CN107999093A - A kind of cobalt doped two dimension tungsten selenide elctro-catalyst and preparation method thereof - Google Patents
A kind of cobalt doped two dimension tungsten selenide elctro-catalyst and preparation method thereof Download PDFInfo
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- CN107999093A CN107999093A CN201711479880.5A CN201711479880A CN107999093A CN 107999093 A CN107999093 A CN 107999093A CN 201711479880 A CN201711479880 A CN 201711479880A CN 107999093 A CN107999093 A CN 107999093A
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- SDDGNMXIOGQCCH-UHFFFAOYSA-N 3-fluoro-n,n-dimethylaniline Chemical compound CN(C)C1=CC=CC(F)=C1 SDDGNMXIOGQCCH-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 33
- 239000010941 cobalt Substances 0.000 title claims abstract description 33
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 235000013495 cobalt Nutrition 0.000 claims abstract description 39
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims abstract description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 6
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 6
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 5
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000011669 selenium Substances 0.000 claims description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052711 selenium Inorganic materials 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000012467 final product Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- -1 Disodium tungstate (Na2WO4) dihydrates Chemical class 0.000 description 1
- 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
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- MJOQJPYNENPSSS-XQHKEYJVSA-N [(3r,4s,5r,6s)-4,5,6-triacetyloxyoxan-3-yl] acetate Chemical compound CC(=O)O[C@@H]1CO[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O MJOQJPYNENPSSS-XQHKEYJVSA-N 0.000 description 1
- ORJNTPGYBORNOD-UHFFFAOYSA-N [W]=[Se].[Co] Chemical compound [W]=[Se].[Co] ORJNTPGYBORNOD-UHFFFAOYSA-N 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to elctro-catalyst preparation field, discloses a kind of preparation method of cobalt doped two dimension tungsten selenide elctro-catalyst.Selenium powder, sodium borohydride are scattered inN, NIn dimethylformamide, stirred evenly under the conditions of 40 ~ 60 DEG C；Disodium tungstate (Na2WO4) dihydrate and four acetate hydrate cobalts are dissolved in the water；Two solution are mixed, are stirred evenly；8 ~ 12 h are reacted under the conditions of 160 ~ 200 DEG C；After reaction, centrifuge washing, gained precipitation is dried under vacuum；Products therefrom 300 ~ 500 DEG C of 3 ~ 5 h of carbonization under inert gas shielding, to obtain the final product.Cobalt doped two dimension tungsten selenide prepared by the method for the present invention all shows the electrocatalytic hydrogen evolution performance more excellent than business tungsten selenide in the range of extensive pH, this has a good application prospect in catalytic field.
Description
Technical field
The invention belongs to elctro-catalyst preparation field, and in particular to a kind of preparation of cobalt doped two dimension tungsten selenide elctro-catalyst
Method.
Background technology
Transition-metal dichalcogenide has the characteristic similar to graphene as a kind of new two-dimensional layer material,
It is widely used in field-effect transistor, sensing, energy storage and catalysis etc..Test and theoretical research shows, transition metal sulfur family
The edge of compound exposure has the electrocatalysis characteristic for the noble metal platinum that can match in excellence or beauty.But due to Transition-metal dichalcogenide two-dimensional layer
The characteristic of shape structure, it is easy to assemble under van der Waals interaction and overlap, greatly reduce its edge active site
Exposure.Therefore how preparing the Transition-metal dichalcogenide with high density active site, there are problem.So far, improve
The preparation method of Transition-metal dichalcogenide avtive spot density, which is mainly peeled off, disperses and reduces size, but the process
Low output and complexity are operated, and the avtive spot density improved is limited, significantly limit its answering in terms of catalytic field
With.Tungsten selenide is the promising non-precious metal catalyst of tool as a Transition-metal dichalcogenide not being widely deployed,
The influence of the density in its same receptor 1 activity site of performance.Therefore, find a kind of row method obtain the two-dimentional selenium of high activity
The elctro-catalyst for changing tungsten is still a challenge.In addition, hydrogen is as a kind of efficient, reproducible clean fuel, two-dimensional material
Catalyst prepares its electrochemistry more limitations in acid condition.Therefore, development cost it is low and under the conditions of alkaline water electrolytic work
The new and effective Electrocatalytic Activity for Hydrogen Evolution Reaction agent made is of great significance.
