CN108579769A - Composite material, the preparation method and the usage of stratiform two-dimensional material interlayer confinement metal or metallic compound - Google Patents
Composite material, the preparation method and the usage of stratiform two-dimensional material interlayer confinement metal or metallic compound Download PDFInfo
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- CN108579769A CN108579769A CN201810353508.8A CN201810353508A CN108579769A CN 108579769 A CN108579769 A CN 108579769A CN 201810353508 A CN201810353508 A CN 201810353508A CN 108579769 A CN108579769 A CN 108579769A
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- 239000000463 material Substances 0.000 title claims abstract description 97
- 239000002131 composite material Substances 0.000 title claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 51
- 239000002184 metal Substances 0.000 title claims abstract description 51
- 239000011229 interlayer Substances 0.000 title claims abstract description 40
- 229910000765 intermetallic Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 239000001257 hydrogen Substances 0.000 claims abstract description 53
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 53
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 25
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 23
- 150000003839 salts Chemical class 0.000 claims abstract description 20
- 239000010410 layer Substances 0.000 claims abstract description 14
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 238000012545 processing Methods 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 230000000694 effects Effects 0.000 claims description 23
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 239000012298 atmosphere Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 17
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 239000003792 electrolyte Substances 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002791 soaking Methods 0.000 claims description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- 230000001681 protective effect Effects 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000007865 diluting Methods 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 235000016768 molybdenum Nutrition 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 239000002023 wood Substances 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- JAAVTMIIEARTKI-UHFFFAOYSA-N [S--].[S--].[Ta+4] Chemical compound [S--].[S--].[Ta+4] JAAVTMIIEARTKI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims 3
- 150000002576 ketones Chemical class 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- KVXHGSVIPDOLBC-UHFFFAOYSA-N selanylidenetungsten Chemical class [Se].[W] KVXHGSVIPDOLBC-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 41
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000007769 metal material Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 238000010586 diagram Methods 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 8
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 229910052750 molybdenum Inorganic materials 0.000 description 6
- 239000013049 sediment Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000001465 metallisation Methods 0.000 description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002207 thermal evaporation Methods 0.000 description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 230000007812 deficiency Effects 0.000 description 3
- 150000002240 furans Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 150000004040 pyrrolidinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- -1 thioamide analog compound Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Metallurgy (AREA)
- Electrochemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of stratiform two-dimensional material interlayer confinement metal or composite material, the preparation method and the usages of metallic compound.The composite material includes the metal or metallic compound between layers of stratiform two-dimensional material and confinement in layered two-dimensional material.The method includes：1) lithiumation processing is carried out to stratiform two-dimensional material, obtains the stratiform two-dimensional material of lithiumation；2) the stratiform two-dimensional material of dry lithiumation, metal salt are mixed with solvent, is sealed in reaction kettle, hydro-thermal reaction obtains the composite material of stratiform two-dimensional material interlayer confinement metal or metallic compound.A series of controllable preparation of the composite material of two-dimensional material interlayer confinement metals and metallic compound can be realized using the preparation method of the present invention, and, the composite material of the especially two-dimentional molybdenum disulfide interlayer confinement metal hydroxides of composite material obtained has the advantages that electro catalytic activity is high, stability is good as liberation of hydrogen catalyst, has application prospect in electrolysis aquatic products hydrogen field.
Description
Technical field
Hydrogen catalyst field is prepared and produced the invention belongs to composite material, is related to a kind of stratiform two-dimensional material interlayer confinement
The composite material of metal or metallic compound, preparation method and the usage more particularly to a kind of two-dimentional molybdenum disulfide interlayer confinement
The composite material of metal hydroxides, preparation method and as efficient Electrocatalytic Activity for Hydrogen Evolution Reaction agent for electrolysis water evolving hydrogen reaction
Purposes.
Background technology
Currently, the mankind cause environment and energy problem to become increasingly conspicuous the excessive use of fossil energy, are urged using electrochemistry
Change method decomposes a kind of effective ways that aquatic products hydrogen is renewable energy conversion, while being also to be expected to solve current energy crisis
Most safely and effectively technology.However, the problem of electrolysis aquatic products hydrogen maximum is high energy consumption.Institute is reacted to reduce driving electrolysis water
The electric energy needed, is most effective means using elctro-catalyst.Platinum based catalyst is most effective production hydrogen catalyst generally acknowledged at present,
But noble metal platinum reserves are small, expensive, which has limited the uses of its industrial-scale.Therefore, the production of Cheap highly effective is developed
Hydrogen catalyst is significant.
CN105562035A discloses a kind of liberation of hydrogen catalyst and preparation method thereof, and the liberation of hydrogen catalyst includes substrate
And the cobalt acid nickel and copper sulfide of growth on it.The method includes：1) substrate is dipped in containing nickel salt, cobalt salt and surface
In the water solution A of activating agent, heated sealed 10-30h under conditions of 100-150 DEG C is washed out and dries；2) by step
Treated that substrate is annealed by S2, obtains liberation of hydrogen catalyst preparation product；3) the liberation of hydrogen catalyst preparation product is placed in
In aqueous solution B containing mantoquita and surfactant, it is heated to 80-100 DEG C, keeps 2-6h；4) by step S4 treated analysis
Hydrogen preparation product is placed in aqueous solution C, and elemental sulfur, thioamide analog compound, thiocarbamide are contained in wherein aqueous solution C and its is spread out
At least one of biology is heated to 80-100 DEG C, keeps 2-6h；5) treated the washing of liberation of hydrogen preparation product, drying, obtain
To final products.The liberation of hydrogen catalyst is the liberation of hydrogen catalyst of self-supporting base metal high activity heterojunction structure, is had fine
Electric conductivity, surface area is big, exists simultaneously a large amount of active site.These factors make the present invention have the analysis of good hydrogen
Go out catalytic performance.In addition, it is with good stability, it can at least stablize 50 hours.But the synthesis work of this method
Skill is cumbersome, catalyst amount is big, is unfavorable for industrialized production and popularization and application.
