其中，β相WN(β-WN)较为易得但其产氢性能有限；δ相WN(δ-WN)在宽pH范围(酸性和碱性)电解环境中具有优异的产氢性能，但现有氮化钨均采用高温高压条件制备(如专利US9624604B2与论文Inorg.Chem.2017,56,7,3970–3975中所述)，所得氮化钨多为粉体颗粒或薄膜材料。该类材料较难直接作为制氢电极材料，需与导电材料进一步结合作为产氢电极材料，但由于催化剂与导电材料结合力有限，氮化钨的产氢效率受损且电极材料整体稳定性欠佳。Transition metal compound-tungsten nitride (WN) is an economical and practical catalytic material that exhibits surface properties, adsorption characteristics, and catalytic activity similar to Pt, and can replace traditional noble metal catalysts for efficient hydrodesulfurization and hydrodesorption Nitrogen and other reactions. WN mainly has two crystal phases, cubic phase (ie, β phase) and hexagonal phase (ie, δ phase). Among them, the β-phase WN (β-WN) is relatively easy to obtain but its hydrogen production performance is limited; the δ-phase WN (δ-WN) has excellent hydrogen production performance in a wide pH range (acidic and alkaline) electrolytic environment, but the current All tungsten nitrides are prepared under high temperature and high pressure conditions (as described in the patent US9624604B2 and the paper Inorg.Chem.2017, 56, 7, 3970-3975), and the obtained tungsten nitrides are mostly powder particles or film materials. This type of material is difficult to be directly used as a hydrogen production electrode material, and it needs to be further combined with a conductive material as a hydrogen production electrode material. However, due to the limited binding force between the catalyst and the conductive material, the hydrogen production efficiency of tungsten nitride is impaired and the overall stability of the electrode material is insufficient. good.
发明内容Contents of the invention
本公开的目的是提供一种δ相氮化钨电极材料及其制备方法和应用，本 公开的δ相氮化钨电极材料可以作为酸性或碱性电解液产氢电极或电极材料，催化剂与导电材料结合紧密，具有优良的产氢性能和稳定性，本公开的δ相氮化钨电极材料的制备方法工艺条件温和、耗能较低。The purpose of the present disclosure is to provide a δ-phase tungsten nitride electrode material and its preparation method and application. The δ-phase tungsten nitride electrode material of the present disclosure can be used as an acidic or alkaline electrolyte hydrogen-producing electrode or electrode material, a catalyst and a conductive material. The materials are tightly bonded, have excellent hydrogen production performance and stability, and the preparation method of the δ-phase tungsten nitride electrode material disclosed in the present disclosure has mild process conditions and low energy consumption.
为了实现上述目的，本公开第一方面提供一种δ相氮化钨电极材料，所述δ相氮化钨电极材料包括具有孔缝结构的导电基底和δ相氮化钨层，至少部分的所述δ相氮化钨层覆于所述孔缝结构的内壁表面；In order to achieve the above purpose, the first aspect of the present disclosure provides a δ-phase tungsten nitride electrode material, the δ-phase tungsten nitride electrode material includes a conductive substrate with a slit structure and a δ-phase tungsten nitride layer, at least part of the tungsten nitride electrode material The δ-phase tungsten nitride layer is coated on the inner wall surface of the pore structure;
所述孔缝结构包括在所述导电基底表面向内部延伸的孔和/或大体沿所述导电基体表面延伸的狭缝；所述表面孔缝占比为5-70％，所述孔缝结构的开口尺寸为500nm-500μm，所述孔缝结构的深度为所述开口尺寸的1.5倍以上。The slit structure includes holes extending inwardly on the surface of the conductive substrate and/or slits extending generally along the surface of the conductive substrate; the surface slits account for 5-70%, and the slit structure The size of the opening is 500nm-500μm, and the depth of the slit structure is more than 1.5 times the size of the opening.
本公开第二方面提供一种制备δ相氮化钨电极材料的方法，该方法包括：在氨气氛围中使含有氧化钨和/或钨酸的导电基底进行氨化反应；The second aspect of the present disclosure provides a method for preparing a δ-phase tungsten nitride electrode material, the method comprising: subjecting a conductive substrate containing tungsten oxide and/or tungstic acid to an ammoniation reaction in an ammonia gas atmosphere;
其中，所述含有氧化钨和/或钨酸的导电基底具有孔缝结构，至少部分的所述氧化钨和/或钨酸附于所述孔缝结构的内壁表面；所述表面孔缝占比为5-70％，所述孔缝结构的开口尺寸为500nm-500μm，所述孔缝结构的深度为所述开口尺寸的1.5倍以上；Wherein, the conductive substrate containing tungsten oxide and/or tungstic acid has a slit structure, and at least part of the tungsten oxide and/or tungstic acid is attached to the inner wall surface of the slit structure; the proportion of the surface slits is 5-70%, the opening size of the pore structure is 500nm-500μm, and the depth of the pore structure is more than 1.5 times the opening size;
所述氨化反应的条件包括：温度为900-1800℃，时间为30-240min。The conditions of the ammoniation reaction include: the temperature is 900-1800°C, and the time is 30-240min.
本公开第三方面提供一种本公开第二方面提供的方法制备得到的δ相氮化钨电极材料。The third aspect of the present disclosure provides a δ-phase tungsten nitride electrode material prepared by the method provided in the second aspect of the present disclosure.
本公开第四方面提供一种本公开第一方面和/或第三方面提供的δ相氮化钨电极材料在电解水制氢中的应用。The fourth aspect of the present disclosure provides an application of the δ-phase tungsten nitride electrode material provided in the first aspect and/or the third aspect of the present disclosure in hydrogen production by electrolysis of water.
通过上述技术方案，本公开的δ相氮化钨电极材料可以作为酸性或碱性电解液产氢电极或电极材料，在宽pH值范围(酸性和碱性)的电解环境中具有优异的产氢性能；本公开的δ相氮化钨电极材料的制备方法工艺条件温和、耗能较低。Through the above technical scheme, the δ-phase tungsten nitride electrode material disclosed in the present disclosure can be used as an electrode or electrode material for hydrogen production in acidic or alkaline electrolytes, and has excellent hydrogen production in electrolytic environments with a wide pH range (acidic and alkaline) Performance: The preparation method of the δ-phase tungsten nitride electrode material disclosed in the present disclosure has mild process conditions and low energy consumption.
本公开的其他特征和优点将在随后的具体实施方式部分予以详细说明。Other features and advantages of the present disclosure will be described in detail in the detailed description that follows.
上述说明仅是本公开技术方案的概述，为了能够更清楚了解本公开的技术手段，而可依照说明书的内容予以实施，并且为了让本公开的上述和其它目的、特征和优点能够更明显易懂，以下特举本公开的具体实施方式。The above description is only an overview of the technical solution of the present disclosure. In order to better understand the technical means of the present disclosure, it can be implemented according to the contents of the description, and in order to make the above and other purposes, features and advantages of the present disclosure more obvious and understandable , the specific embodiments of the present disclosure are enumerated below.
为了更清楚地说明本公开实施例或相关技术中的技术方案，下面将对实施例或相关技术描述中所需要使用的附图作一简单地介绍，显而易见地，下面描述中的附图是本公开的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present disclosure or related technologies, the following will briefly introduce the drawings that need to be used in the descriptions of the embodiments or related technologies. Obviously, the drawings in the following description are the For some disclosed embodiments, those skilled in the art can also obtain other drawings based on these drawings without any creative work.
附图是用来提供对本公开的进一步理解，并且构成说明书的一部分，与下面的具体实施方式一起用于解释本公开，但并不构成对本公开的限制。在附图中：The accompanying drawings are used to provide a further understanding of the present disclosure, and constitute a part of the description, together with the following specific embodiments, are used to explain the present disclosure, but do not constitute a limitation to the present disclosure. In the attached picture:
图1是本公开实施例1制备的δ相氮化钨电极材料的XRD谱图；Figure 1 is the XRD spectrum of the δ-phase tungsten nitride electrode material prepared in Example 1 of the present disclosure;
图2是本公开实施例1制备的δ相氮化钨电极材料的扫描电镜照片；2 is a scanning electron micrograph of the delta-phase tungsten nitride electrode material prepared in Example 1 of the present disclosure;
图3是本公开实施例1制备的δ相氮化钨电极材料和对比例1制备的β相氮化钨电极材料在酸性电解液中的产氢极化曲线图；Fig. 3 is the hydrogen production polarization curve of the δ-phase tungsten nitride electrode material prepared in Example 1 of the present disclosure and the β-phase tungsten nitride electrode material prepared in Comparative Example 1 in an acidic electrolyte;
图4是本公开实施例1制备的δ相氮化钨电极材料和对比例1制备的β相氮化钨电极材料在碱性电解液中的产氢极化曲线图；4 is a graph showing the hydrogen production polarization curves of the δ-phase tungsten nitride electrode material prepared in Example 1 of the present disclosure and the β-phase tungsten nitride electrode material prepared in Comparative Example 1 in an alkaline electrolyte;
图5是本公开实施例1制备的δ相氮化钨电极材料的产氢的时间-电流曲线图。Fig. 5 is a time-current graph of hydrogen production of the δ-phase tungsten nitride electrode material prepared in Example 1 of the present disclosure.
为使本公开实施例的目的、技术方案和优点更加清楚，下面将结合本公开实施例中的附图，对本公开实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本公开一部分实施例，而不是全部的实施例。基于本公开中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本公开保护的范围。In order to make the purpose, technical solutions and advantages of the embodiments of the present disclosure clearer, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below in conjunction with the drawings in the embodiments of the present disclosure. Obviously, the described embodiments It is a part of the embodiments of the present disclosure, but not all of them. Based on the embodiments in the present disclosure, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present disclosure.
以下结合附图对本公开的具体实施方式进行详细说明。应当理解的是，此处所描述的具体实施方式仅用于说明和解释本公开，并不用于限制本公开。Specific embodiments of the present disclosure will be described in detail below in conjunction with the accompanying drawings. It should be understood that the specific embodiments described here are only used to illustrate and explain the present disclosure, and are not intended to limit the present disclosure.
