CN108607582B - Molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material, and preparation method and application thereof - Google Patents
Molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material, and preparation method and application thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 146
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 118
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 108
- 230000002829 reductive effect Effects 0.000 title claims abstract description 98
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 77
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 70
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- 239000003792 electrolyte Substances 0.000 claims abstract description 16
- 239000000758 substrate Substances 0.000 claims abstract description 15
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000011541 reaction mixture Substances 0.000 claims description 20
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 18
- 229910052750 molybdenum Inorganic materials 0.000 claims description 18
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 17
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- 239000011593 sulfur Substances 0.000 claims description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000011733 molybdenum Substances 0.000 claims description 16
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
- 239000011609 ammonium molybdate Substances 0.000 claims description 4
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 4
- 229940010552 ammonium molybdate Drugs 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 18
- 230000002378 acidificating effect Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 2
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- 239000000243 solution Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
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- 230000000052 comparative effect Effects 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910015667 MoO4 Inorganic materials 0.000 description 3
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
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- 230000010287 polarization Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
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- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
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- 150000002751 molybdenum Chemical class 0.000 description 1
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- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 150000003463 sulfur Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- -1 transition metal sulfides Chemical class 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
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Abstract
The embodiment of the invention provides a molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material, and a preparation method and application thereof, wherein the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material takes reductive graphene oxide as a substrate, molybdenum disulfide nanosheets are dispersed on the bottom of the reductive graphene oxide substrate, and nickel nanoparticles are dispersed on the reductive graphene oxide substrate and the molybdenum disulfide nanosheets. The molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material provided by the invention has hydrogen evolution reaction catalytic activity in an acidic electrolyte and an alkaline electrolyte, and particularly has better hydrogen evolution reaction catalytic activity in the alkaline electrolyte. Meanwhile, the preparation method provided by the invention is simple and feasible, and has cheap and easily-obtained raw materials and good economic prospect.
Description
Technical Field
The invention relates to the technical field of preparation of hydrogen evolution reaction catalysts, in particular to a molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material, and a preparation method and application thereof.
Background
Hydrogen energy, with its cleanliness and high efficiency, is the most promising renewable energy source. Water electrolysis is one of the important means of obtaining hydrogen energy, where a hydrogen evolution reaction occurs at the cathode. The overpotential of the hydrogen evolution reaction is high, and platinum noble metals are generally used as catalysts. However, noble metals are costly and have limited resources, limiting their use in hydrogen evolution reactions. Therefore, it is necessary to prepare a hydrogen evolution reaction catalyst with high efficiency, low cost and high storage capacity.
The nano particles of transition metal simple substance nickel have certain hydrogen evolution reaction catalytic activity in an alkaline medium, but have poor catalytic performance in an acid electrolyte. In addition, the nickel nano particles are easy to agglomerate into large particles in the synthesis process, so that the number of active sites is reduced, and the catalytic performance is reduced.
Disclosure of Invention
The embodiment of the invention aims to provide a molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material which has hydrogen evolution reaction catalytic activity in an acidic electrolyte and an alkaline electrolyte. Meanwhile, the invention also provides a preparation method and application of the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material. The specific technical scheme is as follows:
the invention firstly provides a molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material, wherein reductive graphene oxide is used as a substrate, molybdenum disulfide nanosheets are dispersed on the reductive graphene oxide substrate, and nickel nanoparticles are dispersed on the reductive graphene oxide substrate and the molybdenum disulfide nanosheets.
The invention also provides a preparation method of the molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material, which comprises the following steps:
(1) dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid;
(2) mixing a molybdenum source, a sulfur source and the graphene oxide dispersion liquid to obtain a first reaction mixture;
(3) carrying out hydrothermal reaction on the first reaction mixture at 180-220 ℃ for 18-30 hours, and separating and washing after the reaction is finished to obtain a molybdenum disulfide/reductive graphene oxide composite material;
(4) dispersing the molybdenum disulfide/reductive graphene oxide composite material in an organic solvent to obtain a molybdenum disulfide/reductive graphene oxide composite material dispersion liquid;
(5) adding a nickel source and hydrazine hydrate into the molybdenum disulfide/reductive graphene oxide composite dispersion liquid, and adjusting the pH value to 8-10 to obtain a second reaction mixture;
(6) and reacting the second reaction mixture at 50-70 ℃ for 0.5-3 hours, and separating and washing after the reaction is finished to obtain the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material.