Transient metal sulfide is a kind of natural layer material that reserves are larger.Studies have shown that by the thickness of molybdenum disulfide
More molybdenum disulfide edge sites with hydrogen evolution activity can be exposed by being thinned, to greatly improve the catalysis of molybdenum disulfide
Activity；But for the alkaline electrolyte evolving hydrogen reaction for more having industrial applications foreground, molybdenum disulfide be difficult by water decomposition Cheng Qing,
Which has limited its applications in alkaline electrolyte liberation of hydrogen.
Invention content
For problems of the prior art and deficiency, the main purpose of the present invention is to provide a kind of stratiform two dimensions
Composite material, the preparation method and the usage of material interlayer confinement metal or metallic compound.It has been provided in particular in a kind of be applicable in
In the efficient Electrocatalytic Activity for Hydrogen Evolution Reaction agent of alkaline electrolyte, to overcome deficiency in the prior art.
In order to achieve the above object, the present invention uses following technical scheme：
In a first aspect, the present invention provides the composite wood of a kind of stratiform two-dimensional material interlayer confinement metal or metallic compound
Material, the composite material includes the metal between layers of stratiform two-dimensional material and confinement in layered two-dimensional material
Or metallic compound.
In the present invention, " confinement " refers to：Metal or metallic compound are directly intercalation between the interlayer of two-dimensional layer material
In gap, rather than utilize the confinement of two-dimensional material encapsulated nanoparticles.
The composite material of the present invention has unique interlayer confinement structure, this so that intercalated particles are effective by two-dimensional material
Protect (avoid falling off and reunite), at the same two-dimensional material interlayer can effective mass transfer, these factors make the present invention with very good
Catalytic activity, stability and durable wear-resistant.
As the optimal technical scheme of composite material of the present invention, the metallic compound include metal oxide or
Any one in metal hydroxides, preferably metal hydroxides further preferably include Co (OH)2、Ni(OH)2Or Fe
(OH)3In any one or at least two combination.
Preferably, layered two-dimensional material includes molybdenum disulfide, molybdenum disulfide, tungsten disulfide, two selenizing molybdenums, two selenium
Change in tungsten, tantalum disulfide or graphene any one or at least two combination, but be not limited to the above-mentioned stratiform enumerated
Two-dimensional material, other stratiform two-dimensional materials that can reach same effect commonly used in the art can also be used for the present invention, preferably two
Molybdenum sulfide.
Preferably, the thickness of layered two-dimensional material be 2nm~100nm, such as 2nm, 10nm, 20nm, 25nm,
30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm or 100nm etc., preferably 2nm~10nm.
Preferably, the lateral dimension of layered two-dimensional material be 20nm~5000nm, such as 20nm, 35nm, 50nm,
60nm、80nm、100nm、125nm、150nm、200nm、300nm、500nm、750nm、 1000nm、1300nm、1500nm、
1650nm、2000nm、2500nm、2700nm、3000nm、 3200nm、3400nm、3700nm、4000nm、4250nm、4500nm
Or 5000nm etc., preferably 50nm~500nm are more advantageous to lithium with molten difference within the scope of this preferred scope 50nm~500nm
Between the mode of diffusion progresses into two-dimensional slice from edge, to which uniform lithiumation processing be better achieved, further
Preferably 80nm.
Second aspect, the present invention provide stratiform two-dimensional material interlayer confinement metal or metallization as described in relation to the first aspect
The preparation method for closing the composite material of object, the described method comprises the following steps：
(1) lithiumation processing is carried out to stratiform two-dimensional material, obtains the stratiform two-dimensional material of lithiumation；
(2) the stratiform two-dimensional material of lithiumation, metal salt are mixed with solvent, is sealed in reaction kettle, hydro-thermal reaction obtains
To stratiform two-dimensional material interlayer confinement metal or the composite material of metallic compound.
The present invention makes lithium be inserted into the interlayer of stratiform two-dimensional material, utilizes by first carrying out lithiumation to stratiform two-dimensional material
The exchange of metal ion and lithium is realized in molten difference diffusion, to obtain stratiform two-dimensional material interlayer confinement metal or metallic compound
Composite material.
As the optimal technical scheme of the method for the invention, the method includes after lithiumation is handled, carrying out precipitation point
From and dry step.
Preferably, the step of precipitation separation includes：Using solvent (such as hexamethylene) diluting reaction product and in
20min~30min is centrifuged under the conditions of 5000rpm~8000rpm, centrifugation number is preferably 3 times~5 times.
As the optimal technical scheme of the method for the invention, step (1) described lithiumation carries out under protective atmosphere,
The protective atmosphere preferably includes argon gas atmosphere, nitrogen atmosphere, helium atmosphere, neon atmosphere, Krypton atmosphere or xenon atmosphere
Deng.
Preferably, the time of step (1) described lithiumation be 2h~72h, such as 2h, 5h, 10h, 12h, 16h, 20h, for 24 hours,
30h, 32h, 36h, 40h, 42h, 45h, 50h, 56h, 60h, 66h, 70h or 72h etc., preferably 48h.
Preferably, the temperature of step (1) described lithiumation is 15 DEG C~45 DEG C, such as 15 DEG C, 25 DEG C, 35 DEG C or 45 DEG C
Deng preferably 25 DEG C.
