CN111778517A - Electrode material and preparation method and application thereof - Google Patents
Electrode material and preparation method and application thereof Download PDFInfo
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- CN111778517A CN111778517A CN202010502805.1A CN202010502805A CN111778517A CN 111778517 A CN111778517 A CN 111778517A CN 202010502805 A CN202010502805 A CN 202010502805A CN 111778517 A CN111778517 A CN 111778517A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 239000000463 material Substances 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 39
- 239000000758 substrate Substances 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 239000002070 nanowire Substances 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000001816 cooling Methods 0.000 claims description 15
- 150000002815 nickel Chemical class 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 238000005868 electrolysis reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 13
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 13
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- 229910005809 NiMoO4 Inorganic materials 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002751 molybdenum Chemical class 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 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
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 3
- 239000011609 ammonium molybdate Substances 0.000 claims description 3
- 229940010552 ammonium molybdate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 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
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 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
- 238000005265 energy consumption Methods 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 11
- 229910000510 noble metal Inorganic materials 0.000 description 10
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000004090 dissolution Methods 0.000 description 8
- 230000010287 polarization Effects 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 239000010411 electrocatalyst Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical group O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 5
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical group [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- 229910052976 metal sulfide Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
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- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001420 photoelectron spectroscopy Methods 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 230000003467 diminishing effect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Catalysts (AREA)
Abstract
The invention provides an electrode material and a preparation method and application thereof, belonging to the technical field of electrocatalytic materials. The electrode material is N-doped NiMoS4Forming a nanowire vertically grown on a conductive substrate. The electrode material is mainly used in electrolytic water reaction, and the low-cost nitrogen-doped NiMoS is obtained by adopting a simple, easy-to-operate and low-energy-consumption hydrothermal synthesis method4The electrode material has excellent hydrogen and oxygen production full-hydrolysis performance, good stability and good application prospect.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic materials, and particularly relates to an electrode material and a preparation method and application thereof.
Background
With the increasing demand for energy and the accompanying crisis of environmental pollution, the need for developing other renewable and clean energy sources is becoming more urgent, and hydrogen as a clean green energy source with zero emission products has become a diminishing alternative to fossil fuels.
Electrocatalytic water decomposition to produce hydrogen and oxygen is a continuous, cost effective process, but requires highly efficient electrocatalysts to accelerate the catalytic rate and reduce energy losses. The electrolytic water reaction comprises two half reactions, namely a slow anodic oxygen evolution reaction and a relatively easy cathodic hydrogen evolution reaction, and the theoretical decomposition voltage is 1.23V. However, due to the surface redox reaction and the transmission resistance of charges/ions at the interface, the voltage of the battery in practical application is about 1.8-2.0V, which is far higher than the theoretical value, so that the cost of industrial hydrogen production by water electrolysis is greatly increased. Therefore, it is of great significance to develop a highly efficient catalyst for electrolyzing water to lower the electrolysis voltage.
At present, the electrolytic water catalyst mainly comprises a noble metal electrocatalyst and a non-noble metal electrocatalyst. The Pt-based noble metal catalyst and the Ir or Ru-based noble metal catalyst are the most advanced electrocatalysts for hydrogen production by water electrolysis and oxygen production by water electrolysis respectively, but the noble metal catalyst has high price, scarce storage, low double-functionality and poor stability, and the wide application of the noble metal catalyst is limited. Non-noble metal electrocatalysts, such as transition metal materials (metal sulfides, phosphides, nitrides and carbides), while inexpensive, require greater overpotentials than noble metal-based materials, particularly for the slow kinetics of the water electrolysis to produce oxygen. Therefore, it is of great significance to further develop non-noble metal electrocatalysts to achieve minimization of the perhydrolysis overpotential.
The non-noble metal electrocatalyst ternary metal sulfide has excellent electrochemical performance due to the unique electronic structure, and has important application in the fields of catalytic electrolysis of water, supercapacitors and the like. The ternary metal sulfide has more active sites compared with the binary metal sulfide, and has stronger redox reaction and higher electronic conductivity compared with the corresponding ternary oxide. However, the S atom is easy to combine with the adsorbed H atom to hinder the resolution of the H atom and the electroaquatic oxygen generation process with complex kinetics, so that the ternary sulfide has low double-functionality, generally shows good activity for one half of reactions, and shows moderate activity for the other half of reactions, thereby causing high over-potential of total hydrolysis.
