CN105948126A - Cobalt-doped tungsten sulfide nano sheets, and preparation method and application thereof in electrochemical hydrogen evolution - Google Patents
Cobalt-doped tungsten sulfide nano sheets, and preparation method and application thereof in electrochemical hydrogen evolution Download PDFInfo
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- CN105948126A CN105948126A CN201610266686.8A CN201610266686A CN105948126A CN 105948126 A CN105948126 A CN 105948126A CN 201610266686 A CN201610266686 A CN 201610266686A CN 105948126 A CN105948126 A CN 105948126A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 56
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 239000001257 hydrogen Substances 0.000 title claims abstract description 32
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000002135 nanosheet Substances 0.000 title abstract 7
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000002070 nanowire Substances 0.000 claims abstract description 39
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 33
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000000126 substance Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 52
- 229910017052 cobalt Inorganic materials 0.000 claims description 51
- 239000010941 cobalt Substances 0.000 claims description 51
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 48
- 238000000137 annealing Methods 0.000 claims description 47
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 46
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 39
- 239000004744 fabric Substances 0.000 claims description 38
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 31
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910052799 carbon Inorganic materials 0.000 claims description 25
- 229910052786 argon Inorganic materials 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 22
- 229910052721 tungsten Inorganic materials 0.000 claims description 22
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 21
- 239000010937 tungsten Substances 0.000 claims description 21
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 18
- 235000013877 carbamide Nutrition 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 239000010453 quartz Substances 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000012159 carrier gas Substances 0.000 claims description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- AHKSSQDILPRNLA-UHFFFAOYSA-N rubidium(1+);sulfide Chemical compound [S-2].[Rb+].[Rb+] AHKSSQDILPRNLA-UHFFFAOYSA-N 0.000 claims description 12
- 230000005518 electrochemistry Effects 0.000 claims description 11
- 239000011259 mixed solution Substances 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 11
- 239000003708 ampul Substances 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000000758 substrate Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- 229940097267 cobaltous chloride Drugs 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004073 vulcanization Methods 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 6
- 238000005987 sulfurization reaction Methods 0.000 claims description 6
- 239000007792 gaseous phase Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 238000005660 chlorination reaction Methods 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
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 239000004065 semiconductor Substances 0.000 abstract description 2
- 238000005229 chemical vapour deposition Methods 0.000 abstract 3
- 229910019543 CoxW Inorganic materials 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000002086 nanomaterial Substances 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910019098 CoSx Inorganic materials 0.000 description 3
- -1 Transition metal chalcogenide Chemical class 0.000 description 3
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000002071 nanotube Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/006—Compounds containing, besides cobalt, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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Abstract
The invention relates to a method for preparing cobalt-doped tungsten sulfide nano sheets by a chemical vapor deposition method, and an application of the cobalt-doped tungsten sulfide nano sheets in electrochemical hydrogen evolution, and belongs to the technical field of inorganic semiconductor nanomaterials. With tungsten sulfide nano sheets and cobalt oxide nanowires as raw materials, the cobalt-doped tungsten sulfide nano sheets are prepared by a chemical vapor deposition (CVD) method. The synthesized CoxW(1-x)S2 nano sheets have the advantages of stable chemical properties, good crystallinity, large electrochemical active area and the like; at the same time, the method has the advantages of simple preparation process, convenient operation and low cost; the cobalt-doped tungsten sulfide nano sheets have good electrochemical hydrogen evolution performance and good stability, and can be used in the related field of water electrolysis for hydrogen production.
Description
Technical field
The invention belongs to inorganic semiconductor nanometer material technical field, relate to cobalt doped tungsten sulfide nanometer sheet, its
Preparation method and use, particularly relates to cobalt doped tungsten sulfide nanometer sheet, its preparation method and at electrochemistry liberation of hydrogen
The purposes in field.
Background technology
In the face of global energy crisis and relevant environmental problem, hydrogen is considered as optimal green energy resource carrier,
Because its calorific value is high and combustion product is water.Now, most hydrogen are to come from hydrocarbon steam conversion,
This process is not only to bad environmental, and consumes non-renewable mineral resources.Water content on earth is rich
It is rich, it has been found that, hydrogen can be generated by water electrolysis.In an acidic solution, platinum (Pt) catalyst can be high
Effect ground carries out being electrolysed water evolving hydrogen reaction (HER).But, owing to the costliness of platinum is with rare, it uses model
Enclose and be severely restricted, therefore, find abundant and cheap catalyst material to substitute Pt, be one important
Problem.
Transition metal chalcogenide, due to its interesting physics and chemical property, is extensively studied in recent years,
Tungsten disulfide (WS2), cobalt disulfide (CoS2) etc. can be used as HER catalyst.People use many sides
Method improves the intrinsic activity of catalyst, and wherein, doping can reduce the free energy of hydrogen adsorption, Ke Yixian
Write and accelerate hydrogen precipitation rate.Experiment and theoretical research show, the ternary transition metal chalcogenide ratio of doping
Unadulterated binary compound is more active.Co is doped to WS2In lattice, catalytic can be strengthened significantly
Can, but, the method for common bimetallic oxide sulfuration is prone to CoSxImpurity, rather than Co-W-S
Compound, and, it is similar to Co9S8The generation meeting heavy damage avtive spot of phase, reduces its catalysis effect on the contrary
Rate.Thus, the most conveniently and efficiently Co is doped to WS2Lattice is formed CoxW(1-x)S2, do not produce simultaneously
Raw unrelated CoSxDeng dephasign, it it is a challenging problem.
Summary of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of cobalt doped sulfuration
Tungsten nanometer sheet, Preparation Method And The Use, the method for the invention step is simple and convenient to operate, synthesizes speed
Degree is fast and low cost, the cobalt doped tungsten sulfide nanometer sheet good crystallinity prepared, and stable chemical nature is pure
Degree height, electrochemical surface area is high, there is not cobalt sulfide CoSxDeng dephasign, it is applied to electrochemistry liberation of hydrogen and has
Extraordinary performance, Tafel slope can as little as 67mV/decade；Reaching 10mA/cm2Electric current density
Time, its overpotential as little as 121mV；Liberation of hydrogen good stability, has broad application prospects.