The present invention is not construed as limiting the method for lithiumation, such as can be infusion process or thermal evaporation.
It is highly preferred that step (1) the lithiumation processing is：Stratiform two-dimensional material is dispersed in the hexamethylene of n-BuLi
Lithiumation is carried out in solution.This method is conducive to magnanimity and prepares lithiumation two-dimensional material and easy to operate.In the method, lithiumation when
Between can be adjusted according to the size of the lateral dimension of stratiform two-dimensional material, size is bigger, and the time of lithiumation is longer, to have
Abundant lithiumation is realized conducive to molten difference diffusion；If lateral dimension is smaller, it can suitably shorten the time of lithiumation.
In the method for the present invention, spontaneous combustion occurs in order to avoid n-BuLi and air generation oxidation, it can be by protecting
It is tested under the protection of shield property gas and avoids this safety problem.After the completion of step (1) lithiumation, although security risk drops
It is low, but still there are security risk, can by by the preparation process of entire composite material protective gas glove box
The method of middle operation solves the problems, such as this.
Preferably, a concentration of 0.1M~2.0M of the n-BuLi, for example, 0.1M, 0.5M, 0.8M, 1.0M, 1.2M,
1.5M, 1.7M, 1.8M or 2.0M etc..
Preferably, the mass volume ratio of the cyclohexane solution of layered two-dimensional material and n-BuLi be (100~
1500)mg:15mL, such as 100mg:15mL、200mg:15mL、300mg:15mL、 400mg:15mL、500mg:15mL、
600mg:15mL、700mg:15mL、800mg:15mL、 900mg:15mL、1000mg:15mL、1150mg:15mL、1300mg:
15mL or 1500mg:15mL etc., if mass volume ratio is less than 100mg:15mL can cause lithiation level too low；If quality volume
Than being more than 1500mg:15mL can lead to the waste of n-BuLi.Preferably 1000g:15mL.
As the optimal technical scheme of the method for the invention, in step (2) described reaction kettle, the stratiform two dimension of lithiumation
The mass ratio of material and metal salt is 100mg:(30mg~3g), such as 100mg:30mg、 100mg:50mg、100mg:75mg、
100mg:100mg、100mg:200mg、100mg:300mg、 100mg:400mg、100mg:500mg、100mg:600mg、
100mg:800mg、100mg:1g、 100mg:1.2g、100mg:1.5g、100mg:1.6g、100mg:1.8g、100mg:2.0g、
100mg:2.0g、 100mg:2.5g、100mg:2.8g or 100mg:3.0g etc., preferably 100mg:(1g~2.56g), herein
Preferred scope 100mg:In (1g~2.56g), metal and metallic compound can effectively and in large quantities be inserted into two-dimensional material interlayer.
When being matched between each substance of present invention calculating, " the stratiform two-dimensional material of lithiumation " refers to the stratiform two dimension material of lithiumation
The contents on dry basis of material.
Preferably, in step (2) described reaction kettle, the mass volume ratio of stratiform two-dimensional material and solvent is 100 mg:(5
~20) mL, such as 100mg:5mL、100mg:8mL、100mg:10mL、100mg:12mL、 100mg:14mL、100mg:15mL、
100mg:17mL or 100mg:20mL etc., preferably 100mg:18mL.
It is highly preferred that in step (2) described reaction kettle, the stratiform two-dimensional material of lithiumation, the mass body of metal salt and solvent
Product is than being 100mg:(30mg~3g):(5mL~20mL), preferably 100mg:(30mg~3g):18mL.
Preferably, step (2) described metal salt include in chloride, nitrate or acetate any one or at least
Any one in two kinds of mixture, preferably cobalt, the chloride of iron or nickel, nitrate or acetate or at least two
Mixture, such as CoCl2、Co(OAc)2、FeCl2、NiCl2Or Ni (OAc)2In any one or at least two mixture.
The present invention is nonaqueous solvents to step (2) described solvent, and is required to ensure that metal salt has higher dissolving
Degree improves metal or metallic compound because molten difference reaction occurs for the lithium that higher solubility is more conducive to and is inserted into interlayer
Uniformity and load capacity, with improve its as catalyst be electrolysed liberation of hydrogen when show higher liberation of hydrogen effect.
It is highly preferred that step (2) described solvent is any one or two kinds in methyl pyrrolidone or tetrahydrofuran
Mixture.
Preferably, in step (2), liquid reaction system accounts for the 1/3~3/4 of reaction kettle liner solvent, preferably 2/3~
3/4, the restriction of this volume ratio be in order to obtain suitable pressure under certain hydrothermal temperature conditions, to promote molten difference to spread,
It preferably realizes metal ion and lithium to exchange.
Preferably, the temperature of step (2) described hydro-thermal reaction be 40 DEG C~200 DEG C, such as 40 DEG C, 50 DEG C, 60 DEG C, 70
DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 150 DEG C, 165 DEG C, 180 DEG C or 200 DEG C etc., preferably 60 DEG C~100 DEG C,
Within the scope of 60 DEG C~100 DEG C of this preferred scope, provides not only metal salt and be converted into metal or metallic compound (such as gold
Belong to hydroxide or metal oxide) reaction condition, suitable Hydro-thermal pressure can also be generated, promote molten difference diffusion, more preferably
Ground makes metal ion and lithium realize to exchange, to obtain the compound of stratiform two-dimensional material interlayer confinement metal or metallic compound
Material.
