CN111118539A - Nickel-molybdenum oxide quantum dot loaded on nickel oxide nano sheet prepared by electrodeposition method - Google Patents
Nickel-molybdenum oxide quantum dot loaded on nickel oxide nano sheet prepared by electrodeposition method Download PDFInfo
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- CN111118539A CN111118539A CN201910492748.0A CN201910492748A CN111118539A CN 111118539 A CN111118539 A CN 111118539A CN 201910492748 A CN201910492748 A CN 201910492748A CN 111118539 A CN111118539 A CN 111118539A
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- nickel
- carbon cloth
- molybdenum
- molybdenum oxide
- oxide
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- 229910000480 nickel oxide Inorganic materials 0.000 title claims abstract description 118
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000002135 nanosheet Substances 0.000 title claims abstract description 94
- 239000002096 quantum dot Substances 0.000 title claims abstract description 79
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 134
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 134
- 239000004744 fabric Substances 0.000 claims abstract description 114
- 239000000463 material Substances 0.000 claims abstract description 86
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 42
- 238000000151 deposition Methods 0.000 claims abstract description 35
- CIHYROJTBKFOPR-UHFFFAOYSA-N nickel;oxomolybdenum Chemical class [Ni].[Mo]=O CIHYROJTBKFOPR-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001035 drying Methods 0.000 claims abstract description 32
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 20
- 230000003213 activating effect Effects 0.000 claims abstract description 19
- 150000002815 nickel Chemical class 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 46
- 239000008367 deionised water Substances 0.000 claims description 32
- 229910021641 deionized water Inorganic materials 0.000 claims description 32
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- 238000004140 cleaning Methods 0.000 claims description 18
- 230000008021 deposition Effects 0.000 claims description 17
- 239000011684 sodium molybdate Substances 0.000 claims description 17
- 235000015393 sodium molybdate Nutrition 0.000 claims description 17
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 17
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 15
- 239000011609 ammonium molybdate Substances 0.000 claims description 15
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 15
- 229940010552 ammonium molybdate Drugs 0.000 claims description 15
- 239000003792 electrolyte Substances 0.000 claims description 14
- -1 polytetrafluoroethylene Polymers 0.000 claims description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims description 13
- 239000011733 molybdenum Substances 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 12
- 230000004913 activation Effects 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 11
- 229940078494 nickel acetate Drugs 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 10
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 10
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 9
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 9
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 8
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 8
- 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 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- WZOZCAZYAWIWQO-UHFFFAOYSA-N [Ni].[Ni]=O Chemical compound [Ni].[Ni]=O WZOZCAZYAWIWQO-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 18
- 238000002360 preparation method Methods 0.000 abstract description 11
- 238000005406 washing Methods 0.000 abstract description 10
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 150000002751 molybdenum Chemical class 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 17
- 229910052739 hydrogen Inorganic materials 0.000 description 17
- 230000005540 biological transmission Effects 0.000 description 11
- 239000002131 composite material Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 10
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- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000013112 stability test Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 206010035148 Plague Diseases 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 239000013067 intermediate product Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Images
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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B01J35/23—
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- B01J35/33—
-
- B01J35/393—
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- B01J35/399—
-
- 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
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses an electrodeposition method for preparing nickel oxide nano-sheets loaded with nickel-molybdenum oxide quantum dots, and activating the surface of a carbon cloth to obtain a pretreated carbon cloth; placing the carbon cloth with the activated surface as a working electrode and the carbon rod as a counter electrode in a prepared nickel salt electrolyte solution, and depositing at constant pressure by using a working station to obtain a precursor material; putting the deposited precursor material into a prepared molybdenum salt electrolyte solution, and depositing at constant pressure by using a workstation; and washing the deposited nickel oxide nano-chip by absolute ethyl alcohol, and drying the nickel oxide nano-chip in an oven to obtain the nickel-molybdenum oxide quantum dot loaded on the nickel oxide nano-chip. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material is composed of three phases of nickel oxide, elemental nickel and molybdenum oxide, quantum dots are 2-20 nm in size and are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth. The technical scheme of the invention has the advantages of simple required equipment, convenient operation, controllable conditions, high repeatability and low preparation cost, and is suitable for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of new materials and chemical synthesis, particularly relates to a preparation method for preparing a nickel-molybdenum oxide quantum dot loaded material on a nickel oxide nano-sheet by electrodeposition, and provides a clean preparation method with simple process and low cost.
Background
Currently, coal, petroleum and natural gas are gradually exhausted as main energy sources at present, a large amount of pollutants are generated, environmental pollution and energy shortage become outstanding problems which plague further development of social economy, and development of clean and recyclable hydrogen energy is one of approaches for solving the problems. The hydrogen production technology comprises chemical raw material hydrogen production, photochemical hydrogen production, thermochemical hydrogen production, water electrolysis hydrogen production and the like, wherein the water electrolysis hydrogen production is considered to be the hydrogen production technology with highest efficiency and easy scale production. However, the overpotential caused by slow kinetics leads to electric energy waste, so that the wide application of hydrogen production by water electrolysis is restricted, and reduction of the overpotential of water electrolysis is the current main research direction. Noble metal-based materials (platinum, iridium dioxide, ruthenium dioxide, etc.) are currently the most commonly used commercial catalysts for hydrogen and oxygen evolution, but their high price and low reserves limit large-scale applications. The development of the non-noble metal water electrolysis catalyst with high efficiency, low price and stable performance has extremely important scientific significance and practical value.