In some embodiments of the preparation method provided by the present invention, the molar ratio of the sulfur source to the molybdenum source is (2.5-10): 1; the ratio of the number of moles of the molybdenum source to the mass of the graphite oxide was (0.033-0.1):1 mol/g.
In some embodiments of the preparation method provided by the present invention, the molybdenum source is selected from one or a combination of sodium molybdate and ammonium molybdate; the sulfur source is selected from one or the combination of thiourea and thioacetamide.
In some embodiments of the preparation method provided by the present invention, the nickel source is selected from one of nickel sulfate, nickel nitrate, nickel chloride, or a combination thereof.
In some embodiments of the methods of preparation provided herein, the ratio of the number of moles of nickel source to the mass of the molybdenum disulfide/reduced graphene oxide composite is (0.0018-0.007): 1 mol/g.
In some embodiments of the preparation method provided by the present invention, the ratio of the volume of hydrazine hydrate to the mass of the molybdenum disulfide/reduced graphene oxide composite material is (0.02-0.03): 1 mL/mg.
In some embodiments of the preparation method provided by the present invention, the organic solvent is one of ethylene glycol, ethanol, or a combination thereof.
The invention also provides application of the molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material as a hydrogen evolution reaction catalyst.
In some embodiments of the present invention, wherein the molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite acts as a hydrogen evolution reaction catalyst in an alkaline electrolyte.
According to the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material provided by the invention, reductive graphene oxide is used as a substrate, and a molybdenum disulfide nanosheet, a nickel nanoparticle and reductive graphene oxide are compounded, so that the composite material has hydrogen evolution reaction catalytic activity in an acidic electrolyte and an alkaline electrolyte at the same time, and particularly has better hydrogen evolution reaction catalytic activity in the alkaline electrolyte. Meanwhile, the preparation method provided by the invention is simple and feasible, and has cheap and easily-obtained raw materials and good economic prospect.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows graphene oxide (a in FIG. 1) and MoS prepared in example 12rGO (b in FIG. 1), MoS prepared in example 22rGO-Ni-30 (c in FIG. 1), MoS prepared in example 32rGO-Ni-50 (d in FIG. 1), MoS prepared in example 12-XRD pattern of rGO-Ni-100 (e in fig. 1), Ni-rGO prepared in comparative example 1 (f in fig. 1), unit: nm;
FIG. 2 is the MoS prepared in example 12-rGO and MoS2XPS spectra of rGO-Ni-100, in which (a) - (b) in FIG. 2 represent MoS in sequence2-Mo 3d spectrum and S2 p spectrum of rGO; (d) - (f) denotes MoS in order2-Mo 3d, S2 p and Ni 2p spectra of rGO-Ni-100; (c) is MoS2-rGO (i) and MoS2-full spectrum of rGO-Ni-100 (ii);
FIG. 3 is the MoS prepared in example 12rGO (FIG. 3 (a)) and MoS2SEM photograph of rGO-Ni-100 (FIG. 3 (b));
FIG. 4 shows the MoS prepared in example 12-results of electrocatalytic performance tests of rGO-Ni-100, wherein (a) is Ni-rGO and MoS2-rGO-Ni-100 at 0.5M H2SO4The polarization curve of hydrogen evolution reaction in (a) and (b) is MoS2-rGO and MoS2-rGO-Ni-100 hydrogen evolution reaction polarization curve in 1M KOH, RHE representing reversible hydrogen electrode.