Preferably, the soaking time of step (2) described hydro-thermal reaction be 2h~72h, such as 2h, 8h, 12h, 16h, 20h,
For 24 hours, 30h, 32h, 36h, 42h, 45h, 50h, 56h, 60h, 66h or 72h etc., preferably 20h~30h, in this preferred scope
In 20h~30h, may be implemented lithium and metal ion fully exchange and the formation of metal or metallic compound.
Preferably, the system pH of step (2) described hydro-thermal reaction is 1~14, that is to say, that the system of reaction both may be used
Think acidity, or it is neutral, can also be alkalinity.According to the adjusting of the system pH of hydro-thermal reaction, can control in layer
The substance classes that the confinement between layers of shape two-dimensional material is formed, for example to form metal, metal oxide or metallic hydrogen
Oxide.The above-mentioned method for regulating and controlling the finally formed substance classes of metal salt according to pH is the prior art, those skilled in the art
It can refer to method and theory disclosed in the prior art to be prepared, details are not described herein again.
It is highly preferred that being more than 7 by the system pH of rate-determining steps (2) described hydro-thermal reaction and less than or equal to 14, making gold
The confinement between layers for belonging to salt in stratiform two-dimensional material forms metal hydroxides.
For example, input material proportion can be the molybdenum disulfide of lithiumation:CoCl2:Tetrahydrofuran=100mg:
2.56g:18mL, pH 9.88, hydrothermal temperature are 80 DEG C, soaking time 48h.
As the further preferred technical solution of the method for the invention, the described method comprises the following steps：
(1) under the protection of protective atmosphere, stratiform two-dimensional material is dispersed in the n-BuLi of concentration 0.1M~2.0M
Cyclohexane solution in carry out lithiumation handle 48h, using hexamethylene diluting reaction product and in 5000rpm~8000rpm conditions
Lower centrifugation 20min~30min, it is dry, obtain the stratiform two-dimensional material of dry lithiumation；
The mass volume ratio of the cyclohexane solution of layered two-dimensional material and n-BuLi is (100~1500) mg:
15mL；
(2) by stratiform two-dimensional material, metal salt and the solvent of dry lithiumation according to mass volume ratio 100mg:(30mg
~3g):18mL is mixed, and is sealed in reaction kettle, and liquid reaction system accounts for the 18/25 of reaction kettle liner solvent, and it is anti-to adjust hydro-thermal
It answers system pH to be more than 7 and less than or equal to 14, in 60 DEG C~100 DEG C hydro-thermal reaction 20h~30h, obtains stratiform two-dimensional material layer
Between confinement metal hydroxides composite material；
The metal salt is the mixture of any one or two kinds in acetate or chloride；The solvent is methyl
The mixture of any one or two kinds in pyrrolidones or tetrahydrofuran.
The third aspect, the present invention provide stratiform two-dimensional material interlayer confinement metal or metallization as described in relation to the first aspect
The purposes of the composite material of object is closed, the composite material is used for electrolysis water evolving hydrogen reaction as Electrocatalytic Activity for Hydrogen Evolution Reaction agent, shows
Efficient catalytic performance.
Preferably, layered two-dimensional material interlayer confinement metal or metallic compound are：Two-dimentional molybdenum disulfide confinement gold
Belong to the composite material of hydroxide.
Preferably, the composite material of the two-dimentional molybdenum disulfide confinement metal hydroxides is used as Electrocatalytic Activity for Hydrogen Evolution Reaction agent
Electrolyte in electrolysis water evolving hydrogen reaction, and used in evolving hydrogen reaction is KOH aqueous solutions, and the concentration of the KOH aqueous solutions is preferably
0.01M~1M.
The composite material of two-dimentional molybdenum disulfide confinement metal hydroxides described in this optimal technical scheme is as liberation of hydrogen electricity
Catalyst shows extraordinary hydrogen evolution activity and stability in alkaline electrolyte.
Compared with the prior art, the present invention at least has the advantages that：
The preparation method of the present invention can realize a series of composite wood of two-dimensional material interlayer confinement metals or metallic compound
The controllable preparation of material.The composite structure of the present invention is stablized, metal or metallic compound equably confinement in two-dimensional material
Interlayer not only avoids the reunion between particle, and also solving conventional attached type structure leads to the caducous problem of particle.
Moreover, a series of especially two-dimentional molybdenum disulfide interlayer confinement metal hydroxides of the composite materials being prepared
Composite material as liberation of hydrogen catalyst have electro catalytic activity height (~90mV@10mA cm-2), stability is good, durable
The advantages of.Confinement can promote to hydrolyze in the metal hydroxides one side of interlayer, on the other hand also act as decrease molybdenum disulfide
Binding force between layers improves its active effect, promotes production hydrogen effect, these above-mentioned factor collective effects improve
Electro catalytic activity and stability.
