CN113201765A - Phosphating WS2Preparation method and application of nanosphere catalyst - Google Patents
Phosphating WS2Preparation method and application of nanosphere catalyst Download PDFInfo
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- CN113201765A CN113201765A CN202110347746.XA CN202110347746A CN113201765A CN 113201765 A CN113201765 A CN 113201765A CN 202110347746 A CN202110347746 A CN 202110347746A CN 113201765 A CN113201765 A CN 113201765A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000002077 nanosphere Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 18
- 239000002244 precipitate Substances 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims 4
- 238000001816 cooling Methods 0.000 abstract description 7
- 239000002135 nanosheet Substances 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract 1
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910052961 molybdenite Inorganic materials 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- BJMBNXMMZRCLFY-UHFFFAOYSA-N [N].[N].CN(C)C=O Chemical compound [N].[N].CN(C)C=O BJMBNXMMZRCLFY-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- -1 lithium-sulfur ion Chemical class 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- VKCLPVFDVVKEKU-UHFFFAOYSA-N S=[P] Chemical compound S=[P] VKCLPVFDVVKEKU-UHFFFAOYSA-N 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000002803 fossil fuel 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
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/28—Deposition of only one other non-metal element
-
- 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
-
- 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 Kinetics & Catalysis (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention discloses a phosphating WS2The preparation method of the nanosphere catalyst comprises the following steps: s101, dissolving tungsten hexacarbonyl and sulfur powder in an organic solvent under the protection of inert gas, and uniformly mixing at room temperature to obtain brown mixed liquor; fully reacting the brown mixed solution in a high-pressure reaction kettle at the temperature of between 100 and 250 ℃, and filling the brown mixed solutionThe reaction is carried out for 10 to 24 hours; s102, cooling the reacted high-pressure reaction kettle to room temperature, centrifuging the mixture to obtain a black precipitate, and purifying; s103, reacting the purified black precipitate with sodium hypophosphite in a tubular furnace filled with inert gas at the temperature of between 200 and 300 ℃ for 2 to 3 hours to obtain the sodium hypophosphite. The invention provides WS prepared by the method2An | P nanosphere catalyst and application thereof. WS of the present invention2The preparation method of the | P nanosphere catalyst is simple, and the nanosheet cluster type nanoparticles with uniform size and high specific surface area are obtained.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to phosphorized WS2A preparation method and application of the nanosphere catalyst.
Background
The environmental pollution is further aggravated by the massive combustion of traditional fossil fuels, so that people look for other renewable energy sources. Hydrogen energy sources have a high energy density and the only product produced after combustion is water, which is the most promising candidate energy carrier. Electrochemical water splitting provides a viable route to hydrogen production, involving two half-reactions, Hydrogen Evolution (HER) at the cathode and Oxygen Evolution (OER) at the anode. However, the actual efficiency of hydrogen release during electrochemical water splitting is governed by the kinetics of the hydrogen release reaction (HER, 2H)++2e-→H2) Is limited strictly. Therefore, there is a strong need for high performance HER catalysts that lower the energy barrier and improve energy conversion efficiency. Pt-based metal materials have been considered to be the most advanced HER electrocatalysts so far, but due to their enormous cost and low abundance, their large-scale application is limited and the industrial requirements cannot be met. Therefore, it is of paramount importance to design and develop HER electrocatalysts with high abundance, low cost and high durability to enhance catalytic performance.
In recent years, through the continuous research on electrocatalyst materials, based on MoS2、WS2、TiS2And the layered transition metal-based dihalide metals of FeS (LTMDs) have become alternatives to noble metal catalysts such as platinum (Pt) and gold (Au). In MoS2LTMD represented by nanosheets has been developed and made significant progress. Although to WS2Is not as good as MoS2Broad, but WS2And MoS2All have special sheet structures, which facilitate electron transfer and provide more active sites for HER process. Let WS be2The phosphating can increase the active surface area,improving electron conductivity and improving WS2A decrease in catalytic activity due to fewer exposed edge locations and poor electron/ion conductivity. By composition control, phosphated WS2The material shows excellent water decomposition catalytic performance.