Detailed Description
Molybdenum disulfide is one of transition metal sulfides, and is a layered material. In recent years, research shows that molybdenum disulfide has hydrogen evolution reaction catalytic activity, and active sites of molybdenum disulfide are derived from unsaturated sulfur atoms at edges. And the nano-grade molybdenum disulfide can obviously improve the catalytic activity, and generally, the molybdenum disulfide has better hydrogen evolution catalytic performance in an acid medium. Molybdenum disulfide, however, is less conductive and limits catalytic efficiency.
Due to the advantages of high conductivity, large specific surface area, flexibility, chemical stability and the like of the reductive graphene oxide, the molybdenum disulfide nanosheets, the nickel nanoparticles and the reductive graphene oxide are creatively compounded together by the inventor, so that the conductivity of the composite material can be increased, the agglomeration of the nanoparticles can be reduced, the active sites of the nanoparticles are fully exposed, and the composite material with hydrogen evolution reaction catalytic activity in the acidic electrolyte and the alkaline electrolyte is obtained.
Based on the above, the invention provides a molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material, which takes reduced graphene oxide as a substrate, molybdenum disulfide is dispersed on the reduced graphene oxide substrate in a nanosheet form, and nickel nanoparticles are dispersed on the reduced graphene oxide substrate and the molybdenum disulfide nanosheet.
The molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material prepared by the method has good catalytic action on hydrogen evolution reaction, so that the molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material can be used as a hydrogen evolution reaction catalyst.
Further, the inventor finds that when the molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material provided by the invention is used as a hydrogen evolution reaction catalyst, the hydrogen evolution reaction catalytic activity of the molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material in an alkaline electrolyte is superior to that of an acidic medium; thus, in some embodiments of the invention, the molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite acts as a hydrogen evolution reaction catalyst for the electrolysis of water in an alkaline electrolyte.
However, it is known to those skilled in the art that nanoparticles tend to agglomerate and that it is difficult to control their size and dispersibility. In the presence of a sulfur source, the nickel simple substance is very easy to combine with sulfur element to generate nickel sulfide, so that the nickel simple substance cannot be obtained.
The inventor creatively combines hydrothermal reaction and chemical reduction reaction through a large number of experiments, firstly realizes the compounding of molybdenum disulfide and reductive graphene oxide through the hydrothermal reaction to obtain a molybdenum disulfide/reductive graphene oxide composite material, then introduces a nickel source, successfully compounds the elemental nickel nanoparticles with molybdenum disulfide and reductive graphene oxide while reducing the nickel source into the elemental nickel nanoparticles through the chemical reduction reaction, and finally obtains the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material, thereby ensuring the better dispersibility of the nickel nanoparticles while obtaining the elemental nickel nanoparticles.
Herein, reduced graphene oxide has a general meaning in the art, which refers to a product obtained by reducing graphene oxide with a reducing agent, abbreviated as rGO. In the invention, the graphene oxide is reduced through a hydrothermal reaction to obtain the reduced graphene oxide.
Based on the design thought, the invention provides a preparation method of a molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material, which comprises the following steps:
(1) dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid;
(2) mixing a molybdenum source, a sulfur source and the graphene oxide dispersion liquid to obtain a first reaction mixture;
(3) carrying out hydrothermal reaction on the first reaction mixture at 180-220 ℃ for 18-30 hours, and separating and washing after the reaction is finished to obtain a molybdenum disulfide/reductive graphene oxide composite material;
(4) dispersing the molybdenum disulfide/reductive graphene oxide composite material in an organic solvent to obtain a molybdenum disulfide/reductive graphene oxide composite material dispersion liquid;
(5) adding a nickel source and hydrazine hydrate into the molybdenum disulfide/reductive graphene oxide composite dispersion liquid, and adjusting the pH value to 8-10 to obtain a second reaction mixture;
(6) and reacting the second reaction mixture at 50-70 ℃ for 0.5-3 hours, and separating and washing after the reaction is finished to obtain the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material.
The graphene oxide used in the present invention may be prepared by the prior art, and the preparation method thereof is not limited herein.
