CN110787824B - Preparation method and application of vanadium-doped transition metal nitride - Google Patents
Preparation method and application of vanadium-doped transition metal nitride Download PDFInfo
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- CN110787824B CN110787824B CN201910964187.XA CN201910964187A CN110787824B CN 110787824 B CN110787824 B CN 110787824B CN 201910964187 A CN201910964187 A CN 201910964187A CN 110787824 B CN110787824 B CN 110787824B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 title abstract description 10
- -1 transition metal nitride Chemical class 0.000 title abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 103
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 53
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 29
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910005809 NiMoO4 Inorganic materials 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 7
- 239000011733 molybdenum Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 239000010453 quartz Substances 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 4
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical group [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 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 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000005121 nitriding Methods 0.000 claims 2
- 238000004321 preservation Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 22
- 239000001301 oxygen Substances 0.000 abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 abstract description 22
- 229910009112 xH2O Inorganic materials 0.000 abstract description 9
- 150000003624 transition metals Chemical class 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 239000002156 adsorbate Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000000543 intermediate Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000013112 stability test Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 3
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000002751 molybdenum Chemical class 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 150000002815 nickel Chemical class 0.000 description 2
- 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 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 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 compound [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 2
- 238000012546 transfer Methods 0.000 description 2
- 150000003681 vanadium Chemical class 0.000 description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229940078487 nickel acetate tetrahydrate Drugs 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- OINIXPNQKAZCRL-UHFFFAOYSA-L nickel(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O OINIXPNQKAZCRL-UHFFFAOYSA-L 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing 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
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/069—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of at least one single element and at least one compound; consisting of two or more compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention relates to a technique for preparing transition metal nitrideThe technical field, in particular to a preparation method and application of vanadium doped transition metal nitride. The method comprises the following steps: mixing nickel source, molybdenum source and vanadium source uniformly, and hydrothermally growing vanadium-doped NiMoO on a foamed nickel substrate4·xH2O precursor; the obtained vanadium-doped NiMoO4·xH2Performing high-temperature nitridation treatment on the O precursor to obtain vanadium-doped Ni0.2Mo0.8And an N electrode. The invention has lower overpotential and faster kinetic rate in the aspects of hydrogen evolution and oxygen evolution, and shows excellent performance of electrocatalytic water decomposition. In addition, the vanadium doped Ni prepared by the invention0.2Mo0.8The N electrode material exhibits excellent stability in both hydrogen evolution and oxygen evolution.
Description
Technical Field
The invention relates to the technical field of preparation of transition metal nitrides, in particular to a preparation method and application of a vanadium-doped transition metal nitride.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
As the society develops, the energy crisis becomes increasingly severe due to limited and non-renewable reserves of fossil fuels. Hydrogen energy has received increasing attention in recent years due to its high combustion value, its clean, pollution-free and renewable advantages. Among the hydrogen evolution technologies, the electrocatalytic decomposition of water for hydrogen evolution as a more feasible technology is currently receiving more and more attention. The electrocatalytic decomposition of water is divided into two parts of cathodic hydrogen evolution and anodic oxygen evolution. The hydrogen and oxygen evolution catalysts which currently perform best and are most widely used are the noble metals Pt/C and RuO, respectively2/IrO2. Because precious metal reserves are rare and expensive, the development of efficient non-precious metal based electrocatalytic hydrogen and oxygen evolution materials to replace precious metals is the focus of current research. Among many alternative non-noble metal-based electrocatalytic water decomposition materials, transition metal nitrides, particularly NiMoN-based compounds, are favored by researchers because of their high conductivity and high corrosion resistance, and for example, patent document 201910223899.6 discloses a carbon-coated nickel-molybdenum nitride composite material, which is obtained by mixing and heating a nickel-molybdenum nitride alloy as a core with an organic solid containing nitrogen and carbon, and which exhibits excellent electrocatalytic hydrogen evolution performance and oxidation resistance, and also has good corrosion resistance.