Transition metal oxides including nickel oxide (NiO), cobalt oxide (CoO), manganese oxide (MnO), and the like are materials that have been widely studied in recent years, and among them, nickel oxide is being applied to the fields of supercapacitors, rechargeable batteries, electrolytic water, and the like, because of the characteristics of low price, large storage capacity, environmental friendliness, good stability, and the like, which are receiving increasing attention. However, poor conductivity and inadequate intermediate product adsorption can lead to poor catalytic performance. To improve catalytic performance, the construction of nano-heterostructures is an effective strategy because of the ability to expose more active sites, regulate the interface electronic structure and synergy. The zero-dimensional nano material has an ultrahigh surface atomic ratio, has higher activity and more active sites, but the high surface energy promotes the agglomeration of the zero-dimensional nano material, and how to obtain uniformly dispersed nano particles is the key for limiting the practical application of the zero-dimensional nano material as an electrode material. The electrodeposition method has simple equipment, easy operation, low production cost and normal pressure, and is usually carried out at normal temperature and normal pressure; a good growth layer can be obtained on a substrate with large area and complex shape; the deposition speed is high, and the preparation time can be obviously shortened. Therefore, the preparation of the nano catalyst by adopting the electro-deposition chemical method is a technology which is easy to popularize and apply in a large scale. At present, the nano-sheet loaded nano-particles are only one particle, and the monofunctional hydrogen evolution or oxygen evolution performance is mainly improved.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method for preparing a nickel-molybdenum oxide quantum dot loaded material on a nickel oxide nano sheet by electrodeposition. The preparation process is simple, convenient to operate and high in repeatability; the nickel-molybdenum oxide quantum dots loaded on the carbon cloth in-situ grown nickel oxide nanosheets are uniformly distributed and have fine nano quantum dots; can be directly used as an electrode for application, does not need to additionally add a binder and a conductive agent, and has excellent energy catalysis application prospect.
The purpose of the invention is realized by the following technical scheme:
the nickel oxide nanosheet is loaded with a nickel-molybdenum oxide quantum dot material and consists of three phases of nickel oxide, elemental nickel and molybdenum oxide, wherein the nickel quantum dot is 2-20 nm in size, the molybdenum oxide quantum dot is 2-20 nm in size, the nickel quantum dot and the molybdenum oxide quantum dot are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth; molybdenum oxide contains tetravalent and hexavalent molybdenum.
Moreover, the size of the nickel quantum dots is 5-12 nm; the size of the molybdenum oxide quantum dots is 6-15 nm.
Moreover, the simple substance nickel is zero-valent nickel, and the nickel oxide is divalent nickel.
The method for preparing the nickel oxide nano-sheet loaded with the nickel-molybdenum oxide quantum dots by the electrodeposition method comprises the following steps:
step 1, activating the surface of the carbon cloth
Placing the carbon cloth in acetone, alcohol and deionized water in sequence for ultrasonic cleaning, taking out the carbon cloth after ultrasonic cleaning, immersing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a drying oven, carrying out activation treatment on the carbon cloth, taking out the carbon cloth, placing the carbon cloth in deionized water for ultrasonic cleaning, and drying the carbon cloth for later use; the temperature of the activation reaction is set to be 60-120 ℃, and the time of the activation treatment is set to be 5-24 hours;
in the step 1, the carbon cloth is taken and then placed in acetone, alcohol and deionized water for ultrasonic cleaning, and the cleaning time is 10-20 min.
In step 1, after activation, the substrate is placed in deionized water for ultrasonic cleaning for 5-10 min.
In step 1, the acid solution is a mixed solution of nitric acid and water, and 65-68 wt% of concentrated nitric acid and water are adopted according to the volume ratio of 1: 3, preparation.
In the step 1, a drying oven is used for drying, the temperature of the drying temperature is set to be 60-90 ℃, and the drying time is 10-24 hours.
In the step 1, the temperature of the activation reaction is 80-100 ℃, and the time of the activation treatment is 10-20 h.
Placing the carbon cloth treated in the step 1 as a working electrode and a carbon rod as a counter electrode in a prepared nickel source electrolyte solution, and performing constant-voltage deposition by using a workstation to uniformly distribute nickel oxide-nickel materials in the carbon cloth, wherein the concentration of nickel ions in the nickel source electrolyte solution is 1-20 g/L, the nickel source is nickel acetate, nickel chloride, nickel nitrate or nickel sulfate, the electrodeposition voltage is-1 to-6V, and the deposition time is 600-14400 s;
in the step 2, the concentration of nickel ions is 5-10 g/L.