本公开第一方面提供一种δ相氮化钨电极材料，所述δ相氮化钨电极材料包括具有孔缝结构的导电基底和δ相氮化钨层，至少部分的所述δ相氮化钨层覆于所述孔缝结构的内壁表面；所述孔缝结构包括在所述导电基底表面向内部延伸的孔和/或大体沿所述导电基体表面延伸的狭缝；所述表面孔缝占比为5-70％，所述孔缝结构的开口尺寸为500nm-500μm，所述孔缝结构的深度为所述开口尺寸的1.5倍以上。The first aspect of the present disclosure provides a δ-phase tungsten nitride electrode material, the δ-phase tungsten nitride electrode material includes a conductive substrate with a slit structure and a δ-phase tungsten nitride layer, at least part of the δ-phase tungsten nitride The tungsten layer is covered on the inner wall surface of the hole structure; the hole structure includes holes extending inwardly on the surface of the conductive substrate and/or slits extending generally along the surface of the conductive substrate; the surface hole The proportion is 5-70%, the opening size of the pore structure is 500nm-500μm, and the depth of the pore structure is more than 1.5 times of the opening size.
根据本公开，大体沿所述导电基体表面延伸的狭缝是指狭缝的主体在导电基体表面。孔缝结构是指规则的或无序的扁长或孔道状的狭缝，当孔缝结构为扁长的狭缝时，孔缝结构的开口尺寸是指狭缝的最大宽度；当孔缝结构为孔道状的狭缝时，孔缝结构的开口尺寸是指孔道开口的最大直径。本公开的δ相氮化钨电极材料可以作为酸性或碱性电解液产氢电极或电极材料，在宽pH值范围(酸性和碱性)的电解环境中具有优异的产氢性能和稳定性。According to the present disclosure, the slit extending substantially along the surface of the conductive base means that the main body of the slit is on the surface of the conductive base. The slit structure refers to regular or disordered elongated or channel-like slits. When the slit structure is an elongated slit, the opening size of the slit structure refers to the maximum width of the slit; when the slit structure In the case of channel-like slits, the opening size of the slit structure refers to the maximum diameter of the channel opening. The δ-phase tungsten nitride electrode material disclosed in the present disclosure can be used as a hydrogen-producing electrode or electrode material for an acidic or alkaline electrolyte, and has excellent hydrogen-producing performance and stability in an electrolytic environment with a wide pH range (acidic and alkaline).
根据本公开，本申请的δ相氮化钨电极材料中在狭缝结构不同区域的δ相氮化钨层的平均厚度可以不同，δ相氮化钨层所在的狭缝结构越深，δ相氮化钨层的平均厚度越小。在一种实施方式中，所述δ相氮化钨层的平均厚度为10nm-20μm，优选为1-5μm，δ相氮化钨层的平均厚度可以采用扫描电镜测得。上述范围内的δ相氮化钨层的厚度适宜，有利于最外层δ相氮化钨的导电接触和传质，δ相氮化钨电极材料具有更优的产氢性能。According to the disclosure, the average thickness of the δ-phase tungsten nitride layer in different regions of the slit structure in the δ-phase tungsten nitride electrode material of the present application can be different. The deeper the slit structure where the δ-phase tungsten nitride layer is located, the deeper the δ-phase The average thickness of the tungsten nitride layer is smaller. In one embodiment, the average thickness of the δ-phase tungsten nitride layer is 10 nm-20 μm, preferably 1-5 μm, and the average thickness of the δ-phase tungsten nitride layer can be measured with a scanning electron microscope. The thickness of the delta-phase tungsten nitride layer within the above range is suitable, which is beneficial to the conductive contact and mass transfer of the outermost delta-phase tungsten nitride, and the delta-phase tungsten nitride electrode material has better hydrogen production performance.
本公开第二方面提供一种制备δ相氮化钨电极材料的方法，该方法包括：在氨气氛围中使含有氧化钨和/或钨酸的导电基底进行氨化反应；其中，所述含有氧化钨和/或钨酸的导电基底具有孔缝结构，至少部分的所述氧化钨和/或钨酸附于所述孔缝结构的内壁表面；所述表面孔缝占比为5-70％，所述孔缝结构的开口尺寸为500nm-500μm，所述孔缝结构的深度为所述开口尺寸的1.5倍以上；所述氨化反应的条件包括：温度为900-1800℃，时间为30-240min。The second aspect of the present disclosure provides a method for preparing a δ-phase tungsten nitride electrode material, the method comprising: subjecting a conductive substrate containing tungsten oxide and/or tungstic acid to an ammoniation reaction in an ammonia atmosphere; wherein, the The conductive substrate of tungsten oxide and/or tungstic acid has a pore structure, at least part of the tungsten oxide and/or tungstic acid is attached to the inner wall surface of the pore structure; the surface pore ratio is 5-70% , the opening size of the pore structure is 500nm-500μm, and the depth of the pore structure is more than 1.5 times the opening size; the conditions of the ammoniation reaction include: the temperature is 900-1800°C, and the time is 30 -240min.
本公开的发明人发现，基于孔缝结构的限域效应，即在较为温和的反应条件下，基底孔缝所在的有限区域内产生的特殊氛围(较高的温度、压力或氨气密度)能够促进δ相氮化钨(δ-WN)的形成。与传统的高温高压合成δ-WN的方法相比，本公开的方法工艺条件更为温和、能耗较低。The inventors of the present disclosure have found that based on the confinement effect of the pore structure, that is, under relatively mild reaction conditions, the special atmosphere (higher temperature, pressure or ammonia gas density) generated in the limited area where the substrate pore is located can Promotes the formation of delta-phase tungsten nitride (delta-WN). Compared with the traditional method for synthesizing δ-WN under high temperature and high pressure, the process condition of the disclosed method is milder and the energy consumption is lower.
在本公开的一种具体实施方式中，所述氨化反应的条件包括：温度为950-1150℃，时间为60-180min；更优选地，所述温度为1000-1100℃，时间为90-120min。在上述条件制备得到的δ相氮化钨电极材料应用于电解水制氢过程中具有更优的产氢性能。In a specific embodiment of the present disclosure, the conditions of the ammoniation reaction include: the temperature is 950-1150°C, and the time is 60-180min; more preferably, the temperature is 1000-1100°C, and the time is 90- 120min. The δ-phase tungsten nitride electrode material prepared under the above conditions has better hydrogen production performance when applied to the process of hydrogen production by electrolysis of water.
根据本公开，所述导电基底的材料为具有孔缝结构且高温稳定性良好的导体材料。在一种实施方式中，导电基底的材料可以选自石墨、碳化钛和二硼化钛中的一种或几种，上述材料可以为商购或者自行合成。在另一种实施方式中，导电基底经过表面处理，表面处理例如可以为氢氧化钾活化处理或 表面刻蚀处理。本公开对导电基底的形状及尺寸不做具体限制，可以为任意规则的形状或不规则的形状，例如可以为片状、棒状、圆环柱状、块状或粉状，优选为片状、棒状、圆环柱状或块状。当导电基底的尺寸较大时，例如长宽高之一大于50mm时，制备得到δ相氮化钨电极材料无需后续加工成型，可直接作为δ-WN三维独立产氢电极，接触电阻相对较小；当导电基底的尺寸较大时，例如长宽高均小于1mm时，制备得到δ相氮化钨电极材料为小块状或粉状的材料，可以将后续加工成型后再作为电极，例如将小块状材料和/或粉体材料于玻碳电极表面制成膜电极作为工作电极。According to the present disclosure, the material of the conductive base is a conductive material with a porous structure and good high temperature stability. In one embodiment, the material of the conductive substrate can be selected from one or more of graphite, titanium carbide and titanium diboride, and the above materials can be purchased from commercial sources or synthesized by oneself. In another embodiment, the conductive substrate is subjected to surface treatment, such as potassium hydroxide activation treatment or surface etching treatment. The present disclosure does not specifically limit the shape and size of the conductive substrate, which can be in any regular or irregular shape, such as flake, rod, circular column, block or powder, preferably flake or rod , circular columnar or massive. When the size of the conductive substrate is large, for example, when one of the length, width and height is greater than 50mm, the prepared δ-phase tungsten nitride electrode material does not need subsequent processing and molding, and can be directly used as a δ-WN three-dimensional independent hydrogen production electrode, and the contact resistance is relatively small. ; When the size of the conductive substrate is large, for example, when the length, width and height are less than 1mm, the δ-phase tungsten nitride electrode material is prepared as a small block or powder material, which can be used as an electrode after subsequent processing and molding, for example, the Small block materials and/or powder materials are made into membrane electrodes on the surface of glassy carbon electrodes as working electrodes.
根据本公开，孔缝结构的开口尺寸为500nm-500μm，所述孔缝结构的深度为所述孔缝宽度的1.5倍以上，所述表面孔缝占比为5-70％，表面孔缝占比表示基底表面上孔缝所占的面积与基底表面积之比，表面孔缝占比可以通过采用扫描电镜对材料拍摄电镜照片后，再将电镜照片导入IMAGE G软件中进行分析得到。优选地，所述孔缝结构的开口尺寸为5-200μm，所述孔缝结构的深度为所述孔缝宽度的2-10倍，所述表面孔缝占比为30-60％。According to the present disclosure, the opening size of the pore structure is 500nm-500μm, the depth of the pore structure is more than 1.5 times the width of the pore, the proportion of the surface pores is 5-70%, and the surface pore ratio is 5-70%. Ratio means the ratio of the area occupied by pores on the surface of the substrate to the surface area of the substrate. The proportion of pores on the surface can be obtained by taking electron micrographs of the material with a scanning electron microscope, and then importing the electron micrographs into IMAGE G software for analysis. Preferably, the opening size of the pore structure is 5-200 μm, the depth of the pore structure is 2-10 times the width of the pore, and the proportion of surface pores is 30-60%.
根据本公开，该方法还包括：采用化学合成法原位制备所述含有三氧化钨和/或钨酸的导电基底；所述化学合成法选自水热法、电化学法、共沉淀法和化学沉淀法中的一种或几种。According to the present disclosure, the method also includes: preparing the conductive substrate containing tungsten trioxide and/or tungstic acid in situ by a chemical synthesis method; the chemical synthesis method is selected from hydrothermal method, electrochemical method, co-precipitation method and One or more of the chemical precipitation methods.