Disclosure of Invention
However, the inventor researches and discovers that: since the adsorption of NiMoN water, active hydrogen and oxygen-containing intermediates is still not to an ideal extent, the overpotential for decomposing water by NiMoN is still large and still cannot meet the current demand.
Therefore, the invention provides a vanadium-doped Ni based on transition metal nitride0.2Mo0.8The preparation method of N is used for further reducing the overpotential of the water decomposed by the transition metal nitride NiMoN, and when the material is used for electrocatalytic water decomposition, the excellent water decomposition effect is shown, and the overpotential of the water decomposed is effectively reduced.
The first object of the present invention: providing a vanadium-doped Ni0.2Mo0.8A preparation method of N.
The second object of the present invention: vanadium doped Ni prepared by the method0.2Mo0.8And (4) application of N.
In order to realize the purpose, the invention discloses the following technical scheme:
firstly, the invention discloses a vanadium-doped Ni0.2Mo0.8The preparation method of N comprises the following steps:
(1) vanadium doped NiMoO synthesis by hydrothermal method4·xH2And (3) O material.
(2) Doping vanadium with NiMoO4·xH2Taking O material as a precursor, and carrying out high-temperature nitridation treatment to obtain vanadium-doped Ni0.2Mo0.8N。
Secondly, the invention discloses vanadium-doped Ni prepared by the method0.2Mo0.8The application of N in electrocatalytic decomposition of water, such as the electrocatalytic decomposition of water to produce hydrogen.
Compared with the prior art, the vanadium-doped Ni prepared by the invention0.2Mo0.8N has the following beneficial effects:
(1) the invention finds that in terms of hydrogen evolution, vanadium doped Ni is produced0.2Mo0.8N electrode at 10mA cm-2After iR compensation, the overpotential is only 39mV (vs. rhe), which is because the vanadium doping optimizes the adsorption energy of the material to active hydrogen, so that the desorption process of hydrogen is easier, and the hydrogen evolution performance is improved. In terms of oxygen evolution, at 25mA cm-2Under the current of (2), after the iR compensation, the overpotential is only 245mV (vs. RHE), which is because the adsorption energy of the material to oxygen-containing intermediates is optimized by vanadium doping, so that the oxygen evolution overpotential is reduced, and the oxygen evolution performance is improved. Doping of vanadium with Ni0.2Mo0.8The N electrode was assembled as both cathode and anode, and the cell was operated at 10mA cm without iR compensation-2The required voltage is only 1.52V at the current of (1), compared with Pt/C and RuO under the same conditions2The assembled cell was operated at 10mA cm-2The voltage (1.60V) is effectively reduced.
(2) The invention has lower overpotential and faster kinetic rate in the aspects of hydrogen evolution and oxygen evolution.
(3) The electrode material of the present invention exhibits excellent stability in both hydrogen evolution and oxygen evolution.
(4) The materials used in the invention are non-noble metal materials, and have low price and abundant reserves.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 shows vanadium doped Ni prepared in example 1 of the present invention0.2Mo0.8XRD pattern of N electrode.
FIG. 2 shows vanadium doped Ni prepared in example 1 of the present invention0.2Mo0.8SEM image of N electrode.
FIG. 3 shows vanadium doped Ni prepared in example 1 of the present invention0.2Mo0.8HRTEM of N electrodes.
FIGS. 4a and 4b are respectively the Ni doped with vanadium prepared in example 1 of the present invention0.2Mo0.8The current density-voltage relation maps of the N electrode hydrogen evolution and oxygen evolution.
FIGS. 5a and 5b are respectively the Ni doped with vanadium prepared in example 1 of the present invention0.2Mo0.8Stability test chart of N electrode hydrogen evolution and oxygen evolution.
FIG. 6 shows vanadium doped Ni prepared in example 1 of the present invention0.2Mo0.8The N electrode is used as a current density-voltage relation map of cathode and anode electrolytic water at the same time.
