CN110180569A - Sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and its preparation method - Google Patents
Sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and its preparation method Download PDFInfo
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- CN110180569A CN110180569A CN201910431965.9A CN201910431965A CN110180569A CN 110180569 A CN110180569 A CN 110180569A CN 201910431965 A CN201910431965 A CN 201910431965A CN 110180569 A CN110180569 A CN 110180569A
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 46
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 44
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 42
- JAGQSESDQXCFCH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo].[Mo] JAGQSESDQXCFCH-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 239000003610 charcoal Substances 0.000 claims abstract description 22
- 239000000758 substrate Substances 0.000 claims abstract description 21
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 9
- -1 transition metal salt Chemical class 0.000 claims abstract description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 239000004312 hexamethylene tetramine Substances 0.000 claims abstract description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 239000004744 fabric Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 7
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 229940011182 cobalt acetate Drugs 0.000 claims 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 235000015393 sodium molybdate Nutrition 0.000 claims 1
- 239000011684 sodium molybdate Substances 0.000 claims 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 239000007789 gas Substances 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- 235000016768 molybdenum Nutrition 0.000 description 7
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 6
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 229910052750 molybdenum Inorganic materials 0.000 description 5
- 239000011733 molybdenum Substances 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012456 homogeneous solution Substances 0.000 description 4
- 239000001273 butane Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910039444 MoC Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- LGLOITKZTDVGOE-UHFFFAOYSA-N boranylidynemolybdenum Chemical compound [Mo]#B LGLOITKZTDVGOE-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 239000002023 wood 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/33—
-
- 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
-
- 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
Abstract
The present invention provides sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and its preparation method, under the heating condition no more than 800 DEG C, it is reacted by reducing gas through one-step method, the sheet dimolybdenum carbide with excellent electrocatalysis characteristic/transition metal matter knot electro-catalysis composite material can be synthesized.Preparation method provided by the invention includes: that step 1. dissolves transition metal salt, molybdate, ammonium fluoride in a solvent, adds urea or hexamethylenetetramine reconciles mixed solution in alkalinity, obtain alkaline mixed solution；The charcoal substrate of alkaline mixed solution and film-form is put into reaction kettle by step 2., carries out hydro-thermal reaction, and reaction temperature is 120 DEG C~180 DEG C, prepares the sheet molybdate presoma using charcoal substrate as carrier；Under conditions of being no more than higher than 800 DEG C, charcoal substrate is heat-treated together with sheet molybdate presoma in reducing gas atmosphere for step 3., prepares sheet dimolybdenum carbide/transition metal heterojunction composite.
Description
Technical field
The invention belongs to electro-catalysis field of compound material, and in particular to a kind of sheet dimolybdenum carbide/transition metal hetero-junctions
Electro-catalysis composite material and preparation method.
Background technique
Hydrogen energy source be considered as most can the substitute fossil fuels energy a kind of new energy.But during electrolysis water,
Dynamic process in evolving hydrogen reaction and oxygen evolution reaction is very slow, it needs higher overvoltage that could generate biggish electric current
Density, so as to cause entire reaction process low energy conversion efficiency.The voltage of industrial electrolysis water is in 1.8V or so, and the reason of water
It is 1.23V by decomposition voltage, cathode hydrogen evolution reaction and Oxygen anodic evolution reaction occupy entire voltage 1/3, therefore reduction overvoltage is
The key of electrolysis water, although noble metal possesses the characteristic of high activity and low overvoltage, because it is expensive, content is rare and limits
Its large-scale application, so scholars have been devoted to Low-cost, liberation of hydrogen (analysis oxygen) catalyst of high activity carrys out generation
For Pt (IrO2And RuO2)。
For this kind of carbide of dimolybdenum carbide because of the d electronics of its outer layer, catalytic performance is similar to noble metal (Pt), therefore is used to
As liberation of hydrogen catalyst, transition metal has not pairs of 3d electronics, with hydrone and OH-There is stronger adsorption capacity, shows
Preferable catalytic activity out, therefore transition metal is used as oxygen-separating catalyst.And two-dimensional sheet carbide material is excellent because of its
Different thermal stability, electric conductivity, big specific surface area, in electronics, the fields such as sensor and catalysis have broad application prospects.
