CN108411322A - A kind of preparation method of the cobalt sulfide with molybdenum disulfide In-situ reaction electrode and its application on water electrolysis hydrogen producing - Google Patents
A kind of preparation method of the cobalt sulfide with molybdenum disulfide In-situ reaction electrode and its application on water electrolysis hydrogen producing Download PDFInfo
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- CN108411322A CN108411322A CN201810196366.9A CN201810196366A CN108411322A CN 108411322 A CN108411322 A CN 108411322A CN 201810196366 A CN201810196366 A CN 201810196366A CN 108411322 A CN108411322 A CN 108411322A
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- molybdenum disulfide
- cobalt sulfide
- molybdenum
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 56
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 41
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 21
- 239000001257 hydrogen Substances 0.000 title claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims description 7
- 238000005868 electrolysis reaction Methods 0.000 title claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 34
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000758 substrate Substances 0.000 claims abstract description 24
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims abstract description 19
- 235000019441 ethanol Nutrition 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 239000005864 Sulphur Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 20
- 229910052750 molybdenum Inorganic materials 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 12
- 238000005660 chlorination reaction Methods 0.000 claims description 10
- 238000004073 vulcanization Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims 2
- 230000001681 protective effect Effects 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000010574 gas phase reaction Methods 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 14
- IXOYCBDPOUBCAL-UHFFFAOYSA-J C(C)O.[Mo](Cl)(Cl)(Cl)Cl Chemical compound C(C)O.[Mo](Cl)(Cl)(Cl)Cl IXOYCBDPOUBCAL-UHFFFAOYSA-J 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 239000010410 layer Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910052961 molybdenite Inorganic materials 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 239000002134 carbon nanofiber Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003775 Density Functional Theory Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical group [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- -1 cobalt sulfide compound Chemical class 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention provides a kind of preparation method of cobalt sulfide and molybdenum disulfide In-situ reaction electrode, and under the conditions of being specifically stirred at room temperature, molybdenum chloride is dissolved in ethyl alcohol, obtains precursor solution；Above-mentioned precursor solution, which is applied to growth, to be had in the substrate of cobaltosic oxide array, it is dry after in Ar+S atmosphere or N2In+S atmosphere, vulcanize through one step of high temperature, furnace cooling taking-up can be obtained molybdenum disulfide/molybdenum disulfide composite in-situ electrode.Technical scheme of the present invention utilizes cobaltosic oxide under high temperature to generate nanometer cobalt sulfide with reaction of Salmon-Saxl, while leaving nano pore, the molybdenum disulfide that molybdenum chloride and sulfur chemistry gas phase reaction generate is deposited on around nanometer cobalt sulfide, formed the cobalt sulfide that contact is close, contact area is big cooperateed with having for molybdenum disulfide, the heterogeneous interface of high catalytic effect.
Description
Technical field
The present invention relates to In-situ reaction electrodes and its one-step method to prepare, and belongs to energy stores and conversion new material and device
Field.
Background technology
Molybdenum disulfide is a kind of two-dimensional layer transient metal sulfide of novel similar graphite, and layer is interior by S-Mo-S tri-
A atomic layer is to be covalently keyed, and S-Mo-S interlayers with Van der Waals, close by your bond.Because of its special photoelectricity, physicochemical characteristics,
Molybdenum disulfide can apply to numerous areas, such as hydrodesulfurization, dye-sensitized solar cells to electrode, water electrolysis hydrogen production, biography
Sensor, field-effect transistor, lithium ion electronics and ultracapacitor etc..Research shows that molybdenum disulfide is a kind of efficient and stablizes
Catalyst, Density function theory indicate that the layer edge of molybdenum disulfide has excellent hydrogen is clear to go out to react in an acidic solution
(hydrogen evolution reaction, HER) performance.However, HER of the molybdenum disulfide in alkalinity and neutral aqueous solution
Catalytic performance is poor, generally requires the overpotential of 100mV and the current density on production hydrogen electrode could be made to be more than 10mA/cm2。
In view of the above problems, Density function theory, which indicates, utilizes the molybdenum disulfide for having stronger characterization of adsorption to Hydrogen Proton
With the heterogeneous interface energy concerted catalysis alkalinity and neutral solution being made of the other materials of stronger characterization of adsorption to hydroxyl and water
In HER.Mingliang Du et al. are prepared for Co9S8@MoS2The composite material of/carbon fiber (CNFs) is compound compared with not
Co9S8/ CNFs and MoS2The HER performances of/CNFs in alkaline aqueous solution be all greatly improved (Adv.Mater.2015,27,
4752.).However, when production hydrogen electrode by current density be 10mA/cm2When, it is still necessary to the overpotential of 190mV.Ke Fan
Et al. be prepared for NiS2With MoS2(ACS is all greatly improved in the nanometer rods of composition, the purer HER performances of this composite material
Catal., 2017,7,6179.), when production hydrogen electrode by current density be 10mA/cm2When, in alkali, acid, neutral aqueous solution
The middle overpotential for needing 204,235,284mV successively respectively.Although there is the material width PH application prospects, performance to still need into one
Step improves, and the sample is that powder needs later stage film-forming process, technique to be relatively prepared in situ complicated.It is prepared by ShiheYang et al.