FIG. 7 shows vanadium doped Ni prepared in example 1 of the present invention0.2Mo0.8And the N electrode is used as a stability test map of cathode and anode electrolyzed water.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms also are intended to include the plural forms as well, unless the context clearly indicates otherwise, and it should be further understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of the stated features, steps, operations, devices, components, and/or combinations thereof.
As mentioned above, since NiMoN still does not adsorb water, active hydrogen and oxygen-containing intermediates to a desired degree, the overpotential for decomposing water by NiMoN is still large, and thus the current demand cannot be satisfied. Therefore, the invention provides a vanadium-doped Ni based on transition metal nitride0.2Mo0.8A preparation method of N.
In some exemplary embodiments, the hydrothermal synthesis of vanadium doped NiMoO4·xH2The method of the O material comprises the following steps: uniformly mixing a nickel source, a molybdenum source and a vanadium source, and reacting the mixed solution with a substrate under a hydrothermal condition, thereby hydrothermally growing vanadium-doped NiMoO on the substrate4·xH2And (3) washing the substrate with deionized water and ethanol respectively after the precursor O is removed, and drying and storing the material obtained by washing to obtain vanadium-doped NiMoO4·xH2And (3) O material.
In some exemplary embodiments, the high temperature nitridation process is performed by: doping vanadium with NiMoO4·xH2And (3) putting the O precursor into a porcelain boat, putting the porcelain boat into a quartz tube, putting the quartz tube into a tube furnace, introducing ammonia gas, heating the tube furnace to a set temperature, and preserving heat to obtain the ceramic material.
In some typical embodiments, the addition ratio of the nickel salt, the molybdenum salt and the vanadium salt is as follows: the molar ratio of nickel atoms to molybdenum atoms to vanadium atoms is 25-35: 28-42: 4-12.
In some exemplary embodiments, the substrate is made of nickel foam.
In some exemplary embodiments, the method further comprises the step of cleaning the nickel foam before use: in order to remove an oxide layer on the surface of the foamed nickel and residual organic matters, the foamed nickel is respectively put into dilute hydrochloric acid, acetone and ethanol for respective ultrasonic cleaning, and then the cleaned foamed nickel is taken out, dried in vacuum and stored to obtain the foamed nickel.
In some typical embodiments, the nickel salt is nickel acetate, nickel nitrate, or nickel chloride.
In some exemplary embodiments, the molybdenum salt is ammonium molybdate or sodium molybdate.
In some exemplary embodiments, the vanadium salt is sodium orthovanadate, sodium metavanadate, or ammonium metavanadate.
In some typical embodiments, the hydrothermal conditions are: the temperature is maintained at 120-160 ℃ for 4-8 hours.
In some exemplary embodiments, the nitridation treatment conditions are 450 ℃ and 650 ℃ for 1-4 hours.
The invention will now be further described with reference to the accompanying figures 1-7 and the detailed description.
Example 1
Vanadium-doped Ni0.2Mo0.8The preparation method of N comprises the following steps:
(1) substrate cleaning: and respectively putting the foamed nickel into 2M hydrochloric acid, acetone and ethanol, respectively ultrasonically cleaning for 15 minutes, taking out the cleaned foamed nickel, vacuum drying and storing to obtain the nickel-based composite material.
(2) Preparation of vanadium doped NiMoO4·xH2O precursor:
3mmol of nickel acetate tetrahydrate, 0.48mmol of ammonium molybdate tetrahydrate (H) were weighed32Mo7N6O28) And 0.6mmol of sodium orthovanadate, and the sodium orthovanadate is put into 40mL of deionized water and stirred for 20 minutes to obtain a mixed solution; taking 16mL of the mixed solution, transferring the mixed solution into a 20mL reaction kettle, putting a piece of foamed nickel obtained in the step (1) into the reaction kettle as a substrate, and putting the reaction kettle into an oven at 140 ℃ for reaction for 5 hours; after the reaction is finished, cooling the reaction kettle to room temperature, and taking out the foamed nickel with the grown materialRespectively washing the foamed nickel by using deionized water and ethanol, and drying and storing the washed material to obtain the vanadium-doped NiMoO4·xH2And an O electrode.
