CN115772681A - Nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper as well as preparation method and application thereof - Google Patents
Nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper as well as preparation method and application thereof Download PDFInfo
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- CN115772681A CN115772681A CN202211634379.2A CN202211634379A CN115772681A CN 115772681 A CN115772681 A CN 115772681A CN 202211634379 A CN202211634379 A CN 202211634379A CN 115772681 A CN115772681 A CN 115772681A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 105
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 102
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 76
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000008367 deionised water Substances 0.000 claims abstract description 33
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 22
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000004729 solvothermal method Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 12
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011733 molybdenum Substances 0.000 claims abstract description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 9
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims description 26
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 15
- 238000007605 air drying Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- 239000011684 sodium molybdate Substances 0.000 claims description 6
- 235000015393 sodium molybdate Nutrition 0.000 claims description 6
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims description 6
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000007686 potassium Nutrition 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 4
- 239000011259 mixed solution Substances 0.000 claims 2
- 235000019441 ethanol Nutrition 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 18
- 239000000203 mixture Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000003738 black carbon Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 20
- 239000011669 selenium Substances 0.000 description 11
- 229910052711 selenium Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 6
- 239000006229 carbon black Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001075 voltammogram Methods 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000011865 Pt-based catalyst Substances 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- RPZHFKHTXCZXQV-UHFFFAOYSA-N mercury(i) oxide Chemical compound O1[Hg][Hg]1 RPZHFKHTXCZXQV-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 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
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
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- 230000009467 reduction Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper and a preparation method and application thereof. The preparation method comprises the steps of firstly respectively preparing nickel-doped molybdenum disulfide (Ni-MoS) 2 ) And NaHSe solution. Uniformly stirring a nickel source, a molybdenum source and a sulfur source in deionized water, and then putting the mixture into a polytetrafluoroethylene lining high-pressure reaction kettle containing clean carbon paper for hydrothermal reaction to obtain Ni-MoS 2 A catalyst; in an inert atmosphere, selenium powder and sodium borohydride completely react in absolute ethyl alcohol, and then deionized water is added to obtain NaHSe solution. Transferring the NaHSe solution to a container containing Ni-MoS 2 The polytetrafluoroethylene lining autoclave is subjected to solvothermal reaction to obtain the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper, and the nickel-selenium co-doped molybdenum disulfide catalyst is applied to the electrocatalytic hydrogen evolution reaction. Book (I)The method has the characteristics of simple preparation, low cost and environmental friendliness.
Description
Technical Field
The invention belongs to the technical field of electrocatalysis, and particularly relates to a nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper, and a preparation method and application thereof.
Background
Since the industrial revolution, a large amount of fossil energy is exploited and utilized, toxic gas emission and huge energy gaps are caused, and people need to develop other green energy sources to realize sustainable development of society. Hydrogen as oneThe energy density of the green energy carrier with great potential is as high as 1.2 multiplied by 10 5 kJ/kg, it is an efficient, green method to produce hydrogen by cathodic reduction of electrolyzed water-Hydrogen Evolution Reaction (HER). The catalyst reaches 10mA/cm 2 The overpotential (. Eta.) required for the current density of 10 ) Is an important index for measuring HER catalyst, eta 10 The smaller the size, the more excellent the HER performance of the material. Currently, the mainstream HER electrocatalyst is a Pt-based catalyst (e.g. 20% Pt/C). However, the limited earth reserves, the high industrial costs limit the large-scale industrial application of Pt-based catalysts. Therefore, it is one of the current research hotspots to prepare HER electrocatalysis with low cost and high catalytic performance to replace Pt.