Documents (High specific surface-area carbides of silicon and
Transition-metals for catalysis.Catal.Today, 1992,15 (2): 263-284.) it describes using golden
The method that carbonization that category and carbon black (are greater than 1500 DEG C) under the high temperature conditions prepares carbide, however the pattern of prepared sample is difficult to
Control is unfavorable for playing the catalytic performance of obtained carbide.Documents (Preparation of molybdenum
carbides using butane and their catalytic performance.Chem.Mater.2000,12(12):
3896-3905.), it describes using temperature-programmed reaction, molybdenum trioxide is first passed through into hydrogen also by butane/hydrogen mixed gas
If original is at molybdenum dioxide, then reacts the method for preparing carbide with butane, but reaction is not enough, sample surfaces easy to form
Carbon distribution influences contact of the active site with solution, so as to cause reduced performance.Documents (A novel route to
nanosized molybdenum boride and carbide and/or metallic molybdenum by thermo-
synthesis method from MoO3,KBH4,andCCl4.Solid State Chem.,2003,170(l):135-
141.) it describes using solution reduction, molybdenum trioxide is reduced into molybdenum carbide, but this method reaction is complicated, it is difficult to control.It is existing
Have in the method for prepare carbide there are many unfavorable factors, such as high temperature cabonization, needs using hydrogen, pattern is not easy to control, table
Area carbon is serious, and reaction is not enough, and constrains the development of two-dimensional sheet carbide material.
Summary of the invention
The present invention is to carry out to solve the above-mentioned problems, and it is an object of the present invention to provide sheet dimolybdenum carbide/transition metal is different
Matter knot electro-catalysis composite material and preparation method, under the heating condition not higher than 800 DEG C, by reducing gas through one-step method
Reaction, can synthesize the sheet dimolybdenum carbide with excellent electrocatalysis characteristic/transition metal matter knot electro-catalysis composite material, operate
Simply, product morphology is uniform controllable.
The present invention to achieve the goals above, uses following scheme:
<preparation method>
The present invention also provides sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material preparation methods, special
Sign is, including, following steps: step 1. by transition metal salt, molybdate, ammonium fluoride dissolution in a solvent, add urea or
Hexamethylenetetramine reconciles mixed solution in alkalinity, obtains alkaline mixed solution；Step 2. is by the charcoal of alkaline mixed solution and film-form
Substrate is put into reaction kettle, carries out hydro-thermal reaction, and reaction temperature is 120 DEG C~180 DEG C, prepares the piece using charcoal substrate as carrier
Shape molybdate presoma；Step 3. is in reducing gas atmosphere, under conditions of being not higher than 800 DEG C, to charcoal substrate together with sheet
Molybdate presoma is heat-treated, and sheet dimolybdenum carbide/transition metal heterojunction composite is prepared.
Preferably, sheet dimolybdenum carbide provided by the invention/transition metal hetero-junctions electro-catalysis composite material preparation side
Method can also have the feature that in step 1 transition metal salt is ferric nitrate, cobalt nitrate, nickel nitrate, ferric acetate, acetic acid
Cobalt, nickel acetate, iron chloride, cobalt chloride, any one or a few in nickel chloride, in step 1, molybdate is ammonium molybdate, molybdenum
Any one or a few in sour sodium, potassium molybdate.
Preferably, sheet dimolybdenum carbide provided by the invention/transition metal hetero-junctions electro-catalysis composite material preparation side
Method can also have the feature that in step 1, calculate according to molar ratio, transition metal salt: molybdate: ammonium fluoride: urea or six
Methine tetramine=1:1:1~20:1~20.
Preferably, sheet dimolybdenum carbide provided by the invention/transition metal hetero-junctions electro-catalysis composite material preparation side
Method can also have the feature that in step 1 solvent is water or ethyl alcohol.
Preferably, sheet dimolybdenum carbide provided by the invention/transition metal hetero-junctions electro-catalysis composite material preparation side
Method can also have the feature that in step 2, and charcoal substrate is carbon cloth, graphene paper, any one in carbon fiber paper.Separately
Outside, the thickness of charcoal substrate is preferably within 1mm.
Preferably, sheet dimolybdenum carbide provided by the invention/transition metal hetero-junctions electro-catalysis composite material preparation side
Method can also have the feature that in step 2 the reaction time is 3~12h.
Preferably, sheet dimolybdenum carbide provided by the invention/transition metal hetero-junctions electro-catalysis composite material preparation side
Method can also have the feature that in step 2 reducing gas is pure CO gas, pure CH4Gas, CO and Ar mixed gas,
CH4With any one in the mixed gas of Ar, when reducing gas is the mixed gas of CO and Ar, the volume fraction of CO is
5%~99.9%, when reducing gas is CH4When with the mixed gas of Ar, CH4Volume fraction be 5%~99.9%.