Disclosure of Invention
The invention provides an electrode material and a preparation method and application thereof, the method is simple and convenient to operate, high-efficiency and energy-saving, the obtained electrode material has good catalytic activity of hydrogen production and oxygen production by water electrolysis, the overpotential is low, the stability is good, and the electrode material is a durable and high-efficiency bifunctional catalyst.
The present invention provides an electrode material, which is provided with a plurality of electrodes,
the electrode material is N-doped NiMoS4Forming a nanowire vertically grown on a conductive substrate.
The invention also provides a preparation method of the electrode material,
the method comprises the following steps:
a) dissolving an S source and an N source in an organic solvent to obtain a first solution.
b) The precursor NiMoO is added4The material is vertically placed in the center of a reaction kettle, the first solution is added for hydrothermal reaction, and the obtained electrode material is a product.
Further, after the hydrothermal reaction, taking out the electrode material, cooling, washing and drying.
Further, in the step a), the S source and the N source comprise at least one of thioacetamide and thiourea; the concentrations of the S source and the N source are respectively 0.02-0.15 mol/L.
Further, in the step a), the organic solvent comprises at least one of ethanol, ethylene glycol and n-hexane.
Further, in the step b), the temperature of the hydrothermal reaction is 80-150 ℃; the duration of the hydrothermal reaction is 4-24 h.
Further, a precursor NiMoO4The preparation method of the material comprises the following steps:
b1) dissolving molybdate in deionized water, adding nickel salt, and mixing to obtain a second solution;
b2) vertically placing a conductive substrate in a reaction kettle, adding the second solution obtained in the step b1) into the reaction kettle, carrying out hydrothermal reaction, cooling to room temperature after the reaction is finished, taking out the conductive substrate, washing and drying to obtain a precursor NiMoO4A material.
Further, in step b 1):
the molybdate comprises at least one of ammonium molybdate or sodium molybdate; the concentration of molybdate is 0.01-0.5 mol/L;
the nickel salt comprises at least one of nickel nitrate, nickel sulfate and nickel chloride; the concentration of the nickel salt is 0.01-0.5 mol/L;
the mass ratio of the molybdenum salt to the nickel salt is (1-100): (1-100).
Step b 2):
the temperature of the hydrothermal reaction is 150-250 ℃; the duration of the hydrothermal reaction is 4-24 h.
The invention also provides the application of the electrode material in the electrolytic water.
Further, the electrolyzed water comprises at least one of an electrolyzed water hydrogen evolution reaction, an electrolyzed water oxygen evolution reaction or a full water hydrolysis reaction.
The invention has the following advantages:
the invention adopts a simple, easy-to-operate and low-energy-consumption hydrothermal synthesis method to obtain the low-cost nitrogen-doped NiMoS4The electrode material has excellent hydrogen production, oxygen production and full water decomposition performances, and has good stability and good application prospect.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a Scanning Electron Microscope (SEM) image of the electrode material prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the electrode material prepared in example 2;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the electrode material prepared in example 3;
FIG. 4 is an Element Distribution (EDS) diagram of the electrode material prepared in example 1;
FIG. 5 is an X-ray diffraction (XRD) pattern of the electrode material prepared in example 1; (abscissa: 2 θ, unit: degree; ordinate: relative abundance.)
FIG. 6 is an X-photoelectron spectroscopy (XPS) broad spectrum of the electrode material prepared in example 1; (abscissa: binding energy; ordinate: relative abundance.)
FIG. 7 is a graph showing electrochemical Hydrogen Evolution Reaction (HER) polarization of the electrode material prepared in example 1; (abscissa: voltage (relative to saturated calomel electrode); ordinate: current density.)
FIG. 8 is a graph showing electrochemical Hydrogen Evolution Reaction (HER) polarization of the electrode material prepared in example 2;
FIG. 9 is a graph showing electrochemical Oxygen Evolution Reaction (OER) polarization of the electrode material prepared in example 1;
FIG. 10 is a graph showing electrochemical Oxygen Evolution Reaction (OER) polarization of the electrode material prepared in example 2;
FIG. 11 is a polarization curve of the electrode material prepared in example 1 under a two-electrode test; (abscissa: voltage; ordinate: current density.)
Fig. 12 is a time-current graph of the electrode material prepared in example 1 tested under a two-electrode using a chronoamperometry. (abscissa: time; ordinate: current density.)
