CN105200450A - Molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material and preparation method therefor - Google Patents
Molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material and preparation method therefor Download PDFInfo
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- CN105200450A CN105200450A CN201510573873.6A CN201510573873A CN105200450A CN 105200450 A CN105200450 A CN 105200450A CN 201510573873 A CN201510573873 A CN 201510573873A CN 105200450 A CN105200450 A CN 105200450A
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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
Abstract
The invention relates to a molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material and a preparation method therefor and belongs to the field of electrocatalytic hydrogen evolution. According to the preparation method, firstly, a carbon black oxide with low degree of oxidation is prepared by adopting an improved Hummer method; and then, the molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material is prepared through one-step solvothermal reaction at the temperature of 220 DEG C in a manner of taking sodium molybdate crystals as a molybdenum source, taking sulfourea as a sulfur source and taking dimethylformamide as a solvent. According to the method provided by the invention, the carbon black oxide with low degree of oxidation is simple in preparation process and high in yield; the molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material is prepared by adopting a simple, convenient and mild one-step solvothermal method, the cost is low, the repeatability is high, and large-scale synthesis is facilitated. When the molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material is applied to electrocatalytic hydrogen evolution reaction, excellent catalysis performance is shown, the reduced current density reaches 25.0mA/cm<2> when tested overpotential is 200mV, and the reduced current density reaches 36.2mA/cm<2> when tested overpotential is 226mV; the molybdenum disulfide/carbon black composite hydrogen-evolution electrocatalytic material has good electrocatalytic stability.
Description
Technical field
The invention belongs to electrocatalytic hydrogen evolution field, be specifically related to a kind of molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material and preparation method thereof.
Background technology
Along with the sustainable development of economy, demand for energy is growing, causes the energy supply and demand contradiction of day by day aggravating in world wide.In China, current energy source consumption ways is still to utilize fossil oil; While non-renewable fossil energy consumes in a large number, also result in serious problem of environmental pollution.Finding novel, green, renewable energy source is the inevitable choice realizing China's energy, economy, Ecological Sustainable Development.Renewable energy source comprises sun power, wind energy, biomass energy, Hydrogen Energy etc., and wherein hydrogen is a kind of generally acknowledged ideal fuels, and its calorific value, up to 118.4kJ/g, is 3 times of oil; Meanwhile, the products of combustion of hydrogen is water, is a kind of high energy efficiency, clean energy, thus becomes the key solved the problem.
Current, people's hydrogen manufacturing mainly adopts two kinds of forms: one is (as CH with fossil oil
4) be raw material hydrogen manufacturing, this method production cost is high, while causing Fossil fuel consumption, produces the gas causing Greenhouse effect in a large number.Another kind take sun power as the hydrogen manufacturing of feed material degradation water, and this is a kind of green, continuable hydrogen manufacturing mode, is the emphasis of hydrogen preparation field exploitation, research.Utilize decomposing water with solar energy hydrogen manufacturing in specific implementation process, main employing two kinds of approach: one is solar energy electrolyzing water hydrogen manufacturing, converts solar energy into electrical energy, water electrolysis hydrogen production; Another kind is solar energy photocatalytic hydrogen production by water decomposition, converts solar energy into Hydrogen Energy and stores.The use of efficient Electrocatalytic Activity for Hydrogen Evolution Reaction material, most important to the above-mentioned decomposing water with solar energy hydrogen production efficiency of raising.Current, best with the performance such as precious metals pt, Pd in Electrocatalytic Activity for Hydrogen Evolution Reaction material, but precious metal reserves rareness on earth, expensive, cannot large-scale promotion be realized.For realizing the needs of suitability for industrialized production, development research is efficient, stable, cheap, the earth amount of containing is high and the Electrocatalytic Activity for Hydrogen Evolution Reaction material that can synthesize in enormous quantities has important theory significance and practical value.
Recent research shows, the disulphide of stratiform transition metal, has good electrocatalytic hydrogen evolution performance; Because of its rich reserves, cheap, be easy to synthesis and enjoy people to pay close attention to.Molybdenumdisulphide (MoS
2) be one of Typical Representative wherein, its Chang Zuowei lubricant and Hydrobon catalyst are applied in industrial production.MoS
2the avtive spot of electrocatalytic hydrogen evolution reaction is arranged in the edge of the exposed S-Mo-S layer of laminate structure.MoS
2electroconductibility is poor, and tends to the number that stacked in multi-layers decreases the exposed avtive spot in edge, reduces electrocatalytic hydrogen evolution performance, limits its industrial applications.Carbon black has good electroconductibility, and in its structure, carbon atom has the arrangement mode being similar to graphite, but price is far below graphite, has higher practical value.
At preparation MoS
2composite electro catalytic liberation of hydrogen material aspect, YanguangLi etc. adopt the Hummer legal system of improvement for graphene oxide with people such as XiaoliZheng, with four thio ammonium molybdate, hydrazine hydrate for raw material is at DMF (or DMF/H
2o), in solution, solvent-thermal method has prepared the molybdenumdisulphide/graphene composite material (MoS with good electrical catalytic hydrogen evolution performance
2/ RGO) (reference 1:Li.Y.G., Wang.H.L., Xie.L.M., Liang.Y.Y., Hong.G.S., Dai.H.J., MoS
2nanoparticlesGrownonGraphene:AnAdvancedCatalystfortheHyd rogenEvolutionReaction.JournaloftheAmericanChemicalSocie ty2011,133 (19), 7296-7299. reference 2:Zheng.X., Xu.J., Yan.K., Wang.H., Wang.Z., Yang.S., Space-ConfinedGrowthofMoS
2nanosheetswithinGraphite:TheLayeredHybridofMoS
2andGrapheneasanActiveCatalystforHydrogenEvolutionReactio n.ChemistryofMaterials2014.).But graphite in this process, four thio ammonium molybdate are expensive, and graphene oxide preparation process productive rate is low, the use of a large amount of hypertoxicity hydrazine hydrate simultaneously all limits its practical application.