First aspect, the present invention provides the preparation method of a kind of cobalt doped tungsten sulfide nanometer sheet, described method bag
Include following steps:
With tungsten sulfide nanometer sheet and cobalt oxide nano wire as raw material, by chemical gaseous phase depositing process, it is prepared into
To cobalt doped tungsten sulfide nanometer sheet.
Preferably, described tungsten sulfide is prepared by the following method and obtains: vulcanize tungsten oxide nanometer tree,
Obtain tungsten sulfide nanometer sheet.
Preferably, the concretely comprising the following steps of described sulfuration: tungsten oxide nanometer tree and sulfur powder are respectively placed in dual temperature district
The downstream of tube furnace and upstream, heating carries out vulcanization reaction.
Preferably, the furnace temperature in the downstream of double temperature-area tubular furnaces is 600～800 DEG C, can be such as 600 DEG C, 625 DEG C,
650 DEG C, 680 DEG C, 700 DEG C, 735 DEG C, 750 DEG C or 800 DEG C etc., preferably 800 DEG C.
Preferably, the furnace temperature of the upstream of double temperature-area tubular furnaces is 100～200 DEG C, can be such as 100 DEG C, 120 DEG C,
140 DEG C, 150 DEG C, 165 DEG C, 185 DEG C or 200 DEG C etc., preferably 150 DEG C.
Preferably, being connected with argon in described pair of temperature-area tubular furnace, the flow of described argon is preferably
50～100sccm, can be such as 50sccm, 60sccm, 70sccm, 85sccm, 90sccm or 100sccm
Deng.
Preferably, the intraductal pressure of described pair of temperature-area tubular furnace is 100～200Pa, can be such as 100Pa,
120Pa, 140Pa, 150Pa, 175Pa or 200Pa etc..
Preferably, the time of described vulcanization reaction is 45～65min, can be such as 45min, 48min, 50min,
55min, 60min or 65min etc., preferably 60min.
Preferably, before described method is additionally included in vulcanization reaction, it is carried out quartz socket tube and by two
Quartz socket tube is respectively placed in the step of upstream and downstream.
Preferably, clean in the step of quartz socket tube, use argon to be carried out.
Preferably, described tungsten oxide nanometer tree vertical-growth is in tungsten paper tinsel substrate.
Preferably, the height of described tungsten oxide nanometer tree is 500～900nm, can be such as 500nm, 520nm,
550nm, 600nm, 625nm, 650nm, 700nm, 750nm, 800nm or 900nm etc., preferably
For 500nm.
Preferably, described tungsten oxide nanometer tree is prepared by the following method and obtains:
(1) tungsten paper tinsel is made annealing treatment；
(2) the tungsten paper tinsel cooling after step (1) being made annealing treatment, puts into the mixed of oxalic acid, rubidium sulfide and nitric acid
Close in solution, high-temperature water thermal response, then, product will be obtained and make annealing treatment, and obtain being grown in tungsten paper tinsel
Suprabasil oxidate nano tree.
Preferably, in the preparation method of described tungsten oxide nanometer tree, the temperature of step (1) described annealing
It is 450～550 DEG C, such as, can be 450 DEG C, 480 DEG C, 500 DEG C, 510 DEG C, 525 DEG C, 535 DEG C or 550 DEG C
Deng, preferably 500 DEG C.
Preferably, in the preparation method of described tungsten oxide nanometer tree, the time of step (1) described annealing
It is 30～45min, such as, can be 30min, 33min, 35min, 40min, 42min or 45min etc., excellent
Elect 30min as.
Preferably, in the preparation method of described tungsten oxide nanometer tree, step (2) described oxalic acid, rubidium sulfide and
In the mixed solution of nitric acid, the concentration of oxalic acid is 0.3～0.5mol/L, such as can 0.3mol/L, 0.35mol/L,
0.4mol/L, 0.45mol/L or 0.5mol/L etc., preferably 0.4mol/L.
Preferably, in the preparation method of described tungsten oxide nanometer tree, step (2) described oxalic acid, rubidium sulfide and
In the mixed solution of nitric acid, the concentration of rubidium sulfide is 10～40mmol/L, such as can 10mmol/L,
15mmol/L, 20mmol/L, 25mmol/L, 30mmol/L, 35mmol/L or 40mmol/L etc., excellent
Elect 25mmol/L as.
Preferably, in the preparation method of described tungsten oxide nanometer tree, step (2) described oxalic acid, rubidium sulfide and
In the mixed solution of nitric acid, the concentration of nitric acid is 0.1～0.3mol/L, such as can 0.1mol/L, 0.15mol/L,
0.2mol/L, 0.25mol/L or 0.3mol/L etc., preferably 0.15mol/L.
Preferably, in the preparation method of described tungsten oxide nanometer tree, the temperature of step (2) high-temperature water thermal response
It is 145～165 DEG C, such as, can be 145 DEG C, 150 DEG C, 152 DEG C, 155 DEG C, 160 DEG C or 165 DEG C etc., excellent
Elect 150 DEG C as.
Preferably, in the preparation method of described tungsten oxide nanometer tree, the time of step (2) high-temperature water thermal response
It is preferably 60～75h, such as, can be 60h, 65h, 68h, 70h, 72h or 75h etc., preferably 72h；
Preferably, in the preparation method of described tungsten oxide nanometer tree, the temperature of step (2) described annealing
It is 450～550 DEG C, such as, can be 450 DEG C, 500 DEG C, 515 DEG C, 520 DEG C, 525 DEG C, 540 DEG C or 550 DEG C
Deng, preferably 500 DEG C.
Preferably, in the preparation method of described tungsten oxide nanometer tree, the time of step (2) described annealing
It is 30～45min, such as, can be 30min, 32min, 35min, 40min, 43min or 45min etc., excellent
Elect 30min as；
Preferably, in the preparation method of described tungsten oxide nanometer tree, walk before being additionally included in step (1)
Suddenly (1) ': with deionized water, ethanol and acetone ultrasonic clean tungsten paper tinsel, then use N2Dry up.