在本公开的一种具体实施方式中，采用包括如下步骤的水热法原位制备所述含有氧化钨和/或钨酸的导电基底：S1、将第一钨源、强酸和溶剂混合并调节pH值为1-2，得到第一溶液；S2、将所述第一溶液与弱酸混合，得到钨酸前驱体；S3、使所述钨酸前驱体与第一导电基底在耐热密闭容器内进行水热反应，得到所述含有氧化钨和/或钨酸的导电基底。In a specific embodiment of the present disclosure, the conductive substrate containing tungsten oxide and/or tungstic acid is prepared in situ by a hydrothermal method comprising the following steps: S1, mixing and adjusting the first tungsten source, strong acid and solvent The pH value is 1-2, and the first solution is obtained; S2, the first solution is mixed with a weak acid to obtain a tungstic acid precursor; S3, the tungstic acid precursor and the first conductive substrate are placed in a heat-resistant airtight container The hydrothermal reaction is carried out to obtain the conductive substrate containing tungsten oxide and/or tungstic acid.
根据本公开，将水热反应得到的产物进行清洗和干燥，清洗采用的溶液为本领域的技术人员所常规采用的，例如可以为乙醇、去离子水等，干燥的温度可以为50-150℃，时间为8-48小时。According to the present disclosure, the product obtained by the hydrothermal reaction is cleaned and dried. The solution used for cleaning is conventionally used by those skilled in the art, such as ethanol, deionized water, etc., and the drying temperature can be 50-150°C , the time is 8-48 hours.
根据本公开，步骤S3可以包括：将所述钨酸前驱体、封端剂、表面活性剂、模板剂与第一导电基底在耐热密闭容器内在进行水热反应。封端剂可以为本领域的技术人员所熟知的，例如可以选自硫酸铵、硫酸钠、十二烷基硫酸钠和柠檬酸中的一种或几种；表面活性剂和模板剂可以各自独立地选自正丁醇、环己烷和十六烷基三甲基溴化铵中的一种或几种。According to the present disclosure, step S3 may include: performing a hydrothermal reaction on the tungstic acid precursor, capping agent, surfactant, template agent and the first conductive substrate in a heat-resistant airtight container. Capping agent can be well known to those skilled in the art, for example can be selected from one or more in ammonium sulfate, sodium sulfate, sodium lauryl sulfate and citric acid; Surfactant and templating agent can be independently One or more selected from n-butanol, cyclohexane and cetyltrimethylammonium bromide.
根据本公开，步骤S2中，所述第一溶液与所述弱酸的用量的摩尔比可以在较大的范围内变化，例如可以为1：(2-3)，优选为1：(2-2.5)，所述第一溶液以所述第一钨源计。步骤S3中，所述水热反应为本领域的技术人员所熟知的，可以在耐热密闭容器内进行，例如可以在聚四氟乙烯为内衬的水热釜内进行，水热反应的条件可以包括：温度为120-220℃，时间为6-48小时；优选地，温度为160-200℃，时间为12-24小时。所述第一钨源可以选自钨酸钠、钨酸钾、钨酸锌、偏钨酸铵和氯化钨中的一种或几种；所述强酸可以选自盐酸、硝酸和稀硫酸中的一种或几种，所述强酸的浓度可以在较大的范围内变化，优选为1-5mol/L；所述溶剂可以选自去离子水、乙醇、乙二醇、异丙醇、N,N-二甲基甲酰胺和乙腈中的一种或几种；所述弱酸可以选自草酸、甲酸、醋酸和碳酸中的一种或几种；所述第一导电基底的材料为具有孔缝结构且高温稳定性良好的导体材料，优选为石墨、碳化钛和二硼化钛中的一种或几种。According to the present disclosure, in step S2, the molar ratio of the first solution to the amount of the weak acid can be changed within a wide range, for example, it can be 1:(2-3), preferably 1:(2-2.5 ), the first solution is based on the first tungsten source. In step S3, the hydrothermal reaction is well known to those skilled in the art, and can be carried out in a heat-resistant airtight container, for example, it can be carried out in a polytetrafluoroethylene-lined hydrothermal kettle. The conditions of the hydrothermal reaction It may include: the temperature is 120-220°C, and the time is 6-48 hours; preferably, the temperature is 160-200°C, and the time is 12-24 hours. The first tungsten source can be selected from one or more of sodium tungstate, potassium tungstate, zinc tungstate, ammonium metatungstate and tungsten chloride; the strong acid can be selected from hydrochloric acid, nitric acid and dilute sulfuric acid One or more of them, the concentration of the strong acid can vary within a relatively large range, preferably 1-5mol/L; the solvent can be selected from deionized water, ethanol, ethylene glycol, isopropanol, N , one or more of N-dimethylformamide and acetonitrile; the weak acid can be selected from one or more of oxalic acid, formic acid, acetic acid and carbonic acid; the material of the first conductive substrate has holes The conductor material with seam structure and good high temperature stability is preferably one or more of graphite, titanium carbide and titanium diboride.
在本公开的另一种具体实施方式中，采用包括如下步骤的电化学法制备所述含有氧化钨和/或钨酸的导电基底：(1)、使第二钨源与过氧化氢溶液接触反应后，可选地除去反应后的溶液中含有的过氧化氢，得到第二溶液；(2)、采用稀释剂对所述第二溶液进行稀释，得到电解液；(3)、以第二导电基底为工作电极，并将其置于所述电解液中，采用恒电位方法在所述第二导电基底上沉积氧化钨和/或钨酸，得到含有氧化钨和/或钨酸的导电基底。In another specific embodiment of the present disclosure, the electrochemical method comprising the following steps is used to prepare the conductive substrate containing tungsten oxide and/or tungstic acid: (1), making the second tungsten source contact with hydrogen peroxide solution After the reaction, optionally remove the hydrogen peroxide contained in the reacted solution to obtain a second solution; (2), dilute the second solution with a diluent to obtain an electrolyte; (3), use the second The conductive substrate is a working electrode, and it is placed in the electrolyte, and tungsten oxide and/or tungstic acid are deposited on the second conductive substrate by a constant potential method to obtain a conductive substrate containing tungsten oxide and/or tungstic acid .
根据本公开，步骤(1)中，所述的除去反应后的溶液中含有的过氧化氢包括：将催化剂与反应后的溶液接触反应，得到第二溶液；或者，将所述反应后的溶液在50-90℃下加热，得到第二溶液；其中，所述催化剂为铂、银、铬、二氧化锰、氯化铁、氧化铜和过氧化氢酶中的一种或几种，当所述第二溶液的体积与步骤(1)中初始加入的所述过氧化氢溶液的体积之比为0.75-0.85时，取出所述催化剂或停止所述加热。过氧化氢溶液的浓度可以在较大的范围内变化，优选质量分数为25-35％。According to the present disclosure, in step (1), the removal of hydrogen peroxide contained in the reacted solution includes: contacting the catalyst with the reacted solution to obtain a second solution; or, removing the reacted solution Heating at 50-90°C to obtain a second solution; wherein, the catalyst is one or more of platinum, silver, chromium, manganese dioxide, ferric chloride, copper oxide and catalase, when the When the ratio of the volume of the second solution to the volume of the hydrogen peroxide solution initially added in step (1) is 0.75-0.85, take out the catalyst or stop the heating. The concentration of the hydrogen peroxide solution can vary within a relatively large range, and the preferred mass fraction is 25-35%.
根据本公开，步骤(2)中，所述第二溶液与所述稀释剂用量的体积比可以在较大的范围内变化，优选为1：(9-29)；所述稀释剂中含有水、异丙醇、乙醇、乙二醇、丙酮、乙腈和N,N-二甲基甲酰胺中的一种或几种，优选地，所述稀释剂含有水和异丙醇，所述水与异丙醇的体积比为1：(0.4-1)。According to the present disclosure, in step (2), the volume ratio of the second solution to the amount of the diluent can vary within a relatively large range, preferably 1: (9-29); the diluent contains water , isopropanol, ethanol, ethylene glycol, acetone, acetonitrile and one or more of N, N-dimethylformamide, preferably, the diluent contains water and isopropanol, and the water and The volume ratio of isopropanol is 1:(0.4-1).
根据本公开，步骤(3)中，所述沉积的条件包括：沉积电位为-0.4V至-5V，沉积时间为1-60min；优选地，沉积电位为-1V至-3V，沉积时间为5-30min。According to the present disclosure, in step (3), the deposition conditions include: the deposition potential is from -0.4V to -5V, and the deposition time is 1-60min; preferably, the deposition potential is from -1V to -3V, and the deposition time is 5 min. -30min.
在一种优选的具体实施方式中，将第二导电基底置于所述电解液中浸泡5-15小时，再采用恒电位方法在所述第二导电基底上沉积氧化钨和/或钨酸。In a preferred embodiment, the second conductive substrate is immersed in the electrolyte solution for 5-15 hours, and then tungsten oxide and/or tungstic acid are deposited on the second conductive substrate by a constant potential method.
根据本公开，所述第二钨源可以选自金属钨粉、钨丝和钨片中的一种或几种，更优选为钨粉；所述第二导电基底的材料为具有孔缝结构且高温稳定性良好的导体材料，优选为可以为石墨、碳化钛和二硼化钛中的一种或几种。According to the present disclosure, the second tungsten source can be selected from one or more of metal tungsten powder, tungsten wire and tungsten sheet, more preferably tungsten powder; the material of the second conductive substrate has a slit structure and The conductor material with good high temperature stability is preferably one or more of graphite, titanium carbide and titanium diboride.