(3) Preparation of vanadium doped NiMoO4·xH2O electrode:
mixing the vanadium-doped NiMoO obtained in the step (2)4·xH2Putting the O electrode into a porcelain boat, then putting the porcelain boat into a quartz tube, then putting the quartz tube into a tube furnace, introducing ammonia gas, then heating the tube furnace to 500 ℃ and preserving heat for 2 hours, and taking out the electrode after the furnace is naturally cooled to room temperature, namely the vanadium-doped NiMoO4·xH2And an O electrode.
Example 2
Vanadium-doped Ni0.2Mo0.8The preparation method of N comprises the following steps:
(1) substrate cleaning: the same as in example 1.
(2) Preparation of vanadium doped NiMoO4·xH2O precursor:
weighing 3.2mmol of nickel nitrate hexahydrate, 2.8mmol of sodium molybdate dihydrate and 0.4mmol of sodium metavanadate, putting the nickel nitrate hexahydrate, the sodium molybdate dihydrate and the sodium metavanadate into 40mL of deionized water, and stirring for 20 minutes to obtain a mixed solution; taking 16mL of the mixed solution, transferring the mixed solution into a 20mL reaction kettle, putting a piece of foamed nickel obtained in the step (1) into the reaction kettle as a substrate, and putting the reaction kettle into a 120 ℃ oven for reaction for 8 hours; after the reaction is finished, cooling the reaction kettle to room temperature, taking out the foamed nickel growing with the material, respectively washing the foamed nickel with deionized water and ethanol, and drying and storing the washed material to obtain the vanadium-doped NiMoO4·xH2And an O electrode.
(3) Preparation of vanadium doped NiMoO4·xH2O electrode:
mixing the vanadium-doped NiMoO obtained in the step (2)4·xH2Putting the O electrode into a porcelain boat, then putting the porcelain boat into a quartz tube, then putting the quartz tube into a tube furnace, introducing ammonia gas, then heating the tube furnace to 450 ℃ and preserving heat for 4 hours, and naturally cooling the furnace to room temperatureTaking out the electrode to obtain the vanadium doped NiMoO4·xH2And an O electrode.
Example 3
Vanadium-doped Ni0.2Mo0.8The preparation method of N comprises the following steps:
(1) substrate cleaning: the same as in example 1.
(2) Preparation of vanadium doped NiMoO4·xH2O precursor:
2.5mmol of nickel chloride hexahydrate, 0.6mmol of ammonium molybdate tetrahydrate (H) were weighed32Mo7N6O28) And 0.8mmol of ammonium metavanadate, and the ammonium metavanadate is put into 40mL of deionized water and stirred for 20 minutes to obtain a mixed solution; taking 16mL of the mixed solution, transferring the mixed solution into a 20mL reaction kettle, putting a piece of foamed nickel obtained in the step (1) into the reaction kettle as a substrate, and putting the reaction kettle into a 160 ℃ oven for reaction for 4 hours; after the reaction is finished, cooling the reaction kettle to room temperature, taking out the foamed nickel growing with the material, respectively washing the foamed nickel with deionized water and ethanol, and drying and storing the washed material to obtain the vanadium-doped NiMoO4·xH2And an O electrode.
(3) Preparation of vanadium doped NiMoO4·xH2O electrode:
mixing the vanadium-doped NiMoO obtained in the step (2)4·xH2Putting the O electrode into a porcelain boat, then putting the porcelain boat into a quartz tube, then putting the quartz tube into a tube furnace, introducing ammonia gas, then heating the tube furnace to 650 ℃ and preserving heat for 1 hour, and taking out the electrode after the furnace is naturally cooled to room temperature, namely the vanadium-doped NiMoO4·xH2And an O electrode.
