CN117966202A - Nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material and preparation method and application thereof - Google Patents
Nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material and preparation method and application thereof Download PDFInfo
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- CN117966202A CN117966202A CN202410129643.XA CN202410129643A CN117966202A CN 117966202 A CN117966202 A CN 117966202A CN 202410129643 A CN202410129643 A CN 202410129643A CN 117966202 A CN117966202 A CN 117966202A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 87
- GPBUGPUPKAGMDK-UHFFFAOYSA-N azanylidynemolybdenum Chemical compound [Mo]#N GPBUGPUPKAGMDK-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000004202 carbamide Substances 0.000 claims abstract description 52
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910052802 copper Inorganic materials 0.000 claims abstract description 46
- 239000010949 copper Substances 0.000 claims abstract description 46
- 239000006260 foam Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000002815 nickel Chemical class 0.000 claims abstract description 16
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 15
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 15
- 238000000197 pyrolysis Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 17
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 5
- 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 claims description 5
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 3
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 36
- 239000001257 hydrogen Substances 0.000 abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 32
- 238000005868 electrolysis reaction Methods 0.000 abstract description 16
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 239000002070 nanowire Substances 0.000 abstract description 4
- 239000002243 precursor Substances 0.000 abstract description 4
- 150000002431 hydrogen Chemical class 0.000 abstract description 3
- 238000012546 transfer Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 29
- 239000003792 electrolyte Substances 0.000 description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 239000003054 catalyst Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 21
- 239000001301 oxygen Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000003647 oxidation Effects 0.000 description 19
- 238000007254 oxidation reaction Methods 0.000 description 19
- 229910052751 metal Inorganic materials 0.000 description 15
- 239000002184 metal Substances 0.000 description 15
- 238000004519 manufacturing process Methods 0.000 description 14
- 239000000758 substrate Substances 0.000 description 14
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 229910052723 transition metal Inorganic materials 0.000 description 12
- 230000008569 process Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- -1 transition metal nitride Chemical class 0.000 description 8
- 150000003624 transition metals Chemical class 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004832 voltammetry Methods 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002071 nanotube Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000011144 upstream manufacturing Methods 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005273 aeration Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 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 description 1
- 239000002028 Biomass Substances 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910015667 MoO4 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical 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
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 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
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0615—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium
- C01B21/062—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with transition metals other than titanium, zirconium or hafnium with chromium, molybdenum or tungsten
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/16—Preparation
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- 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
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
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- C25B11/031—Porous electrodes
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to the technical field of composite materials, in particular to a nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material, and a preparation method and application thereof. According to the invention, molybdate and nickel salt are used as precursors to be converted into a nickel molybdate nanowire array on foam copper through hydrothermal reaction, the array and dicyandiamide are subjected to further pyrolysis reaction, and the nickel molybdate nanowire is converted into the nickel-doped molybdenum nitride composite material encapsulated in the nitrogen-doped carbon nanotube in situ. The composite material has rich active sites, good electronic conductivity and ion conductivity, rapid mass transfer and gas escape channels, realizes long-time, efficient and stable electrolysis of water to produce hydrogen and urea-assisted electrolysis of water to produce hydrogen, effectively solves the problems of high energy consumption and poor stability of the current electrolysis of water to produce hydrogen, and has good application prospect in the fields of new energy and catalysis.
Description
Technical Field
The invention relates to the technical field of composite materials, in particular to a nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material, and a preparation method and application thereof.
Background
The hydrogen energy is the most promising fossil fuel substitute due to the characteristics of high quality energy density, abundant reserves, environmental friendliness and the like. Electrochemical hydrogen production by using renewable energy sources (such as solar energy, wind energy, geothermal energy and the like) is an effective way for realizing green hydrogen production. At present, catalysts for producing hydrogen by electrolysis are mainly noble metal catalysts, and the industrial application of the catalysts is limited by low reserves and high price although the catalytic activity of the catalysts is high. Therefore, the non-noble metal catalyst with high earth abundance, low price and high and stable catalytic performance of the research and development raw material is the key point of the development of the current green hydrogen production technology and is also the difficulty for restricting the industrialization process.