In the specific implementation process, after the graphene oxide is mixed with water in the step (1), ultrasonic treatment can be performed, so that the graphene oxide can be dispersed in the water more quickly and uniformly, and the time of the ultrasonic treatment can be 10-30 minutes; the proportion of the graphene oxide to the water has no special requirement, and the graphene oxide can be fully dispersed in the water; the volume of the reaction kettle is also considered. Generally, the ratio of the mass of graphene oxide to the volume of water is 1: (1-2) mg/mL.
The molybdenum source and the sulfur source adopted by the technical scheme of the invention are both soluble in water, such as water-soluble molybdenum salt and sulfur salt (sulfide); in some embodiments of the invention, the molybdenum source is selected from one or a combination of sodium molybdate, ammonium molybdate, or a combination thereof. In some embodiments of the invention, the sulfur source is selected from one or a combination of thiourea, thioacetamide. The sulfur source adopted by the invention is a sulfur source with reducibility, and can be used as a reducing agent to reduce graphene oxide into reduced graphene oxide through a hydrothermal reaction.
In some embodiments of the present invention, since the atomic ratio of sulfur to molybdenum in molybdenum disulfide is 2: 1, therefore, the molar ratio of sulfur source to molybdenum source during the preparation is generally greater than 2: 1; a slightly larger proportion is beneficial to the forward direction of the reaction; preferably, the molar ratio of the sulfur source to the molybdenum source is (2.5-10): 1; the ratio of the number of moles of the molybdenum source to the mass of the graphite oxide was (0.033-0.1):1 mol/g.
The hydrothermal reaction of step (3) may be carried out in a hydrothermal kettle. In particular embodiments, the volume of the first reaction mixture may be 60-90% of the hydrothermal kettle volume.
It should be noted that the operation steps of the hydrothermal reaction are well known to those skilled in the art, and the hydrothermal reaction of the present invention can be achieved without inventive labor by those skilled in the art according to the relevant hydrothermal reaction parameters provided herein, such as temperature, time, etc. of the hydrothermal reaction.
In some embodiments of the present invention, after the hydrothermal reaction in step (3) is finished, centrifugal separation may be performed, and the separated solid is washed with water and ethanol alternately until the washing solution is colorless and has a pH of about neutral; drying to obtain a molybdenum disulfide/reductive graphene oxide composite material; of course, in addition to ethanol, a volatile and low-toxic organic solvent such as acetone may be used instead of ethanol to wash and separate the resulting solid.
In some embodiments of the present invention, the organic solvent in step (4) is one of ethylene glycol, ethanol, or a combination thereof. In the specific implementation process of the step (4), the molybdenum disulfide/reduced graphene oxide composite material and an organic solvent can be mixed, and then ultrasonic treatment is performed, so that the molybdenum disulfide/reduced graphene oxide composite material can be more quickly and uniformly dispersed in the organic solvent, and the ultrasonic treatment time can be 10-30 minutes; the ratio of the molybdenum disulfide/reductive graphene oxide composite material to the organic solvent has no special requirement, and the molybdenum disulfide/reductive graphene oxide composite material can be fully dispersed in the organic solvent; generally, the ratio of the mass of the molybdenum disulfide/reduced graphene oxide composite to the volume of the organic solvent is 1: (1-2) mg/mL.
After the molybdenum disulfide/reduced graphene oxide composite dispersion is obtained, the nickel source and hydrazine hydrate are added, and the pH value is adjusted to 8-10, preferably, the nickel source and hydrazine hydrate are added and the pH value is adjusted under stirring, for example, magnetic stirring, so that the substances can be dispersed more uniformly, and a uniform second reaction mixture is obtained.
In the step (5) implementation process, the nickel source can be selected from one or a combination of nickel sulfate, nickel nitrate and nickel chloride. In some embodiments, the ratio of the number of moles of nickel source to the mass of the molybdenum disulfide/reduced graphene oxide composite is (0.0018-0.007): 1 mol/g.
