CN111841579A - Molybdenum disulfide with three-dimensional hierarchical pore structure and preparation method and application thereof - Google Patents
Molybdenum disulfide with three-dimensional hierarchical pore structure and preparation method and application thereof Download PDFInfo
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- CN111841579A CN111841579A CN201910351880.XA CN201910351880A CN111841579A CN 111841579 A CN111841579 A CN 111841579A CN 201910351880 A CN201910351880 A CN 201910351880A CN 111841579 A CN111841579 A CN 111841579A
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- molybdenum disulfide
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 96
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002149 hierarchical pore Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011148 porous material Substances 0.000 claims abstract description 157
- 238000001035 drying Methods 0.000 claims abstract description 54
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 20
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 16
- 239000011733 molybdenum Substances 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 10
- 239000011593 sulfur Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 36
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 23
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 235000012239 silicon dioxide Nutrition 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 13
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 13
- 239000012498 ultrapure water Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 12
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 11
- 239000011609 ammonium molybdate Substances 0.000 claims description 11
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 11
- 229940010552 ammonium molybdate Drugs 0.000 claims description 11
- 239000002245 particle Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000004408 titanium dioxide Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002808 molecular sieve Substances 0.000 claims description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 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
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- XFKSEEQMCYEBNY-UHFFFAOYSA-N [O-]CC.[Mo+4].[O-]CC.[O-]CC.[O-]CC Chemical compound [O-]CC.[Mo+4].[O-]CC.[O-]CC.[O-]CC XFKSEEQMCYEBNY-UHFFFAOYSA-N 0.000 claims description 2
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 2
- YJEJUIVHAMABCA-UHFFFAOYSA-J molybdenum(4+);oxalate Chemical compound [Mo+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O YJEJUIVHAMABCA-UHFFFAOYSA-J 0.000 claims description 2
- TXCOQXKFOPSCPZ-UHFFFAOYSA-J molybdenum(4+);tetraacetate Chemical compound [Mo+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O TXCOQXKFOPSCPZ-UHFFFAOYSA-J 0.000 claims description 2
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 2
- 230000007935 neutral effect Effects 0.000 claims description 2
- BFXSYWWEMMKKRS-UHFFFAOYSA-I pentabromomolybdenum Chemical compound Br[Mo](Br)(Br)(Br)Br BFXSYWWEMMKKRS-UHFFFAOYSA-I 0.000 claims description 2
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 2
- 229940116357 potassium thiocyanate Drugs 0.000 claims description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 125000004434 sulfur atom Chemical group 0.000 claims description 2
- YPFBRNLUIFQCQL-UHFFFAOYSA-K tribromomolybdenum Chemical compound Br[Mo](Br)Br YPFBRNLUIFQCQL-UHFFFAOYSA-K 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 17
- 238000000967 suction filtration Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 41
- 238000009826 distribution Methods 0.000 description 31
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 27
- 239000003054 catalyst Substances 0.000 description 23
- 230000005540 biological transmission Effects 0.000 description 13
- 238000003491 array Methods 0.000 description 10
- 239000012535 impurity Substances 0.000 description 10
- 229910052961 molybdenite Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012546 transfer Methods 0.000 description 5
- 229910021397 glassy carbon Inorganic materials 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000001699 photocatalysis Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a preparation method of molybdenum disulfide with a three-dimensional hierarchical pore structure. Specifically, the method comprises the steps of firstly preparing templates with various scales, then fully and uniformly mixing a molybdenum-based compound and the templates, reacting the molybdenum-based compound and a sulfur-containing compound at a certain temperature, finally carrying out solution treatment, and carrying out suction filtration and drying to obtain a target product. The material prepared by the method has a complete three-dimensional hierarchical pore structure, no cluster and no collapse phenomenon, and the pore wall of the material is formed by a molybdenum disulfide nanosheet array. The type of the template and the size of the pore channel are easy to be modulated. The material has excellent activity when being used for electrocatalytic hydrogen evolution reaction. The method is a universal method for molybdenum disulfide with a three-dimensional hierarchical pore structure, and has the characteristics of simplicity and easiness in operation.
Description
Technical Field
The invention belongs to the field of nano two-dimensional materials, and particularly relates to molybdenum disulfide with a three-dimensional hierarchical pore structure, and a preparation method and application thereof.
Background
Two-dimensional molybdenum disulfideDue to its unique structure and electronic properties, it has attracted extensive attention in the field of catalysis, including electrocatalysis, photocatalysis and traditional catalysis. Meanwhile, the molybdenum disulfide has the advantages of large natural reserve, low price, excellent performance and the like, so that the molybdenum disulfide is expected to be a substitute of a noble metal hydrogen evolution electrocatalyst. Currently, the hydrogen evolution active sites of molybdenum disulfide are mainly derived from their small number of marginal sulfur sites, whereas their large number of in-plane sulfur sites are relatively inert (b.hinnemann, j.k). 