The non-noble metal-based catalyst mainly comprises transition metal alloy, nitride, sulfide, carbide, phosphide and the like. Wherein, the transition metal nitride exhibits electrocatalytic activity comparable to that of noble metals due to intercalation of nitrogen as a spacer, resulting in lattice distortion, d-band shrinkage, and redistribution of state density near the fermi level of the corresponding metal. Numerous studies have shown that pre-transition metal nitrides (e.g., molybdenum nitride, tungsten nitride, etc.) have excellent electrocatalytic Hydrogen Evolution (HER) properties, but the corresponding oxide electrocatalytic Oxygen Evolution (OER) properties generated during oxygen evolution are not prominent, so that such compounds generally only exhibit HER monofunctional catalytic activity.
Compared with the front transition metal, the outer electrons of the rear transition metal (such as nickel, cobalt and the like) are more easily transferred to the strong electronegative nitrogen, so that oxygen supply species are more easily adsorbed at the rear transition metal site, become an electrocatalytic oxygen evolution reaction active center, promote the conversion of oxygen evolution reactants and intermediate products, and further lead the rear transition metal to show OER electrocatalytic activity superior to that of the front transition metal nitride. Therefore, the late transition metal nickel can be doped into the early transition metal nitride (molybdenum nitride), and a heterojunction is constructed between the late transition metal nickel and the early transition metal nitride, and the HER and OER activities of the catalyst can be considered by utilizing the 3d electron complementary effect. Meanwhile, interface engineering such as heterojunction and the like can also increase the electroactive area of materials, accelerate interface electron transport, adjust the adsorption free energy of reaction intermediates and the like. However, at present, the synthesis of molybdenum nitride mainly adopts a mode of pyrolyzing corresponding precursors in ammonia gas, so that equipment is severely corroded, and toxic ammonia gas has great harm to human bodies and the environment. In addition, agglomeration of materials during electrocatalytic processes can severely impact the number of active sites available, thereby affecting the electrocatalytic stability and hydrogen production efficiency of such materials.
Meanwhile, the cathode of the electrolytic water for producing hydrogen is the precipitation of hydrogen, and the anode reaction coupled with the cathode is the precipitation of oxygen. Although the oxygen precipitated from the anode is friendly to the environment, the theoretical potential of the oxygen precipitated from the anode is 1.23V, the energy consumption is high, and the effective hydrogen evolution and the large-scale hydrogen production are limited. From the thermodynamic point of view, replacing oxygen evolution by oxidation of other substances with lower oxidation potential (such as urea, hydrazine hydrate, biomass, etc.) on the anode is a good energy saving strategy. For example, the theoretical oxidation potential of urea is 0.37V, the oxidized products are nontoxic nitrogen, carbon dioxide and the like, and the energy consumption can be greatly reduced by using urea to oxidize and hydrogen evolution, but urea oxidation is a six-electron transfer process with slow dynamics, so that a high-efficiency catalyst is also required to promote the reaction.
Disclosure of Invention
The invention aims to provide a nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material, and a preparation method and application thereof, so that efficient and stable catalysis of an electrochemical hydrogen production process is realized.
In order to achieve the above object, the present invention provides the following technical solutions:
A preparation method of a nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material comprises the following steps:
1) Mixing foam copper, nickel salt, molybdate, urea and water to perform hydrothermal reaction to obtain foam copper loaded with a nickel molybdate array;
2) And mixing the foam copper loaded with the nickel molybdate array with dicyandiamide in a protective atmosphere, and carrying out pyrolysis reaction under the catalysis of the foam copper to obtain the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material.
Optionally, the nickel salt comprises at least one of nickel chloride hexahydrate, nickel sulfate hexahydrate, and nickel nitrate hexahydrate.
Optionally, the molybdate comprises at least one of ammonium molybdate tetrahydrate and sodium molybdate dihydrate;
the ratio of the mass of nickel in the nickel salt to the mass of molybdenum in the molybdate is 4-12: 7.
Optionally, the ratio of urea to molybdenum in molybdate is 8 to 24:7.
Optionally, the nickel salt to water dosage ratio is 2mmol: 10-30 mL.
Optionally, the temperature of the hydrothermal reaction is 60-120 ℃ and the time is 6-10 h.
Alternatively, the molybdenum content of the molybdate to dicyandiamide content ratio is 1.75mmol: 0.5-1.5 g.
Optionally, the temperature of the pyrolysis reaction is 700-900 ℃ and the time is 1-3h.
The invention provides a nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared by the preparation method, which comprises foam copper, nitrogen-doped carbon nanotubes grown on the foam copper in situ and nickel-doped molybdenum nitride encapsulated in the nitrogen-doped carbon nanotubes.
The invention also provides application of the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material in the field of electrocatalysis.