Preferably, sheet dimolybdenum carbide provided by the invention/transition metal hetero-junctions electro-catalysis composite material preparation side
Method can also have the feature that in step 2, to hydro-thermal reaction after, to charcoal substrate together with being grown on charcoal substrate surface
On sheet molybdate presoma cleaned, be then placed in drying for standby in freeze drier.
Preferably, sheet dimolybdenum carbide provided by the invention/transition metal hetero-junctions electro-catalysis composite material preparation side
Method can also have the feature that in step 3 heat treatment time is 1~5h, and temperature is 500~800 DEG C.
<electro-catalysis composite material>
Further, the present invention also provides sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material, feature exists
In: it is made using preparation method described in above-mentioned<preparation method>.The action and effect of invention
The present invention provides sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material and preparation methods, no
The high temperature of thousands of degree is needed, is not higher than under conditions of 800 DEG C, the carbonization two of sheet can be prepared using reducing gas single step reaction
Molybdenum/transition metal hetero-junctions electro-catalysis composite material, uniformly, sheet dimolybdenum carbide/transition metal is uniformly distributed, and pattern is equal for reaction
One is controllable, can analyse the bifunctional electrocatalyst of oxygen again using the electrode material of preparation as liberation of hydrogen, electrocatalysis characteristic obtains significantly
It is promoted, better than most of bifunctional electrocatalyst.And the electro-catalysis composite material is with good stability at normal temperature, energy
Acid-alkali-corrosive-resisting.
Detailed description of the invention
Fig. 1 is the sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material scanning prepared in embodiment one
Electron microscope, wherein a and b is respectively the scanning electron microscope (SEM) photograph under different scales (different amplification conditions)；
Fig. 2 is the sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material liberation of hydrogen prepared in embodiment one
Reaction polarization curve graph, wherein a is the evolving hydrogen reaction polarization curve in 1MKOH solution, and b is that liberation of hydrogen is anti-in 1MKOH solution
Polarization curve after answering 5000 circles to recycle, c are the oxygen evolution reaction polarization curve in 1MKOH solution, and d is in 1MKOH solution
Polarization curve after the middle circle of oxygen evolution reaction 5000 circulation.
Specific embodiment
Below in conjunction with attached drawing to sheet dimolybdenum carbide of the present invention/transition metal hetero-junctions electro-catalysis composite material
Specific embodiment is described in detail.
<embodiment one>
Preparation method:
Cobalt diacetate tetrahydrate 0.249g and Ammonium Molybdate Tetrahydrate 0.1765g is put into hydrothermal reaction kettle by step 1., and (capacity is
In 50mL), and 30ml water is added and is mixed into homogeneous solution, 0.12g urea is then added, 0.1852g ammonium fluoride is sufficiently mixed, makes
Solution alkaline is obtained, alkaline mixed solution is obtained；
Commercially available carbon cloth (long * wide * is thick: 3cm*9cm*360 μm) is curled into tubular by step 2., and against in kettle
Wall, which is erect, to be placed, and 150 DEG C of hydrothermal temperature, time 6h, is prepared using carbon cloth as the sheet molybdic acid cobalt precursor (molybdenum in sheet form of carrier
Sour cobalt precursor is grown on carbon cloth), then carbon cloth is taken out, is cleaned three times, is placed into freeze drier with deionized water
Drying is for 24 hours.
Carbon cloth after drying together with the sheet molybdic acid cobalt precursor grown thereon, is placed in pure CO atmosphere by step 3.,
It is heat-treated under the conditions of 800 DEG C, time 3h, sheet dimolybdenum carbide/transition metals cobalt hetero-junctions electro-catalysis composite wood is made
Material.
Performance characterization:
As shown in Figure 1, can be seen that catalyst is good with carrier associativity from the scanning electron microscopic picture of combination electrode material, electricity
Pole material is not easily to fall off during reaction, can play the appearance structure advantage of its sheet.