Preferably, described cobalt oxide nano wire is prepared by the following method and obtains:
A carbon cloth is immersed in the aqueous solution of cobalt source and carbamide by (), take out carbon cloth annealing, and obtaining fabric has CoO
The carbon cloth of Seed Layer；
B fabric that step (a) is obtained by () has the carbon cloth of CoO Seed Layer to put into the water-soluble of cobalt source and carbamide
In liquid, hydro-thermal reaction, then make annealing treatment, obtain being grown in carbon cloth suprabasil cobalt oxide nano wire.
Preferably, in the preparation method of described cobalt oxide nano wire, the described cobalt source of step (a) be cobalt nitrate,
Any one or the mixture of at least two in cobaltous chloride, cobaltous sulfate or cobaltous acetate.
Preferably, in the preparation method of described cobalt oxide nano wire, the described cobalt source of step (a) and the water of carbamide
In solution, the concentration of cobalt source is 0.2～0.5mol/L, such as can 0.2mol/L, 0.25mol/L, 0.3mol/L,
0.35mol/L, 0.4mol/L, 0.45mol/L or 0.5mol/L etc., preferably 0.3mol/L.
Preferably, in the preparation method of described cobalt oxide nano wire, the described cobalt source of step (a) and the water of carbamide
In solution, the concentration of carbamide is 0.5～1.0mol/L, such as can 0.5mol/L, 0.6mol/L, 0.7mol/L,
0.8mol/L, 0.9mol/L or 1.0mol/L etc., preferably 0.8mol/L.
Preferably, in the preparation method of described cobalt oxide nano wire, the time of the described immersion of step (a) is
10～30min, can be such as 10min, 13min, 15min, 20min, 22min, 25min or 30min
Deng, preferably 10min.
Preferably, in the preparation method of described cobalt oxide nano wire, the described annealing of step (a) is in argon gas atmosphere
Under carry out, the temperature of described annealing is preferably 400～550 DEG C, can be such as 400 DEG C, 420 DEG C, 450 DEG C,
470 DEG C, 500 DEG C or 550 DEG C etc., more preferably 450 DEG C.
Preferably, in the preparation method of described cobalt oxide nano wire, the time of the described annealing of step (a) is 3～6h,
Can be such as 3h, 3.5h, 4h, 5h or 6h etc., preferably 4h.
Preferably, in the preparation method of described cobalt oxide nano wire, during the described hydro-thermal reaction of step (b), instead
Answering containing cobalt source and the aqueous solution of carbamide in still, the composition of this aqueous solution can be with the cobalt source of fabric use and urine
The composition of the aqueous solution of element is identical.
Preferably, in the preparation method of described cobalt oxide nano wire, the temperature of the described hydro-thermal reaction of step (b)
It is 85～100 DEG C, such as, can be 85 DEG C, 88 DEG C, 90 DEG C, 92 DEG C, 95 DEG C, 98 DEG C or 100 DEG C etc., excellent
Elect 90 DEG C as.
Preferably, in the preparation method of described cobalt oxide nano wire, the time of the described hydro-thermal reaction of step (b)
It is 3.5～6h, such as, can be 3.5h, 4h, 4.5h, 5h or 6h etc., preferably 4h.
Preferably, in the preparation method of described cobalt oxide nano wire, the described annealing of step (b) is in argon gas atmosphere
Under carry out, the temperature of described annealing is preferably 400～550 DEG C, can be such as 400 DEG C, 420 DEG C, 450 DEG C,
475 DEG C, 490 DEG C, 520 DEG C or 550 DEG C etc., more preferably 450 DEG C, the time of described annealing is preferred
For 4h.
As the optimal technical scheme of the method for the invention, prepared by the most described chemical gaseous phase depositing process
CoxW(1-x)S2Concretely comprising the following steps of nanometer sheet:
Cobalt oxide nano wire and tungsten sulfide nanometer sheet are placed in the center warm area of reacting furnace, with argon purge quartz
Guan Hou, is increased to 600～800 DEG C, with argon as carrier gas, intraductal pressure by the temperature of the center warm area of reacting furnace
Being 100～200Pa, growth obtains CoxW(1-x)S2Nanometer sheet.
In this optimal technical scheme, the temperature of the center warm area of reacting furnace is 600～800 DEG C, such as, can be
600 DEG C, 625 DEG C, 650 DEG C, 670 DEG C, 700 DEG C, 750 DEG C or 800 DEG C etc., preferably 800 DEG C.
In this optimal technical scheme, intraductal pressure is 100～200Pa, can be such as 100Pa, 120Pa, 140Pa,
150Pa, 170Pa or 200Pa etc..
Preferably, described reacting furnace is pipe reaction stove.
Preferably, the flow of described carrier gas is 50～100sccm, can be such as 50sccm, 60sccm, 70sccm,
80sccm, 90sccm or 100sccm etc..
Preferably, the time of described growth is 30～50min, can be such as 30min, 32min, 35min,
40min, 45min or 50min etc., preferably 30min.