Molybdenum disulfide (MoS) as a sulfide of a transition metal 2 ) Has a two-dimensional layered structure similar to graphene. Since the discovery of MoS by researchers through calculations 2 The material has been widely noticed and studied after molybdenum with edge unsaturation coordination has a very small free energy for hydrogen adsorption. However, moS 2 HER performance is severely hampered by factors such as poor conductivity, small interlamellar spacing, and few catalytic sites. In recent years, researches show that the transition metal doping, such as cobalt, iron and the like, can be effectively applied to MoS 2 Creating more catalytically active sites on the basal plane. Chinese patent application discloses a cobalt-doped molybdenum disulfide electrocatalytic material, a preparation method and application thereof, and discloses a method for preparing cobalt-doped MoS by utilizing a one-step hydrothermal method 2 . The material is simple to prepare, but the material eta 10 Still large; on the other hand, non-metal doping, such as selenium, can effectively increase MoS 2 And the conductivity thereof is improved. The preparation and application of Chinese patent application in-situ load selenium-doped molybdenum disulfide/transition metal boride nano material discloses a selenium-doped MoS 2 The composite material with the transition metal boride has good electrocatalytic performance, but the preparation process is complicated, and the tail gas generated in the high-temperature gas-solid phase selenization process can cause certain environmental pollution. Currently, moS, which has high catalytic activity and is inexpensive, is prepared by a simple method 2 Use of base catalysts in electrocatalytic precipitationHydrogen remains a significant challenge.
Disclosure of Invention
The invention aims to solve the problems of few catalytic active sites, poor conductivity and poor electrocatalytic hydrogen evolution performance of molybdenum disulfide, and provides a nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper, and a preparation method and application thereof. The nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper prepared by the invention has good HER performance, the preparation method is low in cost and simple to operate, and other MoS can be prepared 2 The base catalyst has reference significance.
In the invention, the nickel-selenium co-doped molybdenum disulfide loaded on the carbon paper is prepared through 2-step reaction, the operation is simple, the experimental cost is low, and the prepared catalyst has excellent HER performance in an alkaline environment and has reference value for industrial production of hydrogen production by electrolyzing water.
The invention is realized by the following technical scheme:
the preparation method of the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper comprises the following steps:
(1) Pretreatment of carbon paper: cutting the purchased carbon paper into a rectangular shape, and sequentially carrying out ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water to remove impurities and organic matters on the surface of the carbon paper so as to obtain the cleaned carbon paper.
(2) Nickel doped molybdenum disulfide (Ni-MoS) 2 ) The preparation of (1): sequentially adding a molybdenum source, a sulfur source and a nickel source into deionized water, stirring uniformly, transferring the solution and the clean carbon paper into a polytetrafluoroethylene lining high-pressure reaction kettle, placing the kettle into a drying oven for hydrothermal reaction, and after the reaction is finished, washing and drying the carbon paper to obtain Ni-MoS loaded on the carbon paper 2 。
(3) Preparation of NaHSe solution: in an inert atmosphere, adding selenium powder and sodium borohydride into absolute ethyl alcohol, fully reacting, adding deionized water for diluting, and continuously stirring until the solution becomes wine red, wherein the solution is NaHSe solution.
(4) Solvent thermal selenization: loading the Ni-MoS loaded on the carbon paper in the step (2) 2 High pressure with polytetrafluoroethylene liningAnd (4) transferring the NaHSe solution obtained in the step (3) to a polytetrafluoroethylene lining in a reaction kettle, and putting the NaHSe solution into an oven for solvothermal reaction. And after the reaction is finished, taking out the carbon paper, washing and drying. And obtaining the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper.
Further, the size of the rectangle in the step (1) is 1cm multiplied by 3cm.
Further, in the step (1), the carbon paper is sequentially subjected to ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water for 10-20 minutes respectively.
Further, the molybdenum source in the step (2) is more than one of sodium molybdate, ammonium molybdate and potassium molybdate; the sulfur source in the step (2) is thiourea; and (3) the nickel source in the step (2) is more than one of nickel chloride hexahydrate, nickel nitrate hexahydrate and nickel acetylacetonate.
Further, in the step (2), the ratio of the amount of the molybdenum source substance to the volume of the added water is 0.03125-0.04000mol/L.
Further, the molar ratio of the molybdenum source, the sulfur source and the nickel source in the step (2) is 1 (4-6): 0.1-0.2, and the adding amount of the molybdenum source in the step (2) is 0.8-2.0mmol.
Further, the time of the hydrothermal reaction in the step (2) is 18-24h, and the temperature of the hydrothermal reaction in the step (2) is 190-210 ℃.