FIG. 13 is a graph showing electrochemical oxygen evolution reaction (HER) polarization of the electrode material prepared in comparative example 1;
FIG. 14 is a graph showing electrochemical hydrogen evolution reaction (OER) polarization of the electrode material prepared in comparative example 1;
FIG. 15 is a high resolution X-photoelectron spectroscopy (XPS) plot of S2 p for the electrode material prepared in example 1;
FIG. 16 is a high resolution X-photoelectron spectroscopy (XPS) of N1s of the electrode material prepared in example 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention and the accompanying drawings, 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. The embodiments and features of the embodiments of the present invention may be combined with each other without conflict.
An embodiment of the present invention provides an electrode material, wherein the electrode material is N-doped NiMoS4Forming a nanowire vertically grown on a conductive substrate. The embodiment of the invention provides nitrogen-doped NiMoS4The electrode material has the advantages of ternary sulfide in electrocatalysis and is electronically regulated and controlled by N dopingMakes up for the deficiency of the double functions and has lower over-potential of the total hydrolysis.
An embodiment of the present invention further provides a method for preparing an electrode material, including the following steps:
a) dissolving an S source and an N source in an organic solvent to obtain a first solution.
b) The precursor NiMoO is added4The material is vertically placed in the center of a reaction kettle, the first solution is added for hydrothermal reaction, and the obtained electrode material is a product.
In the prior art, NiMoS4The other elements are doped by adopting a high-temperature calcination method. The embodiment of the invention provides nitrogen-doped NiMoS4Electrode material and method for producing the same in NiMoO4On a precursor material, an S source and an N source are dissolved in an organic solvent for hydrothermal reaction, and the regulation and control effect on the electron space distribution of the material is realized through N doping, so that the obtained nitrogen-doped NiMoS4Electrode material (denoted as N-NiMoS)4) Meanwhile, the water electrolysis hydrogen production and oxygen production activity is good.
The method is simple and easy to operate, low in energy consumption and cost, has the full-water electrolysis double-function catalysis effect, is low in overpotential and good in stability, and has a good application prospect.
In a preferred embodiment of the present invention, the preparation method further includes, after the hydrothermal reaction, taking out the electrode material, cooling, washing, and drying.
Specifically, the conductive substrate is a conventional conductive substrate, and may include nickel foam, carbon fiber paper, carbon cloth, and the like. Specifically, the hydrothermal reaction is carried out under a closed condition. Specifically, the reaction kettle is a reaction kettle with a polytetrafluoroethylene lining.
In an embodiment of the present invention, in step a), the S source and the N source include at least one of thioacetamide and thiourea. Preferably, the S source and the N source are thioacetamide. According to the embodiment of the invention, thioacetamide and thiourea are selected, and both can provide an N source and an S source, so that vulcanization and nitridation can be realized simultaneously under mild conditions, and the N-doped ternary sulfide material is obtained, and has the electrocatalytic advantage of ternary sulfide, and the defects of dual functions of the N-doped ternary sulfide material are overcome through N-doped electronic regulation, so that the total hydrolysis overpotential is lower.
In one embodiment of the present invention, in step a), the concentrations of the S, N sources are 0.02-0.15mol/L, respectively. Preferably, the source S, N has a concentration of 0.03 to 0.05 mol/L.
In an embodiment of the present invention, in the step a), the organic solvent includes at least one of ethanol, ethylene glycol, and n-hexane. Preferably, in step a), the organic solvent is ethanol.
In one embodiment of the present invention, in the step b), the temperature of the hydrothermal reaction is 80-150 ℃. Preferably, the temperature of the hydrothermal reaction is 100-. The hydrothermal reaction temperature is milder, which is beneficial to N doping.
In one embodiment of the present invention, in step b), the duration of the hydrothermal reaction is 4 to 24 hours. Preferably, the duration of the hydrothermal reaction is 14 to 18 hours.
In one embodiment of the present invention, the precursor NiMoO4The preparation method of the material comprises the following steps:
b1) dissolving molybdate in deionized water, adding nickel salt, and mixing to obtain a second solution;
b2) vertically placing a conductive substrate in a reaction kettle, adding the second solution obtained in the step b1) into the reaction kettle, carrying out hydrothermal reaction, cooling to room temperature after the reaction is finished, taking out the conductive substrate, washing and drying to obtain a precursor NiMoO4A material. In the embodiment of the invention, the conductive substrate is vertically arranged in the reaction kettle, so that the influence of gravity settling on two surfaces of the substrate is equal. If the inclination is made, the load amounts on both sides are different.