As the further preferred technical scheme of the method for the invention, a kind of CoxW(1-x)S2The system of nanometer sheet
Preparation Method, said method comprising the steps of:
(1) with deionized water, ethanol and acetone ultrasonic cleaning tungsten paper tinsel, N is used2Dry up, be placed in stove 500 DEG C
Annealing 30min, after cooling, puts in the mixed solution containing oxalic acid, rubidium sulfide and nitric acid, puts into reactor
In, keep 72h in 150 DEG C, washing is the most dried, will obtain product in stove 500 DEG C make annealing treatment
30min, obtains being grown in tungsten paper tinsel suprabasil tungsten oxide nanometer tree；
(2) oxidate nano tree step (1) obtained and sulfur powder are respectively placed under double temperature-area tubular furnace
Trip and the center warm area of upstream, after argon purge quartz ampoule, be increased to upstream center temperature furnace temperature
100～200 DEG C, downstream central warm area furnace temperature is increased to 600～800 DEG C, keeps carrier gas Ar flow 50～100sccm,
Intraductal pressure is 100～200Pa, and natural cooling after vulcanization reaction 60min obtains tungsten sulfide nanometer sheet；
(3) carbon cloth is immersed 10min in the aqueous solution containing cobaltous chloride and carbamide, then in argon gas atmosphere
450 DEG C of annealing 4h obtain CoO Seed Layer, insert in reactor by the carbon cloth of fabric, containing chlorination in reactor
Cobalt and the aqueous solution of carbamide, be warmed up to 90 DEG C and keep 4h, and annealing obtains substrate the most under an argon atmosphere is carbon
The cobalt oxide nano wire of cloth；
(4) the tungsten sulfide nanometer sheet that cobalt oxide nano wire step (3) obtained and step (2) obtain is put
In the center warm area of pipe reaction stove, after argon purge quartz ampoule, center warm area furnace temperature is increased to
600～800 DEG C, keeping carrier gas Ar flow 50～100sccm, intraductal pressure is 100～200Pa, grows 30 points
Natural cooling after clock, obtains cobalt doped tungsten sulfide nanometer sheet.
Heretofore described " natural cooling " refers to naturally cool to room temperature.
Second aspect, the present invention provides the cobalt doped tungsten sulfide nanometer that method as described in relation to the first aspect prepares
Sheet, the chemical composition of described cobalt doped tungsten sulfide nanometer sheet is CoxW(1-x)S2, 0 ＜ x ＜ 1.
The value of described x can be such as 0.1,0.2,0.25,0.3,0.4,0.45,0.5,0.6,0.7,0.75,
0.8,0.9 or 0.95 etc., Co atom content is adjustable, and the amount that the numerical value difference of x represents cobalt doped is different.
Preferably, a diameter of the 50～500nm of described cobalt doped tungsten sulfide nanometer sheet, can be such as 50nm,
70nm、85nm、100nm、120nm、140nm、150nm、175nm、200nm、230nm、245nm、
265nm, 285nm, 300nm, 320nm, 350nm, 400nm, 450nm or 500nm etc..
Preferably, the thickness of described cobalt doped tungsten sulfide nanometer sheet is 5～30nm, can be such as 5nm, 6nm,
7nm, 8nm, 9nm, 10nm, 12nm, 15nm, 18nm, 20nm, 25nm, 27nm or 30nm
Deng.
The third aspect, the present invention provides Co as described in second aspectxW(1-x)S2The purposes of nanometer sheet, described
CoxW(1-x)S2Nanometer sheet is used for electrochemistry liberation of hydrogen.
Compared with prior art, there is advantages that
(1) present invention is by with tungsten sulfide nanometer sheet and cobalt oxide nano wire as raw material, is sunk by chemical gaseous phase
Long-pending method prepares cobalt doped tungsten sulfide nanometer sheet, and described method has preparation technology and is simple and convenient to operate, closes
Become speed fast and the advantage of low cost；
(2) good crystallinity of the cobalt doped tungsten sulfide nanometer sheet of the present invention, stable chemical nature, purity is high,
Electrochemical surface area is big, there is not the dephasigns such as cobalt sulfide, and being applied to electrochemistry liberation of hydrogen has extraordinary performance,
Tafel slope can as little as 67mV/decade；Reaching 10mA/cm2Electric current density time, its overpotential is low
To 121mV；At overpotential-0.15V in the electrolytic experiment of 20h, its electric current density is stablized
1.6mA/cm2, show that liberation of hydrogen has good stability.
Accompanying drawing explanation
Fig. 1 a is the Co that embodiment 1 preparesxW(1-x)S2The scanning electron microscopy of (0 ＜ x ＜ 1) nanometer sheet
Mirror (SEM) top view；Fig. 1 b-Fig. 1 e Co that respectively embodiment 1 preparesxW(1-x)S2(0 ＜ x
＜ 1) mapping (the TEM-EDX elemental mapping) figure of transmission electron microscope not same element of nanometer sheet；
Fig. 2 a is the Co that embodiment 1 preparesxW(1-x)S2The energy spectrum analysis figure of (0 ＜ x ＜ 1) nanometer sheet
(EDX)；Fig. 2 b is CoxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet and WS2The Raman analysis figure of nanometer sheet
(Raman)；
Fig. 3 a is the Co that embodiment 1 preparesxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet preparation process schematic diagram；
Fig. 3 b is that electrochemistry liberation of hydrogen (HER) tests schematic diagram；
Fig. 4 a and Fig. 4 b is the Co that embodiment 1 preparesxW(1-x)S2(0 ＜ x ＜ 1) and WS2Nanometer sheet
And the HER Performance comparision figure of Pt thin slice；
Fig. 5 is the Co that embodiment 1 preparesxW(1-x)S2The HER stability of (0 ＜ x ＜ 1) nanometer sheet is surveyed
Examination analysis chart.
Detailed description of the invention
Further illustrate technical scheme below in conjunction with the accompanying drawings and by detailed description of the invention.