According to the preparation method, ammonium molybdate tetrahydrate and nickel chloride hexahydrate are used as metal precursors, a hydrothermal method is used for converting the metal precursors into a nickel molybdate nanowire array on the foam copper, dicyandiamide is used as a carbon source and a nitrogen source of the nitrogen-doped carbon nano tube in the further pyrolysis process of the array and dicyandiamide, the foam copper can be used as a catalyst for generating the nitrogen-doped carbon nano tube, and the nickel molybdate nanowire is in-situ converted into nickel-doped molybdenum nitride nano particles encapsulated in the nitrogen-doped carbon nano tube.
In the pyrolysis process, the nitrogen-doped carbon nano tube grows on the foam copper in situ under the catalysis of the foam copper, so that the conductive substrate (foam copper) and the prepared composite material are integrated.
The nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material supported on the foam copper prepared by the invention limits nickel-doped molybdenum nitride in the nitrogen-doped carbon nano tube, and the electrocatalyst of the structure has the characteristics of good conductivity, multiple active sites, strong electrocatalysis stability and mechanical stability and the like.
In the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared by the invention, the nickel-doped molybdenum nitride particles have HER, OER and UOR activities, and the nitrogen-doped carbon nanotube has high conductivity and good reaction activity. The nickel-doped molybdenum nitride catalyst is packaged in the nitrogen-doped carbon nano tube, so that the electron transmission rate in the electrocatalytic process can be accelerated, the agglomeration of the catalyst can be effectively inhibited, the electrocatalytic activity and stability of the material are obviously improved, meanwhile, the doping of nitrogen atoms changes the charge distribution of a carbon plane, and extra hydrogen evolution active sites are added, so that the requirement of long-time, high-current and high-efficiency electrocatalytic hydrogen production is realized.
The nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material can be used as a cathode catalyst and an anode catalyst for hydrogen production by electrolysis water, realizes long-time, high-efficiency and stable hydrogen production by electrolysis water and urea-assisted hydrogen production by electrolysis water, and effectively solves the problems of high energy consumption and poor stability in the current hydrogen production by electrolysis.
When the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared by the invention is used for catalyzing urea oxidation, ni 2+δO(OH)ads generated in situ in the anodic oxidation process of metallic nickel is used as an active center of electrocatalytic urea oxidation, and Ni 2+δ with unsaturated d orbits and OH ads with excessive electrons are used for respectively and directionally capturing nucleophilic O and electrophilic H in urea, so that adsorption and activation of urea molecules and proton coupling electron transfer reactions are promoted. The coupling of urea oxidation at the anode and hydrogen evolution at the cathode can greatly reduce the energy consumption of hydrogen production by electrolysis, improve the hydrogen production efficiency and effectively treat the urea-containing wastewater.
The nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material can also be used as an electrode material and applied to the fields of lithium ion batteries, sodium ion batteries, fine chemical synthesis and the like.
Drawings
FIG. 1 is an SEM image of a nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 of the present invention;
FIG. 2 is a TEM image of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 of the present invention;
FIG. 3 is an XRD pattern of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 of the present invention;
FIG. 4 shows XPS total spectra (a) and high resolution spectra of Mo 3d (b), N1 s (c) and Ni 2p (d) of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 of the present invention;
FIG. 5 is a LSV graph of electrocatalytic hydrogen evolution of the nitrogen doped carbon nanotube-nickel doped molybdenum nitride composite material and Pt/C catalyst prepared in example 1 of the present invention in 1mol/L KOH solution;
FIG. 6 shows the electrocatalytic hydrogen evolution stability of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 of the present invention at different current densities in a 1mol/LKOH solution;
FIG. 7 is a LSV graph showing the electrocatalytic oxygen evolution and urea oxidation of the nitrogen doped carbon nanotube-nickel doped molybdenum nitride composite material and RuO 2 catalyst prepared in example 1 of the present invention in 1mol/LKOH and 1mol/LKOH+0.33mol/L urea solution, respectively;
FIG. 8 is a graph showing the potentials required for electrocatalytic oxygen evolution and urea oxidation in 1mol/LKOH and 1mol/LKOH+0.33mol/L urea solutions, respectively, of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 of the present invention and of the RuO 2 catalyst to different current densities;
FIG. 9 shows the electrocatalytic oxygen evolution and urea oxidation stability of the nitrogen doped carbon nanotube-nickel doped molybdenum nitride composite material prepared in example 1 of the present invention at different current densities in a 1mol/LKOH solution;
FIG. 10 is an LSV diagram of electrocatalytic electrolyzed water and urea assisted electrolyzed water in 1mol/LKOH and 1mol/LKOH+0.33mol/L urea solution respectively for the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 of the present invention;
FIG. 11 shows the stability of the N-doped carbon nanotube-Ni-doped molybdenum nitride composite material prepared in example 1 of the present invention in electrocatalytic electrolysis water and urea-assisted electrolysis water at different current densities in 1mol/LKOH and 1mol/LKOH+0.33mol/L urea solution, respectively.