Further, the carbon paper in the step (2) is washed 3-6 times by deionized water; the drying in the step (2) is drying for 6 to 18 hours in a forced air drying oven at the temperature of between 60 and 80 ℃.
Further, in the step (3), the ratio of the amount of the selenium powder to the volume of the absolute ethyl alcohol is 0.020-0.025mol/L.
Further, the molar ratio of the selenium powder and the sodium borohydride in the step (3) is 1 (1-1.3).
Further, the volume of the absolute ethyl alcohol added in the step (3) is 20-25mL; the volume of the deionized water added in the step (3) is 10-20mL.
Further, in the step (3), the inert atmosphere is an atmosphere of nitrogen or argon.
Further, the temperature of the solvothermal reaction in the step (4) is 180-210 ℃; the solvothermal reaction time in the step (4) is 3-5h.
Further, in the step (4), the carbon paper is taken out and washed clean by deionized water for 3-5 times; and (4) drying in a forced air drying oven at the temperature of 60-80 ℃ for 6-18h.
The invention provides a nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper, which is prepared by the preparation method.
The invention also provides application of the nickel selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper in electrocatalysis of HER reaction.
Further, the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper is used as a working electrode, mercury-mercury oxide is used as a reference electrode, a graphite rod is used as a counter electrode, a 1.0M potassium hydroxide solution is used as electrolyte, and an electrocatalytic Hydrogen Evolution Reaction (HER) is performed in a three-electrode system.
The invention has the following advantages and beneficial effects:
(1) The method prepares the nickel and selenium co-doped MoS loaded on the carbon paper by hydrothermal-solvothermal 2-step reaction 2 The preparation method is simple and the cost is low.
(2) In the preparation method provided by the invention, the nickel-selenium co-doped molybdenum disulfide vertically grows on the carbon paper in situ, and the edge active sites of the material are fully exposed; the co-doping of nickel and selenium is beneficial to the generation of defects; larger selenium atoms can enlarge the interlayer spacing of the molybdenum disulfide and reduce stacking; these factors are all beneficial to the nickel-selenium co-doped molybdenum disulfide to show better electrocatalytic hydrogen evolution performance.
(3) The invention provides a novel method for doping selenium in a molybdenum disulfide-based material. Different from the prior method of doping selenium into MoS by utilizing high-temperature gas-solid reaction 2 The method has the advantages of mild reaction conditions, environmental friendliness and the like, and the prepared nickel-selenium co-doped molybdenum disulfide catalyst loaded on carbon paper reaches 10mAcm -2 The overpotential required is reduced by 130mV compared to molybdenum disulfide.
Drawings
Fig. 1 is an SEM representation of the washed carbon paper.
Fig. 2 is an SEM characterization diagram of the nickel selenium co-doped molybdenum disulfide catalyst supported on carbon paper obtained in example 1.
FIG. 3 is a SEM-EDS representation of the nickel selenium co-doped molybdenum disulfide catalyst supported on carbon paper obtained in example 1.
Fig. 4 is a TEM representation of the nickel selenium co-doped molybdenum disulfide catalyst supported on carbon paper obtained in example 1. Wherein, the a diagram and the b diagram are the topography diagrams of the embodiment 1; FIG. c is an HR-TEM image of this example 1.
FIG. 5 shows the Ni-Se co-doped MoS loaded on carbon paper obtained in example 1 2 Catalyst, nickel doped MoS supported on carbon paper obtained in comparative example 1 2 Catalyst, selenium doped MoS supported on carbon paper obtained in comparative example 2 2 Catalyst and MoS on carbon paper obtained in comparative example 3 2 Raman characterization of the catalyst.
FIG. 6 is a linear sweep voltammogram of an electrocatalytic hydrogen evolution reaction using the catalysts prepared in examples 1-3 as working electrodes.
Fig. 7 is a linear sweep voltammogram of an electrocatalytic hydrogen evolution reaction using the catalysts prepared in example 1, comparative example 2, and comparative example 3 as working electrodes.