The compound of MoS2 and the double hydroxides of stratiform, the purer molybdenum disulfide of this compound, the HER performances in alkaline aqueous solution
It greatlys improve (Joule, 2017,1,383.).When production hydrogen electrode by current density be 10mA/cm2When, it is only necessary to 78mV
Overpotential.However, it needs two step microwave hydrothermals to prepare, technique is still more complex.
Invention content
In view of this, the object of the present invention is to provide it is a kind of prepare molybdenum disulfide and other sulfide compounds it is simple,
An in situ, step chemical vapor deposition method, with equipment requirement, low, required low raw-material cost, reaction condition are easy to this method
The advantages that control, is formed by good product consistency at simple production process, and environmental pollution is small gives birth to the batch of electrode in situ
Production is of great importance.
For this purpose, the present invention provides one kind using cobaltosic oxide original position array as template, the sulphur in the steam of salt containing Mo and S
Change the method that one step of reaction generates cobalt sulfide and molybdenum disulfide In-situ reaction electrode, includes the following steps：
Molybdenum chloride under the conditions of being stirred at room temperature, is dissolved in ethyl alcohol, a concentration of 100~900 mM of molybdenum chloride by the first step.It should
The meaning of step is：Almost without hydrone in precursor liquid, prevent molybdenum chloride from hydrolyzing, reaction reagent is evenly dispersed, obtains uniform
Mo salting liquids without precipitation, this is to prepare the molybdenum disulfide that uniform vertical is grown to lay good basis.
Second step, by above-mentioned forerunner's drop-coated or be spun to growth have in the substrate of cobaltosic oxide array, or will growth
It is taken out after thering is the substrate of cobaltosic oxide array to be immersed in precursor liquid, substrate such as graphite paper, carbon paper, carbon cloth, copper or nickel foil, Yu Gan
Dry air drying, or in 70~100 DEG C of rapid draing in thermal station, the meaning of the step is：The easy volatile solvents such as ethyl alcohol are fast
The molybdenum chloride forerunner's film layer being left attached to after speed volatilization on cobaltosic oxide array, and forerunner's film thickness is uniform, after guarantee
Uniform molybdenum disulfide and cobalt sulfide compound are still obtained after continuous vulcanization reaction.
Third step, the sample that obtains step 2 are in Ar+S atmosphere or N2In+S atmosphere, it is sintered through 400~800 DEG C
The In-situ reaction electrode that can be obtained cobalt sulfide and molybdenum disulfide is taken out in 10min~4h, furnace cooling.The meaning of the step exists
In：Nanometer cobalt sulfide is generated using cobaltosic oxide under high temperature and reaction of Salmon-Saxl, while leaving nano pore, molybdenum chloride and vulcanization
It learns the molybdenum disulfide that gas phase reaction generates to be deposited on around nanometer cobalt sulfide, forms the vulcanization that contact is close, contact area is big
Cobalt cooperates with having for molybdenum disulfide, the heterogeneous interface of high catalytic effect.
The preparation principle of cobalt sulfide and molybdenum disulfide In-situ reaction electrode is exactly：1. easily being waved using Mo salt precursor liquid solvents
Hair, easy homogeneous film formation；2. utilizing 400~800 DEG C of high temperature, cobaltosic oxide is allowed to generate nanometer cobalt sulfide with sulphur reaction in-situ
Meanwhile molybdenum chloride and sulphur gas phase reaction generate molybdenum disulfide in nanometer cobalt sulfide duct, form cobalt sulfide and molybdenum disulfide
In-situ reaction electrode.Chemical equation is as follows：
2Co3O4+6MoCl5+24S→6CoS2+6MoS2+4O2↑+15Cl2↑
Description of the drawings
Fig. 1 Co3O4(a) SEM and (b) XRD diagram of array.
(a) SEM of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Fig. 2 embodiments 1 and (b) XRD diagram.
Linear volt-ampere of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Fig. 3 embodiments 1 in 1M KOH
Scanning figure.
(a) SEM of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Fig. 4 embodiments 2 schemes and in (b) 1M
Linear voltammetric scan figure in KOH.
The In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Fig. 5 embodiments 3 in (a) 0.5M H2SO4In
Linear voltammetric scan performance, (b) in 1M PBS solutions (PH=7.17) linear voltammetric scan performance.