Description of the drawings
Fig. 1 is the metal hydroxides liberation of hydrogen electricity that embodiment 1-6 synthesizes two-dimentional molybdenum disulfide interlayer confinement using two-step method
The schematic diagram of catalyst；
Fig. 2 is the transmission electron microscope figure of the metal hydroxides of two-dimentional molybdenum disulfide interlayer confinement in embodiment 1；
Fig. 3 a and Fig. 3 b are respectively the thickness of the elctro-catalyst synthesized in embodiment 1 and the statistical chart of lateral dimension；
Fig. 4 a are the high angle annular dark transmission electron microscope picture that elctro-catalyst is synthesized in embodiment 1；
Fig. 4 b- Fig. 4 d are the corresponding distribution diagram of element of Fig. 4 a, and the scale of Fig. 4 b- Fig. 4 d is identical as Fig. 4 a, and Fig. 4 b- figures
4d corresponds to the distribution diagram of element of S, S+Mo, Co respectively；
Fig. 5 is synthesis elctro-catalyst and commercialization MoS in embodiment 12The X-ray diffraction spectrum comparison diagram of powder；
Fig. 6 is the x-ray photoelectron spectroscopy comparison diagram that elctro-catalyst Co elements and cobalt hydroxide are synthesized in embodiment 1；
Fig. 7 a are that synthesis elctro-catalyst and commercial platinum carbon catalyst liberation of hydrogen in 1.0M KOH electrolyte are anti-in embodiment 1
The linear scan correlation curve answered；
Fig. 7 b are that electric current-time of synthesis elctro-catalyst evolving hydrogen reaction in 1.0M KOH electrolyte in embodiment 1 is bent
Line；
Fig. 8 a are the high resolution scanning electron microscope that elctro-catalyst is synthesized in embodiment 3, and Fig. 8 b- Fig. 8 d are that Fig. 8 a are corresponding
The scale of distribution diagram of element, Fig. 8 b- Fig. 8 d is identical as Fig. 8 a, and Fig. 8 b- Fig. 8 d correspond to S, Mo, Ni Elemental redistribution respectively；
Fig. 9 is that the linear scanning of synthesis elctro-catalyst evolving hydrogen reaction in 1.0M KOH electrolyte in embodiment 3 is bent
Line.
Specific implementation mode
In view of many deficiencies of the prior art, inventor is able to propose the present invention through studying for a long period of time and largely putting into practice
Technical solution, technical scheme of the present invention work will in more detail be explained in conjunction with attached drawing and exemplary embodiments as follows
It is bright.
Present embodiment specifically provides following two-step synthesis method：
Lithiumation is carried out to stratiform two-dimensional material under the protectiveness of protective gas, it is dry, then by the lithiumation after drying
Stratiform two-dimensional material powder and metal salt and solvent seal in hydrothermal reaction kettle, and adjust the pH value of solution, utilize hydro-thermal
Method prepares the composite material of stratiform two-dimensional material interlayer confinement metal or metallic compound.
The protective gas is preferably argon gas or nitrogen etc., and layered two-dimensional material is preferably molybdenum disulfide, described
Stratiform two-dimensional material is preferably dispersed in lithiumation in the cyclohexane solution of n-BuLi by lithiation.
Embodiment 1
Two-dimentional molybdenum disulfide (1g) is dispersed in n-BuLi cyclohexane solution (2.0M, 15 mL) under protection of argon gas
Hexamethylene dilution lithiumation molybdenum sulfide product and high speed (5000rpm) centrifugation (30min) difference three is used alternatingly in lithiumation (48h)
It is secondary, take bottom sediment to spontaneously dry under protection of argon gas.Then according to dry lithiumation molybdenum disulfide:CoCl2·6H2O:Tetrahydrochysene
The ratio of furans is 100mg:2.56g:18mL mixing is enclosed in hydrothermal reaction kettle, and the pH of reaction kettle system is 9.88, control
Hydrothermal temperature is 80 DEG C, soaking time is 48 hours, after reaction cooled to room temperature, and obtained product is two dimension two
The composite material of molybdenum sulfide confinement metal hydroxides (cobalt hydroxide) is a kind of efficient elctro-catalyst.This two-step method is closed
It is as shown in Figure 1 at schematic diagram.
Transmission scanning electron microscope, atomic force microscope, X-ray diffraction, x-ray photoelectron spectroscopy pair are combined later
Obtained product carries out structure and chemical composition characterization (pattern of product refers to Fig. 2-Fig. 6 with crystal structure information), and follow-up
Carry out alkaline electrolyte catalytic activity of hydrogen evolution test (the results are shown in Figure 7).
Fig. 2 is the transmission electron microscope figure of the metal hydroxides of two-dimentional molybdenum disulfide interlayer confinement in embodiment 1,
As seen from the figure, molybdenum disulfide has typical two-dimensional layered structure.
Fig. 3 a and Fig. 3 b are respectively the thickness of the elctro-catalyst synthesized in embodiment 1 and the statistical chart of lateral dimension, by scheming
As can be seen that the average thickness of material is about 8nm, average transverse is about 85nm.
Fig. 4 a are the high angle annular dark transmission electron microscope picture that elctro-catalyst is synthesized in embodiment 1, and Fig. 4 b- Fig. 4 d are
The scale of the corresponding distribution diagram of element of Fig. 4 a, Fig. 4 b- Fig. 4 d is identical as Fig. 4 a, and Fig. 4 b- Fig. 4 d correspond to S, S+Mo, Co respectively
Elemental redistribution, as seen from the figure, these elements are uniformly distributed in the material.
Fig. 5 is synthesis elctro-catalyst and commercialization MoS in embodiment 12The X-ray diffraction spectrum comparison diagram of powder, can be with by figure
Find out, the elctro-catalyst of synthesis is relative to commercial MoS2With smaller thickness and the destruction of crystal long-range order, this is indirectly
It demonstrates metal or metallic compound inserts the interlayer of two-dimensional material.
Fig. 6 is the x-ray photoelectron spectroscopy comparison diagram that elctro-catalyst Co elements and cobalt hydroxide are synthesized in embodiment 1, by
Figure is as can be seen that the Co for being inserted into two-dimensional material interlayer is mainly cobalt hydroxide.
Fig. 7 a are that synthesis elctro-catalyst and commercial platinum carbon catalyst liberation of hydrogen in 1.0M KOH electrolyte are anti-in embodiment 1
The linear scan correlation curve answered, as seen from the figure, the elctro-catalyst of synthesis have and the analogous electro-catalysis of business platinum carbon
Activity.