al.am.c hem.soc.,127, 5308-. In addition, due to the van der waals force between the molybdenum disulfide layers, the catalyst is easy to agglomerate in the reaction process, covers the original active sites, and also seriously hinders mass transfer in the hydrogen evolution reaction process, thereby finally causing the inactivation of the catalyst (J.Y.Luo, J.X.Huang et al.ACS Nano, 5,8943-8949 (2011)). Therefore, many researchers thought how to make the molybdenum disulfide more prone to expose the side with high activity by structure modulation, and more beneficial to mass transfer and stability in the reaction process. The Jaramillo project group regulates and controls the surface structure of molybdenum disulfide, so that the molybdenum disulfide forms a double-helix mesoporous structure on a certain template, and the molybdenum disulfide is more prone to expose a high-activity edge and shows excellent hydrogen evolution activity and stability (J.Kibsgaard, T.F. Jaramillo et al. Nat mater, 11, 963-. However, the existing structure regulation strategy is limited by the existing preparation technology, and the constructed catalyst has only a single pore structure and cannot fully improve the specific surface area and the mass transfer efficiency of the catalyst. Therefore, the developed molybdenum disulfide catalyst with the hierarchical pore structure can not only greatly improve the specific surface area, but also improve the mass transfer rate of substances in the catalyst. However, regulation of the hierarchical pore structure of molybdenum disulfide has not been reported effectively, but according to the reported preparation methods of hierarchical pore structures of other materials, when the pore structure of one scale is regulated, the pore structure of the other scale is collapsed and broken, and then the whole structure becomes disordered and is easy to agglomerate. Therefore, how to form the template by effectively adjusting the dimension and the proportion of each template Formation of molybdenum disulfide in a three-dimensional hierarchical pore structure still faces significant challenges.
Disclosure of Invention
The invention provides a preparation method of molybdenum disulfide with a three-dimensional hierarchical pore structure. According to the method, the molybdenum disulfide material with the three-dimensional hierarchical pore structure is effectively constructed by reasonably regulating and controlling the multi-template agent, and has excellent activity when being used for the electrocatalytic hydrogen evolution reaction. The template adopted by the method comprises two scales or more than two scales, a multi-level pore structure can be formed after the template agent is removed, and the structure can be a multi-scale mesopore, multi-scale macropore, multi-scale micropore, micropore-mesopore, micropore-macropore, mesopore-macropore and micropore-mesopore-macropore structure, and the pore wall of each single pore is composed of a molybdenum disulfide nanosheet array. The method is easy to operate, has wide application range and is suitable for constructing other two-dimensional material structures. The material has wide application prospect in the fields of electro-catalysis, photocatalysis, energy storage and conversion and the like.
The technical scheme of the invention is as follows: the invention provides a molybdenum disulfide material with a three-dimensional hierarchical pore structure, which is molybdenum disulfide with a structure at least comprising two pore canal sizes; the pore wall of the pore channel is composed of a molybdenum disulfide nanosheet array.
Preferably, in the molybdenum disulfide material with the three-dimensional hierarchical pore structure, "two" of the two pore sizes can refer to two sizes in the same pore type (micropore, mesopore and macropore), and can also refer to two pore types; the hierarchical pore structure is mesopores with at least two sizes, macropores with at least two sizes or micropores with at least two sizes; or the hierarchical pore structure is microporous with at least one pore size and mesoporous with one pore size, microporous with at least one pore size and macroporous with at least one pore size, mesoporous with at least one pore size and macroporous with at least one pore size, microporous with at least one pore size and mesoporous with at least one pore size and macroporous with at least one pore size.
The invention also provides a preparation method of the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is characterized by comprising the following steps:
(1) selecting a pore template with the size consistent with that of the pore in claim 1, ultrasonically dispersing the pore template in a solvent A, stirring the mixture at the temperature of 25-100 ℃ for 1-48 hours, drying and grinding the mixture to obtain a template A;
(2) uniformly mixing the template A and the molybdenum-based compound in the step (1) in a solvent B, stirring for 1-48 h at 25-100 ℃, drying to obtain a solid A, then mixing the solid A and a sulfur-containing compound under the protection of inert gas, transferring to a high-pressure reaction kettle, and keeping at 100-600 ℃ for 1-24 h to obtain a product B;
(3) And (3) transferring the product B obtained in the step (2) to a solution from which the template agent is removed, sealing, standing for 2-24 hours, washing, and drying to obtain the molybdenum disulfide material with the three-dimensional hierarchical pore structure.
Based on the above technical scheme, preferably, the preparation method in step (1) is characterized in that the pore template in step (1) is polystyrene, nano alumina, cerium oxide, silicon dioxide, carbon nanotube, titanium dioxide and molecular sieve; the particle size of the polystyrene is 100-600 nm; the particle size of the nano alumina is 10-200 nm; the particle size of the cerium oxide is 30-100 nm; the particle size of the silicon dioxide is 1-600 nm; the size of the pore channel of the carbon nano tube is 1.5-200 nm; the particle size of the titanium dioxide is 10-80 nm; the size of the pore channel of the molecular sieve is 0.5-50 nm.