The content of the invention
In view of the above-mentioned defects in the prior art with deficiency, it is an object of the invention to provide a kind of cobalt doped two dimension tungsten selenide
The preparation method of elctro-catalyst.
To achieve the above object, the technical solution that the present invention takes is as follows：
A kind of preparation method of cobalt doped two dimension tungsten selenide elctro-catalyst, step are as follows：
（1）, selenium powder, sodium borohydride be scattered inN, NIn-dimethylformamide, stir evenly, match somebody with somebody under the conditions of 40 ~ 60 DEG C
Mass concentration into selenium powder, sodium borohydride is respectively（10~15）×10-3 g/mL、（5~6）×10-3 The solution of g/mL；
（2）, Disodium tungstate (Na2WO4) dihydrate and four acetate hydrate cobalts be dissolved in the water, be made into Disodium tungstate (Na2WO4) dihydrate and four acetate hydrates
The mass concentration of cobalt is（100~150）×10-3 g/mL、（10~30）×10-3 The solution of g/mL；WhereinN, N- dimethyl formyl
The volume ratio of amine and water is（4~5）: 1,
（3）, by step（2）Resulting solution adds step（1）In resulting solution, stir evenly；
（4）, by step（3）Resulting solution reacts 8 ~ 12 h under the conditions of 160 ~ 200 DEG C；
（5）, step（4）After reaction, centrifuge washing, gained precipitation is dried under vacuum；
（6）, by step（5）Products therefrom 300 ~ 500 DEG C of 3 ~ 5 h of carbonization under inert gas shielding, up to cobalt doped two dimension selenium
Change tungsten elctro-catalyst.
Preferably, during centrifuge washing, first it is washed with water and is washed again with ethanol；Every time during centrifugation, speed is 7000 ~ 9000
Rpm, time are 5 ~ 10 min.
Preferably, water and ethanol each wash three times.
Preferably, vacuum drying temperature is 40 ~ 60 DEG C.
The cobalt doped two dimension tungsten selenide elctro-catalyst prepared using the preparation method.
The present invention has the advantage that relative to the prior art：
1st, preparation method technique of the present invention is simple, easy to operate, post processing is simple, safety, has repeatability；
2nd, the preparation process provides a kind of preparation method of cobalt doped two dimension tungsten selenide elctro-catalyst, relative to gas phase gold
Belong to the high temperature of the doping method harsh operating environment such as a long time, the method compared with gentle safety and also yield it is big, apply in device
Potentiality on part；
3rd, cobalt doped two dimension tungsten selenide prepared by the method for the present invention is all shown more excellent than business tungsten selenide in the range of extensive pH
Different electrocatalytic hydrogen evolution performance, this has a good application prospect in catalytic field.
Brief description of the drawings
Fig. 1：The scanning electron microscope (SEM) photograph of cobalt doped two dimension tungsten selenide prepared by the embodiment of the present invention 1.
Fig. 2：The x-ray photoelectron spectroscopy figure of cobalt doped two dimension tungsten selenide prepared by the embodiment of the present invention 1,（a）Wolfram element,
（b）Selenium element,（c）Cobalt element.
Fig. 3：The transmission electron microscope photo of cobalt doped two dimension tungsten selenide prepared by the embodiment of the present invention 1.
Fig. 4：The X-ray diffraction spectrogram of cobalt doped two dimension tungsten selenide prepared by the embodiment of the present invention 1（a）With Raman spectrogram
（b）.
Fig. 5：The cobalt doped two dimension tungsten selenide that business tungsten selenide is prepared with 1-3 of the embodiment of the present invention is in 0.5 M H2SO4It is acid
（a）With 1 M KOH alkalescence（b）Polarization curve contrast in electrolyte.