Linear volt-ampere of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Fig. 6 embodiments 3 in 1M KOH
Scanning figure.
(a) SEM of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Fig. 7 embodiments 4 schemes and in (b) 1M
Linear voltammetric scan figure in KOH.
Linear volt-ampere of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Fig. 8 embodiments 5 in 1M KOH
Scanning figure.
Linear volt-ampere of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Fig. 9 embodiments 6 in 1M KOH
Scanning figure.
Linear volt-ampere of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Figure 10 embodiments 7 in 1M KOH
Scan performance.
The In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Figure 11 embodiments 8 is in 1M KOH (a) and 0.5M
H2SO4(b) the linear voltammetric scan figure in.
Linear volt-ampere in the 1M KOH of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide prepared by Figure 12 embodiments 9
Scanning figure.
Specific implementation mode
Embodiment 1：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 450mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 80 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 2SCCM, and tube furnace top is placed with 0.5g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar
Lower 600 DEG C of+S atmosphere reacts 30min, is taken out after natural cooling.Fig. 1 makes a living with Co3O4(a) SEM of the carbon paper of array and
(b) XRD diagram, Co3O4The method (ACS nano, 2012,6,7016.) using Kuo-Chuan Ho et al. reports of array, tool
Body is by 10.6667g urea, 5.7108g CoCl2·6H2O is dissolved in 160mL water, by 4 carbon paper (2.5 × 5cm2) to be put into this molten
In liquid, 90 DEG C of heat preservation 2h, taking-up is placed in thermal station after being rinsed with deionized water and dries.Fig. 2 is the cobalt sulfide prepared by embodiment 1
With (a) SEM of the In-situ reaction electrode of molybdenum disulfide and (b) XRD diagram, the ingredient of the original position electrode is cobalt disulfide as seen from the figure
With molybdenum disulfide, remaining peak is from carbon substrate and is attached to the excessive sulphur powder of electrode surface.Fig. 3 is prepared by embodiment 1
Linear voltammetric scan performance of the In-situ reaction electrode of cobalt sulfide and molybdenum disulfide in 1M KOH.As seen from the figure when production hydrogen electrode
By current density be 10mA/cm2When, it is only necessary to the overpotential of 112mV；When production hydrogen electrode by current density be
200mA/cm2When, it is only necessary to the overpotential of 242mV.
Embodiment 2：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 450mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 90 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 1SCCM, and tube furnace top is placed with 1g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar+S
Lower 600 DEG C of atmosphere reacts 1h, is taken out after natural cooling.Fig. 4 is the original of the cobalt sulfide and molybdenum disulfide prepared by embodiment 2
(a) SEM figures of position combination electrode and the linear voltammetric scan performance in (b) 1M KOH.As seen from the figure when production hydrogen electrode passes through
Current density be 10mA/cm2When, it is only necessary to the overpotential of 117mV.
Embodiment 3：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 570mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 80 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 1SCCM, and tube furnace top is placed with 1g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar+S
Lower 600 DEG C of atmosphere reacts 2h, is taken out after natural cooling.Fig. 5 is the original of the cobalt sulfide and molybdenum disulfide prepared by embodiment 3
(a) of position combination electrode is in 0.5M H2SO4In linear voltammetric scan performance, (b) in 1M PBS solutions (PH=7.17) line
Property voltammetric scan performance, Fig. 6 is its linear voltammetric scan performance in 1M KOH.As seen from the figure when production hydrogen electrode by electricity
Current density is 10mA/cm2When, corresponding acid, neutral and alkaline solution needs the overpotential of 156mV, 579mV, 105mV successively.
Embodiment 4：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 450mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 80 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 5SCCM, and tube furnace top is placed with 2g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar+S
Lower 600 DEG C of atmosphere reacts 4h, is taken out after natural cooling.Fig. 7 is the original of the cobalt sulfide and molybdenum disulfide prepared by embodiment 4
(a) SEM figures of position combination electrode and the linear voltammetric scan performance in (b) 1M KOH.As seen from the figure when production hydrogen electrode passes through
Current density be 10mA/cm2When, it is only necessary to the overpotential of 123mV.
Embodiment 5：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 330mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 80 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 1SCCM, and tube furnace top is placed with 1g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar+S
Lower 600 DEG C of atmosphere reacts 2h, is taken out after natural cooling.Fig. 8 is the original of the cobalt sulfide and molybdenum disulfide prepared by embodiment 5
Linear voltammetric scan performance of the position combination electrode in 1M KOH.As seen from the figure when production hydrogen electrode by current density be
10mA/cm2When, it is only necessary to the overpotential of 97mV.