Example 4
Vanadium-doped Ni0.2Mo0.8The preparation method of N comprises the following steps:
(1) substrate cleaning: the same as in example 1.
(2) Preparation of vanadium doped NiMoO4·xH2O precursor:
weigh 3.5mmol of tetrakisNickel acetate hydrate, 0.52mmol ammonium molybdate tetrahydrate (H)32Mo7N6O28) And 1.2mmol of ammonium metavanadate, and the ammonium metavanadate is put into 40mL of deionized water and stirred for 20 minutes to obtain a mixed solution; taking 16mL of the mixed solution, transferring the mixed solution into a 20mL reaction kettle, putting a piece of foamed nickel obtained in the step (1) into the reaction kettle as a substrate, and putting the reaction kettle into a 150 ℃ oven for reaction for 5 hours; after the reaction is finished, cooling the reaction kettle to room temperature, taking out the foamed nickel growing with the material, respectively washing the foamed nickel with deionized water and ethanol, and drying and storing the washed material to obtain the vanadium-doped NiMoO4·xH2And an O electrode.
(3) Preparation of vanadium doped NiMoO4·xH2O electrode:
mixing the vanadium-doped NiMoO obtained in the step (2)4·xH2Putting the O electrode into a porcelain boat, then putting the porcelain boat into a quartz tube, then putting the quartz tube into a tube furnace, introducing ammonia gas, then heating the tube furnace to 600 ℃ and preserving heat for 2 hours, and taking out the electrode after the furnace is naturally cooled to room temperature, namely the vanadium-doped NiMoO4·xH2And an O electrode.
Performance testing
NiMoO doped with vanadium prepared in example 14·xH2The O electrode is a test object, and the electrochemical performance of the O electrode is tested by the following test method: the electrode is used as a working electrode, the Hg/HgO electrode is used as a reference electrode, the graphite rod electrode is used as a counter electrode to form a three-electrode system, and the electrolyte is 1M KOH solution. The test results are shown in FIGS. 1-7, in which:
FIG. 1 shows the vanadium doped Ni0.2Mo0.8XRD pattern of N electrode, it can be seen that: XRD and Ni of vanadium doped material except diffraction peak of metallic nickel (scraped from the upper surface of the nickel foam)0.2Mo0.8The standard card of N still corresponds well, that is to say, after doping, the crystal structure of the material does not change obviously, and hexagonal Ni is still maintained0.2Mo0.8And (4) an N structure.
FIG. 2 shows the vanadium dopingHetero Ni0.2Mo0.8SEM image of N electrode, it can be seen that: the material is composed of many nanowires, which are composed of many small particles.
FIG. 3 shows the vanadium doped Ni0.2Mo0.8HRTEM of N electrodes, it can be seen that: after vanadium doping, Ni can still be found0.2Mo0.8The (100) and (101) crystal planes of N, which is also consistent with the XRD results.
FIGS. 4a and 4b are the vanadium-doped Ni0.2Mo0.8The current density-voltage relation maps of the N electrode hydrogen evolution and oxygen evolution can be seen as follows: in terms of hydrogen evolution, the vanadium-doped material shows a higher ratio than Ni because vanadium doping causes the center of the d energy band of the material to shift downwards, namely to be farther away from the Fermi level, so that the binding capacity of the material and the active hydrogen of an adsorbate is weakened, and the adsorption energy of the material to the active hydrogen is optimized, so that the vanadium-doped material shows a higher ratio than Ni0.2Mo0.8N has higher performance, and the performance is even close to Pt/C; in the aspect of oxygen evolution, the vanadium doping can cause the electron state density of the material near the Fermi level to increase, namely, the conductivity of the material can be improved, the charge transfer between the material and the adsorbate is promoted, the vanadium doping can cause the charge density distribution on the surface of the material to change, so that N obtains more electrons, Ni and Mo lose less electrons, the adsorption capacity of the material on the adsorbate is changed, namely, the adsorption capacity of the material on oxygen-containing intermediates is optimized, the overpotential of the oxygen evolution reaction is reduced, and the material shows a larger potential than Ni0.2Mo0.8N and RuO2Higher performance.