The hydrazine hydrate added in the step (5) is used as a reducing agent, and since the commercially available hydrazine hydrate is generally a 40-80% hydrazine hydrate aqueous solution by volume percentage, the volume of the hydrazine hydrate aqueous solution to be actually added can be determined by simple calculation according to the determined volume of pure hydrazine hydrate during actual feeding.
In some embodiments of the invention, the ratio of the volume of pure hydrazine hydrate to the mass of the molybdenum disulfide/reduced graphene oxide composite is (0.02-0.03): 1 mL/mg.
In step (5), the pH value can be adjusted by adding 1M KOH aqueous solution, although the skilled person can also adjust the pH value by using KOH or NaOH with other concentrations; the hydrazine hydrate has stronger reducibility by adjusting the pH value.
After the second reaction mixture is obtained, the second reaction mixture may be subjected to a reduction reaction at 50-70 ℃ for 0.5-3 hours, and after the reaction is finished, the temperature is preferably reduced to room temperature, and then the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material is obtained by separation and washing. After the reduction reaction in the step (6) is finished, centrifugal separation can be performed, and the crude product of the molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material obtained by separation is washed with ethanol for several times until the washing liquid is colorless and the pH value is about neutral. Drying to obtain a molybdenum disulfide/reductive graphene oxide composite material; of course, in addition to ethanol, the crude product obtained may be washed and separated by using a volatile, low-toxic organic solvent such as acetone.
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
First, a method for producing Graphene Oxide (GO) will be described. The graphene oxide adopted in the invention can be prepared by an improved Hummer method, and the specific flow comprises the following steps:
weighing 2.5g of graphite powder and 2.5g of NaNO3115mL of concentrated H were added2SO4Placing in an ice-water bath, slowly adding 15g of KMnO while stirring4. After about 40min, the ice-water bath was removed, placed in a 35 ℃ water bath, and 230mL of distilled water was added slowly, over the course of about 30min, with the product fading from black to brown. Then placing the mixture in an oil bath at the temperature of 98 ℃ for heat preservation for 15 min. After the oil bath was removed, 700mL of warm water (50-60 ℃) was added, stirred, and 50mL of H was added2O2At this point the product turned golden yellow. Filtering, washing with 5% diluted hydrochloric acid solution, and washing with distilled water for several times until Ba (NO) is added3)2Checking for absence of SO4 2-Until now. The resulting product was air dried at 70 ℃.
Preparation example of molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite Material
Example 1
30mg of graphene oxide is weighed, 45mL of secondary distilled water (common deionized water is also available) is added, and ultrasonic dispersion is carried out for 10 minutes to obtain a graphene oxide dispersion liquid.
The graphene oxide dispersion was transferred to a 50mL reaction kettle and 0.4g (1.7mmol) Na was added2MoO4·2H2O and 0.63g (8.3mmol) of thiourea were stirred for 10min to obtain a first reaction mixture.
The first reaction mixture was subjected to a hydrothermal reaction at 200 ℃ for 24 hours. Cooling the system to room temperature, centrifuging, washing with water and ethanol alternately for 3 timesSecondly, vacuum drying the obtained product at 50 ℃ to obtain the molybdenum disulfide/reductive graphene oxide composite material, MoS for short2-rGO。
Weighing 16mg MoS2Adding 20mL of glycol into rGO, and uniformly dispersing by ultrasonic treatment for 10 minutes to obtain a molybdenum disulfide/reductive graphene oxide composite dispersion liquid.
Under magnetic stirring, 100 μ L of 1M NiCl was added to the molybdenum disulfide/reduced graphene oxide composite dispersion2·6H2Oglycol solution (0.1mmol) and 0.5mL of aqueous hydrazine hydrate solution (concentration: 80%) were added, and 1mL of 1M aqueous KOH solution was added to adjust the system pH to 9, to obtain a second reaction mixture.