Summary of the invention
The object of the present invention is to provide a kind of molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material and preparation method thereof, solve that compound Electrocatalytic Activity for Hydrogen Evolution Reaction material produce cost is high, graphene oxide prepares the problem that productive rate is low, preparation process is complicated, energy consumption is high.The MoS of preparation
2/ RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material has lower overpotential of hydrogen evolution and excellent electrocatalytic hydrogen evolution performance.The preparation method of a kind of molybdenumdisulphide of the present invention/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, the Hummer method oxygenated black of improvement is adopted to obtain the carbon black oxide compound (CarbonBlackOxide of low degree of oxidation first, CBO), and as conductive substrates raw material, adopt solvent thermal process to obtain molybdenumdisulphide/carbon black (MoS
2/ RCBO) compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.Adding of carbon black, at raising material conductivity, in quickening electrode process while electron transmission speed, decrease MoS in product
2the overlap of layer, substantially increases the number of the exposed avtive spot in edge, enhances the electrocatalytic hydrogen evolution performance of matrix material.The concrete steps of described preparation method are as follows:
The first step, the Hummer legal system of improvement is for the carbon black oxide compound of low degree of oxidation;
Take carbon black, be placed in there-necked flask, add the vitriol oil that mass concentration is 98%, room temperature lower magnetic force stirs 24h; There-necked flask is transferred to oil bath in oil bath pan, after constant temperature, in there-necked flask, adds anhydrous nitric acid sodium, potassium permanganate successively, magnetic agitation 30min; In there-necked flask, add high purity water, stir; There-necked flask is shifted out from oil bath pan, adds high purity water, superoxol successively, stir, be cooled to room temperature; Be transferred in centrifuge tube by the solution in there-necked flask, centrifugal treating 30min, remove supernatant liquor in centrifuge tube, be precipitated thing A, throw out A hydrochloric acid soln, high purity water each centrifugal (30min) wash twice, and are precipitated thing B; Sediment B is proceeded in dialysis bag, dialysis, be neutral to dialyzate, be precipitated thing C; Be dissolved in high purity water by throw out C, ultrasonic, centrifugal 30min, removes supernatant liquor, is precipitated thing D; Sediment D is transferred in watch-glass, is placed in drying in oven, obtain the carbon black oxide powder of low degree of oxidation, for subsequent use.
The temperature of oil bath in described oil bath pan is 50 ~ 55 DEG C, and the mass concentration of described superoxol is 30%, and the mass concentration of described hydrochloric acid soln is 5%, and described oven temperature is 60 DEG C.The speed of described centrifugal treating is 5000rpm.
Second step, a step solvent-thermal method prepares molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
The carbon black oxide compound of the low degree of oxidation the first step obtained is placed in beaker, adds dimethyl formamide (DMF) in beaker, ultrasonic; Add Sodium orthomolybdate crystal (Na
2moO
42H
2o) and thiocarbamide, continue ultrasonic, obtain mixed solution; Proceeded to by above-mentioned mixed solution in tetrafluoroethylene reactor, reactor is placed in 220 DEG C of insulation 24h in baking oven, takes out reactor, is cooled to room temperature; By the solid product centrifugal treating in reactor, use ethanol, high purity water centrifuge washing twice respectively, be precipitated thing; Be transferred to by throw out in watch-glass, 60 DEG C of oven dry, obtain molybdenumdisulphide/carbon black (MoS
2/ RCBO) compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.The speed of described centrifugal treating is 7500 ~ 12000rpm, and the time is 15 ~ 30min.
Described Na
2moO
42H
2the mol ratio of O and thiocarbamide meets 1:6, and the quality that adds of the carbon black oxide compound of described low degree of oxidation is Na
2moO
42H
210 ~ 40% of O quality.
The above-mentioned MoS prepared
2in/RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, stratiform MoS
2be grown in the substrate of carbon black nano particle, MoS
2ply number be less than 10.
The invention has the advantages that:
(1) the present invention selects carbon black to be conductive substrates raw material and MoS
2growth substrate, carries out the low degree of oxidation process of high yield to carbon black, form oxygen-containing functional group, thus be MoS at carbon blacksurface
2site is provided in the selective growth of carbon black conductive substrate; Compared with existing molybdenumdisulphide/Graphene compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, the present invention's carbon black used is cheap, and its oxidising process is easy, productive rate is high.
(2) the raw materials used Na of the present invention
2moO
42H
2o and thiocarbamide cheap, a step solvent thermal used prepares MoS
2the method of/RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is simple, efficient, be easy to extensive synthesis.
(3) by gained MoS of the present invention
2/ RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is used as electrochemistry liberation of hydrogen catalyzer, MoS
2when the test overpotential of/RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is 200mV, reduction current density reaches 25.0mA/cm
2, when test overpotential is 226mV, reduction current density reaches 36.2mA/cm
2there is good electrocatalysis characteristic.