In addition, composite material is put into use in 1MKOH solution and is linearly swept in order to test the electrocatalysis characteristic of composite material
Voltammetry test is retouched, as shown in Fig. 2 a and c, when current density is 10mA cm-2When, oxygen evolution reaction overpotential reaches 280mV, excellent
In RuO2Catalyst, evolving hydrogen reaction overpotential reach 152mV.Molybdic acid cobalt precursor is subjected to electrocatalysis characteristic comparison, discovery is worked as
Current density is 10mA cm-2When, the oxygen evolution potential of cobalt molybdate is 352mV, hydrogen-evolution overpotential 277mV, the results showed that, sheet carbon
Change two molybdenums and transition metals cobalt heterojunction composite performance is better than the electrocatalysis characteristic of cobalt molybdate.As shown in Fig. 2 b and d, respectively
Sheet dimolybdenum carbide and transition metals cobalt heterojunction composite stability are tested, the electricity after cyclic voltammetric 5000 is enclosed
Catalytic performance is compared with original performance, and the performance after 5000 circle of discovery circulation does not have too big reduction.
<embodiment two>
Preparation method:
Step 1. puts into nine water ferric nitrate 0.4g and Sodium Molybdate Dihydrate 0.214g in hydrothermal reaction kettle, and 30ml water is added
It is mixed into homogeneous solution, 0.28g hexamethylenetetramine is then added, 0.296g ammonium fluoride is sufficiently mixed, so that solution alkaline,
Obtain alkaline mixed solution；
Commercially available carbon fiber paper (long * wide * is thick: 3cm*9cm*360 μm) is curled into tubular by step 2., and against kettle
Inner wall erect place, 120 DEG C of hydrothermal temperature, time 12h, prepare using carbon fiber paper as the sheet iron molybdate forerunner of carrier
Body (sheet iron molybdate presoma is grown on carbon cloth)；Then carbon fiber paper is taken out, is cleaned three times, is placed into deionized water
It is dried for 24 hours in freeze drier.
Carbon fiber paper after drying together with the sheet iron molybdate presoma grown thereon, is placed in CH by step 3.4/Ar(CH4
Content is to be heat-treated, time 2h under the conditions of 700 DEG C, sheet dimolybdenum carbide/transition metal iron is made 5%) in atmosphere
Hetero-junctions electro-catalysis composite material.<embodiment three>
Preparation method:
Step 1. puts into six water nickel chloride 2.37g and Ammonium Molybdate Tetrahydrate 1.765g in hydrothermal reaction kettle, and is added
30ml water is mixed into homogeneous solution, and 0.6g urea is then added, and 0.03704g ammonium fluoride is sufficiently mixed, so that solution alkaline,
Obtain alkaline mixed solution；
Commercially available graphene carbon paper (long * wide * is thick: 3cm*9cm*360 μm) is curled into tubular by step 2., and against
The inner wall of kettle, which is erect, to be placed, and 180 DEG C of hydrothermal temperature, time 3h, is prepared using graphene carbon paper as the sheet nickel molybdate of carrier
Presoma (sheet nickel molybdate presoma is grown on carbon cloth)；Then graphene carbon paper is taken out, is cleaned three times with deionized water,
It places into freeze drier and dries for 24 hours.
Graphene carbon paper after drying together with the sheet nickel molybdate presoma grown thereon, is placed in pure CH by step 3.4Gas
It in atmosphere, is heat-treated under the conditions of 500 DEG C, time 3h, sheet dimolybdenum carbide/transiting metal nickel hetero-junctions electro-catalysis is made
Composite material.
<example IV>
Preparation method:
Step 1. puts into six water nickel nitrate 2.9g and potassium molybdate 2.38g in hydrothermal reaction kettle, and the mixing of 30ml water is added
At homogeneous solution, 1.4g hexamethylenetetramine is then added, 0.074g ammonium fluoride is sufficiently mixed, so that solution alkaline, obtains
Alkaline mixed solution；
Commercially available carbon fiber paper (long * wide * is thick: 3cm*9cm*360 μm) is curled into tubular by step 2., and against kettle
Inner wall erect place, 140 DEG C of hydrothermal temperature, time 8h, prepare using carbon fiber paper as the sheet nickel molybdate forerunner of carrier
Body (sheet nickel molybdate presoma is grown on carbon cloth)；Then carbon fiber paper is taken out, is cleaned three times, is placed into deionized water
It is dried for 24 hours in freeze drier.
Step 3. is by the carbon fiber paper after drying together with the sheet nickel molybdate presoma grown thereon, and being placed in CO/Ar, (CO contains
Sheet dimolybdenum carbide/transiting metal nickel is made to be heat-treated under the conditions of 600 DEG C, time 3h in 10%) atmosphere in amount
Hetero-junctions electro-catalysis composite material.