The second reaction mixture was reacted at 60 ℃ for 1 hour. After the reaction is finished, cooling the system to room temperature, centrifuging, washing for 3 times by using ethanol, and drying the obtained product in vacuum at 50 ℃ to obtain the molybdenum disulfide/reductive graphene oxide/nickel nano particle composite material, namely MoS for short2-rGO-Ni-100。
Example 2
Example 2 differs from example 1 in that: mixing 1M NiCl2·6H2The dosage of the O glycol solution is changed to 30 mu L, and the obtained molybdenum disulfide/reductive graphene oxide/nickel nano particle composite material, MoS for short2-rGO-Ni-30。
Example 3
Example 3 differs from example 1 in that: mixing 1M NiCl2·6H2The dosage of the O glycol solution is changed to 50 mu L, and the obtained molybdenum disulfide/reductive graphene oxide/nickel nano particle composite material, MoS for short2-rGO-Ni-50。
Example 4
Example 4 differs from example 1 in that: the temperature of the hydrothermal reaction is 180 ℃ and the reaction time is 30 hours.
Example 5
Example 5 differs from example 1 in that: the hydrothermal reaction temperature was 220 ℃ and the reaction time was 18 hours.
Example 6
Example 6 differs from example 1 in that: the sulfur source is thioacetamide; the molybdenum source is ammonium molybdate; the nickel source is nickel sulfate.
Example 7
Example 7 differs from example 1 in that: the molar amount of thiourea was 17 mmol.
Example 8
Example 8 differs from example 1 in that: na (Na)2MoO4·2H2The mole number of O is 1 mmol.
Example 9
Example 9 differs from example 1 in that: na (Na)2MoO4·2H2The mole number of O was 3 mmol.
Comparative example 1 preparation of nickel nanoparticle/reduced graphene oxide composite (Ni-rGO)
The synthesis method of Ni-rGO is as follows: dispersing 20mg of graphite oxide in 30mL of N-methyl-2-pyrrolidone, ultrasonically dispersing for 3h, adding 0.2695g (1mmol) of nickel acetylacetonate, 2g (7mmol) of octadecylamine and 1g of KOH (18mmol) into the dispersion, and dropwise adding 4mL of N2H4·H2And O, introducing argon for 5 min. The solution was transferred to a 40mL reaction vessel and reacted at 180 ℃ for 2 h. After the reaction is finished, the product is alternately washed with n-hexane and acetone for three times, then alternately washed with water and ethanol for two times, and dried in an oven at 40 ℃.
Characterization and testing of composite materials
1. XRD analysis
MoS prepared in example 1 of the present invention was subjected to X-ray powder diffractometer (model: X Pert PRO MPD) manufactured by Pasacaceae, Netherlands2-rGO and composite MoS prepared in examples 1-32-rGO-Ni-100、MoS2-rGO-Ni-30、MoS2-rGO-Ni-50, and GO and Ni-rGO were subjected to X-ray diffraction analysis, the results of which are shown in figure 1; the radioactive source in the analysis process is Cu-Ka, the measuring step length is 0.017 degrees, and the scanning time is 10 seconds per step.
As can be seen from fig. 1, GO (a in fig. 1) shows a diffraction peak at d ═ 0.84nm, corresponding to an interlayer spacing of 0.84 nm. MoS2-rGO (b in fig. 1) shows two peaks at d ═ 0.99nm and d ═ 0.48nm, indicating an interlayer spacing of 0.99 nm. Normal MoS2Interlayer spacing of 0.61nm, MoS2MoS in rGO2The expansion of the interlayer spacing may be due to intercalation of the O element. The peak at about 24 degrees is the C peak of rGO, and the rest peaks are assigned as MoS2(PDF 65-1951), sharp peak shape, high crystallinity.
Three complexes MoS formed after adding nickel salt for reaction2-rGO-Ni-30 (c in FIG. 1), MoS2-rGO-Ni-50 (d in FIG. 1) and MoS2The XRD peaks of the-rGO-Ni-100 (e in FIG. 1) are similar, and MoS with the interlayer spacing expanded to 0.99nm can be observed2And C peak of rGO. In addition, diffraction peaks of cubic phase Ni (PDF 65-0380) were also observed, demonstrating MoS2Successful complexation of rGO and Ni.