Based on the technical scheme, preferably, when the pore template added in the step (1) is pore templates with two different sizes, the mass ratio of the pore template with the larger size to the pore template with the smaller size is 20: 1-15; when the pore templates added in the step (1) are pore templates with more than two sizes, the mass ratio of the pore template with the larger size to the pore template with the relatively smaller size in any two pore templates is 20: 1-10.
Based on the technical scheme, preferably,
the ultrasonic time in the step (1) is 1-8 h;
in the step (1), the solvent A is at least one of water, acetone, methanol, ethanol, ammonia water, toluene, acetonitrile and ethylene glycol;
in the step (1), the drying time is 4-16 h, and the drying temperature is 25-120 ℃;
the grinding time in the step (1) is 0.1-0.5 h.
Based on the technical scheme, preferably,
the molybdenum-based compound in the step (2) is at least one of molybdenum trioxide, sodium molybdate, phosphomolybdic acid, molybdenum chloride, potassium molybdate, ammonium tetrathiomolybdate, molybdenum acetate, ammonium molybdate, molybdenum ethoxide, molybdenum oxalate, molybdenum pentabromide, molybdenum acetylacetonate, molybdenum hexacarbonyl, molybdenum phosphide and molybdenum bromide; the mass ratio of molybdenum atoms in the molybdenum-based compound to the total mass of the pore channel template is 1: 1-100;
the mixing in the step (2) is ultrasonic dispersion mixing, and the ultrasonic time is 0.5-6 h;
in the step (2), the solvent B is at least one of water, acetone, methanol, ethanol, ammonia water, ethylene glycol, N-dimethylformamide, toluene, acetonitrile, ethylenediamine, chloroform, formic acid and diethyl ether;
the drying in the step (2) is vacuum drying or normal pressure drying, the drying temperature is 25-120 ℃, and the drying time is 4-24 hours;
The inert gas in the step (2) is at least one of nitrogen, argon or helium;
the sulfur-containing compound in the step (2) is one or more than two of sulfur powder, carbon disulfide, thioacetamide, dimethyl sulfoxide, thiourea, butyl mercaptan, ammonium thiocyanate, potassium thiocyanate, sodium sulfide, potassium sulfide, ammonium tetrathiomolybdate and sodium sulfite; the molar ratio of sulfur atoms in the sulfur-containing compound to molybdenum atoms in the molybdenum source is 1: 10-500: 1;
based on the technical scheme, preferably,
the solution for removing the template agent in the step (3) is at least one of hydrofluoric acid solution, sodium hydroxide solution, potassium hydroxide solution, ammonia water solution, hydrochloric acid solution and sulfuric acid solution; the concentration of the hydrofluoric acid solution, the sodium hydroxide solution, the ammonia water solution, the potassium hydroxide solution, the sulfuric acid solution and the hydrochloric acid solution is 5-70 wt%
The washing in the step (3) is carried out for multiple times in ultrapure water and ethanol until the solution is neutral;
in the step (3), the drying temperature is 25-150 ℃, and the drying time is 6-24 h.
The invention also provides the application of the molybdenum disulfide material with the three-dimensional hierarchical pore structure or the molybdenum disulfide material with the three-dimensional hierarchical pore structure obtained by the preparation method in an electrocatalytic hydrogen evolution reaction, and the molybdenum disulfide material with the three-dimensional hierarchical pore structure has good activity and stability.
Advantageous effects
1. The molybdenum disulfide material with the three-dimensional hierarchical pore structure prepared by the invention has a pore channel structure with various scales, so that the specific surface area can be greatly improved, and the mass transfer rate of substances in the catalyst can be improved; molybdenum disulfide forms a regular nanosheet array on the hole wall, has rich active side sites, and can greatly improve the number of active sites; the three-dimensional structure ensures that the molybdenum disulfide is not easy to agglomerate and deactivate, and is beneficial to prolonging the service life of the catalyst.
2. The prepared molybdenum disulfide material with the three-dimensional hierarchical pore structure has rich types of multi-scale pore channel templates and wide selectable scale range, and the addition amount of the template agents with different sizes and the mixed form of the template agent, a molybdenum source and a sulfur source are favorable for the stability of the formed pore channel structure, are not easy to collapse and can be suitable for reactions without systems.
3. The prepared molybdenum disulfide material with the multi-three-dimensional hierarchical pore structure is high in hydrogen evolution activity by electrocatalysis and stable in catalyst.
4. The template required by the preparation material is wide in source, can realize macro preparation, and is easy for large-scale production.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) image of a sample of example 1.
FIG. 2 is a High Resolution Transmission Electron Microscopy (HRTEM) image of the sample of example 1.
FIG. 3 is a Transmission Electron Microscope (TEM) image of a sample of example 2.
FIG. 4 is a High Resolution Transmission Electron Microscopy (HRTEM) image of the sample of example 2.
FIG. 5 is a Scanning Electron Microscope (SEM) image of a sample of example 3.
FIG. 6 is a Transmission Electron Microscopy (TEM) image of a sample of example 4.
FIG. 7 is a Transmission Electron Microscope (TEM) image of a sample of example 5.
FIG. 8 is a graph of pore size distribution for the sample of example 1 versus the sample of comparative example 1.