Embodiment 1
CoxW(1-x)S2The preparation (preparation process schematic diagram sees Fig. 3 a) of nanometer sheet:
(1) with deionized water, ethanol and acetone ultrasonic clean W paper tinsel, N is used2Dry up, be placed in stove 500 DEG C
Annealing 30min, puts into after cooling containing 1.56g oxalic acid (H2C2O4·2H2O), 0.2g rubidium sulfate (Rb2SO4)
With 313 μ L nitric acid (HNO3) mixed solution reactor (50mL) in be warmed up to 150 DEG C keep 72h,
The sample washing obtained is dried, and in stove, 500 DEG C of annealing 30min, obtain being grown in the suprabasil WO of W3
Nanotrees；
(2) by sulfur powder (S) and (1) step gained WO3Nanotrees is respectively placed in dual temperature district pipe reaction
The upstream and downstream center warm area of stove, after cleaning quartz ampoule with argon (Ar), by upstream center warm area furnace temperature
Being increased to 150 DEG C, downstream central warm area furnace temperature is increased to 800 DEG C, keeps carrier gas Ar flow 50sccm, pipe
Interior pressure is 110Pa, naturally cools to room temperature, obtain WS after growing 60 minutes2Nanometer sheet；
(3) clean carbon cloth is immersed the cobaltous chloride (CoCl Han 1.90g2) and 2.424g carbamide (CO (NH2)2)
50mL aqueous solution in 10min, then in Ar 450 DEG C annealing 4h obtain CoO Seed Layer, by fabric
Carbon cloth inserts in reactor (aqueous solution of the solution in reactor and the chloride containing cobalt used by fabric and carbamide
Form identical), it is warmed up to 90 DEG C and keeps 4h, it is carbon cloth that the 4h that finally anneals in Ar atmosphere obtains substrate
CoO nano wire；
(4) by the WS of the CoO nano wire of (3) step gained He (2) step gained2Nanometer sheet is placed in
The center warm area of pipe reaction stove, after cleaning quartz ampoule with Ar, is increased to 800 DEG C by center warm area furnace temperature,
Keeping carrier gas Ar flow 50sccm, intraductal pressure is 110Pa, naturally cools to room temperature after growing 30 minutes,
Obtain CoxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet.
Its performance indications are briefly illustrated with lower part:
Fig. 1 a is the Co that embodiment 1 preparesxW(1-x)S2The scanning electron microscopy of (0 ＜ x ＜ 1) nanometer sheet
Mirror (SEM) top view, by Fig. 1 a it can be seen that CoxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet diameter exists
Between 50～500nm, shape is triangular in shape or sequin.
Fig. 1 b-Fig. 1 e Co that respectively embodiment 1 preparesxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet saturating
Mapping (the TEM-EDX elemental mapping) figure of radio mirror not same element, can by Fig. 1 b-Fig. 1 e
To find out, cobalt, tungsten, element sulphur are evenly dispersed in nanometer sheet, illustrate that cobalt atom is entrained in sulfuration really
Among tungsten nanometer sheet.
Fig. 2 a is the Co that embodiment 1 preparesxW(1-x)S2The energy spectrum analysis of (0 ＜ x ＜ 1) nanometer sheet
(EDX), by Fig. 2 a it can be seen that the nanometer sheet for preparing of embodiment 1 comprises S, Co and W unit
Element, and each atom content respectively is 66.77%, 1.34% and 31.88%.
Fig. 2 b is the Co that embodiment 1 preparesxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet and comparative example 1
WS2The Raman analysis (Raman) of nanometer sheet, by Fig. 2 b it can be seen that relative to WS2Nanometer sheet,
CoxW(1-x)S2The Raman peaks of (0 ＜ x ＜ 1) nanometer sheet has an obvious displacement, and this is due to Co atom
Doping causes.Similar peak position moves in the research of the matrix material a small amount of atom of doping the most universal.
Fig. 4 compares the WS of comparative example 12Co with embodiment 1xW(1-x)S2The analysis of (0 ＜ x ＜ 1) nanometer sheet
Hydrogen performance, electrochemistry liberation of hydrogen (HER) test schematic diagram sees Fig. 3 b, by Fig. 4 it will be seen that Co adulterates
It is greatly improved WS2The liberation of hydrogen efficiency of nanometer sheet, is reaching 10mA/cm2Electric current time, CoxW(1-x)S2
The overpotential (121mV) that nanometer sheet needs compares WS2Nanometer sheet (229mV) is much lower, Tafel slope
Also from WS2The 97mV/decade of sample is reduced to CoxW(1-x)S2The 67mV/decade of nanometer sheet.
Fig. 5 reacts CoxW(1-x)S2The liberation of hydrogen stability of nanometer sheet, in the test of 20 hours, its
Electric current density is stable at 1.6mA/cm2, Hydrogen Evolution Performance is moderately good.
Embodiment 2
CoxW(1-x)S2The preparation (prepare schematic diagram and see Fig. 3 a) of nanometer sheet:
(1) with deionized water, ethanol and acetone ultrasonic clean W paper tinsel, N is used2Dry up, be placed in stove 450 DEG C
Annealing 45min, puts into after cooling containing 1.17g oxalic acid (H2C2O4·2H2O), 0.08g rubidium sulfate (Rb2SO4)
With 209 μ L nitric acid (HNO3) mixed solution reactor (50mL) in be warmed up to 145 DEG C keep 72h,
The sample washing obtained is dried, and in stove, 465 DEG C of annealing 40min, obtain being grown in the suprabasil WO of W3
Nanotrees；
(2) by sulfur powder (S) and (1) step gained WO3Nanotrees is respectively placed in dual temperature district pipe reaction
The upstream and downstream center warm area of stove, after cleaning quartz ampoule with argon (Ar), by upstream center warm area furnace temperature
Being increased to 100 DEG C, downstream central warm area furnace temperature is increased to 650 DEG C, keeps carrier gas Ar flow 70sccm, pipe
Interior pressure is 100Pa, naturally cools to room temperature, obtain WS after growing 65 minutes2Nanometer sheet；
(3) clean carbon cloth is immersed the cobaltous chloride (CoCl Han 1.27g2) and 1.515g carbamide (CO (NH2)2)
50mL aqueous solution in 30min, then in Ar 400 DEG C annealing 6h obtain CoO Seed Layer, by fabric
Carbon cloth inserts in reactor (aqueous solution of the solution in reactor and the chloride containing cobalt used by fabric and carbamide
Form identical), it is warmed up to 100 DEG C and keeps 3.5h, it is carbon cloth that the 4h that finally anneals in Ar atmosphere obtains substrate
CoO nano wire；
(4) by the WS of the CoO nano wire of (3) step gained He (2) step gained2Nanometer sheet is placed in
The center warm area of pipe reaction stove, after cleaning quartz ampoule with Ar, is increased to 800 DEG C by center warm area furnace temperature,
Keeping carrier gas Ar flow 60sccm, intraductal pressure is 140Pa, naturally cools to room temperature after growing 35 minutes,
Obtain CoxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet；
Its performance indications are briefly illustrated with lower part:
The cobalt doped tungsten sulfide Co that the present embodiment preparesxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet is because of sulfuration not
Contain a certain amount of oxygen atom completely；Nanometer sheet diameter between 50～500nm, shape triangular in shape or
Sequin；Cobalt, tungsten, sulfur, oxygen element are evenly dispersed in nanometer sheet；Electrochemistry liberation of hydrogen (HER) is surveyed
Examination display, nanometer sheet has certain liberation of hydrogen ability, and Tafel slope reaches 117mV/decade；Reaching
10mA/cm2Electric current density time, its overpotential is 242mV.