Detailed Description
The present invention is further explained in the following with reference to specific embodiments, and a person skilled in the art can understand the present invention more fully and completely through the embodiments. It should be noted that the equipment and reagents used in the experiment are not indicated by the manufacturer, and can be obtained commercially.
A preparation method of clean carbon paper comprises the following steps:
(1) The purchased carbon paper was cut into a rectangular shape of 1cm × 3cm.
(2) And (2) sequentially carrying out ultrasonic treatment on the rectangular carbon paper cut in the step (1) in acetone for 15 minutes, carrying out ultrasonic treatment in absolute ethyl alcohol for 10 minutes and carrying out ultrasonic treatment in deionized water for 20 minutes to remove impurities and organic matters on the surface of the carbon paper.
(3) And collecting the cleaned carbon paper for subsequent experiments.
Fig. 1 is an SEM image of the obtained clean carbon paper, and from fig. 1, the smooth surface of the washed carbon paper can be observed.
Example 1
The embodiment provides a nickel-selenium co-doped MoS loaded on carbon paper 2 A method for preparing a catalyst, the method comprising the steps of:
(1) Sequentially adding 1mmol of sodium molybdate, 5mmol of thiourea and 0.12mmol of nickel nitrate hexahydrate into 30mL of deionized water, uniformly stirring, transferring the solution and the cleaned carbon paper to a polytetrafluoroethylene-lined high-pressure reaction kettle, and putting the kettle into an oven for hydrothermal reaction at 200 ℃ for 22 hours.
(2) After the reaction is finished, taking out the black carbon paper, washing the black carbon paper by deionized water for 4 times, and placing the black carbon paper in a 70 ℃ forced air drying box for drying for 10 hours to obtain Ni-MoS loaded on the carbon paper 2 。
(3) Under the protection of nitrogen, 0.5mmol of selenium powder and 0.6mmol of sodium borohydride are added into 20mL of absolute ethyl alcohol and stirred for 10 minutes, and after full reaction, 15mL of deionized water is added. And continuously stirring until the solution turns into wine red, wherein the solution is NaHSe solution.
(4) Loading Ni-MoS loaded on carbon paper in step (2) 2 And (4) placing the solution into a polytetrafluoroethylene lining, transferring the NaHSe solution obtained in the step (3) into the polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into an oven for solvothermal reaction, wherein the temperature of the solvothermal reaction is 200 ℃, and the solvothermal reaction time is 4h.
(5) After the reaction is finished, taking out the carbon black color paper, washing the carbon black color paper by deionized water for 4 times, and placing the carbon black color paper in a 70 ℃ forced air drying oven for drying for 10 hours to obtain the nickel-selenium co-doped MoS loaded on the carbon paper 2 Catalyst, labelled Ni-Se-MoS 2 -1。
Example 2
The embodiment provides a nickel-selenium co-doped MoS loaded on carbon paper 2 A method for preparing a catalyst, the method comprising the steps of:
(1) Sequentially adding 0.8mmol of ammonium molybdate, 3.2mmol of thiourea and 0.08mmol of nickel nitrate hexahydrate into 20mL of deionized water, uniformly stirring, transferring the solution and the cleaned carbon paper together into a polytetrafluoroethylene-lined high-pressure reaction kettle, and putting the kettle into an oven for hydrothermal reaction at 190 ℃, wherein the reaction time is 24 hours.
(2) After the reaction is finished, taking out the black carbon paper, washing the black carbon paper by deionized water for 3 times, and placing the black carbon paper in a 60 ℃ forced air drying box for drying for 6 hours to obtain Ni-MoS loaded on the carbon paper 2 。
(3) Under the protection of argon, 0.5mmol of selenium powder and 0.5mmol of sodium borohydride are added into 22mL of absolute ethyl alcohol and stirred for 15 minutes, and 10mL of deionized water is added after full reaction. And continuously stirring until the solution turns into wine red, wherein the solution is NaHSe solution.
(4) Loading the Ni-MoS loaded on the carbon paper in the step (2) 2 And (3) putting the solution into a polytetrafluoroethylene lining, transferring the NaHSe solution obtained in the step (3) into the polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into an oven for solvothermal reaction, wherein the temperature of the solvothermal reaction is 180 ℃, and the time of the solvothermal reaction is 3 hours.