In recent years, with the development of science and technology, the application of phosphorus sulfide catalysts in the fields of ion batteries, photoelectrocatalysis water decomposition and the like is more and more extensive, and WP is disclosed in the prior art2The nanospheres can significantly improve the cycle life and charge-discharge rate of the lithium-sulfur ion battery when used as the anode material, and WS is also disclosed2Growing on nanotubes as layered electrodes can significantly enhance the catalytic performance of Hydrogen Evolution Reactions (HER). Through related applicability tests of phase mixtures of two substances, it is reported that the phase mixtures can effectively accelerate the hydrogen evolution reaction under acidic conditions, and the electrochemical hydrogen evolution catalyst with low cost and high efficiency can be produced by extension. The above prior art shows phosphated WS2The nanosphere has good prospects in the aspects of energy storage, energy transfer and the like.
Through the above analysis, although there are many WS in the prior art2But there is no WS on phosphating2Nor for WS2And the relative disclosure of the excellence and the weakness of the electrochemical performance of the | P.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a phosphorized WS2A preparation method and application of the nanosphere catalyst.
In order to achieve the purpose, the invention provides the following technical scheme:
phosphating WS2The preparation method of the nanosphere catalyst comprises the following steps:
s101, dissolving a proper amount of tungsten hexacarbonyl and sulfur powder in an organic solvent in an inert atmosphere, and uniformly mixing at room temperature to obtain brown mixed liquor; fully reacting the brown mixed solution in a high-pressure reaction kettle at the temperature of between 100 and 250 ℃; preferably, the ratio of the tungsten hexacarbonyl, the sulfur powder and the organic solvent is 1:3-18:60-500 in g: g: mL.
Preferably, the brown mixed solution is fully reacted for 10 to 24 hours; preferably, the organic solvent is selected from any one of toluene, p-xylene or nitrogen-nitrogen dimethylformamide.
S102, after the high-pressure reaction kettle after the reaction is cooled to the room temperature, centrifuging the mixture in the high-pressure reaction kettle to obtain a black precipitate;
s103, purifying the black precipitate, and then reacting the black precipitate with sodium hypophosphite in a tubular furnace in an inert atmosphere at the temperature of between 200 and 300 ℃ for 2 to 3 hours to obtain WS2An | P nanosphere catalyst.
In one embodiment according to the present invention,
in S101 and S103, the inert atmosphere is formed by introducing an inert gas into the reaction vessel, wherein the inert gas is one selected from nitrogen, xenon, neon, helium, argon or krypton.
In one embodiment according to the present invention,
in S102, the centrifugal rotating speed is 12000 r/min, and the centrifugal time is 10 min.
In one embodiment according to the present invention,
in S103, the purification treatment is achieved by a method comprising the steps of:
carrying out ultrasonic treatment on the black precipitate, then washing the black precipitate for a plurality of times by water and acetone in sequence, and finally drying the black precipitate; preferably, the drying process comprises drying in a vacuum dryer or freeze drying.
In one embodiment according to the present invention,
in the step S103, the ratio of the black precipitate to the sodium hypophosphite after purification is 1: 2-10.
The invention also provides WS prepared by the preparation method2An | P nanosphere catalyst.
The invention also provides the WS2The application of the | P nanosphere catalyst in hydrogen catalysis in electrochemical decomposition of water.
The invention also provides a method for realizing the WS2An electrode prepared by the | P nanosphere catalyst.
The present invention further provides WS as defined above2An application of the | P nanosphere catalyst or electrode in the preparation of a battery.
WS provided by the present invention2The | P nanosphere catalyst material has the following beneficial effects:
in the invention, WS is added into inert gas through regulation and control2The nano-sheet cluster type WS with controllable appearance, uniform size and high specific surface area is obtained by the feeding ratio of sodium hypophosphite2The | P nanosphere catalyst is expected to play an important role in wider emerging fields, such as electrocatalysis, lithium-sulfur ion batteries and the like.
The invention relates to a method for synthesizing WS by solvothermal and chemical vapor deposition2Dissolving tungsten hexacarbonyl and sulfur powder in an organic solvent, performing solvothermal reaction, centrifugally washing and drying the obtained product to obtain a black precipitate, and reacting the purified black precipitate with sodium hypophosphite for 3 hours at 300 ℃ in a tubular furnace filled with inert gas to obtain WS (tungsten sulfide) nanosphere catalyst2An | P nanosphere catalyst. The invention has low cost and simple operation. WS can be obtained by simple 'one-pot' hydrothermal reaction and chemical vapor deposition2An | P nanosphere catalyst. It is expected to play an important role in more extensive new fields, such as electrocatalysis, ion batteries and the like.