Embodiment 3
CoxW(1-x)S2The preparation (prepare schematic diagram and see Fig. 3 a) of nanometer sheet:
(1) with deionized water, ethanol and acetone ultrasonic clean W paper tinsel, N is used2Dry up, be placed in stove 520 DEG C
Annealing 30min, puts into after cooling containing 1.95g oxalic acid (H2C2O4·2H2O), 0.32g rubidium sulfate (Rb2SO4)
With 626 μ L nitric acid (HNO3) mixed solution reactor (50mL) in be warmed up to 165 DEG C keep 60h,
The sample washing obtained is dried, and in stove, 520 DEG C of annealing 30min, obtain being grown in the suprabasil WO of W3
Nanotrees；
(2) by sulfur powder (S) and (1) step gained WO3Nanotrees is respectively placed in dual temperature district pipe reaction
The upstream and downstream center warm area of stove, after cleaning quartz ampoule with argon (Ar), by upstream center warm area furnace temperature
Being increased to 180 DEG C, downstream central warm area furnace temperature is increased to 750 DEG C, keeps carrier gas Ar flow 100sccm, pipe
Interior pressure is 150Pa, naturally cools to room temperature, obtain WS after growing 55 minutes2Nanometer sheet；
(3) clean carbon cloth is immersed the cobaltous chloride (CoCl Han 3.12g2) and 3.03g carbamide (CO (NH2)2)
50mL aqueous solution in 20min, then in Ar 500 DEG C annealing 3h obtain CoO Seed Layer, by fabric
Carbon cloth inserts in reactor (aqueous solution of the solution in reactor and the chloride containing cobalt used by fabric and carbamide
Form identical), it is warmed up to 85 DEG C and keeps 5h, it is carbon cloth that the 4h that finally anneals in Ar atmosphere obtains substrate
CoO nano wire；
(4) by the WS of the CoO nano wire of (3) step gained He (2) step gained2Nanometer sheet is placed in
The center warm area of pipe reaction stove, after cleaning quartz ampoule with Ar, is increased to 600 DEG C by center warm area furnace temperature,
Keeping carrier gas Ar flow 90sccm, intraductal pressure is 160Pa, naturally cools to room temperature after growing 40 minutes,
Obtain CoxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet.
Its performance indications are briefly illustrated with lower part:
The cobalt doped tungsten sulfide Co that the present embodiment preparesxW(1-x)S2(0 ＜ x ＜ 1) nanometer sheet diameter exists
Between 50～500nm, shape is triangular in shape or sequin；Tungsten, element sulphur are evenly dispersed in nanometer sheet,
But the doping of Co element is few, it is not enough to change the performance of material；Electrochemistry liberation of hydrogen (HER) test is aobvious
Show, the nanometer sheet of synthesis and WS2Having identical liberation of hydrogen ability, Tafel slope reaches 98mV/decade；
Reaching 10mA/cm2Electric current density time, its overpotential is 230mV.
Comparative example 1
Use in substrate, synthesize tungsten oxide (WO3) and the method for after cure prepares tungsten sulfide (WS2) nanometer
Structure, sees the adjustable WS of article composition of Xu Kai (Kai Xu) et al.2(1-x)Se2xNanotube is efficient
Liberation of hydrogen (Component-Controllable WS2(1–x)Se2x Nanotubes for Efficient Hydrogen
Evolution Reaction,Acs Nano,2014,8(8),8468-8476)。
Comparative example 2
This comparative example 2 prepares the tungsten sulfide nanometer sheet of cobalt doped for the method that bimetallic oxide vulcanizes, specifically
Process brief introduction is as follows: first, utilizes the method for electrochemistry or magnetron sputtering to deposit WO in substrate3-CoO
Bimetallic oxide；Then, the bimetallic oxide obtained is through the high temperature vulcanized sulfur with acquisition cobalt doped
Change tungsten nanometer sheet.
After testing, there is cobalt sulfide dephasign in the cobalt doped tungsten sulfide nanometer sheet of gained, its poor-performing, electricity
The Tafel slope that chemistry collecting gas records is 132mV/dec, is reaching 10mA/cm2Electric current time, need
The overpotential wanted is more than 300mV.Details refer to the article of Jacob Bond (Jacob Bonde) et al.
Liberation of hydrogen research (the Hydrogen evolution on of Nanoparticulate transient metal sulfide
nano-particulate transition metal sulfides,Faraday discussions,2009,140,
219-231)。
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention
It is not limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.
Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, each former to product of the present invention
The equivalence of material is replaced and the interpolation of auxiliary element, concrete way choice etc., all falls within the protection model of the present invention
Within the scope of enclosing and disclosing.
Claims (10)
1. the preparation method of a cobalt doped tungsten sulfide nanometer sheet, it is characterised in that described method includes following
Step:
With tungsten sulfide nanometer sheet and cobalt oxide nano wire as raw material, by chemical gaseous phase depositing process, prepare cobalt
Doping tungsten sulfide nanometer sheet.
Preparation method the most according to claim 1, it is characterised in that described tungsten sulfide is by with lower section
Method prepares:
Tungsten oxide nanometer tree is vulcanized, obtains tungsten sulfide nanometer sheet.