Accompanying drawing explanation
Fig. 1 a, 1b are the SEM figure of the CBO of low degree of oxidation;
Fig. 2 is the C1sXPS figure of the CBO of low degree of oxidation;
Fig. 3 is CBO, MoS of low degree of oxidation
2nano particle, MoS
2the XRD figure of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
Fig. 4 a, 4b are MoS
2the SEM figure of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
Fig. 4 c, 4d are MoS
2the TEM figure of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
Fig. 5 is MoS
2the C1sXPS figure of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
Fig. 6 is MoS
2/ RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, MoS
2/ RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, MoS
2/ RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, MoS
2/ RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material and MoS
2(glass carbon is working electrode to the linear sweep voltammetry curve of nano particle, and catalyst loadings is 0.285mg/cm
2);
Fig. 7 is MoS
2nano particle, MoS
2(glass carbon is working electrode to the linear sweep voltammetry graphic representation of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material and commercial Pt catalyzer, and catalyst loadings is 0.428mg/cm
2);
Fig. 8 is MoS
2(hydrophilic carbon paper is working electrode to the linear sweep voltammetry graphic representation of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, and catalyst loadings is 1mg/cm
2);
Fig. 9 is MoS
2(glass-carbon electrode is working electrode to the steady testing result figure of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, and catalyst loadings is 0.428mg/cm
2).
Embodiment
Below in conjunction with drawings and Examples, the present invention is further elaborated:
The preparation method of a kind of molybdenumdisulphide provided by the invention/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, concrete steps are as follows:
The first step, the Hummer legal system of improvement is for the carbon black oxide compound of low degree of oxidation;
Take carbon black, be placed in there-necked flask, add the vitriol oil that mass concentration is 98%, room temperature lower magnetic force stirs 24h; There-necked flask is transferred to oil bath heating in oil bath pan, after constant temperature, in there-necked flask, adds anhydrous nitric acid sodium, potassium permanganate successively, magnetic agitation 30min; It is 0.1:0.3:1 that the mass ratio of described anhydrous nitric acid sodium, potassium permanganate, carbon black closes.
In there-necked flask, add high purity water (described high purity water adopts three modes added, and then regulates speed of reaction, makes sufficient reacting), stir; There-necked flask is shifted out from oil bath pan, adds high purity water, superoxol successively, stir, be cooled to room temperature; Solution in there-necked flask is transferred in centrifuge tube, centrifugal treating (centrifugal speed 5000rpm, centrifugation time 30min), remove supernatant liquor in centrifuge tube, be precipitated thing A, throw out A hydrochloric acid soln, high purity water each centrifugal (centrifugal speed 5000rpm, centrifugation time 30min) wash twice, and are precipitated thing B; Sediment B is proceeded in dialysis bag, dialysis, be neutral to dialyzate, be precipitated thing C; Be dissolved in high purity water by throw out C, ultrasonic, centrifugal (centrifugal speed 5000rpm, centrifugation time 5min), removes supernatant liquor, is precipitated thing D; Sediment D is transferred in watch-glass, is placed in drying in oven, obtain the carbon black oxide powder of low degree of oxidation, for subsequent use.
The temperature of described oil bath pan is 50 ~ 55 DEG C, and the mass concentration of described superoxol is 30%, and the mass concentration of described hydrochloric acid soln is 5%, and described oven temperature is 60 DEG C.
Second step, a step solvent-thermal method prepares molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
The carbon black oxide compound of the low degree of oxidation the first step obtained is placed in beaker, adds dimethyl formamide (DMF) in beaker, ultrasonic; Add Sodium orthomolybdate crystal (Na
2moO
42H
2o) and thiocarbamide, continue ultrasonic, obtain mixed solution; Proceeded to by above-mentioned mixed solution in tetrafluoroethylene reactor, reactor is placed in 220 DEG C of insulation 24h in baking oven, takes out reactor, is cooled to room temperature; By the solid product centrifugal treating (centrifugal speed 7500 ~ 12000rpm in reactor, centrifugation time 15 ~ 30min), use ethanol, high purity water centrifugal (centrifugal speed 7500 ~ 12000rpm, centrifugation time 15 ~ 30min) to wash twice respectively, be precipitated thing E; Be transferred in watch-glass by throw out E, 60 DEG C of oven dry, obtain molybdenumdisulphide/carbon black (MoS
2/ RCBO) compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.
Described Na
2moO
42H
2the mol ratio of O and thiocarbamide meets 1:6, and the quality that adds of the carbon black oxide compound of described low degree of oxidation is Na
2moO
42H
210 ~ 40% of O quality.
The MoS that above-mentioned preparation method obtains
2/ RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, MoS
2for layered arrangement, ply number is less than 10; RCBO is nano particle, stratiform MoS
2be grown in the substrate of carbon black nano particle.
Provide specific embodiment below.
embodiment 1:
The first step, the Hummer legal system of improvement is for the carbon black oxide compound of low degree of oxidation;
Take 1.0g carbon black in 250ml there-necked flask, add the vitriol oil that 23ml mass concentration is 98% in there-necked flask, room temperature condition lower magnetic force stirs 24h; There-necked flask is transferred to oil bath heating in the oil bath pan of 50 ~ 55 DEG C, after constant temperature, in there-necked flask, adds 100mg anhydrous nitric acid sodium; Add 300mg potassium permanganate after 5min, this process oil bath temperature controls at 50 ~ 55 DEG C, magnetic agitation 30min; In there-necked flask, add 3ml high purity water, after 5min, again add 3ml high purity water, after 5min, add 40ml high purity water, continue to stir 15min; There-necked flask is shifted out from oil bath pan, adds 140ml high purity water successively, 6ml mass concentration is the superoxol of 30%, stir 5min, be cooled to room temperature; Solution in there-necked flask is transferred in 6 50ml centrifuge tubes, centrifugal speed 5000rpm, centrifugation time 30min, remove the supernatant liquor in centrifuge tube, be precipitated thing A, throw out A washes twice with hydrochloric acid soln, high purity water centrifugal (centrifugal speed 5000rpm, centrifugation time 30min) that mass concentration is 5% successively, is precipitated thing B; Sediment B is proceeded in dialysis bag, dialysis, be neutral to dialyzate, be precipitated thing C; Taking out dialysis bag is dissolved in 100ml high purity water by throw out C, ultrasonic 30min, centrifugal treating, centrifugal speed 5000rpm, and centrifugation time 5min, removes supernatant liquor, is precipitated thing D; Sediment D be transferred in watch-glass, watch-glass is placed in 60 DEG C of drying in oven sediment D, obtains the carbon black oxide powder of low degree of oxidation.