根据本公开，氨化反应可以在马弗炉、管式炉或流化床中进行，当氨化反应在马弗炉、管式炉等密封的反应炉中进行时，所述氨气气氛中氨气的体积浓度可以为10-100％；当氨化反应在流化床中进行时，氨气的流量可以为任意流量，优选为10-100mL/min。氨气氛围可以通过直接通入氨气获得，或者由易分解产生氨气的化合物(例如尿素、三聚氰胺、醋酸铵等)在升温过程中分解获得。According to the present disclosure, the ammoniation reaction can be carried out in a muffle furnace, a tube furnace or a fluidized bed. When the ammoniation reaction is carried out in a sealed reaction furnace such as a muffle furnace or a tube furnace, the ammonia atmosphere The volume concentration of ammonia can be 10-100%; when the ammoniation reaction is carried out in a fluidized bed, the flow of ammonia can be any flow, preferably 10-100mL/min. The ammonia gas atmosphere can be obtained by directly feeding ammonia gas, or by decomposing compounds that are easy to decompose to generate ammonia gas (such as urea, melamine, ammonium acetate, etc.) during the heating process.
本公开第三方面提供一种本公开第二方面提供的方法制备得到的δ相氮化钨电极材料。本公开的δ相氮化钨电极材料为满足不同电解槽类型需求的、宽pH范围适用的、高效经济的产氢电极材料。The third aspect of the present disclosure provides a δ-phase tungsten nitride electrode material prepared by the method provided in the second aspect of the present disclosure. The δ-phase tungsten nitride electrode material of the present disclosure is an efficient and economical hydrogen-producing electrode material that meets the requirements of different types of electrolytic cells, is applicable to a wide pH range.
本公开第四方面提供一种本公开第一方面和/或第三方面提供的δ相氮化钨电极材料在电解水制氢中的应用。在一种具体实施方式中，所述δ相氮化钨电极材料用于电解槽的产氢电解材料。The fourth aspect of the present disclosure provides an application of the δ-phase tungsten nitride electrode material provided in the first aspect and/or the third aspect of the present disclosure in hydrogen production by electrolysis of water. In a specific embodiment, the δ-phase tungsten nitride electrode material is used as a hydrogen-producing electrolytic material in an electrolytic cell.
下面通过实施例来进一步说明本公开，但是本公开并不因此而受到任何限制。The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereby.
以下实施例和对比例采用XRD检测电极材料含有的氮化钨的相态，采用扫描电镜测量氮化钨层的厚度。以下实施例中原料均由商购得到。The following examples and comparative examples use XRD to detect the phase state of tungsten nitride contained in the electrode material, and use a scanning electron microscope to measure the thickness of the tungsten nitride layer. The raw materials in the following examples are all commercially available.
实施例1Example 1
S1、将4.1g的二水钨酸钠溶于去离子水中并剧烈搅拌30min，接着将3mol/L的盐酸逐滴缓慢加入钨酸钠溶液，直到pH值为1.2，得到黄色透明的第一溶液；S1. Dissolve 4.1 g of sodium tungstate dihydrate in deionized water and stir vigorously for 30 minutes, then slowly add 3 mol/L hydrochloric acid into the sodium tungstate solution drop by drop until the pH value is 1.2 to obtain a yellow transparent first solution ;
S2、将3.1g的草酸加入到第一溶液中，得到钨酸前驱体；S2, adding 3.1g of oxalic acid into the first solution to obtain a tungstic acid precursor;
S3、取40mL的钨酸前驱体，加入2g硫酸铵作为封端剂，而后将该溶液转移至提前放置有φ3mm×50mm的表面具有孔缝结构的石墨棒(表面孔缝占 比约为30％，孔缝结构的开口尺寸为50-200μm，深度为孔缝宽度的3-10倍)的、以聚四氟乙烯为内衬的水热釜中，在180℃下进行水热反应16小时。水热釜自然冷却后，将长有深蓝色氧化钨(WO
3)的石墨棒(WO
3/GR)取出，用乙醇和水分别润洗5-7次，置于80℃烘箱中干燥，得到含有氧化钨的导电基底，导电基底的孔缝结构中生长有氧化钨；
S3. Take 40mL of tungstic acid precursor, add 2g of ammonium sulfate as an end-capping agent, and then transfer the solution to a graphite rod with a φ3mm×50mm surface with a pore structure (the proportion of surface pores is about 30%). , the opening size of the slit structure is 50-200 μm, and the depth is 3-10 times of the slit width), and the hydrothermal reaction is carried out at 180 ° C for 16 hours in a polytetrafluoroethylene-lined hydrothermal kettle. After the hydrothermal kettle was naturally cooled, the graphite rod (WO 3 /GR) with dark blue tungsten oxide (WO 3 ) was taken out, rinsed with ethanol and water for 5-7 times, and dried in an oven at 80°C to obtain A conductive substrate containing tungsten oxide, tungsten oxide is grown in the pore structure of the conductive substrate;
S4、将含有氧化钨的导电基底置于管式炉中，用氮气去除管内空气后，通入50mL/min的氨气，以6℃/min升温至1000℃并在该温度下保持120min，冷却后即可得以三维石墨棒为基底的δ相氮化钨电极材料，δ相氮化钨层的厚度为1-5μm。δ相氮化钨电极材料的XRD谱图见图1，扫描电镜照片见图2。S4. Place the conductive substrate containing tungsten oxide in a tube furnace, remove the air in the tube with nitrogen, and then pass in 50mL/min of ammonia gas, raise the temperature to 1000°C at 6°C/min and keep it at this temperature for 120min, then cool After that, the delta-phase tungsten nitride electrode material with the three-dimensional graphite rod as the substrate can be obtained, and the thickness of the delta-phase tungsten nitride layer is 1-5 μm. The XRD spectrum of the delta-phase tungsten nitride electrode material is shown in Figure 1, and the scanning electron microscope photo is shown in Figure 2.
实施例2Example 2
S1、将8.2g偏钨酸铵溶于去离子水中并剧烈搅拌1小时，接着将3mol/L的盐酸逐滴缓慢加入该溶液，直到pH值为1.2，得到黄色透明的第一溶液；S1. Dissolve 8.2 g of ammonium metatungstate in deionized water and stir vigorously for 1 hour, then slowly add 3 mol/L hydrochloric acid to the solution dropwise until the pH value is 1.2, and obtain a yellow transparent first solution;
S2、将6.2g的草酸加入到第一溶液中，获得钨酸前驱体；S2, adding 6.2g of oxalic acid into the first solution to obtain a tungstic acid precursor;
S3、取40mL的钨酸前驱体置于提前放置有20mm×50mm×2mm的粗糙石墨片(表面孔缝占比约为40％，孔缝结构的开口尺寸为100-250μm，深度为孔缝宽度的3-10倍)的以聚四氟乙烯为内衬的水热釜中，在200℃下进行水热反应12小时。水热釜自然冷却后，将所得材料取出，用乙醇和水分别润洗5-7次，置于80℃烘箱中干燥，得到含有氧化钨的导电基底，导电基底的孔缝结构中生长有氧化钨；S3. Take 40mL of tungstic acid precursor and place it on a rough graphite sheet with 20mm×50mm×2mm placed in advance (the surface pores account for about 40%, the opening size of the pore structure is 100-250μm, and the depth is the width of the pores 3-10 times of that) in a polytetrafluoroethylene-lined hydrothermal kettle, the hydrothermal reaction was carried out at 200° C. for 12 hours. After the hydrothermal kettle is cooled naturally, the obtained material is taken out, rinsed with ethanol and water for 5-7 times, and dried in an oven at 80°C to obtain a conductive substrate containing tungsten oxide. Tungsten;
S4、将含有氧化钨的导电基底置于3L的管式炉中，用氮气去除管内空气后，再用高纯氨气充满，维持一定的0.1MPa正压，接着，以2℃/min升温至950℃并在该温度下保持240min，冷却后获得以三维石墨片为基底的δ相氮化钨电极材料，δ相氮化钨层的厚度为2-7μm。S4. Put the conductive substrate containing tungsten oxide in a 3L tube furnace, remove the air in the tube with nitrogen, then fill it with high-purity ammonia, maintain a certain positive pressure of 0.1MPa, and then raise the temperature to 2°C/min. 950°C and kept at this temperature for 240min, after cooling, a delta-phase tungsten nitride electrode material based on a three-dimensional graphite sheet is obtained, and the thickness of the delta-phase tungsten nitride layer is 2-7μm.
实施例3Example 3
S1、将8.2g偏钨酸铵溶于去离子水中并剧烈搅拌30min，接着将3mol/L的盐酸逐滴缓慢加入该溶液，直到pH值为1.2，得到黄色透明的第一溶液；S1. Dissolve 8.2 g of ammonium metatungstate in deionized water and stir vigorously for 30 minutes, then slowly add 3 mol/L hydrochloric acid to the solution dropwise until the pH value is 1.2, and obtain a yellow transparent first solution;
S2、将6.2g的草酸加入到第一溶液中，获得钨酸前驱体；S2, adding 6.2g of oxalic acid into the first solution to obtain a tungstic acid precursor;
S3、取70mL的钨酸前驱体置于100mL以聚四氟乙烯为内衬的水热釜中， 釜内提前放置有30mm×30mm×1mm的经氢氧化钾活化处理的石墨方片(表面孔缝占比约为50％，孔缝结构的开口尺寸为10-50μm，深度为孔缝宽度的5-15倍)，在120℃下进行水热处理24小时。水热釜自然冷却后，将所得材料从水热釜中取出，用乙醇和水分别润洗5-7次，至于80℃烘箱中干燥，得到狭缝内生长有钨酸的石墨导电基底；S3. Take 70mL of tungstic acid precursor and place it in a 100mL hydrothermal kettle lined with polytetrafluoroethylene. A 30mm×30mm×1mm square graphite sheet (surface hole Slits account for about 50%, the opening size of the slit structure is 10-50 μm, and the depth is 5-15 times the width of the slit), and the hydrothermal treatment is carried out at 120 ° C for 24 hours. After the hydrothermal kettle is cooled naturally, the obtained material is taken out from the hydrothermal kettle, rinsed with ethanol and water for 5-7 times respectively, and dried in an oven at 80°C to obtain a graphite conductive substrate with tungstic acid grown in the slit;
S4、将狭缝内生长有钨酸的石墨导电基底置于管式炉中，用氮气去除管内空气后，通以50mL/min的氨气，以4℃/min升温至1150℃并在该温度下保持30min，冷却后即获得以氢氧化钾活化三维石墨方片为基底的δ相氮化钨电极材料，δ相氮化钨层的厚度为50nm-2μm。S4. Place the graphite conductive substrate with tungstic acid grown in the slit in a tube furnace, remove the air in the tube with nitrogen, pass through ammonia gas at 50mL/min, raise the temperature to 1150°C at 4°C/min and hold at this temperature Keep it for 30 minutes, and after cooling, the δ-phase tungsten nitride electrode material based on potassium hydroxide-activated three-dimensional graphite square sheet is obtained, and the thickness of the δ-phase tungsten nitride layer is 50nm-2μm.