Fig. 7 b are that electric current-time of synthesis elctro-catalyst evolving hydrogen reaction in 1.0M KOH electrolyte in embodiment 1 is bent
Line, as seen from the figure, the elctro-catalyst of synthesis have good stability.
Embodiment 2
Two-dimentional molybdenum disulfide (1g) is dispersed in n-BuLi cyclohexane solution (2.0M, 15 mL) under protection of argon gas
Hexamethylene dilution lithiumation molybdenum sulfide product and high speed (8000rpm) centrifugation (20min) difference three is used alternatingly in lithiumation (72h)
It is secondary, take bottom sediment to spontaneously dry under protection of argon gas.Then according to dry lithiumation molybdenum disulfide:CoCl2·6H2O:Tetrahydrochysene
The ratio of furans is 100mg:0.256g:18mL mixing is enclosed in hydrothermal reaction kettle, and the pH value of reaction kettle system is 8.5, control
Hydrothermal temperature processed is 80 DEG C, soaking time is 24 hours, after reaction cooled to room temperature, and obtained product is two dimension
The composite material of molybdenum disulfide confinement metal hydroxides (cobalt hydroxide).It is as shown in Figure 1 that two-step method synthesizes schematic diagram.
The composite structure of the present embodiment is similar to Example 1, and is analysed using method same as Example 1
Hydrogen reaction detection, activity and stability are all similar to Example 1.
Embodiment 3
Two-dimentional molybdenum disulfide (0.5g) is dispersed in n-BuLi cyclohexane solution (2.0M, 15mL) under protection of argon gas
Hexamethylene dilution lithiumation molybdenum sulfide product and high speed (8000rpm) centrifugation (20min) difference three is used alternatingly in middle lithiumation (72h)
It is secondary, take bottom sediment to spontaneously dry under protection of argon gas.Then according to dry lithiumation molybdenum disulfide:NiCl2·6H2O:Tetrahydrochysene
The ratio of furans is 100mg:0.274g:18mL mixing is enclosed in hydrothermal reaction kettle, and the pH value of reaction kettle system is 10, control
Hydrothermal temperature processed is 80 DEG C, soaking time is 48 hours, after reaction cooled to room temperature, and obtained product is two dimension
The composite material of molybdenum disulfide confinement metal hydroxides (nickel hydroxide) is a kind of efficient elctro-catalyst.This two-step method
It is as shown in Figure 1 to synthesize schematic diagram.
Fig. 8 a are the high resolution scanning electron microscope that elctro-catalyst is synthesized in embodiment 3, and Fig. 8 b- Fig. 8 d are that Fig. 8 a are corresponding
The scale of distribution diagram of element, Fig. 8 b- Fig. 8 d is identical as Fig. 8 a, and Fig. 8 b- Fig. 8 d correspond to S, Mo, Ni Elemental redistribution respectively, by scheming
As can be seen that these elements are uniformly distributed in the material.
Fig. 9 is that the linear scanning of synthesis elctro-catalyst evolving hydrogen reaction in 1.0M KOH electrolyte in embodiment 3 is bent
Line, as seen from the figure, the elctro-catalyst of synthesis have activity well.
Embodiment 4
Two-dimentional molybdenum disulfide (1g) is dispersed in n-BuLi cyclohexane solution (2.0M, 15 mL) under nitrogen protection
Hexamethylene dilution lithiumation molybdenum sulfide product and high speed (5000rpm) centrifugation (30min) difference three is used alternatingly in lithiumation (72h)
It is secondary, take bottom sediment to spontaneously dry under protection of argon gas.Then according to dry lithiumation molybdenum disulfide:CoCl2·6H2O:
NiCl2·6H2O:The ratio of tetrahydrofuran is 100mg:0.256g:0.274 g:18mL mixing is enclosed in hydrothermal reaction kettle, instead
It is 9 to answer the pH value of pot systems, and control hydrothermal temperature is 80 DEG C, soaking time is 48 hours, naturally cools to room after reaction
Temperature, obtained product are the composite material of two-dimentional molybdenum disulfide confinement metal hydroxides (cobalt hydroxide and nickel hydroxide).This
It is as shown in Figure 1 that two-step method synthesizes schematic diagram.
The composite structure of the present embodiment is similar to Example 1, and is analysed using method same as Example 1
Hydrogen reaction detection, activity and stability are all similar to Example 1.
Embodiment 5
Two-dimentional molybdenum disulfide (1g) is dispersed in n-BuLi cyclohexane solution (0.1M, 15 mL) under nitrogen protection
Hexamethylene dilution lithiumation molybdenum disulfide product and high speed (6000rpm) centrifugation (25min) difference four is used alternatingly in lithiumation (for 24 hours)
It is secondary, take bottom sediment to spontaneously dry under nitrogen protection.Then according to dry lithiumation molybdenum disulfide:Co(OAc)2:Tetrahydrochysene furan
The ratio muttered is 100mg:2.00g:18mL mixing is enclosed in hydrothermal reaction kettle, and the pH of reaction kettle system is 11.0, controls water
Hot temperature is 180 DEG C, soaking time is 6 hours, after reaction cooled to room temperature, and obtained product is two-dimentional two sulphur
Change the composite material of molybdenum confinement metal hydroxides (cobalt hydroxide).It is as shown in Figure 1 that this two-step method synthesizes schematic diagram.
The composite structure of the present embodiment is similar to Example 1, and is analysed using method same as Example 1
Hydrogen reaction detection, activity and stability are all similar to Example 1.