(5) After the reaction is finished, taking out the carbon black color paper, washing the carbon black color paper by deionized water for 3 times, and placing the carbon black color paper in a 60 ℃ forced air drying oven for drying for 18 hours to obtain the nickel-selenium co-doped MoS loaded on the carbon paper 2 Catalyst, labelled Ni-Se-MoS 2 -2。
Example 3
The embodiment provides a nickel-selenium co-doped MoS loaded on carbon paper 2 A method for preparing a catalyst, the method comprising the steps of:
(1) Sequentially adding 2mmol of potassium molybdate, 12mmol of thiourea and 0.4mmol of nickel chloride hexahydrate into 64mL of deionized water, uniformly stirring, transferring the solution and the cleaned carbon paper to a polytetrafluoroethylene-lined high-pressure reaction kettle, and putting the kettle into an oven to perform hydrothermal reaction at 210 ℃ for 18 hours.
(2) After the reaction is finished, taking out the black carbon paper, washing the black carbon paper for 6 times by using deionized water, and placing the black carbon paper in a forced air drying oven at 80 ℃ for drying for 18h to obtain Ni-MoS loaded on the carbon paper 2 。
(3) Under the protection of argon, 0.50mmol of selenium powder and 0.65mmol of sodium borohydride are added into 25mL of absolute ethyl alcohol and stirred for 15 minutes, and after full reaction, 20mL of deionized water is added. And continuously stirring until the solution turns into wine red, wherein the solution is NaHSe solution.
(4) Loading the Ni-MoS loaded on the carbon paper in the step (2) 2 And (4) placing the solution into a polytetrafluoroethylene lining, transferring the NaHSe solution obtained in the step (3) into the polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into an oven for solvothermal reaction, wherein the temperature of the solvothermal reaction is 210 ℃, and the solvothermal reaction time is 5 hours.
(5) After the reaction is finished, taking out the black carbon paper, washing the black carbon paper with deionized water for 5 times, and placing the black carbon paper in a forced air drying oven at 80 ℃ for drying for 6 hours to obtain the nickel-selenium co-doped MoS loaded on the carbon paper 2 Catalyst, labelled Ni-Se-MoS 2 -3。
FIG. 2 shows the nickel-selenium co-doped MoS loaded on carbon paper obtained in example 1 2 A Scanning Electron Microscope (SEM) image of the catalyst, and it can be seen from fig. 2 that the prepared catalyst is uniformly supported on the surface of the carbon paper. FIG. 3 shows the nickel-selenium co-doped MoS loaded on carbon paper obtained in example 1 2 Scanning electron microscope-energy spectrum (SEM-EDS) of the catalyst, and the existence of four elements of Mo, S, se and Ni can be seen from figure 3, which shows the successful doping of Ni and Se elements. FIG. 4 shows the nickel selenium co-doped MoS loaded on carbon paper obtained in example 1 2 A Transmission Electron Microscope (TEM) image of the catalyst, from (c) image in fig. 4, it can be seen that defects exist due to co-doping of nickel and selenium.
Comparative example 1
The comparative example provides a nickel-doped molybdenum disulfide (Ni-MoS) supported on carbon paper 2 ) A method for preparing a catalyst, the method comprising the steps of:
(1) Sequentially adding 1mmol of sodium molybdate, 5mmol of thiourea and 0.12mmol of nickel nitrate hexahydrate into 30mL of deionized water, uniformly stirring, transferring the solution and the cleaned carbon paper into a polytetrafluoroethylene-lined high-pressure reaction kettle, and putting the kettle into an oven to perform hydrothermal reaction at 200 ℃ for 22 hours.
(2) After the reaction is finished, taking out the black carbon paper, washing the black carbon paper for 4 times by using deionized water, and placing the black carbon paper in a blast drying oven at 70 ℃ for drying for 10 hours to obtain Ni-MoS loaded on the carbon paper 2 Marked as Ni-MoS 2 。
Comparative example 2
This comparative example provides a selenium doped MoS loaded on carbon paper 2 A method for preparing a catalyst, the method comprising the steps of:
(1) Sequentially adding 1mmol of sodium molybdate and 5mmol of thiourea into 30mL of deionized water, stirring uniformly, transferring the solution and the cleaned carbon paper into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into an oven for hydrothermal reaction at 200 ℃, wherein the reaction time is 22h.