实施例4Example 4
S1、将8.2g钨酸钾溶于去离子水中并剧烈搅拌45min，接着将3mol/L的稀硝酸逐滴缓慢加入该溶液，直到pH值为1.2，得到黄色透明的第一溶液；S1. Dissolve 8.2g potassium tungstate in deionized water and stir vigorously for 45min, then slowly add 3mol/L dilute nitric acid to the solution drop by drop until the pH value is 1.2, and the first yellow transparent solution is obtained;
S2、将6.2g的醋酸加入到第一溶液中，获得钨酸前驱体；S2, adding 6.2g of acetic acid into the first solution to obtain a tungstic acid precursor;
S3、取70mL的钨酸前驱体置于100mL以聚四氟乙烯为内衬的水热釜中，釜内提前放置有尺寸约为500μm×600μm的石墨粉体颗粒(表面孔缝占比约为45％，孔缝结构的开口尺寸为80-100μm，深度为孔缝宽度的5-10倍)，在180℃下进行水热处理18小时后自然冷却后，将所得材料从水热釜中取出，用乙醇和水分别润洗5-7次，置于80℃烘箱中干燥，得到含有氧化钨的导电基底，导电基底的孔缝结构中生长有氧化钨；S3. Take 70mL of tungstic acid precursor and place it in a 100mL polytetrafluoroethylene-lined hydrothermal kettle. Graphite powder particles with a size of about 500μm×600μm are placed in the kettle in advance (the proportion of pores on the surface is about 45%, the opening size of the slit structure is 80-100 μm, and the depth is 5-10 times the width of the slit), after carrying out hydrothermal treatment at 180 ° C for 18 hours, after cooling naturally, the resulting material is taken out from the hydrothermal kettle, Rinse with ethanol and water for 5-7 times respectively, and dry in an oven at 80°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
S4、将含有氧化钨的导电基底置于管式炉中，通以50mL/min的氨气，以4℃/min升温至1000℃并在该温度下保持1小时，冷却后即获得以石墨粉体为基底的δ相氮化钨电极材料的颗粒(δ相氮化钨层的厚度为1-5μm)，将该δ相氮化钨电极材料分散于含一定量Nafion膜溶液的异丙醇中，滴覆于玻碳电极的表面制成膜电极进行测试。S4. Place the conductive substrate containing tungsten oxide in a tube furnace, pass through 50mL/min of ammonia gas, raise the temperature to 1000°C at 4°C/min and keep it at this temperature for 1 hour, and obtain graphite powder after cooling The body is the particle of the δ-phase tungsten nitride electrode material of the substrate (the thickness of the δ-phase tungsten nitride layer is 1-5 μm), and the δ-phase tungsten nitride electrode material is dispersed in isopropanol containing a certain amount of Nafion membrane solution , drop-coated on the surface of the glassy carbon electrode to make a membrane electrode for testing.
实施例5Example 5
S1、将8.2g钨酸钾溶于去离子水中并剧烈搅拌45min，接着将3M稀硝酸逐滴缓慢加入该溶液，直到pH值为1.2，得到黄色透明的第一溶液；S1. Dissolve 8.2g potassium tungstate in deionized water and stir vigorously for 45min, then slowly add 3M dilute nitric acid to the solution drop by drop until the pH value is 1.2 to obtain the first yellow transparent solution;
S2、将6.2g的醋酸加入到第一溶液中，获得钨酸前驱体；S2, adding 6.2g of acetic acid into the first solution to obtain a tungstic acid precursor;
S3、取70mL的钨酸前驱体置于100mL以聚四氟乙烯为内衬的水热釜中，釜内提前放置有尺寸约为800μm×600μm的碳化钛多孔颗粒(表面孔缝占比约为55％，孔缝结构的开口尺寸为50μm，深度为孔缝宽度的5-10倍)，在180℃下进行水热处理18小时后自然冷却后，将所得材料从水热釜中取出，用乙醇和水分别润洗5-7次，置于80℃烘箱中干燥，得到含有氧化钨的导电基底，导电基底的孔缝结构中生长有氧化钨；S3. Take 70mL of tungstic acid precursor and put it in a 100mL polytetrafluoroethylene-lined hydrothermal kettle. Titanium carbide porous particles with a size of about 800μm×600μm are placed in advance in the kettle (the proportion of pores on the surface is about 55%, the opening size of the slit structure is 50 μm, and the depth is 5-10 times of the slit width), after carrying out hydrothermal treatment at 180 ° C for 18 hours, after cooling naturally, the resulting material is taken out from the hydrothermal kettle, and washed with ethanol Rinse with water for 5-7 times respectively, and dry in an oven at 80°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
S4、将含有氧化钨的导电基底置于管式炉中，通以50mL/min的氨气，以4℃/min升温至1000℃并在该温度下保持1小时，冷却后即获得以多孔碳化钛为基底的δ相氮化钨电极材料的颗粒(δ相氮化钨层的厚度为500nm-4μm)，将该δ相氮化钨电极材料分散于含一定量Nafion膜溶液的异丙醇中，滴覆于玻碳电极的表面制成膜电极进行测试。S4. Place the conductive substrate containing tungsten oxide in a tube furnace, pass through 50mL/min of ammonia gas, raise the temperature to 1000°C at 4°C/min and keep it at this temperature for 1 hour, and obtain porous carbonization after cooling Titanium-based δ-phase tungsten nitride electrode material particles (the thickness of the δ-phase tungsten nitride layer is 500nm-4μm), the δ-phase tungsten nitride electrode material is dispersed in isopropanol containing a certain amount of Nafion membrane solution , drop-coated on the surface of the glassy carbon electrode to make a membrane electrode for testing.
实施例6Example 6
(1)、将1.85g的钨粉分散于15mL质量分数30％的过氧化氢溶液，于室温下搅拌，使其均匀反应。待反应后的溶液将至室温，***铂片催化未反应的过氧化氢分解，当反应后溶液体积V2(mL)/加入的过氧化氢溶液体积V1(mL)＝0.75～0.85时，取出铂片，得到第二溶液；(1) Disperse 1.85g of tungsten powder in 15mL of 30% hydrogen peroxide solution, and stir at room temperature to make it react uniformly. After the reaction solution is brought to room temperature, insert a platinum plate to catalyze the decomposition of unreacted hydrogen peroxide. When the volume of the solution after reaction V2 (mL)/volume of added hydrogen peroxide solution V1 (mL) = 0.75 ~ 0.85, take out the platinum sheet, to obtain the second solution;
(2)、用水/异丙醇为7：3的混合溶液将第二溶液稀释20倍至300mL，并搅拌2小时，至溶液均一透明，得到电解液；(2) Dilute the second solution 20 times to 300mL with a mixed solution of water/isopropanol at 7:3, and stir for 2 hours until the solution is uniform and transparent to obtain an electrolyte;
(3)、以具有孔缝结构的25mm×50mm×1mm的石墨片为工作电极，电沉积前将石墨片(表面孔缝占比约为40％，孔缝结构的开口尺寸为100～250μm，深度为孔缝宽度的3-10倍)浸泡于电解液中10小时。设定沉积电位为-1.0V，在石墨片上恒电位沉积30min。沉积完成后将该材料取出，用去离子水冲洗3～5次，置于60℃的烘箱干燥，得到含有氧化钨的导电基底，导电基底的孔缝结构中生长有氧化钨；(3), with a graphite sheet of 25 mm × 50 mm × 1 mm with a pore structure as the working electrode, the graphite sheet (the surface pores account for about 40%, and the opening size of the pore structure is 100 to 250 μm, The depth is 3-10 times of the width of the hole) soaked in the electrolyte for 10 hours. Set the deposition potential to -1.0V, and deposit at a constant potential on the graphite sheet for 30 min. After the deposition is completed, the material is taken out, rinsed with deionized water for 3 to 5 times, and dried in an oven at 60°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
(4)、将氧化钨的导电基底置于100mL坩埚中，覆盖10g尿素，置于可密闭可抽真空的加热炉中，抽真空后密封，以10℃/min升温至950℃，保温2小时后自然降温，得到δ相氮化钨电极材料，δ相氮化钨层的厚度为10nm-2μm。(4) Put the conductive substrate of tungsten oxide in a 100mL crucible, cover with 10g of urea, put it in a heating furnace that can be sealed and vacuumed, seal it after vacuuming, heat up to 950°C at 10°C/min, and keep it warm for 2 hours After cooling down naturally, the δ-phase tungsten nitride electrode material is obtained, and the thickness of the δ-phase tungsten nitride layer is 10nm-2μm.