Second step, a step solvent-thermal method prepares molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
The carbon black oxide compound taking 24.2mg low degree of oxidation is placed in 50ml beaker, adds 35mlDMF, ultrasonic 10min; Add 121mgNa
2moO
42H
2o and 228mg thiocarbamide, continues ultrasonic 20min, obtains mixed solution; Be transferred to by mixed solution in the tetrafluoroethylene reactor of 45ml, reactor is placed in the baking oven of 220 DEG C, insulation reaction 24h; Reactor is taken out, is cooled to room temperature; Solid product centrifugal treating (centrifugal speed 7500rpm, centrifugation time 15min) in reactor, washes twice through ethanol, high purity water centrifugal (centrifugal speed 7500rpm, centrifugation time 15min) respectively, is precipitated thing E; Throw out E is placed in watch-glass, and 60 DEG C of oven dry, obtain MoS
2/ RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.
Fig. 1 is the scanning electron microscope image (SEM figure) of the carbon black oxide compound (CBO) of low degree of oxidation, and can find out, the CBO of low degree of oxidation is spherical nanoparticles, and median size is 50nm.Solid line shown in Fig. 2 is the C1sX X-ray photoelectron spectroscopy X figure (XPS figure) that the present invention obtains the CBO of low degree of oxidation, combine shown in curve 1,2 and 3 and can be respectively C-C, C-O and-COOH characteristic peak in peak, show that the CBO surface of low degree of oxidation prepared by the present invention defines oxygen-containing functional group, but feature peak-to-peak is strong more weak, and without C=O characteristic peak, show that the oxidisability of gained CBO is lower.Fig. 3 is CBO, MoS of low degree of oxidation
2nano particle, MoS
2the X ray diffracting spectrum of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, in Fig. 3, curve 1 is the XRD test result of the CBO of low degree of oxidation, its diffraction peak is corresponding with below Graphite-2H (JCPDS41-1487) standard crystal face, diffraction peak-to-peak strong more weak, peak shape is wider, shows that the CBO of low degree of oxidation exists with unformed state.In Fig. 3, dotted line shown in curve 2 is MoS
2the XRD test result of nano particle, MoS
2moS shown in the diffraction peak of nano particle and lower broken line
2-2H (JCPDS37-1492) standard crystal face is corresponding, diffraction peak-to-peak strong more weak, peak shape is wider, shows MoS
2nano particle degree of crystallinity is lower, MoS
2nano particle exists with unformed shape; Without (002) diffraction peak in curve 2, show in solvent thermal process without extensive MoS
2ply phenomenon occurs.In Fig. 3, curve 3 is MoS
2the XRD test result of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, MoS
2the diffraction peak of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material corresponds respectively to MoS
2the base peak of-2H, Graphite-2H, peak by force more weak, peak shape is wider, shows MoS
2/ RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material exists with unformed shape.
Fig. 4 a, 4b are MoS prepared by embodiment 1
2the SEM image of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, can find out stratiform MoS
2nanoparticle growth is in the substrate of carbon black nano particle; MoS
2the TEM image of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, as shown in Fig. 4 c, 4d, clearly show MoS more
2/ RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material laminate MoS
2dispersion is grown in graphitized carbon black substrate, MoS
2ply number be less than 10.Solid line in Fig. 5 is MoS prepared by embodiment 1
2the C1sXPS spectrum of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, curve 1,2 is respectively C-C, C-O characteristic peak, can find out, MoS compared with accompanying drawing 2
2in the C1sXPS spectrum of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, carbon and oxygen functional group feature peak number reduces, and peak weakens by force, shows that CBO is reduced to RCBO through solvent thermal process.
Adopt three-electrode system to MoS
2the electrocatalytic hydrogen evolution performance of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is tested, and is to electrode with Pt sheet, and saturated calomel electrode (SCE) is reference electrode, and working electrode drips for surface and scribbles MoS
2the glass-carbon electrode of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material or hydrophilic carbon paper electrode; Testing tool is Shanghai occasion China CHI750C type electrochemical workstation; Test soln is the H of 0.5mol/L
2sO
4solution.
Adopt drop-coating preparation work electrode, concrete technology is as follows: take 4mgMoS
2/ RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is placed in beaker, adds the Nafion solution that 1ml Virahol and 80 μ l massfractions are 5%, ultrasonic for said mixture more than 30min is formed catalyst solution.During with glass carbon for electrode, the glassy carbon electrode surface being 5mm to the diameter polished smooth drips painting 14 μ l and the above-mentioned catalyst solution of 21 μ l respectively, and (charge capacity is respectively: 0.285mg/cm to form the different working electrode of charge capacity
2, 0.428mg/cm
2), laggard line linearity scanning volt-ampere test (LSV) of glassy carbon electrode surface finish-drying.During with hydrophilic carbon paper for electrode, be 1cm to area
2hydrophilic carbon paper electrode surface drip the above-mentioned catalyst solution of painting 250 μ l (charge capacity: 1mg/cm
2), carry out linear sweep voltammetry test (LSV) of ir compensation after finish-drying.