(2) After the reaction is finished, taking out the black carbon paper, washing the black carbon paper for 4 times by using deionized water, and placing the black carbon paper in a blast drying oven at 70 ℃ for drying for 10 hours to obtain MoS loaded on the carbon paper 2 。
(3) Under the protection of nitrogen, 0.5mmol of selenium powder and 0.6mmol of sodium borohydride are added into 20mL of absolute ethyl alcohol and stirred for 10 minutes, and after full reaction, 15mL of deionized water is added. And continuously stirring until the solution turns into wine red, wherein the solution is NaHSe solution.
(4) MoS loaded on the carbon paper in the step (2) 2 And (4) placing the solution into a polytetrafluoroethylene lining, transferring the NaHSe solution obtained in the step (3) into the polytetrafluoroethylene lining, placing the polytetrafluoroethylene lining into an oven for solvothermal reaction, wherein the temperature of the solvothermal reaction is 200 ℃, and the solvothermal reaction time is 4h.
(5) After the reaction is finished, taking out the black carbon paper, washing the black carbon paper by deionized water for 4 times, and placing the black carbon paper in a 70 ℃ blast drying oven for drying for 10 hours until the selenium-doped MoS loaded on the carbon paper 2 Marked as Se-MoS 2 。
Comparative example 3
This comparative example provides a MoS on carbon paper 2 The preparation method of the catalyst of (1), the preparation method comprising the steps of:
(1) Sequentially adding 1mmol of sodium molybdate and 5mmol of thiourea into 30mL of deionized water, uniformly stirring, transferring the solution and the cleaned carbon paper into a polytetrafluoroethylene-lined high-pressure reaction kettle, and putting the kettle into an oven to carry out hydrothermal reaction at 200 ℃, wherein the reaction time is 22h.
(2) After the reaction is finished, taking out the black carbon paper, washing the black carbon paper for 4 times by using deionized water, and placing the black carbon paper in a blast drying oven at 70 ℃ for drying for 10 hours to obtain MoS loaded on the carbon paper 2 Marked as MoS 2 。
Ni-Se-MoS on carbon paper obtained in example 1 2 Catalyst-1 comparative example 1 Ni-MoS on carbon paper 2 Catalyst, se-MoS on carbon paper obtained in comparative example 2 2 Catalyst and MoS on carbon paper obtained in comparative example 3 2 The Raman characterization of the catalyst is shown in FIG. 5, 406cm -1 And 377cm -1 Respectively correspond to MoS 2 Out of plane A of 1g And in-plane E 2g Vibration mode, showing that the composition of the main composition of comparative example 1 and comparative example 3 is 2HMoS 2 Whereas for example 1 and comparative example 2, at 406cm -1 And 377cm -1 MoS appears 2 Out of plane A of 1g And in-plane E 2g Vibration mode at the same time of 200-300cm -1 The Mo — Se-related vibration mode appears in the low frequency region of (a), which indicates that elemental selenium has been successfully incorporated in example 1 and comparative example 2.
Examples 1 to 3, comparative examples 1 to 3 were used for electrocatalytic hydrogen evolution reactions.
The electrocatalytic hydrogen evolution reaction is carried out in an electrolytic cell of a three-electrode system, the catalysts prepared in examples 1-3 and comparative examples 1-3 are used as working electrodes, mercury-mercury oxide is used as a reference electrode, a graphite rod is used as a counter electrode, and the electrolyte is N 2 Saturated 1.0m koh solution (solvent deionized water). The sweep rate of the linear sweep voltammogram was 2mV/s.