The XRD pattern (f in FIG. 1) of Ni-rGO prepared in comparative example 1 shows three diffraction peaks, which are consistent with cubic phase Ni (PDF 65-0380). Furthermore, no diffraction peak of GO was observed at d ═ 0.84nm, indicating that GO was successfully reduced.
2. XPS (X-ray photoelectron spectroscopy) analysis
The MoS prepared in example 1 was subjected to an X-ray photoelectron spectrometer (model: ESCLAB 250Xi) manufactured by ThermoFisher, England2-rGO and MoS2-rGO-Ni-100 was analyzed by XPS using AlKl radiation as the X-ray source. XPS spectra are shown in FIG. 2;
FIG. 2 shows MoS2-rGO and MoS2XPS plot of rGO-Ni-100. As can be seen from the full spectrum (c) in FIG. 2, MoS2Mo, S, C, O and other elements exist in rGO. From FIG. 2 (a), MoS2Mo in rGO is predominantly Mo4+Present (binding energies 232.2eV and 228.9eV), and also a small amount of Mo5+(binding energy 233.7eV) and Mo6+(binding energy 235.8eV), probably due to Mo4+Is partially oxidized. From FIG. 2 (b), the S element is mainly S2-(binding energies 163.0eV and 161.8eV) and S2 2-(binding energies 164.0eV and 162.0eV) and a small portion of S is oxidized to SO4 2-(binding energy 169.2 eV). For MoS2-rGO-Ni-100, and full spectrum analysis shows that the sample contains Ni elements besides Mo, S, C and O elements. From FIG. 2 (d), MoS2Presence of Mo in-rGO-Ni-100Compared with the precursor, the content of the high valence Mo is not changed, and the content of the high valence Mo is increased. In FIG. 2, (e) is MoS2Binding energy of S2 p of-rGO-Ni-100, also containing S in the sample2-、S2 2-And SO4 2-In which SO4 2-The relative amount of (a) also increases, indicating an increase in the degree of oxidation of the sample surface. From (f) in FIG. 2, the peak having the binding energy of 852.7eV is Ni0, and the peaks having the binding energies of 874.0eV, 870.0eV, 861.7eV and 856.1eV belong to Ni2+The presence of elemental Ni was demonstrated. Ni is easily oxidized in air, so that the surface of the sample contains part of Ni2+。
3. Analysis by Electron microscopy
MoS prepared in example 1 was subjected to Scanning Electron Microscopy (SEM)2-rGO and MoS2The morphology of the-rGO-Ni-100 was analyzed and the results are shown in FIG. 3.
FIG. 3 shows MoS2-rGO and MoS2SEM results for rGO-Ni-100. MoS from FIG. 3 (a)2-an electron microscope photo of rGO, wherein a plurality of flower-like nanosheets grow on the surface of the rGO substrate, the nanosheets are relatively thin in thickness, about 200-300nm in length and smooth in surface. MoS from FIG. 3 (b)2The surface of the nano sheet and the rGO substrate are decorated with a plurality of nickel elementary nano particles with the particle diameter of 10-20nm, the surface of the nano sheet becomes rough and the thickness is increased.
4. Electrocatalytic performance test
MoS prepared as in example 12the-rGO-Ni-100 sample, used as a catalyst, was tested for its electrocatalytic hydrogen evolution performance and was identified as the MoS prepared in example 12-rGO (under basic conditions) and Ni-rGO (under acidic conditions) prepared in comparative example 1 were used as a comparison. The test adopts a standard three-electrode system, the working electrode is a glassy carbon electrode, the counter electrode is a platinum electrode, and the reference electrode is a saturated calomel electrode. Catalyst loading 0.56mg/cm2. Electrolyte solution of 0.5M H2SO4Or 1M KOH. Before testing, argon gas was introduced into the electrolyte for 30min to remove dissolved oxygen. And (3) testing a polarization curve by adopting a linear sweep voltammetry, wherein the sweep speed is 2 mV/s. The results are shown in FIG. 4. Electrolyte solution of 0.5M H2SO4When as in FIG. 4 (a), MoS2-rGO-Ni-100 current density up to 10mA/cm2Required overpotential (η)10) 325mV, the current density increased further with increasing applied voltage. Without containing MoS2Of Ni-rGO comparative sample, eta10428mV indicates MoS2The introduction of the compound can effectively improve the catalytic activity of the composite material under the acidic condition. Furthermore, MoS2the-rGO-Ni-100 composite material has better catalytic activity in alkaline (1M KOH) (as shown in (b) in figure 4), eta10244mV for the control MoS2Eta of rGO10425mV, indicating that the introduction of Ni significantly increased the catalytic activity under alkaline conditions.