Detailed Description
The invention provides a preparation method of a nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material, which comprises the following steps:
1) Mixing foam copper, nickel salt, molybdate, urea and water to perform hydrothermal reaction to obtain foam copper loaded with a nickel molybdate array;
2) And mixing the metal substrate loaded with the nickel molybdate array with dicyandiamide in a protective atmosphere, and carrying out pyrolysis reaction under the catalysis of foam copper to obtain the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material.
In the present invention, the nickel salt preferably contains at least one of nickel chloride hexahydrate, nickel sulfate hexahydrate and nickel nitrate hexahydrate, and more preferably nickel chloride hexahydrate (NiCl 2·6H2 O), and when the nickel salt is two or more of the above, the ratio of the different nickel salts is not particularly limited, and any ratio may be used.
In the present invention, the molybdate preferably contains at least one of ammonium molybdate tetrahydrate and sodium molybdate dihydrate, more preferably ammonium molybdate tetrahydrate ((NH 4)6Mo7O34·4H2 O), and when the molybdate is two or more of the above, the ratio of the different molybdates is not particularly limited, and any ratio may be used;
The ratio of the amount of nickel in the nickel salt to the amount of molybdenum in the molybdate is preferably 4 to 12:7, more preferably 5 to 10:7, more preferably 7 to 8:7.
In the present invention, the ratio of urea to molybdenum in the molybdate is preferably 8 to 24:7, more preferably 10 to 20:7, more preferably 12 to 15:7.
In the present invention, the ratio of the nickel salt to water is preferably 2mmol:10 to 30mL, more preferably 2mmol:18 to 25mL, more preferably 2mmol: 20-22 mL.
In the invention, the mixing in the step 1) is preferably to dissolve nickel salt and molybdate in water, then add urea, stir to get a light green clear solution, and then add a metal substrate into the light green clear solution;
the copper foam is preferably copper foam with the size of 3cm multiplied by 2.5cm, sequentially ultrasonic processing is carried out in acetone and HCl solution, then water washing is carried out until the washing liquid is neutral, ethanol is used for rinsing, and vacuum drying is carried out;
The ultrasonic time in the acetone is preferably 10 minutes, the concentration of the HCl solution is preferably 3mol/LHCl, the ultrasonic time in the HCl solution is preferably 10 minutes, the number of times of ethanol rinsing is not specially specified, the drying temperature is not specially specified, and the drying temperature is adjusted according to the actual conditions.
In the present invention, the temperature of the hydrothermal reaction is preferably 60 to 120 ℃, more preferably 80 to 110 ℃, still more preferably 90 to 100 ℃; the time is preferably 6 to 10 hours, more preferably 7 to 9 hours, and still more preferably 8 hours.
In the present invention, the ratio of the amount of molybdenum species in the molybdate to the amount of dicyandiamide is preferably 1.75mmol:0.5 to 1.5g, more preferably 1.75mmol:0.8 to 1.25g, more preferably 1.75mmol: 0.9-1 g.
In the present invention, the protective atmosphere in step 2) is preferably Ar and H 2, and the volume ratio of Ar to H 2 is preferably 9:1, a step of;
The metal substrate loaded with the nickel molybdate array is preferably cleaned and dried by sequentially using water and ethanol before being mixed with dicyandiamide;
The washing with water is preferably rinsing, and the washing with ethanol is preferably rinsing.
In the invention, the metal substrate loaded with the nickel molybdate array and dicyandiamide are mixed preferably by respectively placing the metal substrate loaded with the nickel molybdate array and the dicyandiamide at two ends of a quartz boat, so that the dicyandiamide is positioned at the upstream of the air flow, and the copper foam loaded with the nickel molybdate array is positioned at the downstream of the air flow.