Preparation method the most according to claim 2, it is characterised in that concretely comprising the following steps of described sulfuration:
Described tungsten oxide nanometer tree and sulfur powder are respectively placed in downstream and the upstream of double temperature-area tubular furnace, and heating carries out sulfur
Change reaction；
Preferably, the furnace temperature in the downstream of described pair of temperature-area tubular furnace is 600～800 DEG C, preferably 800 DEG C；
Preferably, the furnace temperature of the upstream of described pair of temperature-area tubular furnace is 100～200 DEG C, preferably 150 DEG C；
Preferably, being connected with argon in described pair of temperature-area tubular furnace, the flow of described argon is preferably
50～100sccm；
Preferably, the intraductal pressure of described pair of temperature-area tubular furnace is 100～200Pa；
Preferably, the time of described vulcanization reaction is 45～65min, preferably 60min；
Preferably, before described method is additionally included in vulcanization reaction, it is carried out quartz socket tube and by two
Quartz socket tube is respectively placed in the step of upstream and downstream；
Preferably, in the step of described cleaning quartz socket tube, argon is used to be carried out.
The most according to the method in claim 2 or 3, it is characterised in that described tungsten oxide nanometer tree is vertical
It is grown in tungsten paper tinsel substrate；
Preferably, the height of described oxidate nano tree is 500～900nm, preferably 500nm.
5. according to the method described in any one of claim 2-4, it is characterised in that described tungsten oxide nanometer tree
It is prepared by the following method and obtains:
(1) tungsten paper tinsel is made annealing treatment；
(2) the tungsten paper tinsel cooling after step (1) being made annealing treatment, puts into the mixed of oxalic acid, rubidium sulfide and nitric acid
Close in solution, hydro-thermal reaction, then, product will be obtained and make annealing treatment, and obtain being grown in tungsten paper tinsel substrate
On oxidate nano tree；
Preferably, in the preparation method of described tungsten oxide nanometer tree, the temperature of step (1) described annealing
It is 450～550 DEG C, preferably 500 DEG C；
Preferably, in the preparation method of described tungsten oxide nanometer tree, the time of step (1) described annealing
It is 30～45min, preferably 30min；
Preferably, in the preparation method of described tungsten oxide nanometer tree, step (2) described oxalic acid, rubidium sulfide and
In the mixed solution of nitric acid, the concentration of oxalic acid is 0.3～0.5mol/L；
Preferably, in the preparation method of described tungsten oxide nanometer tree, step (2) described oxalic acid, rubidium sulfide and
In the mixed solution of nitric acid, the concentration of rubidium sulfide is 10～40mmol/L；
Preferably, in the preparation method of described tungsten oxide nanometer tree, step (2) described oxalic acid, rubidium sulfide and
In the mixed solution of nitric acid, the concentration of nitric acid is 0.1～0.3mol/L；
Preferably, in the preparation method of described tungsten oxide nanometer tree, the temperature of step (2) described hydro-thermal reaction
It is 145～165 DEG C, preferably 150 DEG C；
Preferably, in the preparation method of described tungsten oxide nanometer tree, the time of step (2) described hydro-thermal reaction
It is preferably 60～75h, preferably 72h；
Preferably, in the preparation method of described tungsten oxide nanometer tree, the temperature of step (2) described annealing
It is 450～550 DEG C, preferably 500 DEG C；
Preferably, in the preparation method of described tungsten oxide nanometer tree, the time of step (2) described annealing
It is 30～45min, preferably 30min；
Preferably, in the preparation method of described tungsten oxide nanometer tree, walk before being additionally included in step (1)
Suddenly (1) ': with deionized water, ethanol and acetone ultrasonic clean tungsten paper tinsel, then use N2Dry up.
6. according to the method described in any one of claim 2-5, it is characterised in that described cobalt oxide nano wire
It is prepared by the following method and obtains:
A carbon cloth is immersed in the aqueous solution of cobalt source and carbamide by (), take out carbon cloth annealing, and obtaining fabric has CoO
The carbon cloth of Seed Layer；
B fabric that step (a) is obtained by () has the carbon cloth of CoO Seed Layer to put into the water-soluble of cobalt source and carbamide
In liquid, hydro-thermal reaction, then make annealing treatment, obtain being grown in carbon cloth suprabasil cobalt oxide nano wire；
Preferably, in the preparation method of described cobalt oxide nano wire, the described cobalt source of step (a) be cobalt nitrate,
Any one or the mixture of at least two in cobaltous chloride, cobaltous sulfate or cobaltous acetate；
Preferably, in the preparation method of described cobalt oxide nano wire, the described cobalt source of step (a) and the water of carbamide
In solution, the concentration of cobalt source is 0.2～0.5mol/L；
Preferably, in the preparation method of described cobalt oxide nano wire, the described cobalt source of step (a) and the water of carbamide
In solution, the concentration of carbamide is 0.5～1.0mol/L；
Preferably, in the preparation method of described cobalt oxide nano wire, the time of the described immersion of step (a) is
10～30min, preferably 10min；
Preferably, in the preparation method of described cobalt oxide nano wire, the described annealing of step (a) is in argon gas atmosphere
Under carry out, the temperature of described annealing is preferably 400～550 DEG C, more preferably 450 DEG C；
Preferably, in the preparation method of described cobalt oxide nano wire, the time of the described annealing of step (a) is 3～6h,
It is preferably 4h；
Preferably, in the preparation method of described cobalt oxide nano wire, the temperature of the described hydro-thermal reaction of step (b)
It is 85～100 DEG C, preferably 90 DEG C；
Preferably, in the preparation method of described cobalt oxide nano wire, the time of the described hydro-thermal reaction of step (b)
It is 3.5～6h, preferably 4h；
Preferably, in the preparation method of described cobalt oxide nano wire, the described annealing of step (b) is in argon gas atmosphere
Under carry out, the temperature of described annealing is preferably 400～550 DEG C, more preferably 450 DEG C, described annealing
Time is preferably 4h.