FIGS. 5a and 5b are the vanadium-doped Ni0.2Mo0.8The stability test chart of the N electrode for hydrogen evolution and oxygen evolution can be seen that: vanadium doped Ni whether hydrogen or oxygen evolving0.2Mo0.8The N materials all exhibit excellent stability.
FIG. 6 shows the vanadium doped Ni0.2Mo0.8The N electrode is respectively used as a current density-voltage relation chart of cathode and anode electrolyzed water, and the following can be seen: the electrocatalytic full-hydrolytic system composed of the vanadium-doped material has Pt/C// RuO ratio to the noble metal material system2The performance is better, because the doping of vanadium can cause the center of the d energy band of the material to move downwards, and the binding capacity of the material and the active hydrogen of an adsorbate is weakened; the electron state density of the material near the Fermi level is increased, namely the conductivity of the material is improved, and the charge transfer between the material and the adsorbate is promoted; and the vanadium doping can change the charge density distribution on the surface of the material, so that N obtains more electrons, and Ni and Mo lose less electrons; thus, in general, such variations result in optimization of the adsorption energy of the material for water, active hydrogen, and oxygen-containing intermediates, thereby allowing the material to exhibit superior performance.
FIG. 7 shows the vanadium doped Ni0.2Mo0.8And the N electrode is used as a stability test map of cathode and anode electrolyzed water. It can be seen that: after 50 hours of testing, the current changes little, and the full water decomposing system shows good stability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (11)
1. Vanadium-doped Ni0.2Mo0.8The preparation method of N is characterized by comprising the following steps: the method comprises the following steps:
(1) vanadium doped NiMoO synthesis by hydrothermal method4·xH2An O material;
(2) doping vanadium with NiMoO4·xH2Taking O material as a precursor, and carrying out high-temperature nitridation treatment to obtain vanadium-doped Ni0.2Mo0.8N；
The vanadium-doped NiMoO is synthesized by the hydrothermal method4·xH2The method of the O material comprises the following steps: uniformly mixing a nickel source, a molybdenum source and a vanadium source, reacting the mixed solution with a substrate under a hydrothermal condition, washing the substrate with deionized water and ethanol respectively after the reaction is finished, and drying and storing the washed materialTo obtain vanadium doped NiMoO4·xH2And (3) O material.
2. The method of claim 1, wherein: the high-temperature nitriding treatment method comprises the following steps: doping vanadium with NiMoO4·xH2And (3) putting the O precursor into a porcelain boat, putting the porcelain boat into a quartz tube, putting the quartz tube into a tube furnace, introducing ammonia gas, heating the tube furnace to a set temperature, and preserving heat to obtain the ceramic material.
3. The method of claim 1, wherein: the adding proportion of the nickel source, the molybdenum source and the vanadium source is as follows: the molar ratio of nickel atoms to molybdenum atoms to vanadium atoms is 25-35: 28-42: 4-12.
4. The method of claim 3, wherein: the nickel source is nickel acetate, nickel nitrate or nickel chloride.
5. The method of claim 3, wherein: the molybdenum source is ammonium molybdate or sodium molybdate.
6. The method of claim 3, wherein: the vanadium source is sodium orthovanadate, sodium metavanadate or ammonium metavanadate.
7. The method of claim 1, wherein: the substrate is made of foamed nickel.
8. The method of claim 1, wherein: the hydrothermal conditions are as follows: the temperature is maintained at 120-160 ℃ for 4-8 hours.
9. The method of claim 1, wherein: the nitriding treatment condition is heat preservation for 1-4 hours at the temperature of 450-650 ℃.
10. The method of any one of claims 1 to 9Prepared vanadium doped Ni0.2Mo0.8The use of N in electrocatalytic decomposition of water.
11. The use of claim 10, wherein: used for preparing hydrogen by electrocatalytic decomposition of water.
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