Drawings
FIG. 1 illustrates an embodiment of WS2A flow chart of a preparation method of the | P nanosphere catalyst.
FIG. 2 shows WS prepared in example 1, provided by an embodiment of the present invention2A Transmission Electron Microscope (TEM) atlas of the | P nanosphere catalyst is shown, and a sample is in a three-dimensional (3D) nanosphere shape.
FIG. 3 shows WS in different proportions prepared in example 1 provided by the present invention2The shape of the sample is controllable according to a Scanning Electron Microscope (SEM) atlas of the | P nanosphere catalyst.
FIG. 4 is a scanning electron microscope mapping (SEM mapping) map provided in example 1 of the present invention, which shows the uniform distribution of the three elements.
FIG. 5 is a block diagram of an embodiment of the present inventionDifferent proportions of WS prepared in example 12lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared.
FIG. 6 shows WS in different ratios prepared in example 2 provided by the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared.
FIG. 7 shows WS in different proportions prepared in example 3 provided by an embodiment of the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared.
FIG. 8 shows WS in different ratios prepared in example 4 provided by the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared.
FIG. 9 shows WS in different ratios prepared in example 5 provided by an embodiment of the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared.
Detailed Description
The following detailed description of the preferred embodiments of the present invention, taken in conjunction with the accompanying drawings, will make the advantages and features of the invention more readily understood by those skilled in the art, and thus will more clearly and distinctly define the scope of the invention.
The invention provides a phosphating WS2The invention relates to a preparation method of a nanosphere catalyst and application thereof, which are described in detail in the following with reference to the accompanying drawings.
As shown in FIG. 1, WS provided by the present invention2The preparation method of the | P nanosphere catalyst comprises the following steps:
s101, dissolving tungsten hexacarbonyl and sulfur powder in an organic solvent under the protection of inert gas, and uniformly mixing at room temperature to obtain brown mixed liquor; fully reacting the brown mixed solution in a high-pressure reaction kettle at the temperature of 100-250 ℃, and fully reacting the brown mixed solution for 10-24 hours;
s102, cooling the reacted high-pressure reaction kettle to room temperature, centrifuging the mixture to obtain a black precipitate, and purifying;
s103, purifyingReacting the black precipitate with sodium hypophosphite at 200-300 deg.C in a tube furnace filled with inert gas for 2-3 hr to obtain WS2An | P nanosphere catalyst.
WS provided by the embodiment of the invention2The preparation method of the | P nanosphere catalyst specifically comprises the following steps:
in the first step, 0.1g to 0.5g of sublimed sulfur powder and 1.50 g to 1.80g of tungsten hexacarbonyl are dissolved in 30 mL to 50mL of organic solvent under the protection of nitrogen and are fully stirred.
Secondly, rapidly magnetically stirring the mixture at room temperature for 10-20 min, then transferring the mixture to a stainless steel high-pressure reaction kettle, and putting the high-pressure reaction kettle into a drying oven at 100-250 ℃ for 6-24 h; and cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, washing the black precipitate for several times by using deionized water and acetone alternately, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 1 to 4 hours to obtain a purified black precipitate.
Thirdly, the purified black precipitate reacts with sodium hypophosphite for 2 to 3 hours in a tubular furnace filled with argon at the temperature of between 200 and 300 ℃ to obtain WS2An | P nanosphere catalyst.
In a preferred embodiment of the present invention, the organic solvent is selected from any one of toluene, p-xylene or nitrogen-nitrogen dimethylformamide.
In a preferred embodiment of the present invention, wherein the magnetic stirring speed in the first step is 700-.
In the preferred embodiment of the present invention, wherein the centrifugation rotation speed is 3000-12000 r/min and the centrifugation time is 1-10min during the centrifugation collection process of the second step.
In a preferred embodiment of the present invention, in the chemical vapor deposition process of the third step, in the step S103, the ratio of the black precipitate after purification to the sodium hypophosphite is 1: 2-10; preferably 1: 5.
WS provided by the present invention2Preparation method of | P nanosphere catalyst one of ordinary skill in the art can also implement the method by adopting other steps, and the invention of fig. 1 providesSupplied WS2The preparation method of the | P nanosphere catalyst is just one specific example.