Test parameter: LSV sweeps fast 2mV/s when testing; In stability test process, the potential range of cyclic voltammetry (CV) is 0 ~ 0.5V (vs.SCE), and the circulation number of turns is 1000 circles.
Figure 6 shows that MoS
2/ RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material and MoS
2the LSV test curve of nano particle, in Fig. 6, curve 1 is MoS
2the LSV test result of nano particle, MoS
2a peak overpotential for the electrocatalytic hydrogen evolution reaction of nano particle is 160mV; When test overpotential is 200mV, reduction current density reaches 2.9mA/cm
2, when test overpotential is 226mV, reduction current density reaches 4.3mA/cm
2.Curve 5 is corresponding to MoS under same test condition
2the LSV test result of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, MoS
2a peak overpotential for the electrocatalytic hydrogen evolution reaction of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is 110mV; When test overpotential is 200mV, reduction current density reaches 18.6mA/cm
2, when test overpotential is 226mV, reduction current density reaches 28.7mA/cm
2.As can be seen here, with MoS
2nano particle is compared, MoS
2the peak overpotential that rises of the electrocatalytic hydrogen evolution reaction of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material significantly reduces, and under same test overpotential, reduction current density value obviously increases, and shows good electrocatalysis characteristic.
Increase glassy carbon electrode surface MoS
2the charge capacity of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is to 0.428mg/cm
2, test the performance of its electrocatalytic hydrogen evolution, and with MoS under identical load amount
2the catalytic performance of nano particle, Pt/ carbon black compares, and result as shown in Figure 7.Curve 2 shows MoS
2a peak overpotential for the electrocatalytic hydrogen evolution of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is 100mV, and when test overpotential is 200mV, reduction current density reaches 25.0mA/cm
2, when test overpotential is 226mV, reduction current density reaches 36.2mA/cm
2.As can be seen here, charge capacity is increased, MoS
2the peak overpotential that rises of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material reduces, and under same test overpotential, reduction current density value increases, and shows higher catalytic activity.The peak overpotential that rises that curve 1 shows Pt/ carbon black electrocatalytic hydrogen evolution is about 0V, and when test overpotential is 74mV, reduction current density value reaches 36.8mA/cm
2, Pt/ carbon black has best electrocatalytic hydrogen evolution performance.Curve 3 shows MoS
2a peak overpotential for nano particle electrocatalytic hydrogen evolution is 180mV, and when test overpotential is 200mV, reduction current density reaches 1.1mA/cm
2, when test overpotential is 226mV, reduction current density reaches 1.6mA/cm
2.As can be seen here, gained MoS of the present invention
2/ RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material has excellent electrocatalytic hydrogen evolution performance, and the compound Electrocatalytic Activity for Hydrogen Evolution Reaction agent that can be used as a kind of alternative Pt/ carbon black uses.
When working electrode is hydrophilic carbon paper, MoS
2the electrocatalytic hydrogen evolution the performance test results of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material as shown in Figure 8, MoS
2a peak overpotential for the electrocatalytic hydrogen evolution reaction of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is 100mV, and when test overpotential is 200mV, reduction current density reaches 38.9mA/cm
2, when test overpotential is 226mV, reduction current density reaches 80.6mA/cm
2, visible, MoS
2/ RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material has excellent electrocatalytic hydrogen evolution performance at hydrophilic carbon paper surface.
As shown in Figure 9, curve 1,2 represents MoS before and after CV circulation to stability test result respectively
2the LSV result of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, result shows, before and after CV loop test, MoS
2a peak overpotential of the electrocatalytic hydrogen evolution reaction of/RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is identical, and when test overpotential is 200mV, the reduction current density before and after CV circulation is respectively 25.0mA/cm
2, 22.6mA/cm
2, when test overpotential is 226mV, reduction current density is respectively 36.2mA/cm
2, 35.1mA/cm
2, after 1000 circle CV circulations, MoS
2the electrocatalysis characteristic of/RCBO-20% slightly declines, as can be seen here, and MoS
2/ RCBO-20% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material has good electrocatalytic hydrogen evolution stability.
embodiment 2:
The first step, the Hummer legal system of improvement is for the carbon black oxide compound of low degree of oxidation;
Take 1.0g carbon black in 250ml there-necked flask, add the vitriol oil that 23ml mass concentration is 98% in there-necked flask, room temperature condition lower magnetic force stirs 24h; There-necked flask is transferred to oil bath heating in the oil bath pan of 50 ~ 55 DEG C, after constant temperature, in there-necked flask, adds 100mg anhydrous nitric acid sodium; Add 300mg potassium permanganate after 5min, this process oil bath temperature controls at 50 ~ 55 DEG C, magnetic agitation 30min; In there-necked flask, add 3ml high purity water, after 5min, again add 3ml high purity water, after 5min, add 40ml high purity water, continue to stir 15min; There-necked flask is shifted out from oil bath pan, adds 140ml high purity water successively, 6ml mass concentration is the superoxol of 30%, stir 5min, be cooled to room temperature; Solution in there-necked flask is transferred to centrifugal treating in 6 50ml centrifuge tubes, centrifugal speed 5000rpm, centrifugation time 30min, remove the supernatant liquor in centrifuge tube, be precipitated thing A, throw out A washes twice with hydrochloric acid soln, high purity water centrifugal (centrifugal speed 5000rpm, centrifugation time 30min) that mass concentration is 5% successively, is precipitated thing B; Sediment B is proceeded in dialysis bag, dialysis, be neutral to dialyzate, be precipitated thing C; Taking out dialysis bag is dissolved in 100ml high purity water by throw out C, ultrasonic 30min, centrifugal treating, centrifugal speed 5000rpm, and centrifugation time 5min, removes supernatant liquor, is precipitated thing D; Sediment D be transferred in watch-glass, watch-glass is placed in 60 DEG C of drying in oven, obtains the carbon black oxide powder of low degree of oxidation.