Above embodiments are only the illustration done to technical solution of the present invention.Sheet carbonization according to the present invention
Two molybdenums/transition metal hetero-junctions electro-catalysis composite material and preparation method is not merely defined in and is retouched in the embodiment above
The content stated, but be defined by the scope defined by the claims..Base of the those skilled in the art of the invention in the embodiment
Any modify or supplement or equivalence replacement done on plinth, all in claim range claimed of the invention.
In the embodiment above, the size of charcoal substrate be determined according to the size of hydrothermal reaction kettle it is fixed, due to hydro-thermal
Reaction kettle capacity is 50mL, therefore the charcoal size of foundation base used is 3cm*9cm.In fact, the selection of dimension principle of charcoal substrate are as follows:
It can be arranged around container side wall.That is the size of charcoal substrate does not have specific size to provide, as long as container can be surrounded
Side wall setting, such raw material can be grown in charcoal substrate, to realize above scheme.In addition, the thickness about charcoal substrate,
360 μm are also not necessarily limited to, within preferably 1mm.
Claims (10)
1. sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material preparation method, which is characterized in that including, with
Lower step:
Transition metal salt, molybdate, ammonium fluoride dissolution in a solvent, are added urea or hexamethylenetetramine are reconciled and mixed by step 1.
Solution alkaline is closed, alkaline mixed solution is obtained；
The charcoal substrate of alkaline mixed solution and film-form is put into reaction kettle by step 2., carries out hydro-thermal reaction, reaction temperature 120
DEG C~180 DEG C, prepare the sheet molybdate presoma using charcoal substrate as carrier；
Step 3. is in reducing gas atmosphere, under conditions of being not higher than 800 DEG C, to charcoal substrate together with sheet molybdate presoma
It is heat-treated, prepares sheet dimolybdenum carbide/transition metal heterojunction composite.
2. sheet dimolybdenum carbide according to claim 1/transition metal hetero-junctions electro-catalysis composite material preparation method,
It is characterized by:
Wherein, in step 1, transition metal salt is ferric nitrate, cobalt nitrate, nickel nitrate, ferric acetate, cobalt acetate, nickel acetate, chlorination
Iron, cobalt chloride, any one or a few in nickel chloride, in step 1, molybdate are ammonium molybdate, sodium molybdate, in potassium molybdate
Any one or a few.
3. sheet dimolybdenum carbide according to claim 1/transition metal hetero-junctions electro-catalysis composite material preparation method,
It is characterized by:
Wherein, in step 1, it is calculated according to molar ratio, transition metal salt: molybdate: ammonium fluoride: urea or hexamethylenetetramine=
1:1:1~20:1~20.
4. sheet dimolybdenum carbide according to claim 1/transition metal hetero-junctions electro-catalysis composite material preparation method,
It is characterized by:
Wherein, in step 1, solvent is water or ethyl alcohol.
5. sheet dimolybdenum carbide according to claim 1/transition metal hetero-junctions electro-catalysis composite material preparation method,
It is characterized by:
Wherein, in step 2, charcoal substrate is carbon cloth, graphene paper, any one in carbon fiber paper.
6. sheet dimolybdenum carbide according to claim 1/transition metal hetero-junctions electro-catalysis composite material preparation method,
It is characterized by:
Wherein, in step 2, the reaction time is 3~12h.
7. sheet dimolybdenum carbide according to claim 1/transition metal hetero-junctions electro-catalysis composite material preparation method,
It is characterized by:
Wherein, in step 2, reducing gas is pure CO gas, pure CH4Gas, the mixed gas of CO and Ar, CH4With the mixing of Ar
Any one in gas,
When reducing gas is the mixed gas of CO and Ar, the volume fraction of CO is 5%~99.9%,
When reducing gas is CH4When with the mixed gas of Ar, CH4Volume fraction be 5%~99.9%.
8. sheet dimolybdenum carbide according to claim 1/transition metal hetero-junctions electro-catalysis composite material preparation method,
It is characterized by:
Wherein, in step 2, after to hydro-thermal reaction, to charcoal substrate together with the sheet molybdic acid being grown on charcoal substrate surface
Salt precursor body is cleaned, and drying for standby in freeze drier is then placed in.
9. sheet dimolybdenum carbide according to claim 1/transition metal hetero-junctions electro-catalysis composite material preparation method,
It is characterized by:
Wherein, in step 3, heat treatment time is 1~5h, and temperature is 500~800 DEG C.
10. sheet dimolybdenum carbide/transition metal hetero-junctions electro-catalysis composite material, it is characterised in that:
It is made using preparation method described in any one of claim 1 to 9.
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