In the present invention, the temperature of the pyrolysis reaction is preferably 700 to 900 ℃, more preferably 720 to 850 ℃, still more preferably 750 to 800 ℃; the time is preferably 1 to 3 hours, more preferably 1.5 to 2.5 hours, and still more preferably 2 hours. In the present invention, the heating rate to the temperature of the pyrolysis reaction is preferably 2 to 10℃per minute, more preferably 4 to 8℃per minute, still more preferably 5 to 6℃per minute.
The invention provides a nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared by the preparation method, which comprises a metal substrate, nitrogen-doped carbon nanotubes grown on the metal substrate in situ and nickel-doped molybdenum nitride encapsulated in the nitrogen-doped carbon nanotubes.
The invention also provides application of the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material in the field of electrocatalysis. The application of the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material in the field of electrocatalysis preferably comprises an electrocatalyst for hydrogen evolution, oxygen evolution and urea oxidation, and the electrocatalyst is used for electrolyzed water and urea-assisted electrolyzed water.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Cutting copper foam into 3cm multiplied by 2.5cm, performing ultrasonic treatment in acetone for 10 minutes, performing ultrasonic treatment in 3mol/L HCl solution for 10 minutes, washing with deionized water until washing liquid is neutral, rinsing with ethanol twice, and vacuum drying to obtain a metal substrate for later use;
2) 2mmol of NiCl 2·6H2 O and 0.25mmol (NH 4)6Mo7O34·4H2 O are dissolved in 20mL of deionized water, 3mmol of urea is added and stirred for 10 minutes to obtain a light green clear solution;
3) Transferring the solution obtained in the step 2) into a 50mL polytetrafluoroethylene liner, vertically placing the metal substrate obtained in the step 1) into the solution, covering a reaction kettle, placing the reaction kettle into a blast drying box, maintaining the temperature at 90 ℃ for 8 hours for hydrothermal reaction to obtain a nickel molybdate array growing on the foam copper in situ, cooling the nickel molybdate array to room temperature, taking out the nickel molybdate array, namely the foam copper loaded with the nickel molybdate array, repeatedly washing the nickel molybdate array with deionized water, rinsing the nickel molybdate array with ethanol, and airing the nickel molybdate array at a ventilation position to obtain the foam copper loaded with the nickel molybdate array;
4) Placing the cleaned foam copper loaded with the nickel molybdate array and 1g of dicyandiamide at two ends of a quartz boat respectively, so that dicyandiamide is positioned at the upstream of air flow, and the cleaned foam copper loaded with the nickel molybdate array is positioned at the downstream of air flow, wherein the volume ratio of Ar to H 2 is 9:1, heating to 800 ℃ at a speed of 5 ℃/min, and keeping for 2 hours to carry out pyrolysis reaction to obtain the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material (named NMN@NC/CF).
Example 2
1) Cutting copper foam into 3cm multiplied by 2.5cm, performing ultrasonic treatment in acetone for 10 minutes, performing ultrasonic treatment in 3mol/L HCl solution for 10 minutes, washing with deionized water until washing liquid is neutral, rinsing with ethanol twice, and vacuum drying to obtain a metal substrate for later use;
2) 2mmolNiCl 2·6H2 O and 1.75mmolNa 2MoO4·2H2 O are dissolved in 20mL of deionized water, 3mmol of urea is added, and stirring is carried out for 10 minutes, so as to obtain a light green clear solution;
3) Transferring the solution obtained in the step 2) into a 50mL polytetrafluoroethylene liner, vertically placing the metal substrate obtained in the step 1) into the solution, covering a reaction kettle, placing the reaction kettle into a blast drying box, maintaining the temperature at 90 ℃ for 8 hours for hydrothermal reaction to obtain a nickel molybdate array growing on the foam copper in situ, cooling the nickel molybdate array to room temperature, taking out the nickel molybdate array, namely the foam copper loaded with the nickel molybdate array, repeatedly washing the nickel molybdate array with deionized water, rinsing the nickel molybdate array with ethanol, and airing the nickel molybdate array at a ventilation position to obtain the foam copper loaded with the nickel molybdate array;
4) Placing the cleaned foam copper loaded with the nickel molybdate array and 1g of dicyandiamide at two ends of a quartz boat respectively, so that dicyandiamide is positioned at the upstream of air flow, and the cleaned foam copper loaded with the nickel molybdate array is positioned at the downstream of air flow, wherein the volume ratio of Ar to H 2 is 9:1, heating to 800 ℃ at a speed of 5 ℃/min, and keeping for 2 hours to carry out pyrolysis reaction to obtain the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material.