FIG. 9 is a graph showing the results of measuring the electrocatalytic hydrogen evolution activity in examples 10 and 11.
Detailed Description
The whole material preparation process is described in detail by the following examples, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
Example 1
1. Taking 1.9g of silicon dioxide (100nm) and 0.9g of silicon dioxide (20nm) to ultrasonically disperse for 3h in an ethylene glycol solution, then stirring for 24h at 50 ℃, drying for 12h at 100 ℃, taking out and grinding for 0.3h to obtain the template A.
2. Dissolving 400mg of ammonium molybdate in 30mL of water, adding the template A, ultrasonically mixing for 1h, stirring for 24h at room temperature, drying for 12h at 60 ℃, and sealing with 10mL of carbon disulfide in a 60mL high-pressure reaction kettle under the protection of argon.
3. The autoclave in (2) was maintained at 200 ℃ for 4 h.
4. And (4) sealing and standing the sample obtained in the step (3) in a 10% hydrofluoric acid solution for 12 hours. Then washing with ultrapure water and ethanol respectively for a plurality of times and filtering with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12 hours to obtain the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is named as 100nm/20nm-MoS2。
The transmission electron microscope (see figure 1) shows that the obtained sample is a regular three-dimensional macroporous-mesoporous structure, wherein the hierarchical pore structure can be clearly seen to mainly consist of pore channels with the sizes of 100nm and 20nm, small-size pore channels are uniformly distributed among the large-size pore channels, and the whole body has no collapse phenomenon; a high-resolution electron microscope (see figure 2) shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve (see fig. 8) shows that the pore size distribution of the multi-level pore structure sample is mainly composed of two intervals of pore sizes compared with single-channel molybdenum disulfide, and further proves that the catalyst has two scales of pore size distribution.
Example 2
1. Taking 1.2g of silicon dioxide (200nm) and 0.5g of silicon dioxide (10nm) to ultrasonically disperse in an ethylene glycol solution for 3h, then stirring at 50 ℃ for 24h, drying at 100 ℃ for 12h, taking out and grinding for 0.3h to obtain the template A.
2. Dissolving 400mg of ammonium molybdate in 30mL of water, adding the template A, ultrasonically mixing for 1h, stirring for 24h at room temperature, drying for 12h at 60 ℃, and sealing with 10mL of carbon disulfide in a 60mL high-pressure reaction kettle under the protection of argon.
3. The autoclave in (2) was maintained at 200 ℃ for 4 h.
4. And (4) sealing and standing the sample obtained in the step (3) in a 10% hydrofluoric acid solution for 12 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12 hours to obtain the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is named as 200nm/10nm-MoS2。
The transmission electron microscope (see figure 3) shows that the obtained sample is a regular three-dimensional macroporous-mesoporous structure, wherein the hierarchical pore structure can be clearly seen to mainly consist of pore channels with the sizes of 200nm and 10nm, and small-size pore channels are uniformly distributed among the large-size pore channels, so that the integral collapse phenomenon does not occur; a high-resolution electron microscope (see figure 4) shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve shows that compared with single-pore molybdenum disulfide, the pore size distribution of the multi-level pore structure sample mainly comprises two intervals of pore sizes, and further proves that the catalyst has two scales of pore size distribution.
Example 3
1. Taking 1.2g of silicon dioxide (400nm) and 0.2g of silicon dioxide (70nm) to ultrasonically disperse in an ethylene glycol solution for 3 hours, then stirring at 50 ℃ for 24 hours, drying at 100 ℃ for 12 hours, taking out and grinding for 0.3 hour to obtain the template A.
2. Dissolving 400mg of ammonium molybdate in 30mL of water, adding the template A, ultrasonically mixing for 1h, stirring for 24h at room temperature, drying for 12h at 60 ℃, and sealing with 10mL of carbon disulfide in a 60mL high-pressure reaction kettle under the protection of argon.
3. The autoclave in (2) was kept at 300 ℃ for 4 hours.
4. And (4) sealing and standing the sample obtained in the step (3) in a 10% hydrofluoric acid solution for 12 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12h to obtain the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is named as 400nm/70nm-MoS2。
The scanning electron microscope (see figure 5) shows that the obtained sample is a regular three-dimensional macroporous-macroporous structure, wherein the hierarchical porous structure can be clearly seen to mainly consist of 400nm and 70 nm-sized pore channels, small-sized pore channels are uniformly distributed among the large-sized pore channels, and the whole body has no collapse phenomenon; the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve shows that compared with single-pore molybdenum disulfide, the pore size distribution of the multi-level pore structure sample mainly comprises two intervals of pore sizes, and further proves that the catalyst has two scales of pore size distribution.
Example 4
1. Taking 2.5g of molecular sieve SBA-15(10nm) and 0.9g of molecular sieve SBA-15(1.5nm) to ultrasonically disperse for 3h in an ethanol solution, then stirring for 24h at 25 ℃, drying for 12h at 100 ℃, taking out and grinding for 0.3h to obtain the template A.