7. according to the method described in any one of claim 1-6, it is characterised in that described chemical gaseous phase deposits
Method prepares concretely comprising the following steps of cobalt doped tungsten sulfide nanometer sheet:
Cobalt oxide nano wire and tungsten sulfide nanometer sheet are placed in the center warm area of reacting furnace, with argon purge quartz
Guan Hou, is 600～800 DEG C by the temperature of the center warm area of reacting furnace, and with argon as carrier gas, intraductal pressure is
100～200Pa, growth obtains cobalt doped tungsten sulfide nanometer sheet；
Preferably, described reacting furnace is pipe reaction stove；
Preferably, the temperature of the center warm area of described reacting furnace is 800 DEG C；
Preferably, the flow of described carrier gas is 50～100sccm；
Preferably, the time of described growth is 30～50min, preferably 30min.
8. according to the method described in any one of claim 1-7, it is characterised in that described method includes following
Step:
(1) with deionized water, ethanol and acetone ultrasonic cleaning tungsten paper tinsel, N is used2Dry up, be placed in stove 500 DEG C
Annealing 30min, after cooling, puts in the mixed solution containing oxalic acid, rubidium sulfide and nitric acid, puts into reaction
In still, keeping 72h in 150 DEG C, washing is the most dried, will obtain product in stove 500 DEG C carry out annealing treatment
Reason 30min, obtains being grown in tungsten paper tinsel suprabasil tungsten oxide nanometer tree；
(2) oxidate nano tree step (1) obtained and sulfur powder are respectively placed under double temperature-area tubular furnace
Trip and the center warm area of upstream, after argon purge quartz ampoule, be increased to upstream center temperature furnace temperature
100～200 DEG C, downstream central warm area furnace temperature is increased to 600～800 DEG C, keeps carrier gas Ar flow
50～100sccm, intraductal pressure is 100～200Pa, and natural cooling after vulcanization reaction 60min is vulcanized
Tungsten nanometer sheet；
(3) carbon cloth is immersed 10min in the aqueous solution containing cobaltous chloride and carbamide, then in argon gas atmosphere
450 DEG C of annealing 4h obtain CoO Seed Layer, insert in reactor by the carbon cloth of fabric, containing chlorination in reactor
Cobalt and the aqueous solution of carbamide, be warmed up to 90 DEG C and keep 4h, and annealing obtains substrate the most under an argon atmosphere is carbon
The cobalt oxide nano wire of cloth；
(4) the tungsten sulfide nanometer sheet that cobalt oxide nano wire step (3) obtained and step (2) obtain is put
In the center warm area of pipe reaction stove, after argon purge quartz ampoule, center warm area furnace temperature is increased to
600～800 DEG C, keeping carrier gas Ar flow 50～100sccm, intraductal pressure is 100～200Pa, grows 30
Natural cooling after minute, obtains cobalt doped tungsten sulfide nanometer sheet.
9. the cobalt doped tungsten sulfide nanometer sheet that the method as described in any one of claim 1-8 prepares, its
Being characterised by, the chemical composition of described cobalt doped tungsten sulfide nanometer sheet is CoxW(1-x)S2, 0 ＜ x ＜ 1；
Preferably, a diameter of the 50～500nm of described cobalt doped tungsten sulfide nanometer sheet, described cobalt doped tungsten sulfide
The thickness of nanometer sheet is 5～30nm.
10. the purposes of cobalt doped tungsten sulfide nanometer sheet as claimed in claim 9, it is characterised in that described
CoxW(1-x)S2Nanometer sheet is used for electrochemistry liberation of hydrogen.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108097281A (en) * | 2017-11-14 | 2018-06-01 | 国家纳米科学中心 | A kind of MnPS3Nanometer sheet and its preparation method and application |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101888974A (en) * | 2007-09-10 | 2010-11-17 | 曳达研究和发展有限公司 | Fullerene-like nanostructures and application thereof and manufacture method |
| CN102892709A (en) * | 2010-03-10 | 2013-01-23 | 耶达研究与发展有限公司 | Nanostructures, their use and process for their production |
| CN104986802A (en) * | 2015-07-08 | 2015-10-21 | 华东师范大学 | Platy nanometer material and preparation method thereof |
-
2016
- 2016-04-26 CN CN201610266686.8A patent/CN105948126B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101888974A (en) * | 2007-09-10 | 2010-11-17 | 曳达研究和发展有限公司 | Fullerene-like nanostructures and application thereof and manufacture method |
| CN102892709A (en) * | 2010-03-10 | 2013-01-23 | 耶达研究与发展有限公司 | Nanostructures, their use and process for their production |
| CN105129854A (en) * | 2010-03-10 | 2015-12-09 | 耶达研究与发展有限公司 | Fullerene-like nanostructures, their use and process for their production |
| CN104986802A (en) * | 2015-07-08 | 2015-10-21 | 华东师范大学 | Platy nanometer material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| BO LI ET AL.: "Synthesis and Transport Properties of Large-Scale Alloy Co0.16Mo0.84S2 Bilayer Nanosheets", 《ACSNANO》 * |
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| CN108097281B (en) * | 2017-11-14 | 2021-04-27 | 国家纳米科学中心 | MnPS3Nanosheet and preparation method and application thereof |
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| CN108585055B (en) * | 2018-05-25 | 2020-12-18 | 复旦大学 | Transition metal vanadium sulfide MV2S4Preparation method of (1) |
| CN109336181A (en) * | 2018-09-20 | 2019-02-15 | 天津大学 | A kind of preparation method of two dimension Transition-metal dichalcogenide |
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| CN113201754A (en) * | 2021-05-10 | 2021-08-03 | 苏州大学 | Electrocatalyst material for hydrogen evolution and oxygen evolution reaction, and preparation method and application thereof |
| CN113201754B (en) * | 2021-05-10 | 2022-04-22 | 苏州大学 | Electrocatalyst material for hydrogen evolution and oxygen evolution reaction, and preparation method and application thereof |
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