As can be seen from fig. 6, examples 1-3 have better HER catalytic performance. As can be seen from FIG. 7, the current density reached 10mA/cm 2 At current density of (2), ni-Se-MoS 2 -1，Ni-MoS 2 ，Se-MoS 2 And MoS 2 The overpotentials of (A) and (B) are 102mV,155mV,168mV and 232mV, respectively. Shows that the nickel-selenium co-doping can effectively improve MoS 2 Hydrogen evolution performance of (1).
Finally, what needs to be supplemented is: the above description of the embodiments and the accompanying drawings are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, and all changes, equivalents, modifications and the like that may occur to those skilled in the art without departing from the spirit and scope of the invention are therefore intended to be embraced by the appended claims.
Claims (10)
1. The preparation method of the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper is characterized by comprising the following steps of:
(1) Pretreatment of carbon paper: sequentially performing ultrasonic treatment on the carbon paper in acetone, ethanol solution and water to remove impurities and organic matters on the surface of the carbon paper, thereby obtaining cleaned carbon paper;
(2) Nickel doped molybdenum disulfide (Ni-MoS) 2 ) The preparation of (1): sequentially adding a molybdenum source, a sulfur source and a nickel source into water, uniformly stirring to obtain a mixed solution, putting the carbon paper cleaned in the step (1) into the mixed solution for hydrothermal reaction, and after the reaction is finished, washing and drying the carbon paper to obtain Ni-MoS loaded on the carbon paper 2 ；
(3) Preparation of NaHSe solution: in an inert atmosphere, adding selenium powder and sodium borohydride into absolute ethyl alcohol, stirring, adding water after full reaction, and continuously stirring to obtain NaHSe solution;
(4) Solvent thermal selenization: loading the Ni-MoS loaded on the carbon paper in the step (2) 2 And (4) putting the carbon paper into the NaHSe solution obtained in the step (3) for solvothermal reaction, taking out the carbon paper after the reaction is finished, washing and drying to obtain the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper.
2. The preparation method of the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper according to claim 1, wherein the molybdenum source in the step (2) is one or more of sodium molybdate, ammonium molybdate and potassium molybdate; the sulfur source in the step (2) is thiourea; and (3) the nickel source in the step (2) is more than one of nickel chloride hexahydrate, nickel nitrate hexahydrate and nickel acetylacetonate.
3. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper according to claim 1, wherein the molar ratio of the molybdenum source, the sulfur source and the nickel source in the step (2) is 1 (4-6) to (0.1-0.2), and the ratio of the amount of the molybdenum source in the step (2) to the volume of the added water is 0.03125-0.04000mol/L.
4. The preparation method of the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper according to claim 1, wherein the temperature of the hydrothermal reaction in the step (2) is 190-210 ℃; the time of the hydrothermal reaction in the step (2) is 18-24 hours.
5. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper as claimed in claim 1, wherein the carbon paper is washed 3-6 times by deionized water in the step (2); the drying in the step (2) is drying in a forced air drying oven at the temperature of 60-80 ℃ for 6-18 hours.
6. The preparation method of the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper according to claim 1, wherein in the step (3), the molar ratio of the selenium powder to the sodium borohydride is 1 (1-1.3); the ratio of the amount of the selenium powder to the volume of the absolute ethyl alcohol is 0.020-0.025mol/L, the ratio of the amount of the selenium powder to the volume of the water is 0.025-0.050mol/L, and the inert atmosphere is nitrogen or argon.
7. The preparation method of the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper as claimed in claim 1, wherein the temperature of the solvothermal reaction in the step (4) is 180-210 ℃; the solvothermal reaction time in the step (4) is 3-5h.
8. The method for preparing the nickel-selenium co-doped molybdenum disulfide catalyst loaded on the carbon paper as claimed in claim 1, wherein the step (4) of taking out the carbon paper and washing is to wash the carbon paper with deionized water for 3-5 times; the drying in the step (4) is drying in a forced air drying oven at the temperature of 60-80 ℃ for 6-18 hours.
9. The nickel selenium co-doped molybdenum disulfide catalyst which is loaded on carbon paper and is prepared by the preparation method of any one of claims 1 to 8.
10. The use of the nickel selenium co-doped molybdenum disulfide catalyst loaded on carbon paper as claimed in claim 9 in electrocatalytic hydrogen evolution reaction.
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