Embodiment
Technical scheme is illustrated with specific embodiment below, but protection scope of the present invention is not limited to
This：
Embodiment 1
（1）, 640 mg selenium powders and 300 mg sodium borohydrides are dispersed in 50 mL N,NIn-dimethylformamide, preservative film is sealed up
Two hours are stirred under the conditions of 60 DEG C until solution is changed into brown color, and formation selenium powder, the mass concentration of sodium borohydride are respectively
12.8×10-3 g/mL、6×10-3The solution of g/mL；
（2）, 1320 mg Disodium tungstate (Na2WO4) dihydrates and 200 mg, tetra- acetate hydrate cobalts added in 10 mL deionized waters, ultrasound 0.5
Hour, the mass concentration for forming Disodium tungstate (Na2WO4) dihydrate and four acetate hydrate cobalts is 132 × 10-3 g/mL、20×10-3G/mL's is molten
Liquid；
（3）, by step（2）Resulting solution adds step（1）In resulting solution, when 60 DEG C of stirrings 0.5 of continuation are small；
（4）, by step（3）Resulting solution is gone in reaction kettle, when reaction 12 is small under the conditions of 200 DEG C；
（5）, respectively washed three times with deionized water and absolute ethyl alcohol, every time during centrifugation, speed be 7000 rpm, and the time is 10 points
Clock, extraction centrifuge tube lower sediment are dried in vacuo at 40 DEG C；
（6）, by step（5）Products therefrom is when 300 DEG C of retort carbonization 5 is small under nitrogen protection, up to cobalt doped two dimension selenizing
Tungsten elctro-catalyst.
Embodiment 2
It is with the difference of embodiment 1：By step（2）In four acetate hydrate cobalts be adjusted to 100 mg, it is other with implementing
Example 1.
Embodiment 3
It is with the difference of embodiment 1：By step（2）In four acetate hydrate cobalts be adjusted to 300 mg, it is other with implementing
Example 1.
Structural characterization and performance test
（One）Structural characterization
Fig. 1 is the scanning electron microscope diagram of cobalt doped two dimension tungsten selenide prepared by the embodiment of the present invention 1, as can be seen from the figure
The product of synthesis is two-dimensional sheet structure, and lateral dimension is 100 nm, and longitudinal size is 25 nm.
Fig. 2 is the x-ray photoelectron spectroscopy figure of cobalt doped two dimension tungsten selenide prepared by the embodiment of the present invention 1, is respectively（a）
W 4f and（b）Se 3d and（c）Co 2p spectrograms, as can be seen from the figure cobalt be doped into the form of positive divalent state it is original
Selenizing tungsten structure in.
The transmission electron microscope figure for the cobalt doped two dimension tungsten selenide that Fig. 3 is prepared for the embodiment of the present invention 1, the material after doping
Material is still the less laminated structure of size.
Fig. 4 is the X-ray diffraction spectrogram of cobalt doped two dimension tungsten selenide prepared by the embodiment of the present invention 1（a）With Raman spectrogram
（b）,（a）All there is the appearance of new peak in figure in addition to retaining the characteristic peak of original tungsten selenide, and by contrasting PDF cards
New peak can be attributed to Co9Se8,（b）Except original 250 cm in figure-1Also have outside tungsten selenide characteristic oscillation modes at position
The appearance of new peak again shows that cobalt is successfully doped into tungsten selenide.
（Two）Performance test
Cobalt doped two dimension tungsten selenide prepared by embodiment 1-3 and business tungsten selenide are loaded into glass-carbon electrode as catalyst respectively
Upper to be used as working electrode, silver/silver chloride electrode is reference electrode, and carbon-point is to electrode, assembling three-electrode system test liberation of hydrogen
Can, electrolyte is 0.5 M H2SO4Or 1 M KOH, sweep speed is 5 mv/s.The preparation process of working electrode is：By 5 mg samples
Product be dissolved in 1 mL absolute ethyl alcohols and add 5 μ L 5wt% naphthol solutions ultrasound 1 it is small when or so until dispersed, with shifting
Liquid rifle takes 10 μ L even applications to be dried at room temperature on glass-carbon electrode.