实施例7Example 7
(1)将1.85g的钨粉分散于15mL质量分数30％的过氧化氢溶液，于室温下搅拌，使其均匀反应。待反应后的溶液将至室温，***银丝催化未反应的过氧化氢分解，当反应后溶液体积V2(mL)/加入的过氧化氢溶液体积V1(mL)＝0.75～0.85时，取出银丝，得到第二溶液；(1) Disperse 1.85g of tungsten powder in 15mL of 30% hydrogen peroxide solution, and stir at room temperature to make it react uniformly. After the reaction solution is brought to room temperature, insert a silver wire to catalyze the decomposition of unreacted hydrogen peroxide. When the reaction solution volume V2 (mL)/the added hydrogen peroxide solution volume V1 (mL) = 0.75 ~ 0.85, take out the silver wire silk, obtain the second solution;
(2)、用水/异丙醇为7：3的混合溶液将第二溶液稀释20倍至300mL，并搅拌2小时，至溶液均一透明，得到电解液；(2) Dilute the second solution 20 times to 300mL with a mixed solution of water/isopropanol at 7:3, and stir for 2 hours until the solution is uniform and transparent to obtain an electrolyte;
(3)、以具有孔缝结构的25mm×50mm×1mm的碳化钛片为工作电极，电沉积前将碳化钛片(表面孔缝占比约为60％，孔缝结构的开口尺寸为50～200μm，深度为孔缝宽度的3-10倍)浸泡于电解液中10小时。设定沉积电位为-3.0V，恒电位沉积5min。沉积完成后，将该材料取出，用去离子水冲洗3～5次，至于60℃烘箱干燥，得到含有氧化钨的导电基底，导电基底的孔缝结构中生长有氧化钨；(3), with a 25mm × 50mm × 1mm titanium carbide sheet with a slit structure as the working electrode, the titanium carbide sheet (surface slits account for about 60%, and the opening size of the slit structure is 50～ 200μm, the depth is 3-10 times the width of the hole) soaked in the electrolyte for 10 hours. Set the deposition potential to -3.0V, and deposit at a constant potential for 5 minutes. After the deposition is completed, the material is taken out, rinsed with deionized water for 3 to 5 times, and dried in an oven at 60°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
(4)、将含有氧化钨的导电基底置于100mL坩埚中，覆盖10g尿素，至于可密闭可抽真空的加热炉中，抽真空后密封，以10℃/min升温至1000℃，保温2小时后自然降温，得到δ相氮化钨电极材料，δ相氮化钨层的厚度为10nm-3μm。(4) Put the conductive substrate containing tungsten oxide in a 100mL crucible, cover with 10g of urea, put it in a heating furnace that can be sealed and vacuumed, seal it after vacuuming, heat up to 1000°C at 10°C/min, and keep it warm for 2 hours After that, the temperature is naturally lowered to obtain a delta-phase tungsten nitride electrode material, and the thickness of the delta-phase tungsten nitride layer is 10nm-3μm.
实施例8Example 8
(1)、将1.85g的钨粉分散于15mL质量分数30％的过氧化氢溶液，于室温下搅拌，使其均匀反应。待反应后的溶液将至室温，用铂片催化未反应的过氧化氢分解，当反应后溶液体积V
2(mL)/加入的过氧化氢溶液体积V
1(mL)＝0.75～0.85时，取出铂片，得到第二溶液；
(1) Disperse 1.85g of tungsten powder in 15mL of 30% hydrogen peroxide solution, and stir at room temperature to make it react uniformly. The solution after the reaction will be brought to room temperature, and the unreacted hydrogen peroxide will be decomposed with a platinum plate. Take out the platinum sheet to obtain the second solution;
(2)、用水/异丙醇为7：3的混合溶液将上述溶液稀释20倍至300mL，并搅拌1小时，至溶液均一透明，得到电解液；(2) Dilute the above solution 20 times to 300mL with a mixed solution of water/isopropanol 7:3, and stir for 1 hour until the solution is uniform and transparent to obtain an electrolyte;
(3)、以具有孔缝结构的25mm×50mm×1mm的二硼化钛片为工作电极，电沉积前将二硼化钛片(表面孔缝占比约为50％，孔缝结构的开口尺寸为50～150μm，深度为孔缝宽度的5-10倍)浸泡于电解液中10小时，设定沉积电位为-0.8V，恒电位沉积25min。沉积完成后，将该材料取出，用去离子水冲洗3～5次，置于70℃烘箱干燥，得到含有氧化钨的导电基底，导电基底的孔缝结构中生长有氧化钨；(3), with a titanium diboride sheet of 25 mm × 50 mm × 1 mm with a slit structure as the working electrode, the titanium diboride sheet (the surface slits account for about 50%, and the openings of the slit structure The size is 50-150 μm, and the depth is 5-10 times of the width of the hole) soaked in the electrolyte for 10 hours, set the deposition potential to -0.8V, and deposited at a constant potential for 25 minutes. After the deposition is completed, the material is taken out, rinsed with deionized water for 3 to 5 times, and dried in an oven at 70°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
(4)、将含有氧化钨的导电基底置于100mL坩埚中，覆盖9.5g醋酸铵，至于可密闭可抽真空的加热炉中，抽真空后密封，以5℃/min升温至1050℃，保温1小时后自然降温，得到δ相氮化钨电极材料，δ相氮化钨层的厚度为10nm-2μm。(4) Put the conductive substrate containing tungsten oxide in a 100mL crucible, cover with 9.5g of ammonium acetate, put it in a heating furnace that can be sealed and vacuumed, seal it after vacuuming, heat up to 1050°C at 5°C/min, and keep warm After 1 hour, the temperature was naturally lowered to obtain a delta-phase tungsten nitride electrode material, and the thickness of the delta-phase tungsten nitride layer was 10nm-2μm.
实施例9Example 9
(1)、将1.85g的钨粉分散于15mL质量分数30％的过氧化氢溶液，于室温下搅拌，使其均匀反应。待反应后的溶液将至室温，用铂片催化未反应的过氧化氢分解，当反应后溶液体积V
2(mL)/加入的过氧化氢溶液体积V
1(mL)＝0.75～0.85时，取出铂片，得到第二溶液；
(1) Disperse 1.85g of tungsten powder in 15mL of 30% hydrogen peroxide solution, and stir at room temperature to make it react uniformly. The solution after the reaction will be brought to room temperature, and the unreacted hydrogen peroxide will be decomposed with a platinum plate. Take out the platinum sheet to obtain the second solution;
(2)、用水/异丙醇为7：3的混合溶液将上述溶液稀释20倍至300mL，并搅拌1小时，至溶液均一透明，得到电解液；(2) Dilute the above solution 20 times to 300mL with a mixed solution of water/isopropanol 7:3, and stir for 1 hour until the solution is uniform and transparent to obtain an electrolyte;
(3)、以具有孔缝结构的φ3mm×60mm的二硼化钛棒为工作电极，电沉积前将二硼化钛棒(表面孔缝占比约为70％，孔缝结构的开口尺寸为50-200μm，深度为孔缝宽度的2-8倍)浸泡于电解液中10小时，设定沉积电位为-0.7V，恒电位沉积25min。沉积完成后，将该材料取出，用去离子水冲洗3～5次，置于70℃烘箱干燥，得到含有氧化钨的导电基底，导电基底的孔缝结构中生长有氧化钨；(3), with a φ3mm×60mm titanium diboride rod with a pore structure as the working electrode, before electrodeposition, the titanium diboride rod (the surface pores account for about 70%, and the opening size of the pore structure is 50-200μm, the depth is 2-8 times the width of the hole) soak in the electrolyte for 10 hours, set the deposition potential to -0.7V, and deposit at a constant potential for 25 minutes. After the deposition is completed, the material is taken out, rinsed with deionized water for 3 to 5 times, and dried in an oven at 70°C to obtain a conductive substrate containing tungsten oxide, and tungsten oxide grows in the pore structure of the conductive substrate;
(4)、将含有氧化钨的导电基底置于100mL坩埚中，覆盖12g三聚氰胺，置于可密闭可抽真空的加热炉中，抽真空后密封，以8℃/min升温至1100℃，保温1.5小时后自然降温，得到δ相氮化钨电极材料，δ相氮化钨层的厚度为10nm-2μm。(4) Put the conductive substrate containing tungsten oxide in a 100mL crucible, cover with 12g of melamine, put it in a heating furnace that can be sealed and vacuumed, seal it after vacuuming, heat up to 1100°C at 8°C/min, and keep warm for 1.5 After hours, the temperature is naturally lowered to obtain a delta-phase tungsten nitride electrode material, and the thickness of the delta-phase tungsten nitride layer is 10nm-2μm.
实施例10Example 10
采用与实施例1相同的方法制备δ相氮化钨电极材料，不同之处仅在于，步骤S4中，以2℃/min升温至1050℃并在该温度下保持120min，所得δ相氮化钨层的厚度为100nm-5μm。The δ-phase tungsten nitride electrode material was prepared by the same method as in Example 1, except that in step S4, the temperature was raised to 1050°C at 2°C/min and kept at this temperature for 120min, and the obtained δ-phase tungsten nitride The thickness of the layer is from 100 nm to 5 μm.
实施例11Example 11
采用与实施例1相同的方法制备δ相氮化钨电极材料，不同之处仅在于， 步骤S4中，以2℃/min升温至900℃并在该温度下保持120min，δ相氮化钨层的厚度为100nm-2μm。The δ-phase tungsten nitride electrode material was prepared by the same method as in Example 1, except that in step S4, the temperature was raised to 900°C at 2°C/min and kept at this temperature for 120min, and the δ-phase tungsten nitride layer The thickness is 100nm-2μm.
实施例12Example 12
采用与实施例1相同的方法制备δ相氮化钨电极材料，不同之处仅在于，步骤S3中，取40mL的钨酸前驱体，加入2g硫酸铵作为封端剂，而后将该溶液转移至提前放置有φ3mm×50mm的表面具有孔缝结构的石墨棒(表面孔缝占比约为30％，孔缝结构的开口尺寸为300～500μm，深度为孔缝宽度的3-10倍)的以聚四氟乙烯为内衬的水热釜中，在200℃下进行水热反应12小时，δ相氮化钨层的厚度为5-10μm。Adopt the same method as Example 1 to prepare δ-phase tungsten nitride electrode materials, the only difference is that in step S3, take 40mL of tungstic acid precursor, add 2g of ammonium sulfate as a capping agent, and then transfer the solution to Graphite rods with a φ3mm×50mm surface and a slit structure are placed in advance (the proportion of surface slits is about 30%, the opening size of the slit structure is 300-500μm, and the depth is 3-10 times the width of the slits) The hydrothermal reaction is carried out at 200° C. for 12 hours in a hydrothermal kettle lined with polytetrafluoroethylene, and the thickness of the delta-phase tungsten nitride layer is 5-10 μm.
实施例13Example 13
采用与实施例1相同的方法制备δ相氮化钨电极材料，不同之处仅在于，步骤S2中，水热反应的温度为140℃，时间为16小时，所得δ相氮化钨层的厚度为500nm-3μm。The δ-phase tungsten nitride electrode material was prepared by the same method as in Example 1, except that in step S2, the temperature of the hydrothermal reaction was 140° C., and the time was 16 hours. The thickness of the obtained δ-phase tungsten nitride layer was 500nm-3μm.