Embodiment 6：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 450mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 80 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 1SCCM, and tube furnace top is placed with 1g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar+S
Lower 600 DEG C of atmosphere reacts 2h, is taken out after natural cooling.Fig. 9 is the original of the cobalt sulfide and molybdenum disulfide prepared by embodiment 6
Linear voltammetric scan performance of the position combination electrode in 1M KOH.As seen from the figure when production hydrogen electrode by current density be
10mA/cm2When, it is only necessary to the overpotential of 90mV.
Embodiment 7：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 800mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 80 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 1SCCM, and tube furnace top is placed with 1g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar+S
Lower 600 DEG C of atmosphere reacts 2h, is taken out after natural cooling.Figure 10 is the cobalt sulfide and molybdenum disulfide prepared by embodiment 7
Linear voltammetric scan performance of the In-situ reaction electrode in 1 M KOH.As seen from the figure when production hydrogen electrode by current density be
10 mA/cm2When, it is only necessary to the overpotential of 153mV.
Embodiment 8：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 450mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 80 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 1SCCM, and tube furnace top is placed with 0.4g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar
Lower 500 DEG C of+S atmosphere reacts 30min, is taken out after natural cooling.Figure 11 is the cobalt sulfide and curing prepared by embodiment 8
The In-situ reaction electrode of molybdenum is in 1M KOH (a) and 0.5M H2SO4(b) the linear voltammetric scan performance in.As seen from the figure when production hydrogen
Electrode by current density be 10mA/cm2When, in 1M KOH and 0.5M H2SO4It is respectively necessary for the excessively electric of 110 mV and 128mV
Position；
Embodiment 9：
At room temperature, molybdenum chloride is dissolved in ethanol solution, stirring and dissolving, obtains the molybdenum chloride ethanol solution of 450mM.It will
Growth has Co3O4The carbon paper substrate of array is immersed in chlorination molybdenum solution, after taking-up in thermal station 80 DEG C of dry 10min.To have
The substrate of coating is put into tube furnace, and logical Ar gas vacuumizes after residual air discharge in tube furnace repeatedly for three times, then logical Ar gas, stream
Amount is 10SCCM, and tube furnace top is placed with 1g sulphur powders, and as tubular type in-furnace temperature increases, sulphur powder evaporates to form sulfur vapor, in Ar+
Lower 700 DEG C of S atmosphere reacts 30min, is taken out after natural cooling.Figure 12 is the cobalt sulfide and curing prepared by embodiment 9
Linear voltammetric scan performance of the In-situ reaction electrode of molybdenum in 1M KOH.As seen from the figure when production hydrogen electrode by current density
For 10 mA/cm2When, it is only necessary to the overpotential of 126mV.When production hydrogen electrode by current density be 180mA/cm2When, it is only necessary to
The overpotential of 256mV.
Claims (6)
1. the preparation method of a kind of cobalt sulfide and molybdenum disulfide In-situ reaction electrode, which is characterized in that specific preparation method is as follows：
（1）Under the conditions of being stirred at room temperature, molybdenum chloride is dissolved in ethyl alcohol, obtains precursor solution；
（2）Above-mentioned precursor solution, which is applied to growth, to be had in the substrate of cobaltosic oxide array, dried for standby；
（3）By step（2）Sample in Ar+S atmosphere or N2In+S atmosphere, vulcanize through one step of high temperature, furnace cooling is taken out
Obtain molybdenum disulfide/molybdenum disulfide composite in-situ electrode.
2. the preparation method of the cobalt sulfide and molybdenum disulfide In-situ reaction electrode described in claim 1, which is characterized in that chlorination
Molybdenum is dissolved in volatilization nonaqueous solvents, a concentration of 100 ~ 900 mM of molybdenum chloride.
3. the preparation method of the cobalt sulfide and molybdenum disulfide In-situ reaction electrode described in claim 1, which is characterized in that described
One step vulcanization reaction temperature of high temperature be 400 ~ 800 DEG C, the reaction time be 0.5 ~ 4 h.
4. the preparation method of the cobalt sulfide and molybdenum disulfide In-situ reaction electrode described in claim 1, which is characterized in that described
One step vulcanization reaction temperature of high temperature be 600 DEG C, the reaction time be 0.5 h.
5. the preparation method of the cobalt sulfide and molybdenum disulfide In-situ reaction electrode described in claim 1, which is characterized in that Ar+S
Atmosphere or N2In+S atmosphere, Ar and N2For protective gas, 1 ~ 10 SCCM of gas flow；S gases are that sulphur powder evaporates to be formed, sulphur powder
Amount is far in excess in molybdenum atom.
6. the cobalt sulfide being prepared described in claim any one of 1-5 is with molybdenum disulfide In-situ reaction electrode in water electrolysis hydrogen production
On application.
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