Embodiment 6
Two-dimentional molybdenum disulfide (1.3g) is dispersed in n-BuLi cyclohexane solution (1.0M, 15mL) under helium protection
Hexamethylene dilution lithiumation molybdenum sulfide product and high speed (5500rpm) centrifugation (27min) difference three is used alternatingly in middle lithiumation (12h)
It is secondary, take bottom sediment to be spontaneously dried under helium protection.Then according to dry lithiumation molybdenum disulfide:FeCl2:Methylpyrrole
The ratio of alkanone is 100mg:0.9g:18mL mixing is enclosed in hydrothermal reaction kettle, and the pH of reaction kettle system is 7.5, controls water
Hot temperature is 65 DEG C, soaking time is 36 hours, after reaction cooled to room temperature, and obtained product is two-dimentional two sulphur
Change the composite material of molybdenum confinement metal hydroxides (iron hydroxide).It is as shown in Figure 1 that this two-step method synthesizes schematic diagram.
The composite structure of the present embodiment is similar to Example 1, and is analysed using method same as Example 1
Hydrogen reaction detection, activity and stability are all similar to Example 1.
Embodiment 7
Under protection of argon gas, lithiumation (8h) is carried out to two-dimentional molybdenum disulfide (0.75g) using the method for thermal evaporation, according to
Dry lithiumation molybdenum disulfide:Ni(OAc)2:The ratio of tetrahydrofuran is 100mg:0.8g:It is anti-that 18mL mixing is enclosed within hydro-thermal
It answers in kettle, the pH value of reaction kettle system is 11, and control hydrothermal temperature is 100 DEG C, soaking time is 40 hours, after reaction
Cooled to room temperature, obtained product are the composite material of two-dimentional molybdenum disulfide confinement metal hydroxides (nickel hydroxide).
The composite structure of the present embodiment is similar to Example 1, and is analysed using method same as Example 1
Hydrogen reaction detection, activity and stability are all similar to Example 1.
Embodiment 8
Under protection of argon gas, lithiumation (8h) is carried out to two dimensionization tungsten sulfide (0.7g) using the method for thermal evaporation, according to dry
Dry lithiumation molybdenum disulfide:Ni(OAc)2:The ratio of tetrahydrofuran is 100mg:0.6g:18mL mixing is enclosed within hydro-thermal reaction
In kettle, the pH value of reaction kettle system is 8.5, and control hydrothermal temperature is 100 DEG C, soaking time is 24 hours, after reaction certainly
It is so cooled to room temperature, obtained product is the composite material of two-dimentional tungsten disulfide confinement metal hydroxides (nickel hydroxide).
The composite structure of the present embodiment is similar to Example 1, and is analysed using method same as Example 1
Hydrogen reaction detection, activity and stability are all similar to Example 1.
Embodiment 9
Under protection of argon gas, lithiumation (8h) is carried out to two dimensionization molybdenum sulfide (0.5g) using the method for thermal evaporation, according to dry
Dry lithiumation molybdenum disulfide:Ni(OAc)2:The ratio of tetrahydrofuran is 100mg:0.6g:18mL mixing is enclosed within hydro-thermal reaction
In kettle, the pH value of reaction kettle system is 6, and control hydrothermal temperature is 100 DEG C, soaking time is 24 hours, natural after reaction
It is cooled to room temperature, obtains the composite material of the nickel oxide of platelike molybdenumdisulfide interlayer confinement.
Comparative example 1
Except being handled without lithiumation, and directly use two-dimentional molybdenum disulfide and CoCl2·6H2O and tetrahydrofuran mixing are close
It closes and is carried out outside subsequent step in hydrothermal reaction kettle, other methods and condition are same as Example 1.
This comparative example can not form interlayer confinement structure, and cobalt hydroxide is mainly attached to the edge of two-dimentional molybdenum disulfide.
After testing, catalytic activity is inferior to embodiment 1, and cyclical stability is greatly reduced.
Applicant states that the present invention illustrates the method detailed of the present invention, but the present invention not office by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implement.Technical field
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, the selection etc. of concrete mode, all fall within protection scope of the present invention and the open scope.
Claims (10)
1. the composite material of a kind of stratiform two-dimensional material interlayer confinement metal or metallic compound, which is characterized in that described compound
Material includes the metal or metal compound between layers of stratiform two-dimensional material and confinement in layered two-dimensional material
Object.
2. composite material according to claim 1, which is characterized in that the metallic compound includes metal oxide or gold
Belong to any one in hydroxide, preferably metal hydroxides, further preferably includes Co (OH)2、Ni(OH)2Or Fe
(OH)3In any one or at least two combination.
3. composite material according to claim 1 or 2, which is characterized in that layered two-dimensional material include molybdenum disulfide,
In tungsten disulfide, two selenizing molybdenums, two tungsten selenides, tantalum disulfide or graphene any one or at least two combination, preferably
For molybdenum disulfide；
Preferably, the thickness of layered two-dimensional material is 2nm~100nm, preferably 2nm~10nm；
Preferably, the lateral dimension of layered two-dimensional material be 20nm~5000nm, preferably 50nm~500nm, further
Preferably 80nm.
4. the composite material of stratiform two-dimensional material interlayer confinement metal as described in any one of claims 1-3 or metallic compound
Preparation method, which is characterized in that the described method comprises the following steps：
(1) lithiumation processing is carried out to stratiform two-dimensional material, obtains the stratiform two-dimensional material of lithiumation；
(2) the stratiform two-dimensional material of lithiumation, metal salt are mixed with solvent, is sealed in reaction kettle, hydro-thermal reaction obtains stratiform
The composite material of two-dimensional material interlayer confinement metal or metallic compound.