Example 3
The nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 was cut to a size of 0.5cm×1cm and used as an integrated working electrode.
Comparative example 1
Preparation of Pt/C electrode: 2mgPt/C powder catalyst was placed in a 5mL centrifuge tube, 250. Mu.L ethanol, 250. Mu. LNafion aqueous solution (0.2 wt.%) was added, and sonicated for 30 minutes to obtain a uniform Pt/C catalyst dispersion. The 250 mu LPt/C catalyst dispersion was applied dropwise to copper foam (0.5 cm. Times.1 cm) with a pipette and dried naturally at aeration to give a Pt/C working electrode.
Comparative example 2
Preparation of RuO 2 electrode: the 2mgRuO 2 powder catalyst was placed in a 5mL centrifuge tube, 250. Mu.L ethanol, 250. Mu. LNafion aqueous solution (0.2 wt.%) was added, and the mixture was sonicated for 30 minutes to obtain a uniform catalyst dispersion. The 250 mu LRuO 2 catalyst dispersion was applied dropwise to copper foam (0.5 cm. Times.1 cm) with a pipette and naturally dried at aeration to give a RuO 2 working electrode.
Performance testing
Scanning electron microscopy is used for detecting the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material loaded on the foam copper, which is prepared in the embodiment 1, and an SEM (scanning electron microscope) diagram is shown in figure 1; as can be seen from fig. 1, the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material loaded on the copper foam is a nanotube with nanoparticles wrapped at the top or in the middle.
The nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material loaded on the foam copper prepared in the example 1 is detected by using a transmission electron microscope, and the obtained TEM image is shown in figure 2; it can be further seen from fig. 2 that the nanotubes are bent and intertwined, and that the nanoparticles are encapsulated in the middle or top of the nanotubes.
The nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material loaded on the foamy copper prepared in example 1 was examined by using an X-ray diffractometer, and the XRD pattern obtained is shown in FIG. 3; fig. 3 shows successful preparation of nickel doped molybdenum nitride on a copper foam substrate, but no carbon peaks indicating nitrogen doped carbon nanotubes were observed, since the peaks of the metal substrate were too strong and the degree of carbon crystallization was not particularly high.
The nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material loaded on the foam copper prepared in example 1 is detected by using an X-ray photoelectron spectrometer, and the obtained XPS total spectrum (a) and high-resolution spectra of corresponding elements (Mo 3d (b), N1 s (c) and Ni 2p (d)) are shown in FIG. 4; the spectrum of fig. 4 shows that the nitrogen doped carbon nanotube-nickel doped molybdenum nitride composite material supported on copper foam consists of Ni, mo, N, C, O (from adsorbed oxygen in air), with Ni being predominantly zero valent, mo being predominantly Mo-N bonds, N being in the form of N-Mo bonds, graphite nitrogen and pyridine nitrogen.
Electrocatalytic Performance test of the electrodes prepared in example 3 and comparative examples 1 to 2
(1) The integrated working electrode described in example 3 was used as a working electrode, a carbon rod was used as a counter electrode, a Hg/HgO electrode was used as a reference electrode, and 80mL of an electrolyte (KOH solution) was used to construct a three-electrode test system, the KOH concentration in the electrolyte was 1mol/L, and the electrocatalytic performance test was performed on an electrochemical workstation (CHI 760E);
(2) The Pt/C working electrode prepared in comparative example 1 is used as a working electrode, a carbon rod is used as a counter electrode, an Hg/HgO electrode is used as a reference electrode, and 80mL of electrolyte (KOH solution) is used for forming a three-electrode test system, the concentration of KOH in the electrolyte is 1mol/L, and the electrocatalytic performance test is carried out on an electrochemical workstation (CHI 760E).
(1) The potential range of the electrocatalytic performance test is 0.1 to-0.6V (vs. RHE), the scanning speed is 2mV s -1, and the linear voltammetry (LSV) curve of the nitrogen doped carbon nanotube-nickel doped molybdenum nitride composite material prepared in the example 1 and Pt/C electrocatalytic hydrogen evolution is shown in FIG. 5;
As can be seen from FIG. 5, although the overpotential (69 mV) required by the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material of the present invention is slightly higher than commercial Pt/C (26 mV) when the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material reaches 10mA cm -2, when the current density is higher than 130mA cm -2, the electrocatalytic hydrogen evolution performance of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material of the present invention is better than commercial Pt/C, and the advantages are more obvious when the current density is higher, the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material of the present invention can electrocatalytically hydrogen evolution under the extremely high current density (1200 mA cm -2).