2. Dissolving 400mg of ammonium molybdate in 30mL of water, adding the template A, ultrasonically mixing uniformly, stirring at room temperature until the solution becomes solid, drying at 60 ℃ for 12 hours, and sealing in a 60mL high-pressure reaction kettle together with 10mL of carbon disulfide under the protection of argon.
3. The autoclave in (2) was kept at 300 ℃ for 4 hours.
4. And (4) sealing and standing the sample obtained in the step (3) in a 15% hydrofluoric acid solution for 12 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12 hours to obtain the three-dimensional polypeptideMolybdenum disulfide with hierarchical pore structure, named as 10nm/1.5nm-MoS2。
The transmission electron microscope (see figure 6) shows that the obtained sample is a regular three-dimensional micropore-mesopore structure, wherein the hierarchical pore structure can be clearly seen to mainly consist of pore channels with the sizes of 10nm and 1.5nm, and small-size pore channels are uniformly distributed among the large-size pore channels, so that the whole body has no collapse phenomenon; the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve shows that compared with single-pore molybdenum disulfide, the pore size distribution of the multi-level pore structure sample mainly comprises two intervals of pore sizes, and further proves that the catalyst has two scales of pore size distribution.
Example 5
1. Taking 2.5g of silicon dioxide (100nm) and 0.9g of silicon dioxide (1nm) to ultrasonically disperse in an aqueous solution for 3h, then stirring at 50 ℃ for 24h, drying at 100 ℃ for 12h, taking out and grinding for 0.3h to obtain the template A.
2. Dissolving 400mg of ammonium molybdate in 30mL of water, adding the template A, ultrasonically mixing uniformly, stirring at room temperature until the solution becomes solid, drying at 60 ℃ for 12 hours, and sealing in a 60mL high-pressure reaction kettle together with 10mL of carbon disulfide under the protection of argon.
3. The autoclave in (2) was maintained at 200 ℃ for 4 h.
4. And (4) sealing and standing the sample obtained in the step (3) in a 10% hydrofluoric acid solution for 12 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12 hours to obtain the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is named as 100nm/1nm-MoS2。
The transmission electron microscope (see figure 7) shows that the obtained sample is a regular three-dimensional macroporous-microporous structure, wherein the hierarchical pore structure can be clearly seen to mainly consist of pore channels with the sizes of 100nm and 1nm, and small-size pore channels are uniformly distributed among the large-size pore channels, so that the integral collapse phenomenon does not occur; the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve shows that compared with single-pore molybdenum disulfide, the pore size distribution of the multi-level pore structure sample mainly comprises two intervals of pore sizes, and further proves that the catalyst has two scales of pore size distribution.
Example 6
1. Taking 2.5g of silicon dioxide (50nm) and 0.9g of silicon dioxide (10nm) to ultrasonically disperse for 3h in an ethanol solution, then stirring for 24h at 25 ℃, drying for 12h at 100 ℃, taking out and grinding for 0.3h to obtain the template A.
2. Dissolving 400mg of ammonium molybdate in 30mL of water, adding the template A, ultrasonically mixing uniformly, stirring at room temperature until the solution becomes solid, drying at 60 ℃ for 12 hours, and sealing in a 60mL high-pressure reaction kettle together with 10mL of carbon disulfide under the protection of argon.
3. The autoclave in (2) was kept at 300 ℃ for 4 hours.
4. And (4) sealing and standing the sample obtained in the step (3) in a 10% hydrofluoric acid solution for 12 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12 hours to obtain the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is named as 50nm/10nm-MoS2。
The transmission electron microscope shows that the obtained sample is a regular three-dimensional mesoporous-mesoporous structure, wherein the hierarchical pore structure can be clearly seen to mainly comprise pore channels with the sizes of 50nm and 10nm, small-size pore channels are uniformly distributed among the large-size pore channels, and the whole structure has no collapse phenomenon; the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve shows that compared with single-pore molybdenum disulfide, the pore size distribution of the multi-level pore structure sample mainly comprises two intervals of pore sizes, and further proves that the catalyst has two scales of pore size distribution.
Example 7
1. Taking 4g of silicon dioxide (100nm), 1.8g of silicon dioxide (20nm) and 0.5g of silicon dioxide (1nm) to ultrasonically disperse for 3h in an ethylene glycol solution, then stirring for 24h at 50 ℃, drying for 12h at 100 ℃, taking out and grinding for 0.3h to obtain the template A.
2. Dissolving 800mg of ammonium molybdate in 20mL of water, adding the template A, ultrasonically mixing uniformly, stirring at room temperature until the solution becomes solid, drying at 60 ℃ for 12 hours, and sealing with 10mL of dimethyl sulfoxide in a 60mL high-pressure reaction kettle under the protection of argon.