Specifically, in step b 1):
the molybdate comprises at least one of ammonium molybdate or sodium molybdate. The concentration of the molybdate is 0.01-0.5 mol/L. Preferably, the molybdate is sodium molybdate dihydrate. The concentration of the molybdate is 0.1-0.2 mol/L.
The nickel salt comprises at least one of nickel nitrate, nickel sulfate and nickel chloride. The concentration of the nickel salt is 0.01-0.5 mol/L. Preferably, the nickel salt is nickel nitrate hexahydrate. The concentration of the nickel salt is 0.1-0.2 mol/L.
The mass ratio of the molybdenum salt to the nickel salt is (1-100): (1-100). Preferably, the amount ratio of the molybdenum salt to the nickel salt species is 1: 1.
specifically, in step b 2):
the temperature of the hydrothermal reaction is 150-250 ℃. Preferably, the temperature of the hydrothermal reaction is 170-.
The duration of the hydrothermal reaction is 4-24 h. Preferably, the duration of the hydrothermal reaction is 8 to 12 hours.
The embodiment of the invention also provides the application of the electrode material in the electrolytic water.
Preferably, the electrolysis of water is carried out under alkaline conditions, and the electrolysis of water comprises at least one of an electrolysis water hydrogen evolution reaction, an electrolysis water oxygen evolution reaction and a full water hydrolysis reaction. The hydrogen evolution reaction or the oxygen evolution reaction is to use the material as a cathode or an anode separately and test the material as a three-electrode system. The total hydrolysis is to make the material as cathode and anode at the same time, and test as a double-electrode system. Preferably, the nitrogen is doped with NiMoS4The application of the electrode material in the full-hydrolytic reaction.
Specifically, the electrode material is applied to the electrolytic water hydrogen evolution reaction under the alkaline condition; and/or the application of the electrode material in the electrolytic water oxygen evolution reaction under the alkaline condition; and/or the application of the electrode material in the full hydrolysis reaction under the alkaline condition.
The present invention will be described in detail with reference to examples.
Example 1Nitrogen-doped NiMoS4An electrode material comprising the steps of:
dissolving 0.2mmol of sodium molybdate dihydrate into 15mL of deionized water, adding 0.2mmol of nickel nitrate hexahydrate after complete dissolution, and stirring until complete dissolution and uniform mixing to obtain a second solution. The concentrations of molybdenum and nickel were both 0.013mol/L at this time.
Vertically placing the conductive substrate in the center of a polytetrafluoroethylene reaction kettle lining, adding the second solution obtained in the step (1) into the reaction kettle, carrying out hydrothermal reaction for 10 hours at 180 ℃ under a closed condition, cooling to room temperature after the reaction is finished, taking out the substrate, washing, and drying to obtain the precursor material.
Dissolving 40mg of thioacetamide into 15mL of absolute ethyl alcohol solvent to obtain a first solution. The concentration of thioacetamide at this time was 0.035 mol/L.
⑷ vertically placing the material obtained in the step (2) in the center of an inner liner of a polytetrafluoroethylene reaction kettle, adding the first solution obtained in the step (3) into the reaction kettle, carrying out hydrothermal reaction for 16h at 120 ℃ under a closed condition, cooling to room temperature after the reaction is finished, taking out the substrate, washing and drying to obtain the N-NiMoS4A catalyst material.
Example 2Nitrogen-doped NiMoS4An electrode material comprising the steps of:
dissolving 0.2mmol of sodium molybdate dihydrate into 15mL of deionized water, adding 0.3mmol of nickel nitrate hexahydrate after complete dissolution, and stirring until complete dissolution and uniform mixing to obtain a second solution. The concentrations of molybdenum and nickel at this time were 0.013 and 0.02mol/L, respectively.
Vertically placing the conductive substrate in the center of a polytetrafluoroethylene reaction kettle lining, adding the second solution obtained in the step (1) into the reaction kettle, carrying out hydrothermal reaction for 10 hours at 180 ℃ under a closed condition, cooling to room temperature after the reaction is finished, taking out the substrate, washing, and drying to obtain the precursor material.
Dissolving 40mg of thioacetamide into 15mL of absolute ethyl alcohol solvent to obtain a first solution. The concentration of thioacetamide at this time was 0.035 mol/L.