The technical solution of the present invention is further described with reference to the following specific examples.
Example 1: preparation of WS according to the invention2| P nanosphere catalyst
Firstly, dissolving 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven at 230 ℃, and keeping for 24 h; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 300 ℃ for 2h to obtain WS2An | P nanosphere catalyst.
The properties of the final product obtained were observed, as shown in particular in fig. 2, 3 and 4.
FIG. 2 shows WS prepared in example 1, provided by an embodiment of the present invention2And (3) a Transmission Electron Microscope (TEM) spectrum of the | P nanosphere catalyst, wherein the sample is in a 3D nanosphere shape.
FIG. 3 shows WS in different proportions prepared in example 1 provided by the present invention2Scanning Electron Microscope (SEM) spectrum of the | P nanosphere catalyst, as shown in FIG. 3, can be known by adjusting and controlling the added WS2The nano-sheet cluster type WS with controllable appearance, uniform size and high specific surface area is obtained by the feeding ratio of sodium hypophosphite2An | P nanosphere catalyst.
FIG. 4 is a scanning electron microscope mapping (SEM mapping) map provided in example 1 of the present invention, which shows the uniform distribution of the three elements.
Example 2: WS provided by the embodiment of the invention2The | P nanosphere catalyst comprises the following steps:
first 0.Dissolving 33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into a 230 ℃ oven, and keeping for 24 h; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 200 ℃ for 2h to obtain WS2An | P nanosphere catalyst.
Example 3: WS provided by the embodiment of the invention2The | P nanosphere catalyst comprises the following steps:
firstly, dissolving 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven at 230 ℃, and keeping for 24 h; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 300 ℃ for 3h to obtain WS2An | P nanosphere catalyst.
Example 4: WS provided by the embodiment of the invention2The | P nanosphere catalyst comprises the following steps:
firstly, dissolving 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven at 210 ℃, and keeping for 24 h; finally, after the temperature of the high-pressure reaction kettle is cooled to room temperature, the mixture is centrifugally washed to obtain black precipitate,performing ultrasonic dispersion treatment on the black precipitate, alternately washing the black precipitate by using deionized water and acetone for a plurality of times, finally performing centrifugal collection, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 300 ℃ for 2h to obtain WS2An | P nanosphere catalyst.
Example 5: WS provided by the embodiment of the invention2The | P nanosphere catalyst comprises the following steps:
firstly, dissolving 0.33g of sublimed sulfur powder and 1.76g of tungsten hexacarbonyl in 35mL of organic solvent under the protection of nitrogen, rapidly and magnetically stirring for 20min at room temperature, then transferring the mixture into a stainless steel high-pressure reaction kettle, putting the high-pressure reaction kettle into an oven at 230 ℃, and keeping for 16 h; finally, cooling the high-pressure reaction kettle to room temperature, centrifugally washing the mixture to obtain a black precipitate, ultrasonically dispersing the black precipitate, alternately washing the black precipitate for a plurality of times by using deionized water and acetone, centrifugally collecting the black precipitate, and drying the black precipitate in a vacuum freeze dryer for 2 hours to obtain a purified black precipitate; reacting the purified black precipitate with sodium hypophosphite in a tube furnace filled with argon at 300 ℃ for 2h to obtain WS2An | P nanosphere catalyst.
Example 6: performance testing
At room temperature, an electrochemical workstation with a standard three-electrode system was used at 0.5M H2SO4In which electrochemical tests of all samples were performed. Working electrode on Carbon Fiber Paper (CFP) from WS2And | P catalyst. To a mixture of 750. mu.L of deionized water and 250. mu.L of ethanol and 40. mu.L of Nafion solution (5 wt%), 5mg of sample catalyst and 5mg of carbon powder were added, followed by ultrasonic treatment for 40 minutes to obtain a uniform suspension. Then, 70. mu.L of WS2The lp catalyst was dropped onto a clean CFP chip (1 cm x 1 cm). Calibration was performed with reference to a reference and converted to a Reversible Hydrogen Electrode (RHE) by a formula.
E RHE＝E(Ag/AgCl)+0.059pH+0.197
The three-electrode system was bubbled with high purity nitrogen for 30 minutes prior to each HER test. To exploreHER activity, linear sweep voltammetry test at a rate of 5mV/s at a sweep rate of 0V to-0.5V. Electrochemical Impedance Spectroscopy (EIS) measurements were obtained over a frequency range of 0.01 to 105Hz and fitted by Zview software. 1M H2SO4An Ag/AgCl electrode in aqueous solution was used as reference electrode.