3. The autoclave in (2) was maintained at 400 ℃ for 4 h.
4. And (4) sealing and standing the sample obtained in the step (3) in a 10% hydrofluoric acid solution for 12 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12 hours to obtain the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is named as 100nm/20nm/1nm-MoS2。
The transmission electron microscope shows that the obtained sample is a regular three-dimensional macroporous-mesoporous-microporous structure, wherein the hierarchical pore structure can be clearly seen to mainly consist of pore channels with the sizes of 100nm, 20nm and 1nm, and small-size pore channels are uniformly distributed among the large-size pore channels, so that the integral collapse phenomenon does not occur; the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve shows that compared with single-pore molybdenum disulfide, the pore size distribution of the multi-level pore structure sample mainly comprises three intervals of pore sizes, and further proves that the catalyst has three scales of pore size distribution.
Example 8
1. Taking 2.5g of titanium dioxide (400nm) and 0.9g of titanium dioxide (50nm) to ultrasonically disperse in an aqueous solution for 3h, then stirring for 24h at 25 ℃, drying for 12h at 100 ℃, taking out and grinding for 0.3h to obtain the template A.
2. Dissolving 400mg of sodium molybdate in 30mL of water, adding the template A, ultrasonically mixing uniformly, stirring at room temperature until the solution becomes solid, drying at 60 ℃ for 12 hours, and sealing in a 60mL high-pressure reaction kettle together with 10mL of carbon disulfide under the protection of nitrogen.
3. The autoclave in (2) was maintained at 400 ℃ for 4 h.
4. And (4) sealing and standing the sample obtained in the step (3) in a 50% hydrochloric acid solution for 12 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12h to obtain the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is named as 400nm/50nm-MoS2-A。
The transmission electron microscope shows that the obtained sample is a regular three-dimensional macroporous-mesoporous structure, wherein the hierarchical pore structure can be clearly seen to mainly consist of pore channels with the sizes of 400nm and 50nm, small-size pore channels are uniformly distributed among the large-size pore channels, and the whole structure has no collapse phenomenon; the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve shows that compared with single-pore molybdenum disulfide, the pore size distribution of the multi-level pore structure sample mainly comprises three intervals of pore sizes, and further proves that the catalyst has three scales of pore size distribution.
Example 9
1. Taking 2.5g of titanium dioxide (400nm) and 0.9g of titanium dioxide (50nm) to ultrasonically disperse in an aqueous solution for 3h, then stirring for 24h at 25 ℃, drying for 12h at 100 ℃, taking out and grinding for 0.3h to obtain the template A.
2. Dissolving 400mg of phosphomolybdic acid in 30mL of ethanol, adding the template A, ultrasonically mixing uniformly, stirring at room temperature until the solution becomes solid, drying at 60 ℃ for 12 hours, and sealing with 3g of thioacetamide in a 60mL high-pressure reaction kettle under the protection of argon.
3. The autoclave in (2) was maintained at 400 ℃ for 4 h.
4. And (4) sealing and standing the sample obtained in the step (3) in a 50% hydrochloric acid solution for 12 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
5. Drying the sample obtained in the step (4) at 100 ℃ for 12h to obtain the molybdenum disulfide with the three-dimensional hierarchical pore structure, which is named as 400nm/50nm-MoS2-B。
The transmission electron microscope shows that the obtained sample is a regular three-dimensional macroporous-mesoporous structure, wherein the hierarchical pore structure can be clearly seen to mainly consist of pore channels with the sizes of 400nm and 50nm, small-size pore channels are uniformly distributed among the large-size pore channels, and the whole structure has no collapse phenomenon; the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve shows that compared with single-pore molybdenum disulfide, the pore size distribution of the multi-level pore structure sample mainly comprises two intervals of pore sizes, and further proves that the catalyst has two scales of pore size distribution.
Comparative example 1
1. Dissolving 400mg of ammonium molybdate in 20mL of water, adding 1.6g of silicon dioxide, carrying out ultrasonic treatment for 1h, mixing uniformly, stirring at room temperature for 24h, drying at 60 ℃ for 12h, and sealing with 10mL of carbon disulfide in a 60mL high-pressure reaction kettle under the protection of argon.
2. The autoclave in (1) was kept at 400 ℃ for 4 h.
3. And (3) sealing and standing the sample obtained in the step (2) in a 10% hydrofluoric acid solution for 12 hours. Then washing with ultrapure water and ethanol respectively for a plurality of times and filtering with suction.
4. Drying the sample obtained in the step (3) at 100 ℃ for 12h to obtain the molybdenum disulfide with the single-stage pore structure, which is named as 100nm-MoS2. The transmission electron microscope shows that the obtained sample is molybdenum disulfide with a single-stage pore structure, wherein the single-stage pore structure mainly comprises pore channels with the size of 100nm, and the whole structure has no collapse phenomenon; the high-resolution electron microscope shows that the obtained samples are all composed of molybdenum disulfide nanosheet arrays, have rich edges and do not contain other impurities and clusters. The pore size distribution curve (see fig. 8) shows that the pore size distribution for the single stage pore structure sample consists primarily of one interval of pore sizes, further demonstrating that the catalyst has one scale of pore size distribution.
Comparative example 2
1. Dissolving 400mg of ammonium molybdate in 20mL of water, ultrasonically dispersing for 1h, stirring for 1h at 25 ℃, drying for 12h at 60 ℃, and sealing with 10mL of carbon disulfide in a 60mL high-pressure reaction kettle under the protection of argon.