对比例1Comparative example 1
采用与实施例1相同的方法制备氮化钨电极材料，不同之处仅在于，步骤S4中，以6℃/min升温至800℃并在该温度下保持120min。经XRD检测知本对比例制备的氮化钨电极材料为β相氮化钨电极材料。The tungsten nitride electrode material was prepared by the same method as in Example 1, except that in step S4, the temperature was raised to 800° C. at 6° C./min and kept at this temperature for 120 minutes. According to XRD detection, the tungsten nitride electrode material prepared in this comparative example is a β-phase tungsten nitride electrode material.
对比例2Comparative example 2
采用与实施例1相同的方法制备氮化钨电极材料，不同之处仅在于，步骤S3中，取40mL的钨酸前驱体，加入2g硫酸铵为封端剂，而后将该溶液转移至提前放置表面孔缝占比3％、孔缝结构的开口尺寸为2-5μm、孔缝结构的深度为开口尺寸的3-5倍的实心石墨棒(φ3mm×50mm)的以聚四氟乙烯为内衬的水热釜中，在180℃下进行水热反应16小时，得到表面大部分生长为β相氮化钨电极材料。The same method as in Example 1 was used to prepare the tungsten nitride electrode material, the only difference being that in step S3, 40mL of tungstic acid precursor was taken, 2g of ammonium sulfate was added as a capping agent, and then the solution was transferred to a pre-placed A solid graphite rod (φ3mm×50mm) lined with polytetrafluoroethylene, which accounts for 3% of the surface pores, the opening size of the pore structure is 2-5μm, and the depth of the pore structure is 3-5 times the opening size. In a hydrothermal kettle, the hydrothermal reaction was carried out at 180°C for 16 hours, and most of the surface was grown as β-phase tungsten nitride electrode material.
对比例3Comparative example 3
采用US9624604B2中实施例1所述方法，以WCl
6和NaN
3(比例3:2)为前驱体，NaCl+10wt％ZrO
2为填充剂，在1400℃和7.7GPa下进行反应，所得产物经水洗、离心、干燥后获得δ相氮化钨粉末。将该δ相氮化钨材料分散于含一定量Nafion膜溶液的异丙醇中，滴覆于玻碳电极的表面制成膜电极进行测试。
Using the method described in Example 1 of US9624604B2, using WCl 6 and NaN 3 (ratio 3:2) as precursors, NaCl+10wt% ZrO 2 as filler, reacting at 1400 ° C and 7.7 GPa, the resulting product was washed with water , centrifugation, and drying to obtain δ-phase tungsten nitride powder. The δ-phase tungsten nitride material is dispersed in isopropanol containing a certain amount of Nafion membrane solution, and dropped on the surface of a glassy carbon electrode to form a membrane electrode for testing.
测试例test case
(1)在酸性电解液(0.5mol/L的硫酸)中，以上述实施例和对比例制备的电极材料或膜电极作为工作电极，以普通石墨棒为对电极，银/氯化银为参比电极，进行电解水制氢反应，达到10mA/cm
-2电流密度所需的过电位如表1所示，实施例1和对比例1制备的电极的产氢极化曲线如图3所示。
(1) In the acid electrolyte (0.5mol/L sulfuric acid), the electrode material or membrane electrode prepared in the above examples and comparative examples is used as the working electrode, the common graphite rod is used as the counter electrode, and silver/silver chloride is used as the reference electrode. For the specific electrode, the overpotential required for hydrogen production by electrolysis of water to achieve a current density of 10mA/cm -2 is shown in Table 1, and the hydrogen production polarization curves of the electrodes prepared in Example 1 and Comparative Example 1 are shown in Figure 3 .
(2)在碱性电解液(1.0mol/L的氢氧化钾)中，以上述实施例和对比例制备的电解材料作为工作电极，普通石墨棒为对电极，汞/***为参比电极，进行电水解制氢反应，达到10mA/cm
-2电流密度所需的过电位如表1所示，实施例1的，实施例1和对比例1制备的电极的产氢极化曲线如图4所示。
(2) In the alkaline electrolyte (potassium hydroxide of 1.0mol/L), the electrolytic material prepared by the above-mentioned examples and comparative examples is used as a working electrode, the common graphite rod is a counter electrode, and mercury/mercuric oxide is a reference electrode , carry out the electrohydrolysis hydrogen production reaction, the overpotential required to reach the current density of 10mA/cm -2 is shown in Table 1, the hydrogen production polarization curves of the electrodes prepared in Example 1, Example 1 and Comparative Example 1 are shown in the figure 4.
(3)在酸性电解液(0.5mol/L的硫酸)中，将实施例和对比例制备的电极材料在恒定过电位下进行15小时的持续电解水制氢反应，检测电流密度随时间的变化，实施例1制备的电极的产氢的时间-电流密度曲线如图5所示。(3) In the acidic electrolyte (0.5mol/L sulfuric acid), the electrode materials prepared in the examples and comparative examples were subjected to a 15-hour continuous hydrogen production reaction by electrolyzing water at a constant overpotential, and the change of the current density over time was detected. , the hydrogen production time-current density curve of the electrode prepared in Example 1 is shown in FIG. 5 .
上述测试通过辰华CHI700E电化学工作站进行，电流密度是指在一定电压下所得单位电极面积的电流。The above test was carried out by Chenhua CHI700E electrochemical workstation, and the current density refers to the current per unit electrode area obtained under a certain voltage.
表1Table 1
由上述可知，本公开的方法工艺条件温和、耗能较低，可以制备δ相氮化钨电极材料，将本公开的方法制备得到δ相氮化钨电极材料作为酸性或碱性电解液产氢电极或电极材料，具有较优的产氢活性和稳定性。优选地，当氨化反应的温度为1000-1100℃，时间为90-120min，制备得到的δ相氮化钨电极材料具有更优的产氢活性和稳定性。优选地，当导电基底材料的孔缝结构的开口尺寸为5-200μm，孔缝结构的深度为所述孔缝宽度的2-10倍，表面孔缝占比为30-60％时，制备得到的δ相氮化钨电极材料具有更优的产氢活性和稳定性。优选地，当水热温度为160-200℃，水热时间为12-24小时，制备 得到的δ相氮化钨电极材料具有更优的产氢活性和稳定性。From the above, it can be seen that the method of the present disclosure has mild process conditions and low energy consumption, and can prepare δ-phase tungsten nitride electrode materials, and the δ-phase tungsten nitride electrode materials prepared by the method of the present disclosure can be used as acidic or alkaline electrolytes to produce hydrogen Electrodes or electrode materials have better hydrogen production activity and stability. Preferably, when the temperature of the ammoniation reaction is 1000-1100° C. and the time is 90-120 minutes, the prepared δ-phase tungsten nitride electrode material has better hydrogen production activity and stability. Preferably, when the opening size of the pore structure of the conductive base material is 5-200 μm, the depth of the pore structure is 2-10 times the width of the pore structure, and the proportion of surface pores is 30-60%, the prepared The δ-phase tungsten nitride electrode material has better hydrogen production activity and stability. Preferably, when the hydrothermal temperature is 160-200°C and the hydrothermal time is 12-24 hours, the prepared delta-phase tungsten nitride electrode material has better hydrogen production activity and stability.
以上结合附图详细描述了本公开的优选实施方式，但是，本公开并不限于上述实施方式中的具体细节，在本公开的技术构思范围内，可以对本公开的技术方案进行多种简单变型，这些简单变型均属于本公开的保护范围。The preferred embodiments of the present disclosure have been described in detail above in conjunction with the accompanying drawings. However, the present disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present disclosure, various simple modifications can be made to the technical solutions of the present disclosure. These simple modifications all belong to the protection scope of the present disclosure.
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征，在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本公开对各种可能的组合方式不再另行说明。In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner if there is no contradiction. The combination method will not be described separately.
此外，本公开的各种不同的实施方式之间也可以进行任意组合，只要其不违背本公开的思想，其同样应当视为本公开所公开的内容。In addition, various implementations of the present disclosure can be combined arbitrarily, as long as they do not violate the idea of the present disclosure, they should also be regarded as the content disclosed in the present disclosure.
最后应说明的是：以上实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方案的精神和范围。Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present disclosure, rather than to limit them; although the present disclosure has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: it can still Modifications are made to the technical solutions described in the foregoing embodiments, or equivalent replacements are made to some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present disclosure.
Claims (13)
- 一种δ相氮化钨电极材料，其特征在于，所述δ相氮化钨电极材料包括具有孔缝结构的导电基底和δ相氮化钨层，至少部分的所述δ相氮化钨层覆于所述孔缝结构的内壁表面；A δ-phase tungsten nitride electrode material, characterized in that the δ-phase tungsten nitride electrode material includes a conductive substrate with a slit structure and a δ-phase tungsten nitride layer, at least part of the δ-phase tungsten nitride layer covering the inner wall surface of the aperture structure;所述孔缝结构包括在所述导电基底表面向内部延伸的孔和/或大体沿所述导电基体表面延伸的狭缝；所述表面孔缝占比为5-70％，所述孔缝结构的开口尺寸为500nm-500μm，所述孔缝结构的深度为所述开口尺寸的1.5倍以上。The slit structure includes holes extending inwardly on the surface of the conductive substrate and/or slits extending generally along the surface of the conductive substrate; the surface slits account for 5-70%, and the slit structure The size of the opening is 500nm-500μm, and the depth of the slit structure is more than 1.5 times the size of the opening.
- 根据权利要求1所述的δ相氮化钨电极材料，其中，所述δ相氮化钨层的平均厚度为10nm-20μm。The δ-phase tungsten nitride electrode material according to claim 1, wherein the average thickness of the δ-phase tungsten nitride layer is 10 nm-20 μm.