⑷ vertically placing the material obtained in the step (2) in the center of an inner liner of a polytetrafluoroethylene reaction kettle, adding the first solution obtained in the step (3) into the reaction kettle, carrying out hydrothermal reaction for 16h at 120 ℃ under a closed condition, cooling to room temperature after the reaction is finished, taking out the substrate, washing and drying to obtain the N-NiMoS4A catalyst material.
Example 3Nitrogen-doped NiMoS4An electrode material comprising the steps of:
dissolving 0.2mmol of sodium molybdate dihydrate into 15mL of deionized water, adding 0.2mmol of nickel nitrate hexahydrate after complete dissolution, and stirring until complete dissolution and uniform mixing to obtain a second solution. The concentrations of molybdenum and nickel were both 0.013mol/L at this time.
Vertically placing the conductive substrate in the center of a polytetrafluoroethylene reaction kettle lining, adding the second solution obtained in the step (1) into the reaction kettle, carrying out hydrothermal reaction for 10 hours at 180 ℃ under a closed condition, cooling to room temperature after the reaction is finished, taking out the substrate, washing, and drying to obtain the precursor material.
Dissolving 100mg of thioacetamide into 15mL of absolute ethyl alcohol solvent to obtain a first solution. The concentration of thioacetamide at this time was 0.089 mol/L.
⑷ vertically placing the material obtained in the step (2) in the center of an inner liner of a polytetrafluoroethylene reaction kettle, adding the first solution obtained in the step (3) into the reaction kettle, carrying out hydrothermal reaction for 16h at 120 ℃ under a closed condition, cooling to room temperature after the reaction is finished, taking out the substrate, washing and drying to obtain the N-NiMoS4A catalyst material.
Example 4Nitrogen-doped NiMoS4An electrode material comprising the steps of:
dissolving 0.2mmol of sodium molybdate dihydrate into 15mL of deionized water, adding 0.2mmol of nickel nitrate hexahydrate after complete dissolution, and stirring until complete dissolution and uniform mixing to obtain a second solution. The concentrations of molybdenum and nickel were both 0.013mol/L at this time.
Vertically placing the conductive substrate in the center of a polytetrafluoroethylene reaction kettle lining, adding the second solution obtained in the step (1) into the reaction kettle, carrying out hydrothermal reaction for 10 hours at 180 ℃ under a closed condition, cooling to room temperature after the reaction is finished, taking out the substrate, washing, and drying to obtain the precursor material.
Dissolving 40mg of thioacetamide into 15mL of absolute ethyl alcohol solvent to obtain a first solution. The concentration of thioacetamide at this time was 0.035 mol/L.
⑷ vertically placing the material obtained in the step (2) in the center of an inner liner of a polytetrafluoroethylene reaction kettle, adding the first solution obtained in the step (3) into the reaction kettle, carrying out hydrothermal reaction for 24 hours at 120 ℃ under a closed condition, cooling to room temperature after the reaction is finished, taking out the substrate, washing and drying to obtain the N-NiMoS4A catalyst material.
Comparative example 1Nitrogen-doped NiMoS4An electrode material comprising the steps of:
(1) (1) to (2) the same as example 1 except thatAnd (3) putting the precursor material obtained in the step (2) into the middle of a quartz tube of a tube furnace, placing 1g of sulfur powder at the upstream as a sulfur source, using ammonia gas as a carrier gas and a nitrogen source, and carrying out heat treatment for 1h at 600 ℃. Cooling and taking out to obtain N-NiMoS4An electrode material.
Test example 1Nitrogen doped NiMoS4Electrode material result characterization
The N-NiMoS obtained in example 1 to 34The electrode material is subjected to scanning electron microscope test, and the result is shown in figures 1-3.
The N-NiMoS obtained in example 1 was subjected to Energy Dispersive Spectroscopy (EDS)4The electrode material was subjected to elemental distribution analysis, and the results are shown in FIG. 4.
The N-NiMoS obtained in example 1 was subjected to X-ray diffractometry (XRD)4The electrode material was subjected to crystal morphology analysis and the results are shown in FIG. 5.
The N-NiMoS obtained in example 1 was subjected to X-ray photoelectron spectroscopy (XPS)4The electrode material was subjected to chemical composition and valence state analysis, and the results are shown in fig. 6, fig. 15, and fig. 16.