The catalysts prepared in examples 1-5 were individually tested for performance according to the methods described above, as shown in figures 5-9.
FIG. 5 shows WS in different ratios prepared in example 1 provided by the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared. By comparison, WS was found to be the same current density2The overpotential of | P-5 is the smallest, and the performance is the best.
FIG. 6 shows WS in different ratios prepared in example 2 provided by the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared. Also by comparison, WS was found to be the same at the same current density2The overpotential of | P-5 is the smallest, and the performance is the best.
FIG. 7 shows WS in different proportions prepared in example 3 provided by an embodiment of the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared. Also by comparison, WS was found to be the same at the same current density2The overpotential of | P-5 is the smallest, and the performance is the best.
FIG. 8 shows WS in different ratios prepared in example 4 provided by the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared. Also by comparison, WS was found to be the same at the same current density2The overpotential of | P-5 is the smallest, and the performance is the best.
FIG. 9 shows WS in different ratios prepared in example 5 provided by an embodiment of the present invention2lP nanosphere catalyst and unphosphorylated WS2Electrochemical performance of the catalyst is compared. Also by comparison, WS was found to be the same at the same current density2The overpotential of | P-5 is the smallest, and the performance is the best.
Thus proving that the experimental conditions are noneHow to change, WS2The performance of P-5 is excellent.
Compared with the prior art, the WS is synthesized by the hydrothermal and chemical vapor deposition of sulfur powder and tungsten hexacarbonyl in a paraxylene solvent2An | P catalyst. The results presented in the present invention may provide new opportunities for finding efficient bifunctional and low cost hydrogen evolution reaction electrocatalyst materials.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention.
Claims (10)
1. Phosphating WS2The preparation method of the nanosphere catalyst is characterized by comprising the following steps:
s101, dissolving a proper amount of tungsten hexacarbonyl and sulfur powder in an organic solvent in an inert atmosphere, and uniformly mixing at room temperature to obtain brown mixed liquor; fully reacting the brown mixed solution in a high-pressure reaction kettle at the temperature of between 100 and 250 ℃; preferably, the brown mixed solution is fully reacted for 10 to 24 hours;
s102, after the high-pressure reaction kettle after the reaction is cooled to the room temperature, centrifuging the mixture in the high-pressure reaction kettle to obtain a black precipitate;
s103, purifying the black precipitate, and then reacting the black precipitate with sodium hypophosphite in a tubular furnace in an inert atmosphere at the temperature of between 200 and 300 ℃ for 2 to 3 hours to obtain WS2An | P nanosphere catalyst.
2. The method according to claim 1, wherein the reaction mixture,
in S101 or S103, the inert atmosphere is formed by introducing an inert gas into the reaction vessel, wherein the inert gas is one selected from nitrogen, xenon, neon, helium, argon or krypton.
3. The method according to claim 1, wherein the reaction mixture,
in S102, the centrifugal rotating speed is 12000 r/min, and the centrifugal time is 10 min.
4. The method according to claim 1, wherein the reaction mixture,
in S103, the purification treatment is achieved by a method comprising the steps of:
and (3) carrying out ultrasonic treatment on the black precipitate, then washing the black precipitate for a plurality of times by using water and acetone in sequence, and finally drying the black precipitate.
5. The method according to claim 4,
the drying treatment comprises drying in a vacuum dryer or freeze-drying.
6. The method according to claim 1, wherein the reaction mixture,
in step S103, the ratio of the black precipitate to sodium hypophosphite after purification is 1: 2-10 in g/g.
7. WS prepared by a process according to any one of claims 1 to 62An | P nanosphere catalyst.
8. WS of claim 72The application of the | P nanosphere catalyst in hydrogen catalysis in electrochemical decomposition of water.
9. A WS as defined in claim 82An electrode prepared by the | P nanosphere catalyst.
10. WS of claim 72Use of an ip nanosphere catalyst or electrode according to claim 9 in the preparation of a battery.
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| CN111604073A (en) * | 2020-06-05 | 2020-09-01 | 辽宁石油化工大学 | Preparation method of sheet-structure tungsten sulfide/tungsten phosphide/carbon catalytic material |
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