- 一种制备δ相氮化钨电极材料的方法，其特征在于，该方法包括：在氨气氛围中使含有氧化钨和/或钨酸的导电基底进行氨化反应；A method for preparing a δ-phase tungsten nitride electrode material, characterized in that the method comprises: performing an ammoniation reaction on a conductive substrate containing tungsten oxide and/or tungstic acid in an ammonia atmosphere;其中，所述含有氧化钨和/或钨酸的导电基底具有孔缝结构，至少部分的所述氧化钨和/或钨酸附于所述孔缝结构的内壁表面；所述表面孔缝占比为5-70％，所述孔缝结构的开口尺寸为500nm-500μm，所述孔缝结构的深度为所述开口尺寸的1.5倍以上；Wherein, the conductive substrate containing tungsten oxide and/or tungstic acid has a slit structure, and at least part of the tungsten oxide and/or tungstic acid is attached to the inner wall surface of the slit structure; the proportion of the surface slits is 5-70%, the opening size of the pore structure is 500nm-500μm, and the depth of the pore structure is more than 1.5 times the opening size;所述氨化反应的条件包括：温度为900-1800℃，时间为30-240min。The conditions of the ammoniation reaction include: the temperature is 900-1800°C, and the time is 30-240min.
- 根据权利要求3所述的方法，其中，所述氨化反应的条件包括：温度为950-1150℃，时间为60-180min；优选地，所述温度为1000-1100℃，时间为90-120min。The method according to claim 3, wherein the conditions of the ammoniation reaction include: the temperature is 950-1150°C, and the time is 60-180min; preferably, the temperature is 1000-1100°C, and the time is 90-120min .
- 根据权利要求3所述的方法，其中，所述导电基底的材料为具有孔缝结构且高温稳定性良好的导体材料，优选为石墨、碳化钛和二硼化钛中的一种或几种，所述导电基底的形状为片状、棒状、圆环柱状、块状或粉状；The method according to claim 3, wherein the material of the conductive substrate is a conductive material having a porous structure and good high temperature stability, preferably one or more of graphite, titanium carbide and titanium diboride, The shape of the conductive base is sheet, rod, circular column, block or powder;所述孔缝结构的开口尺寸为5-200μm，所述孔缝结构的深度为所述孔缝宽度的2-10倍，所述表面孔缝占比为30-60％。The opening size of the pore structure is 5-200 μm, the depth of the pore structure is 2-10 times of the width of the pore, and the proportion of the surface pore is 30-60%.
- 根据权利要求3所述的方法，其中，该方法还包括：采用化学合成法 原位制备所述含有三氧化钨和/或钨酸的导电基底；所述化学合成法选自水热法、电化学法、共沉淀法和化学沉淀法中的一种或几种。The method according to claim 3, wherein, the method also includes: adopting a chemical synthesis method to prepare the conductive substrate containing tungsten trioxide and/or tungstic acid in situ; the chemical synthesis method is selected from hydrothermal method, electric One or more of chemical method, co-precipitation method and chemical precipitation method.
- 根据权利要求3或6所述的方法，其中，采用包括如下步骤的水热法原位制备所述含有氧化钨和/或钨酸的导电基底：The method according to claim 3 or 6, wherein the in-situ preparation of the conductive substrate containing tungsten oxide and/or tungstic acid is carried out by a hydrothermal method comprising the following steps:S1、将第一钨源、强酸和溶剂混合并调节pH值为1-2，得到第一溶液；S1. Mix the first tungsten source, strong acid and solvent and adjust the pH value to 1-2 to obtain the first solution;S2、将所述第一溶液与弱酸混合，得到钨酸前驱体；S2, mixing the first solution with a weak acid to obtain a tungstic acid precursor;S3、使所述钨酸前驱体与第一导电基底在耐热密闭容器内在进行水热反应，得到所述含有氧化钨和/或钨酸的导电基底。S3. Conducting a hydrothermal reaction between the tungstic acid precursor and the first conductive substrate in a heat-resistant airtight container to obtain the conductive substrate containing tungsten oxide and/or tungstic acid.
- 根据权利要求7所述的方法，其中，步骤S2中，所述第一溶液与所述弱酸的用量的摩尔比为1：(2-3)，所述第一溶液以所述第一钨源计；The method according to claim 7, wherein, in step S2, the molar ratio of the first solution to the amount of the weak acid is 1: (2-3), and the first solution uses the first tungsten source count;步骤S3中，所述水热反应的条件包括：温度为120-220℃，时间为6-48小时；优选地，所述水热温度为160-200℃，水热时间为12-24小时；In step S3, the conditions of the hydrothermal reaction include: the temperature is 120-220°C, and the time is 6-48 hours; preferably, the hydrothermal temperature is 160-200°C, and the hydrothermal time is 12-24 hours;所述第一钨源选自钨酸钠、钨酸钾、钨酸锌、偏钨酸铵和氯化钨中的一种或几种；所述强酸选自盐酸、硝酸和稀硫酸中的一种或几种，所述强酸的浓度为1-5mol/L；所述溶剂选自去离子水、乙醇、乙二醇、异丙醇、N,N-二甲基甲酰胺和乙腈中的一种或几种；所述弱酸选自草酸、甲酸、醋酸和碳酸中的一种或几种；所述第一导电基底的材料为具有孔缝结构且高温稳定性良好的导体材料，优选为石墨、碳化钛和二硼化钛中的一种或几种。The first tungsten source is selected from one or more of sodium tungstate, potassium tungstate, zinc tungstate, ammonium metatungstate and tungsten chloride; the strong acid is selected from one of hydrochloric acid, nitric acid and dilute sulfuric acid one or more, the concentration of the strong acid is 1-5mol/L; the solvent is selected from one of deionized water, ethanol, ethylene glycol, isopropanol, N,N-dimethylformamide and acetonitrile one or more; the weak acid is selected from one or more of oxalic acid, formic acid, acetic acid and carbonic acid; the material of the first conductive substrate is a conductive material with a porous structure and good high temperature stability, preferably graphite One or more of titanium carbide and titanium diboride.
- 根据权利要求3或6所述的方法，其中，采用包括如下步骤的电化学法制备所述含有氧化钨和/或钨酸的导电基底：The method according to claim 3 or 6, wherein the electrochemical method comprising the following steps is used to prepare the conductive substrate containing tungsten oxide and/or tungstic acid:(1)、使第二钨源与过氧化氢溶液接触反应后，可选地除去反应后的溶液中含有的过氧化氢，得到第二溶液；(1), after making the second tungsten source contact with the hydrogen peroxide solution, optionally remove the hydrogen peroxide contained in the reacted solution to obtain the second solution;(2)、采用稀释剂对所述第二溶液进行稀释，得到电解液；(2), using a diluent to dilute the second solution to obtain an electrolyte;(3)、以第二导电基底为工作电极，并将其置于所述电解液中，采用恒电位方法在所述第二导电基底上沉积氧化钨和/或钨酸，得到含有氧化钨和/或钨酸的导电基底。(3), using the second conductive substrate as the working electrode, and placing it in the electrolyte, using a constant potential method to deposit tungsten oxide and/or tungstic acid on the second conductive substrate to obtain a solution containing tungsten oxide and / or conductive substrate for tungstic acid.
- 根据权利要求9所述的方法，其中，步骤(1)中，所述的除去反应后的溶液中含有的过氧化氢包括：将催化剂与反应后的溶液接触反应，得到第二溶液；或者，将所述反应后的溶液在50-90℃下加热，得到第二溶液；The method according to claim 9, wherein, in step (1), removing the hydrogen peroxide contained in the reacted solution comprises: contacting the catalyst with the reacted solution to obtain a second solution; or, heating the reacted solution at 50-90°C to obtain a second solution;其中，所述催化剂为铂、银、铬、二氧化锰、氯化铁、氧化铜和过氧化氢酶中的一种或几种，当所述第二溶液的体积与步骤(1)中初始加入的所述过氧化氢溶液的体积之比为0.75-0.85时，取出所述催化剂或停止所述加热；Wherein, the catalyst is one or more of platinum, silver, chromium, manganese dioxide, ferric chloride, copper oxide and catalase, when the volume of the second solution is the same as the initial When the volume ratio of the added hydrogen peroxide solution is 0.75-0.85, take out the catalyst or stop the heating;步骤(2)中，所述第二溶液与所述稀释剂用量的体积比为1：(9-29)；所述稀释剂中含有水、异丙醇、乙醇、乙二醇、丙酮、乙腈和N,N-二甲基甲酰胺中的一种或几种，优选地，所述稀释剂含有水和异丙醇，所述水与异丙醇的体积比为1：(0.4-1)；In step (2), the volume ratio of the second solution to the amount of the diluent is 1: (9-29); the diluent contains water, isopropanol, ethanol, ethylene glycol, acetone, acetonitrile and one or more of N,N-dimethylformamide, preferably, the diluent contains water and isopropanol, and the volume ratio of the water to isopropanol is 1:(0.4-1) ;步骤(3)中，所述沉积的条件包括：沉积电位为-0.4V至-5V，沉积时间为1-60min；In step (3), the deposition conditions include: the deposition potential is -0.4V to -5V, and the deposition time is 1-60min;所述第二钨源选自金属钨粉、钨丝和钨片中的一种或几种，优选为钨粉；The second tungsten source is selected from one or more of metal tungsten powder, tungsten wire and tungsten sheet, preferably tungsten powder;所述第二导电基底的材料为具有孔缝结构且高温稳定性良好的导体材料，优选为石墨、碳化钛和二硼化钛中的一种或几种。The material of the second conductive substrate is a conductive material with a porous structure and good high temperature stability, preferably one or more of graphite, titanium carbide and titanium diboride.
- 根据权利要求3所述的方法，其中，所述氨化反应在马弗炉、管式炉或流化床中进行，所述氨气气氛中氨气的体积浓度为10-100％或者氨气的流量为10-100mL/min。The method according to claim 3, wherein the ammoniation reaction is carried out in a muffle furnace, a tube furnace or a fluidized bed, and the volume concentration of ammonia in the ammonia atmosphere is 10-100% or ammonia gas The flow rate is 10-100mL/min.
- 权利要求3-11中任意一项所述的方法制备得到的δ相氮化钨电极材料。The delta-phase tungsten nitride electrode material prepared by the method described in any one of claims 3-11.
- 权利要求1-2和权利要求12中任意一项所述的δ相氮化钨电极材料在电解水制氢中的应用。Application of the delta-phase tungsten nitride electrode material described in any one of claims 1-2 and claim 12 in hydrogen production by electrolysis of water.
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