Second step, a step solvent-thermal method prepares molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
The carbon black oxide compound taking 12.1mg low degree of oxidation is placed in 50ml beaker, adds 35mlDMF, ultrasonic 10min; Add 121mgNa
2moO
42H
2o and 228mg thiocarbamide, continues ultrasonic 20min, obtains mixed solution; Be transferred to by mixed solution in the tetrafluoroethylene reactor of 45ml, reactor is placed in the baking oven of 220 DEG C, insulation reaction 24h; Reactor is taken out, is cooled to room temperature; Solid product centrifugal treating (centrifugal speed 12000rpm, centrifugation time 30min) in reactor, washes twice through ethanol, high purity water centrifugal (centrifugal speed 12000rpm, centrifugation time 30min) respectively, is precipitated thing E; Throw out E is placed in watch-glass, and 60 DEG C of oven dry, obtain MoS
2/ RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.
MoS prepared by embodiment 2
2/ RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material laminate MoS
2dispersion is grown in graphitized carbon black substrate, MoS
2ply number be less than 10.
Adopt three-electrode system to MoS
2the electrocatalytic hydrogen evolution performance of/RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is tested, and is to electrode with Pt sheet, and saturated calomel electrode (SCE) is reference electrode, and working electrode drips for surface and scribbles MoS
2the glass-carbon electrode of/RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material or hydrophilic carbon paper electrode; Testing tool is Shanghai occasion China CHI750C type electrochemical workstation; Test soln is the H of 0.5mol/L
2sO
4solution.
Adopt drop-coating preparation work electrode, concrete technology is as follows: take 4mgMoS
2/ RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is placed in beaker, adds the Nafion solution that 1ml Virahol and 80 μ l massfractions are 5%, ultrasonic for said mixture more than 30min is formed catalyst solution.During with glass carbon for electrode, (charge capacity is: 0.285mg/cm to drip the above-mentioned catalyst solution of painting 14 μ l respectively to the diameter the polished smooth glassy carbon electrode surface that is 5mm
2), laggard line linearity scanning volt-ampere test (LSV) of glassy carbon electrode surface finish-drying.
Test parameter: LSV sweeps fast 2mV/s when testing.
MoS
2the electrocatalytic hydrogen evolution the performance test results of/RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material as shown in curve in Fig. 62, MoS
2a peak overpotential for the electrocatalytic hydrogen evolution reaction of/RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is 130mV; When test overpotential is 200mV, reduction current density reaches 12.1mA/cm
2, when test overpotential is 226mV, reduction current density reaches 20.8mA/cm
2.Visible, with MoS
2nano particle is compared, MoS
2the electrocatalysis characteristic of/RCBO-10% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material significantly improves.
embodiment 3:
The first step, the Hummer legal system of improvement is for the carbon black oxide compound of low degree of oxidation;
Take 1.0g carbon black in 250ml there-necked flask, add the vitriol oil that 23ml mass concentration is 98% in there-necked flask, room temperature condition lower magnetic force stirs 24h; There-necked flask is transferred to oil bath heating in the oil bath pan of 50 ~ 55 DEG C, after constant temperature, in there-necked flask, adds 100mg anhydrous nitric acid sodium; Add 300mg potassium permanganate after 5min, this process oil bath temperature controls at 50 ~ 55 DEG C, magnetic agitation 30min; In there-necked flask, add 3ml high purity water, after 5min, again add 3ml high purity water, after 5min, add 40ml high purity water, continue to stir 15min; There-necked flask is shifted out from oil bath pan, adds 140ml high purity water successively, 6ml mass concentration is the superoxol of 30%, stir 5min, be cooled to room temperature; Solution in there-necked flask is transferred in 6 50ml centrifuge tubes, centrifugal speed 5000rpm, centrifugation time 30min, remove the supernatant liquor in centrifuge tube, be precipitated thing A, throw out A washes twice with hydrochloric acid soln, high purity water centrifugal (centrifugal speed 5000rpm, centrifugation time 30min) that mass concentration is 5% successively, is precipitated thing B; Sediment B is proceeded in dialysis bag, dialysis, be neutral to dialyzate, be precipitated thing C; Taking out dialysis bag is dissolved in 100ml high purity water by throw out C, ultrasonic 30min, centrifugal treating, centrifugal speed 5000rpm, and centrifugation time 5min, removes supernatant liquor, is precipitated thing D; Sediment D be transferred in watch-glass, watch-glass is placed in 60 DEG C of drying in oven, obtains the carbon black oxide powder of low degree of oxidation.
Second step, a step solvent-thermal method prepares molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
The carbon black oxide compound taking 36.3mg low degree of oxidation is placed in 50ml beaker, adds 35mlDMF, ultrasonic 10min; Add 121mgNa
2moO
42H
2o and 228mg thiocarbamide, continues ultrasonic 20min, obtains mixed solution; Be transferred to by mixed solution in the tetrafluoroethylene reactor of 45ml, reactor is placed in the baking oven of 220 DEG C, insulation reaction 24h; Reactor is taken out, is cooled to room temperature; Solid product centrifugal treating (centrifugal speed 7500rpm, centrifugation time 15min) in reactor, washes twice through ethanol, high purity water centrifugal (centrifugal speed 7500rpm, centrifugation time 15min) respectively, is precipitated thing E; Throw out E is placed in watch-glass, and 60 DEG C of oven dry, obtain MoS
2/ RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.