5. according to the method described in claim 4, it is characterized in that, the method includes after lithiumation is handled, precipitation point is carried out
From and dry step；
Preferably, the step of precipitation separation includes：Using solvent diluting reaction product and in 5000rpm~8000rpm items
20min~30min is centrifuged under part, centrifugation number is preferably 3 times~5 times；
Preferably, step (1) described lithiumation carries out under protective atmosphere, the protective atmosphere preferably include argon gas atmosphere,
The combination of any one or at least two atmosphere in nitrogen atmosphere, helium atmosphere, neon atmosphere, Krypton atmosphere or xenon atmosphere
Atmosphere；
Preferably, the time of step (1) described lithiumation is 2h~72h, preferably 48h；
Preferably, the temperature of step (1) described lithiumation is 15 DEG C~45 DEG C, preferably 25 DEG C.
6. method according to claim 4 or 5, which is characterized in that step (1) lithiumation, which is handled, is：By stratiform two dimension
Material, which is dispersed in the cyclohexane solution of n-BuLi, carries out lithiumation；
Preferably, a concentration of 0.1M~2.0M of the n-BuLi；
Preferably, the mass volume ratio of the cyclohexane solution of layered two-dimensional material and n-BuLi is (100~1500) mg:
15mL, preferably 1000mg:15mL.
7. according to claim 4-6 any one of them methods, which is characterized in that in step (2) described reaction kettle, the layer of lithiumation
The mass ratio of shape two-dimensional material and metal salt is 100mg:(30mg~3g), preferably 100mg:(1g~2.56g)；
Preferably, in step (2) described reaction kettle, the stratiform two-dimensional material of lithiumation and the mass volume ratio of solvent are 100mg:(5
~20) mL, preferably 100mg:18mL；
Preferably, in step (2) described reaction kettle, the mass volume ratio of the stratiform two-dimensional material of lithiumation, metal salt and solvent is
100mg:(30mg~3g):(5mL~20mL), preferably 100mg:(30mg~3g):18mL；
Preferably, step (2) described metal salt includes any one in chloride, nitrate or acetate or at least two
In mixture, preferably cobalt, the chloride of iron or nickel, nitrate or acetate any one or at least two mixture；
Preferably, step (2) described solvent is nonaqueous solvents, preferably any one in methyl pyrrolidone or tetrahydrofuran
Or two kinds of mixture.
8. according to claim 4-7 any one of them methods, which is characterized in that in step (2), liquid reaction system accounts for reaction
The 1/3~3/4 of kettle liner solvent, preferably 2/3~3/4；
Preferably, the temperature of step (2) described hydro-thermal reaction is 40 DEG C~200 DEG C, preferably 60 DEG C~100 DEG C；
Preferably, the soaking time of step (2) described hydro-thermal reaction is 2h~72h, preferably 20h~30h；
Preferably, the system pH of step (2) described hydro-thermal reaction is 1~14；
Preferably, pass through the system pH of regulating step (2) hydro-thermal reaction, layer of the control metal salt in stratiform two-dimensional material
Confinement forms metal, metal oxide or metal hydroxides between layer；
Preferably, it is more than 7 by the system pH of rate-determining steps (2) described hydro-thermal reaction and less than or equal to 14, metal salt is made to exist
The confinement between layers of stratiform two-dimensional material forms metal hydroxides.
9. according to claim 4-8 any one of them methods, which is characterized in that the described method comprises the following steps：
(1) under the protection of protective atmosphere, stratiform two-dimensional material is dispersed in the ring of the n-BuLi of concentration 0.1M~2.0M
Carry out lithiumation in hexane solution and handle 48h, using hexamethylene diluting reaction product and under the conditions of 5000rpm~8000rpm from
Heart 20min~30min, it is dry, obtain the stratiform two-dimensional material of dry lithiumation；
The mass volume ratio of the cyclohexane solution of layered two-dimensional material and n-BuLi is (100~1500) mg:15mL；
(2) by stratiform two-dimensional material, metal salt and the solvent of dry lithiumation according to mass volume ratio 100mg:(30mg~3g):
18mL is mixed, and is sealed in reaction kettle, and liquid reaction system accounts for the 18/25 of reaction kettle liner solvent, adjusts hydro-thermal reaction system
PH value is more than 7 and less than or equal to 14, in 60 DEG C~100 DEG C 20~30h of hydro-thermal reaction, obtains stratiform two-dimensional material interlayer confinement gold
Belong to the composite material of hydroxide；
The metal salt is the mixture of any one or two kinds in acetate or chloride；The solvent is crassitude
The mixture of any one or two kinds in ketone or tetrahydrofuran.
10. the composite wood of stratiform two-dimensional material interlayer confinement metal as described in any one of claims 1-3 or metallic compound
The purposes of material, which is characterized in that the composite material is used for electrolysis water evolving hydrogen reaction as Electrocatalytic Activity for Hydrogen Evolution Reaction agent；
Preferably, layered two-dimensional material interlayer confinement metal or metallic compound are：Two-dimentional molybdenum disulfide confinement metallic hydrogen
The composite material of oxide；
Preferably, the composite material of the two-dimentional molybdenum disulfide confinement metal hydroxides is used to be electrolysed as Electrocatalytic Activity for Hydrogen Evolution Reaction agent
Water evolving hydrogen reaction, and the electrolyte used in evolving hydrogen reaction is KOH aqueous solutions, the concentration of the KOH aqueous solutions be preferably 0.01M~
1M。
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