The nano-wires grow on the conductive substrate uniformly and compactly, and the structure increases the specific surface area of the material and improves the electron transmission capability. Fig. 4 verifies that S and N elements coexist and are evenly distributed. Fig. 5 verifies that the material is amorphous. The presence of Ni 2p, Mo 3d, S2 p and N1S was verified in fig. 6. FIGS. 15 and 16 verify the presence of S-metal and N-metal, respectively, and S has a valence of-2. Proves the NiMoS4In the presence of and the product is N-NiMoS4。
Test example 2N-NiMoS4Electrode material hydrogen-production oxygen-production performance test by electrolyzing water
The N-NiMoS obtained in example 1, example 2 and comparative example 1 was mixed4The electrode material is respectively subjected to hydrogen production, oxygen production and total hydrolysis performance tests, and the results are shown in figures 7-13.
As is clear from FIGS. 7 and 8, the N-NiMoS obtained in examples 1 and 24Material HER process at current density of 10mAcm-2The overpotential was 86.5mV and 111.4mV, respectively. Therefore, the material prepared by the method has better HER performance.
As is clear from FIGS. 9 and 10, those obtained in examples 1 and 2N-NiMoS4Materials OER Process at Current Density of 10mA cm-2The overpotential for time was 238mV and 299mV, respectively. Therefore, the material prepared by the method has better OER performance.
As is clear from FIGS. 11 and 12, the N-NiMoS obtained in example 14Material double-electrode test and full-hydrolysis process at current density of 10mA cm-2The overpotential at this time was 340 mV. And can continuously and stably work for 30 hours. Therefore, the material prepared by the method has good full-hydrolytic activity and stability.
As can be seen from FIGS. 13 and 14, comparative example 1 is N-NiMoS obtained by a conventional high-temperature calcination N doping method4In FIG. 13, the HER process shows a polarization curve of hydrogen and oxygen generation from the electrode material of the hydrothermal synthesis method not proposed in the present invention, and the current density is 10mA cm-2The overpotential in time was 116.2mV, a little larger than in example 1. In FIG. 14, the overpotential for the OER process at a current density of 10mA cm-2 is 465mV, which is significantly higher than 227mV in example 1. It can be seen that this doping method only improves HER performance properly and only has no effect on the OER process with complex reaction mechanism and slow kinetics. And the nanostructure of the material is easy to damage under the high temperature state.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. An electrode material characterized in that,
the electrode material is N-doped NiMoS4Forming a nanowire vertically grown on a conductive substrate.
2. The method for producing an electrode material according to claim 1,
the method comprises the following steps:
a) dissolving an S source and an N source in an organic solvent to obtain a first solution.
b) The precursor NiMoO is added4The material is vertically placed in the center of the reaction kettle, and the first solution is addedCarrying out hydrothermal reaction to obtain the electrode material, namely the product.
3. The production method according to claim 2,
and also comprises the steps of taking out the electrode material after the hydrothermal reaction, cooling, washing and drying.
4. The production method according to claim 2,
in the step a), the S source and the N source comprise at least one of thioacetamide and thiourea; the concentrations of the S source and the N source are respectively 0.02-0.15 mol/L.
5. The production method according to claim 2,
in the step a), the organic solvent comprises at least one of ethanol, ethylene glycol and n-hexane.
6. The production method according to claim 2,
in the step b), the temperature of the hydrothermal reaction is 80-150 ℃; the duration of the hydrothermal reaction is 4-24 hours.
7. The production method according to claim 2,
the precursor NiMoO4The preparation method of the material comprises the following steps:
b1) dissolving molybdate in deionized water, adding nickel salt, and mixing to obtain a second solution;
b2) vertically placing a conductive substrate in a reaction kettle, adding the second solution obtained in the step b1) into the reaction kettle, carrying out hydrothermal reaction, cooling to room temperature after the reaction is finished, taking out the conductive substrate, washing and drying to obtain a precursor NiMoO4A material.
8. The production method according to claim 7,
step b 1):
the molybdate comprises at least one of ammonium molybdate or sodium molybdate; the concentration of molybdate is 0.01-0.5 mol/L;
the nickel salt comprises at least one of nickel nitrate, nickel sulfate and nickel chloride; the concentration of the nickel salt is 0.01-0.5 mol/L;
the mass ratio of the molybdenum salt to the nickel salt is (1-100): (1-100).
Step b 2):
the temperature of the hydrothermal reaction is 150-250 ℃; the duration of the hydrothermal reaction is 4-24 hours.
9. Use of the electrode material of claim 1 in the electrolysis of water.
10. Use according to claim 9,
the electrolytic water comprises at least one of an electrolytic water hydrogen evolution reaction, an electrolytic water oxygen evolution reaction or a full water hydrolysis reaction.
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