MoS prepared by embodiment 3
2/ RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material laminate MoS
2dispersion is grown in graphitized carbon black substrate, MoS
2ply number be less than 10.
Adopt three-electrode system to MoS
2the electrocatalytic hydrogen evolution performance of/RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is tested, and is to electrode with Pt sheet, and saturated calomel electrode (SCE) is reference electrode, and working electrode drips for surface and scribbles MoS
2the glass-carbon electrode of/RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material or hydrophilic carbon paper electrode; Testing tool is Shanghai occasion China CHI750C type electrochemical workstation; Test soln is the H of 0.5mol/L
2sO
4solution.
Adopt drop-coating preparation work electrode, concrete technology is as follows: take 4mgMoS
2/ RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is placed in beaker, adds the Nafion solution that 1ml Virahol and 80 μ l massfractions are 5%, ultrasonic for said mixture more than 30min is formed catalyst solution.During with glass carbon for electrode, (charge capacity is: 0.285mg/cm to drip the above-mentioned catalyst solution of painting 14 μ l respectively to the diameter the polished smooth glassy carbon electrode surface that is 5mm
2), laggard line linearity scanning volt-ampere test (LSV) of glassy carbon electrode surface finish-drying.
Test parameter: LSV sweeps fast 2mV/s when testing.
MoS
2the electrocatalytic hydrogen evolution the performance test results of/RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material as shown in curve in Fig. 64, MoS
2a peak overpotential for the electrocatalytic hydrogen evolution reaction of/RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is 120mV; When test overpotential is 200mV, reduction current density reaches 15.1mA/cm
2, when test overpotential is 226mV, reduction current density reaches 26.1mA/cm
2.Visible, with MoS
2nano particle is compared, MoS
2the electrocatalysis characteristic of/RCBO-30% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material significantly improves.
embodiment 4:
The first step, the Hummer legal system of improvement is for the carbon black oxide compound of low degree of oxidation;
Take 1.0g carbon black in 250ml there-necked flask, add the vitriol oil that 23ml mass concentration is 98% in there-necked flask, room temperature condition lower magnetic force stirs 24h; There-necked flask is transferred to oil bath heating in the oil bath pan of 50 ~ 55 DEG C, after constant temperature, in there-necked flask, adds 100mg anhydrous nitric acid sodium; Add 300mg potassium permanganate after 5min, this process oil bath temperature controls at 50 ~ 55 DEG C, magnetic agitation 30min; In there-necked flask, add 3ml high purity water, after 5min, again add 3ml high purity water, after 5min, add 40ml high purity water, continue to stir 15min; There-necked flask is shifted out from oil bath pan, adds 140ml high purity water successively, 6ml mass concentration is the superoxol of 30%, stir 5min, be cooled to room temperature; Solution in there-necked flask is transferred in 6 50ml centrifuge tubes, centrifugal speed 5000rpm, centrifugation time 30min, remove the supernatant liquor in centrifuge tube, be precipitated thing A, throw out A washes twice with hydrochloric acid soln, high purity water centrifugal (centrifugal speed 5000rpm, centrifugation time 30min) that mass concentration is 5% successively, is precipitated thing B; Sediment B is proceeded in dialysis bag, dialysis, be neutral to dialyzate, be precipitated thing C; Taking out dialysis bag is dissolved in 100ml high purity water by throw out C, ultrasonic 30min, centrifugal treating, centrifugal speed 5000rpm, and centrifugation time 5min, removes supernatant liquor, is precipitated thing D; Sediment D be transferred in watch-glass, watch-glass is placed in 60 DEG C of drying in oven, obtains the carbon black oxide powder of low degree of oxidation.
Second step, a step solvent-thermal method prepares molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
The carbon black oxide compound taking 48.4mg low degree of oxidation is placed in 50ml beaker, adds 35mlDMF, ultrasonic 10min; Add 121mgNa
2moO
42H
2o and 228mg thiocarbamide, continues ultrasonic 20min, obtains mixed solution; Be transferred to by mixed solution in the tetrafluoroethylene reactor of 45ml, reactor is placed in the baking oven of 220 DEG C, insulation reaction 24h; Reactor is taken out, is cooled to room temperature; Solid product centrifugal treating (centrifugal speed 12000rpm, centrifugation time 20min) in reactor, washes twice through ethanol, high purity water centrifugal (centrifugal speed 12000rpm, centrifugation time 20min) respectively, is precipitated thing E; Throw out E is placed in watch-glass, and 60 DEG C of oven dry, obtain MoS
2/ RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material.
MoS prepared by embodiment 4
2/ RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material laminate MoS
2dispersion is grown in graphitized carbon black substrate, MoS
2ply number be less than 10.
Adopt three-electrode system to MoS
2the electrocatalytic hydrogen evolution performance of/RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is tested, and is to electrode with Pt sheet, and saturated calomel electrode (SCE) is reference electrode, and working electrode drips for surface and scribbles MoS
2the glass-carbon electrode of/RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material or hydrophilic carbon paper electrode; Testing tool is Shanghai occasion China CHI750C type electrochemical workstation; Test soln is the H of 0.5mol/L
2sO
4.