Fig. 5 is business tungsten selenide and the cobalt doped two dimension tungsten selenide of 1-3 of embodiment of the present invention preparations in 0.5 M H2SO4Acid
Property（a）With 1 M KOH alkalescence（b）Polarization curve contrast in electrolyte, as we can see from the figure：Relative to business tungsten selenide,
A small amount of cobalt doped catalyst（Embodiment 2）Hydrogen Evolution Performance all improve a lot under acid or alkaline condition, still
When Co doping amounts are relatively large, catalyst（Embodiment 1, embodiment 3）Although Hydrogen Evolution Performance relative commercial tungsten selenide has very big
Improve, but catalyst Hydrogen Evolution Performance is not directly proportional to Co doping amounts, but there are a most suitable doping；The present invention
Prepared by embodiment 1 mixes what cobalt tungsten selenide was not only prepared than business tungsten selenide and embodiment 2 and embodiment 3 in acid condition
The catalytic performance of cobalt doped tungsten selenide is high, and Hydrogen Evolution Performance is also optimal in alkaline conditions.
Claims (5)
1. a kind of preparation method of cobalt doped two dimension tungsten selenide elctro-catalyst, it is characterised in that step is as follows：
（1）, selenium powder, sodium borohydride be scattered inN, NIn-dimethylformamide, stir evenly, match somebody with somebody under the conditions of 40 ~ 60 DEG C
Mass concentration into selenium powder, sodium borohydride is respectively（10~15）×10-3 g/mL、（5~6）×10-3 The solution of g/mL；
（2）, Disodium tungstate (Na2WO4) dihydrate and four acetate hydrate cobalts be dissolved in the water, be made into Disodium tungstate (Na2WO4) dihydrate and four acetate hydrates
The mass concentration of cobalt is（100~150）×10-3 g/mL、（10~30）×10-3 The solution of g/mL；WhereinN, N- dimethyl formyl
The volume ratio of amine and water is（4~5）: 1,
（3）, by step（2）Resulting solution adds step（1）In resulting solution, stir evenly；
（4）, by step（3）Resulting solution reacts 8 ~ 12 h under the conditions of 160 ~ 200 DEG C；
（5）, step（4）After reaction, centrifuge washing, gained precipitation is dried under vacuum；
（6）, by step（5）Products therefrom 300 ~ 500 DEG C of 3 ~ 5 h of carbonization under inert gas shielding, up to cobalt doped two dimension selenium
Change tungsten elctro-catalyst.
2. preparation method as claimed in claim 1, it is characterised in that：During centrifuge washing, first it is washed with water and is washed again with ethanol；
Every time during centrifugation, speed is 7000 ~ 9000 rpm, and the time is 5 ~ 10 min.
3. preparation method as claimed in claim 2, it is characterised in that：Water and ethanol each wash three times.
4. preparation method as claimed in claim 1, it is characterised in that：Vacuum drying temperature is 40 ~ 60 DEG C.
5. the cobalt doped two dimension tungsten selenide electro-catalysis that one kind is prepared using the preparation method as described in claim 1 ~ 4 any one
Agent.
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| CN107519899A (en) * | 2017-10-11 | 2017-12-29 | 陕西科技大学 | A kind of selenizing cobalt catalyst and its preparation method and application |
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| CN106824070A (en) * | 2017-01-22 | 2017-06-13 | 青岛科技大学 | A kind of two tungsten selenide nitrogen-doped graphene photocatalysis sorbing materials and preparation method thereof |
| CN107190361A (en) * | 2017-04-19 | 2017-09-22 | 江苏大学 | A kind of tungsten selenide/graphene/carbon nano-fiber composite material and preparation method thereof |
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