2. The autoclave in (1) was kept at 400 ℃ for 4 h.
3. Mixing the sample obtained in the step (2) with 6mol L-1Is treated for 5 hours. Then washed with ultrapure water and ethanol, respectively, and filtered with suction.
4. And (4) drying the sample obtained in the step (3) at 80 ℃ for 12h to obtain the molybdenum disulfide with the non-porous structure.
The transmission electron microscope shows that the obtained sample is of a non-porous structure, and the high-resolution electron microscope shows that the obtained sample has a two-dimensional layered structure, the number of layers is mostly few, and no other clusters or impure phases appear.
Example 10
The influence of the three-dimensional hierarchical pore structure on the electrocatalytic hydrogen evolution activity is examined by adopting the molybdenum disulfide material with the three-dimensional hierarchical pore structure obtained in example 1, the molybdenum disulfide (100nm) with the single-stage pore structure prepared in comparative example 1 and the molybdenum disulfide with the non-porous structure in comparative example 2 as catalysts for the electrocatalytic hydrogen evolution reaction.
1. The electrocatalytic hydrogen evolution performance evaluation method comprises the following steps: a three-electrode system is adopted to carry out a linear sweep voltammetry experiment, a reference electrode is an Ag/AgCl electrode, a counter electrode is a carbon rod electrode, and an electrolyte is 0.5mol L saturated by argon-1H2SO4In the solution, a glassy carbon electrode with the diameter of 5mm is selected as a working electrode. The catalyst electrode was prepared as follows: 980. mu.L of an ethanol solution was added to 4mg of the sample, and then 20. mu.L of a 5% Nafion/isopropyl alcohol solution was added thereto, followed by ultrasonic dispersion for 40min to obtain a suspension. And (3) dropwise adding 25 mu L of the suspension to the surface of the glassy carbon electrode, and naturally airing for later use.
2. And (3) testing conditions are as follows: and (3) testing temperature: 25 ℃; rotating speed of the rotating electrode: 1600 rpm; linear scan rate: 5 mV/s.
3. The molybdenum disulfide with the three-dimensional hierarchical pore structure shows excellent electrocatalytic hydrogen evolution reaction activity in an acid medium, and compared with the molybdenum disulfide with the pore-free structure and the single pore structure, the activity of the molybdenum disulfide is obviously improved, and the hydrogen evolution activity sequence is as follows: molybdenum disulfide with a three-dimensional hierarchical pore structure (100nm/20nm) > molybdenum disulfide with a three-dimensional single-level pore structure (100nm) > molybdenum disulfide with a non-porous structure (see figure 9).
Example 11
The molybdenum disulfide materials with different-scale three-dimensional hierarchical pore structures obtained in examples 1 and 2, the molybdenum disulfide (100nm) with a single-stage pore structure prepared in comparative example 1 and the molybdenum disulfide with a non-porous structure in comparative example 2 are used as catalysts for electrocatalytic hydrogen evolution reaction, and the influence of the different-scale three-dimensional hierarchical pore structures on the electrocatalytic hydrogen evolution activity is examined.
1. The electrocatalytic hydrogen evolution performance evaluation method comprises the following steps: a three-electrode system is adopted to carry out a linear sweep voltammetry experiment, a reference electrode is an Ag/AgCl electrode, a counter electrode is a carbon rod electrode, and an electrolyte is 0.5mol L saturated by argon-1H2SO4Solution of selected diameterA 5mm glassy carbon electrode was used as the working electrode. The catalyst electrode was prepared as follows: 980. mu.L of an ethanol solution was added to 4mg of the sample, and then 20. mu.L of a 5% Nafion/isopropyl alcohol solution was added thereto, followed by ultrasonic dispersion for 40min to obtain a suspension. And (3) dropwise adding 25 mu L of the suspension to the surface of the glassy carbon electrode, and naturally airing for later use.
2. And (3) testing conditions are as follows: and (3) testing temperature: 25 ℃; rotating speed of the rotating electrode: 1600 rpm; linear scan rate: 5 mV/s.
3. The molybdenum disulfide with the three-dimensional hierarchical pore structure shows excellent electrocatalytic hydrogen evolution reaction activity in an acidic medium, wherein the molybdenum disulfide with the 100nm/20nm hierarchical pore structure has the optimal activity, and the hydrogen evolution activity sequence is as follows: molybdenum disulfide with a three-dimensional hierarchical pore structure (100nm/20nm) > molybdenum disulfide with a three-dimensional hierarchical pore structure (200nm/10nm) > molybdenum disulfide with a single-stage pore structure (100nm) > molybdenum disulfide with a non-porous structure (see figure 9).
Claims (9)
1. A three-dimensional molybdenum disulfide material is characterized in that the molybdenum disulfide material is of a three-dimensional hierarchical pore structure; the hierarchical pore structure is a structure comprising at least two pore sizes; the pore wall of the pore channel is composed of a molybdenum disulfide nanosheet array.