Adopt drop-coating preparation work electrode, concrete technology is as follows: take 4mgMoS
2/ RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is placed in beaker, adds the Nafion solution that 1ml Virahol and 80 μ l massfractions are 5%, ultrasonic for said mixture more than 30min is formed catalyst solution.During with glass carbon for electrode, (charge capacity is: 0.285mg/cm to drip the above-mentioned catalyst solution of painting 14 μ l respectively to the diameter the polished smooth glassy carbon electrode surface that is 5mm
2), laggard line linearity scanning volt-ampere test (LSV) of glassy carbon electrode surface finish-drying.
Test parameter: LSV sweeps fast 2mV/s when testing.
MoS
2the electrocatalytic hydrogen evolution the performance test results of/RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material as shown in curve in Fig. 63, MoS
2a peak overpotential for the electrocatalytic hydrogen evolution reaction of/RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is 125mV; When test overpotential is 200mV, reduction current density reaches 13.5mA/cm
2, when test overpotential is 226mV, reduction current density reaches 23.6mA/cm
2.Visible, with MoS
2nano particle is compared, MoS
2the electrocatalysis characteristic of/RCBO-40% compound Electrocatalytic Activity for Hydrogen Evolution Reaction material significantly improves.
The MoS prepared in above-described embodiment
2/ RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, adopts glassy carbon electrode surface, when test overpotential is 200 ~ 226mV, and reduction current density 12.1 ~ 36.2mA/cm
2, and along with the increase of charge capacity, the peak overpotential that rises of electrocatalysis material reduces, and reduction current density increases, and shows higher catalytic activity.Described MoS
2in/RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, stratiform MoS
2nanoparticle growth in the substrate of carbon black nano particle, MoS
2ply number be less than 10.
Claims (7)
1. a preparation method for molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is characterized in that, include the following step,
The first step, adopts the carbon black oxide compound of Hummer legal system for low degree of oxidation of improvement;
Take carbon black, be placed in there-necked flask, add the vitriol oil, room temperature lower magnetic force stirs 24h; There-necked flask is transferred to oil bath heating in oil bath pan, after constant temperature, in there-necked flask, adds anhydrous nitric acid sodium, potassium permanganate successively, magnetic agitation 30min; In there-necked flask, add high purity water, stir; There-necked flask is shifted out from oil bath pan, adds high purity water, superoxol successively, stir, be cooled to room temperature; Be transferred in centrifuge tube by the solution in there-necked flask, centrifugal treating 30min, remove supernatant liquor in centrifuge tube, be precipitated thing A, each centrifuge washing twice of throw out A hydrochloric acid soln, high purity water, wherein centrifugation time is 30min, is precipitated thing B; Sediment B is proceeded in dialysis bag, dialysis, be neutral to dialyzate, be precipitated thing C; Be dissolved in high purity water by throw out C, ultrasonic, centrifugal treating 5min, removes supernatant liquor, is precipitated thing D; Sediment D is transferred in watch-glass, is placed in drying in oven, obtain the carbon black oxide powder of low degree of oxidation;
The mass concentration of the described vitriol oil is 98%, and the temperature of oil bath in described oil bath pan is 50 ~ 55 DEG C, and described oven temperature is 60 DEG C; The centrifugal speed of described centrifugal treating is 5000rpm;
Second step, a step solvent-thermal method prepares molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is specially:
The carbon black oxide compound of the low degree of oxidation of preparation in claim 1 is placed in beaker, in beaker, adds dimethyl formamide DMF, ultrasonic; Add Sodium orthomolybdate crystal Na
2moO
42H
2o and compound, continue ultrasonic, obtain mixed solution; Proceeded to by mixed solution in tetrafluoroethylene reactor, reactor is placed in baking oven inside holding; Take out reactor, be cooled to room temperature; By the solid product centrifugal treating in reactor, wash twice by ethanol, high purity water centrifugal treating respectively; By the solid transfer in reactor in watch-glass, 60 DEG C of oven dry, obtain molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material;
The temperature of described baking oven inside holding is 220 DEG C, and the time of insulation is 24h.
2. the preparation method of a kind of molybdenumdisulphide according to claim 1/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is characterized in that: the mass ratio between anhydrous nitric acid sodium, potassium permanganate, carbon black three meets 0.1:0.3:1.
3. the preparation method of a kind of molybdenumdisulphide according to claim 1/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is characterized in that: the centrifugal speed 7500 ~ 12000rpm of centrifugal treating, centrifugation time 15 ~ 30min in second step.
4. the preparation method of a kind of molybdenumdisulphide according to claim 1/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is characterized in that: described Na
2moO
42H
2the mol ratio of O and thiocarbamide meets 1:6; The mass concentration of described hydrogen peroxide is 30%, and the mass concentration of described hydrochloric acid soln is 5%.
5. the preparation method of a kind of molybdenumdisulphide according to claim 1/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is characterized in that: the quality of the carbon black oxide compound of low degree of oxidation described in second step is Na
2moO
42H
210 ~ 40% of O quality.
6. molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is characterized in that: described molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material laminate MoS
2dispersion is grown in graphitized carbon black substrate, MoS
2ply number be less than 10.
7. an application for molybdenumdisulphide/carbon black compound Electrocatalytic Activity for Hydrogen Evolution Reaction material, is characterized in that: take 4mgMoS
2/ RCBO compound Electrocatalytic Activity for Hydrogen Evolution Reaction material is placed in beaker, adds the Nafion solution that 1ml Virahol and 80 μ l massfractions are 5%, ultrasonic for said mixture more than 30min is formed catalyst solution; Described catalyst solution is dripped and is coated in glass carbon or hydrophilic carbon paper surface, form the working electrode that charge capacity is different.
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