The stability of electrocatalytic hydrogen evolution of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 was tested by a chronopotentiometric method (E-t) for 100 hours at current densities of 10, 100 and 500mAcm -2, and the results are shown in FIG. 6;
FIG. 6 shows that the composite material of the invention can stably and electrically catalyze hydrogen evolution for a long time (100 h) at 10, 100 and 500mA cm -2 current density.
(3) The integrated working electrode described in example 3 was used as a working electrode, a carbon rod was used as a counter electrode, a Hg/HgO electrode was used as a reference electrode, and 80mL of electrolyte (KOH solution) was used to construct a three-electrode test system, the concentration of KOH in the electrolyte was 1mol/L, and electrocatalytic was performed on an electrochemical workstation (CHI 760E);
(4) The RuO 2 working electrode prepared in comparative example 2 is used as a working electrode, a carbon rod is used as a counter electrode, the Hg/HgO electrode is used as a reference electrode, and 80mL of electrolyte (KOH solution) is used for forming a three-electrode test system, the concentration of KOH in the electrolyte is 1mol/L, and electrocatalytic is carried out on an electrochemical workstation (CHI 760E);
(5) The integrated working electrode described in example 3 was used as a working electrode, a carbon rod was used as a counter electrode, an Hg/HgO electrode was used as a reference electrode, 80mL of a three-electrode test system was constructed with an electrolyte (a mixed solution of KOH and urea) in which the concentration of KOH was 1mol/L and the concentration of urea was 0.33mol/L, and electrocatalytic was performed on an electrochemical workstation (CHI 760E);
(6) The RuO 2 working electrode prepared in comparative example 2 is used as a working electrode, a carbon rod is used as a counter electrode, the Hg/HgO electrode is used as a reference electrode, a three-electrode test system is formed by 80mL of electrolyte (mixed solution of KOH and urea), the concentration of KOH in the electrolyte is 1mol/L, the concentration of urea is 0.33mol/L, and electrocatalytic is carried out on an electrochemical workstation (CHI 760E);
(3) In the electrocatalytic performance test, the electrolyte is KOH of 1mol/L, and hydroxyl in the electrolyte is catalyzed to oxidize and separate out oxygen;
(5) In the electrocatalytic performance test of (6), the electrolyte is 1mol/LKOH+0.33mol/L, and urea in the electrolyte is catalyzed to oxidize.
(3) The electric potential range of the electrocatalysis is 1.0-1.7V (vs. RHE), the scanning speed is 2mV s -1, linear voltammetry scanning is carried out, and the obtained nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material prepared in the example 1 and RuO 2 electrocatalysis oxygen evolution and urea oxidation linear voltammetry (LSV) curves are shown in figure 7;
As can be seen from fig. 7, when the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material of the present invention catalyzes the electrocatalytic oxygen evolution and urea oxidation, the required overpotential is significantly smaller than the required potential for RuO 2 catalysis at any current density; and when the same current density is achieved, the overpotential required by the electrocatalytic urea oxidation is far smaller than that of oxygen evolution.
Quantitatively detecting the electric potentials required by the electrocatalysis to reach different current densities according to (3) to (6), wherein the obtained histogram is shown in figure 8;
The current density marks the rate of the electrolysis process, and as can be found from fig. 8, when the same electrocatalytic process and the same current density are adopted, the potential required by the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material is lower than the potential required by RuO 2, which indicates that in the electrocatalytic process, compared with RuO 2, the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material provided by the invention can achieve the same electrolysis rate under the condition of less energy consumption.
The stability of the electrocatalytic oxygen evolution and urea oxidation of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 is tested for 100 hours by detecting (3) and (5) under the conditions that the current density is 10 and 100mA cm -2 respectively, and the results are shown in figure 9;
FIG. 9 shows that the composite material of the invention has stability in electrocatalytic oxygen evolution and urea oxidation for a long period (100 h) at a current density of 10mA cm -2、100mA cm-2.