2. The molybdenum disulfide material of claim 1, wherein the hierarchical pore structure is mesoporous, macroporous, or microporous of at least two pore sizes; or the hierarchical pore structure is micropore-mesopore, micropore-macropore, mesopore-macropore, micropore-mesopore-macropore.
3. The method of preparing a three-dimensional molybdenum disulfide material of claim 1, comprising the steps of:
(1) Selecting a pore template with the size consistent with that of the pore in claim 1, ultrasonically dispersing the pore template in a solvent A, stirring the mixture at the temperature of 25-100 ℃ for 1-48 hours, drying and grinding the mixture to obtain a template A;
(2) uniformly mixing the template A and the molybdenum-based compound in the step (1) in a solvent B, stirring for 1-48 h at 25-100 ℃, drying to obtain a solid A, then mixing the solid A and a sulfur-containing compound under the protection of inert gas, transferring to a high-pressure reaction kettle, and keeping at 100-600 ℃ for 1-24 h to obtain a product B;
(3) and (3) transferring the product B obtained in the step (2) to a solution from which the template agent is removed, sealing, standing for 2-24 hours, washing, and drying to obtain the molybdenum disulfide material with the three-dimensional hierarchical pore structure.
4. The preparation method according to claim 3, wherein the pore channel template in step (1) is polystyrene, nano alumina, cerium oxide, silicon dioxide, carbon nanotube, titanium dioxide and molecular sieve; the particle size of the polystyrene is 100-600 nm; the particle size of the nano alumina is 10-200 nm; the particle size of the cerium oxide is 30-100 nm; the particle size of the silicon dioxide is 1-600 nm; the size of the pore channel of the carbon nano tube is 1.5-200 nm; the particle size of the titanium dioxide is 10-80 nm; the size of the pore channel of the molecular sieve is 0.5-50 nm.
5. The preparation method according to claim 3, wherein when the pore template added in the step (1) is two pore templates with different sizes, the mass ratio of the pore template with a larger size to the pore template with a smaller size is 20: 1-15; when the pore templates added in the step (1) are pore templates with more than two sizes, the mass ratio of the pore template with the larger size to the pore template with the relatively smaller size in any two pore templates is 20: 1-10.
6. The production method according to claim 3,
the ultrasonic time in the step (1) is 1-8 h;
in the step (1), the solvent A is at least one of water, acetone, methanol, ethanol, ammonia water, toluene, acetonitrile and ethylene glycol;
in the step (1), the drying time is 4-16 h, and the drying temperature is 25-120 ℃;
the grinding time in the step (1) is 0.1-0.5 h.
7. The production method according to claim 3,
the molybdenum-based compound in the step (2) is at least one of molybdenum trioxide, sodium molybdate, phosphomolybdic acid, molybdenum chloride, potassium molybdate, ammonium tetrathiomolybdate, molybdenum acetate, ammonium molybdate, molybdenum ethoxide, molybdenum oxalate, molybdenum pentabromide, molybdenum acetylacetonate, molybdenum hexacarbonyl, molybdenum phosphide and molybdenum bromide; the mass ratio of molybdenum atoms in the molybdenum-based compound to the total mass of the pore channel template is 1: 1-100;
The mixing in the step (2) is ultrasonic dispersion mixing, and the ultrasonic time is 0.5-6 h;
in the step (2), the solvent B is at least one of water, acetone, methanol, ethanol, ammonia water, ethylene glycol, N-dimethylformamide, toluene, acetonitrile, ethylenediamine, chloroform, formic acid and diethyl ether;
the drying in the step (2) is vacuum drying or normal pressure drying, the drying temperature is 25-120 ℃, and the drying time is 4-24 hours;
the inert gas in the step (2) is at least one of nitrogen, argon or helium;
the sulfur-containing compound in the step (2) is at least one of sulfur powder, carbon disulfide, thioacetamide, dimethyl sulfoxide, thiourea, butyl mercaptan, ammonium thiocyanate, potassium thiocyanate, sodium sulfide, potassium sulfide, ammonium tetrathiomolybdate and sodium sulfite; the molar ratio of the sulfur atoms in the sulfur-containing compound to the molybdenum atoms in the molybdenum source is 1: 10-500: 1.
8. The production method according to claim 3,
the solution for removing the template agent in the step (3) is at least one of hydrofluoric acid solution, sodium hydroxide solution, potassium hydroxide solution, ammonia water solution, hydrochloric acid solution and sulfuric acid solution; the concentration of the hydrofluoric acid solution, the sodium hydroxide solution, the potassium hydroxide solution, the ammonia water solution, the hydrochloric acid solution and the sulfuric acid solution is 5-70 wt%
The washing in the step (3) is carried out in ultrapure water and ethanol until the solution is neutral;
in the step (3), the drying temperature is 25-150 ℃, and the drying time is 6-24 h.
9. Use of the three-dimensional molybdenum disulfide material according to claim 1 or the three-dimensional molybdenum disulfide material obtained by the preparation method according to any one of claims 3 to 8 in an electrocatalytic hydrogen evolution reaction.
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