It should be noted that the characterization results of the molybdenum disulfide/reduced graphene oxide/nickel nanoparticles prepared in examples 2 to 9 are substantially consistent with the results of example 1, and it can also be proved that a molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material is prepared; meanwhile, the molybdenum disulfide/reduced graphene oxide/nickel nanoparticles prepared in examples 2 to 9 also have performance substantially identical to that of the composite material in example 1, and can be used as a hydrogen evolution reaction catalyst.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (5)
1. A molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material serving as a hydrogen evolution reaction catalyst in alkaline electrolyte is characterized in that reductive graphene oxide is used as a substrate, molybdenum disulfide nanosheets are dispersed on the reductive graphene oxide substrate, and nickel nanoparticles are dispersed on the reductive graphene oxide substrate and the molybdenum disulfide nanosheets;
the preparation method of the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material comprises the following steps:
(1) dispersing graphene oxide in water to obtain a graphene oxide dispersion liquid, wherein the ratio of the mass of the graphene oxide to the volume of the water is 1: (1-2) mg/mL;
(2) mixing a molybdenum source, a sulfur source and graphene oxide dispersion liquid to obtain a first reaction mixture, wherein the ratio of the mole number of the molybdenum source to the mass of the graphene oxide is (0.033-0.1):1 mol/g; the molar ratio of the sulfur source to the molybdenum source is (2.5-10): 1;
(3) carrying out hydrothermal reaction on the first reaction mixture at 180-220 ℃ for 18-30 hours, and separating and washing after the reaction is finished to obtain a molybdenum disulfide/reductive graphene oxide composite material;
(4) dispersing the molybdenum disulfide/reductive graphene oxide composite material in an organic solvent to obtain a molybdenum disulfide/reductive graphene oxide composite material dispersion liquid, wherein the ratio of the mass of the molybdenum disulfide/reductive graphene oxide composite material to the volume of the organic solvent is 1: (1-2) mg/mL;
(5) adding a nickel source and hydrazine hydrate into the molybdenum disulfide/reductive graphene oxide composite material dispersion liquid, and adjusting the pH value to be 8-10 to obtain a second reaction mixture, wherein the ratio of the mole number of the nickel source to the mass of the molybdenum disulfide/reductive graphene oxide composite material is (0.0018-0.007): 1mol/g, wherein the ratio of the volume of the hydrazine hydrate to the mass of the molybdenum disulfide/reduced graphene oxide composite material is (0.02-0.03): 1 mL/mg;
(6) and reacting the second reaction mixture at 50-70 ℃ for 0.5-3 hours, and separating and washing after the reaction is finished to obtain the molybdenum disulfide/reductive graphene oxide/nickel nanoparticle composite material.
2. The molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material of claim 1, wherein the molybdenum source is selected from one of sodium molybdate, ammonium molybdate, or a combination thereof.
3. The molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material of claim 1, wherein the sulfur source is selected from one of thiourea, thioacetamide, or a combination thereof.
4. The molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material of claim 1, wherein the nickel source is selected from one of nickel sulfate, nickel nitrate, nickel chloride, or a combination thereof.
5. The molybdenum disulfide/reduced graphene oxide/nickel nanoparticle composite material of any one of claims 1-4, wherein the organic solvent is one of ethylene glycol, ethanol, or a combination thereof.
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