(7) The integrated working electrode described in example 3 was used as a cathode, an anode and 80mL of electrolyte (KOH solution) to form a two-electrode test system, the concentration of KOH in the electrolyte was 1mol/L, and electrocatalytic was performed on an electrochemical workstation (CHI 760E);
(8) The integrated working electrode described in example 3 was used as a cathode, an anode and 80mL of electrolyte (mixed solution of KOH and urea) respectively to form a two-electrode test system, the concentration of KOH in the electrolyte was 1mol/L, the concentration of urea was 0.33mol/L, and electrocatalytic was performed on an electrochemical workstation (CHI 760E);
(7) In the electrocatalytic performance test, the electrolyte is KOH with the concentration of 1mol/L, hydroxide in the electrolyte is catalyzed to oxidize, and oxygen is separated out;
(8) In the electrocatalytic performance test, the electrolyte is 1mol/LKOH+0.33mol/L, and urea in the electrolyte is catalyzed to oxidize.
Performing linear voltammetry scanning on the electrocatalysis in the steps (7) and (8), and obtaining linear voltammetry (LSV) curves of the electrocatalytic electrolyzed water and the urea assisted electrolyzed water in 1mol/LKOH and 1mol/LKOH+0.33mol/L urea solution of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in the example 1, wherein the results are shown in FIG. 10;
Fig. 10 shows that when the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material of the invention is used for electrocatalytic full water decomposition, cell voltages of 1.521V and 1.679V are only needed for achieving current densities of 10mA cm -2 and 100mA cm -2, and when urea with oxidation potential far lower than the potential needed by water oxidation is added into the solution, the cell voltage needed for achieving the same current density is obviously reduced (E 10＝1.376V,E100＝1.518V,E500 =1.670V), which indicates that the material can realize high-efficiency hydrogen production through electrocatalytic full water decomposition or urea-assisted water electrolysis.
The stability of the electrocatalytic electrolytic water and the stability of the urea-assisted electrolytic water of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared in example 1 were tested at the current density of 10 and 100mA cm -2 for 100h by the electrocatalytic timer described in (7) and (8), respectively, and the results are shown in FIG. 11.
As can be seen from fig. 11, the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material has small tank voltage variation under the condition of smaller current density (10 mA cm -2) and larger current density (100 mA cm -2), and the composite material is proved to be capable of stably and efficiently electrically catalyzing full water electrolysis and urea-assisted water electrolysis to produce hydrogen.
In conclusion, the electrolytic cell device formed when the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material is simultaneously a cathode and an anode has good electrocatalytic full water decomposition performance and urea-assisted full water decomposition performance, and the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material has excellent electrocatalytic HER, OER and UOR performances.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material is characterized by comprising the following steps of:
1) Mixing foamy copper, nickel salt, molybdate, urea and water, and performing hydrothermal reaction to obtain foamy copper loaded with a nickel molybdate array;
2) And mixing the foam copper loaded with the nickel molybdate array with dicyandiamide in a protective atmosphere, and carrying out pyrolysis reaction under the catalysis of the foam copper to obtain the nitrogen-doped carbon nano tube-nickel-doped molybdenum nitride composite material.
2. The method of preparing according to claim 1, wherein the nickel salt comprises at least one of nickel chloride hexahydrate, nickel sulfate hexahydrate, and nickel nitrate hexahydrate.
3. The method of preparing according to claim 1, wherein the molybdate comprises at least one of ammonium molybdate tetrahydrate and sodium molybdate dihydrate;
the ratio of the mass of nickel in the nickel salt to the mass of molybdenum in the molybdate is 4-12: 7.
4. The method according to claim 1, wherein the ratio of urea to molybdenum in molybdate is 8 to 24:7.
5. The method of claim 1, wherein the ratio of nickel salt to water is 2mmol: 10-30 mL.
6. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 60 to 120 ℃ for a time of 6 to 10 hours.
7. The method according to claim 1, wherein the ratio of the amount of molybdenum species in the molybdate to the amount of dicyandiamide is 1.75mmol: 0.5-1.5 g.
8. The method according to claim 1, wherein the pyrolysis reaction is carried out at a temperature of 700 to 900 ℃ for a time of 1 to 3 hours.
9. The nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared by the preparation method of any one of claims 1-8, which is characterized by comprising copper foam, nitrogen-doped carbon nanotubes grown on the copper foam in situ, and nickel-doped molybdenum nitride encapsulated in the nitrogen-doped carbon nanotubes.
10. Use of the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material prepared by the preparation method of any one of claims 1 to 8 or the nitrogen-doped carbon nanotube-nickel-doped molybdenum nitride composite material of claim 9 in the field of electrocatalysis.
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