In the step 2, the electrodeposition voltage is-3 to-6V, and the deposition time is 3600 to 12000 s.
Placing the carbon cloth treated in the step 2 as a working electrode and a carbon rod as a counter electrode in a prepared molybdenum source electrolyte solution, and performing constant-voltage deposition by using a workstation, wherein in the molybdenum source electrolyte solution, the concentration of molybdenum ions is 0.1-5 g/L, a nickel source is ammonium molybdate or sodium molybdate, the electrodeposition voltage is-1 to-5V, and the deposition time is 600-10800 s;
in the step 3, the concentration of the molybdenum ions is 1-5 g/L.
In the step 3, the electrodeposition voltage is-2 to-3V, and the deposition time is 3600 to 10800 s.
After the three steps are completed, absolute ethyl alcohol is adopted for washing, and drying is carried out in an oven to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nano-sheets, wherein the drying temperature in the oven is 50-80 ℃, and the drying time is 6-12 hours.
The nickel oxide nano sheet loaded nickel-molybdenum oxide quantum dot material grown on the surface of the carbon cloth is used as a cathode working electrode and an anode working electrode in electrode catalysis. The application of the invention comprises a full-hydrolytic or dye battery (full-hydrolytic fuel battery), and KOH or sodium hydroxide aqueous solution of 1.0mol/L is used as electrolyte.
Compared with the prior art, the invention improves the dual-function performance of hydrogen evolution and oxygen evolution, and prepares two types of nano particles (metallic nickel and molybdenum oxide quantum dots) on an ultrathin nano sheet by utilizing the electrodeposition technology to obtain the dual-function electrolytic water catalyst with good performance and high stability, and has the following advantages: (1) the nickel oxide nanosheet prepared by the invention is loaded with metallic nickel and molybdenum oxide quantum dots, and the electron transfer is promoted, the conductivity is increased and more active sites are exposed by constructing a large number of nano heterogeneous structures, so that the improvement of the electrochemical performance is promoted; (2) the preparation method provided by the invention has the advantages of simple required equipment, convenient operation, controllable conditions, high repeatability and low preparation cost, and is suitable for industrial large-scale production; (3) the carbon cloth is used as a substrate supported catalyst, so that on one hand, the conductivity can be improved, and no conductive agent is required to be added; on the other hand, the obtained catalyst material can be directly used as an electrode for electrochemical performance test without adding other binders additionally. Meanwhile, the binding force between the nickel oxide nanosheet loaded metal nickel and molybdenum oxide quantum dots growing in situ and the substrate is firm, the contact resistance is reduced, and the technical problem that active substances are easy to fall off in the traditional process is solved. By the advantages, the electrode shows excellent dual-function hydrogen and oxygen evolution activity and stability in alkaline solution, and has wide application prospect in the aspects of full-hydrolysis fuel cells and the like.
Drawings
FIG. 1 is a scanning electron microscope photograph of a nickel-molybdenum oxide quantum dot material loaded on a nickel oxide nanosheet prepared by the present invention.
FIG. 2 is a transmission electron microscope photograph of the nickel oxide nano-sheet loaded with nickel-molybdenum oxide quantum dot material prepared by the present invention.
FIG. 3 is an XRD spectrum diagram of the nickel oxide nano-sheet loaded with nickel-molybdenum oxide quantum dot material prepared by the invention.
FIG. 4 is an XPS spectrum of a nickel-molybdenum oxide quantum dot loaded material on a nickel oxide nanosheet made in accordance with the present invention.
FIG. 5 is an LSV curve diagram of HER of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material in 1M KOH electrolyte.
FIG. 6 is a graph of the long-period HER stability test result of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared by the invention in 1M KOH electrolyte.
FIG. 7 is an LSV curve diagram of OER of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material in 1M KOH electrolyte.
FIG. 8 is a diagram of the long-period OER stability test result of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared by the invention in 1M KOH electrolyte.
FIG. 9 is an LSV curve diagram of the total hydrolysis of the nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nano-chip prepared by the invention in a 1M KOH electrolyte.
FIG. 10 is a long-period full-hydrolysis stability test result diagram of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared by the invention in a 1M KOH electrolyte.
Fig. 11 is a scanning electron microscope photograph of a nickel oxide nanosheet in the nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the present invention.
FIG. 12 is a high-power transmission electron microscope photograph of the nickel and molybdenum oxide quantum dots in the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared in the present invention.
Detailed Description
The present invention is described in detail below with reference to specific embodiments and accompanying drawings.
Example 1
Respectively weighing nickel acetate and ammonium molybdate, and dissolving the nickel acetate and the ammonium molybdate in deionized water to obtain 5.078g/L nickel acetate electrolyte solution and 1.248g/L ammonium molybdate electrolyte solution; activating the surface of commercially available carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution (68 wt% concentrated nitric acid and water are prepared according to the volume ratio of 1: 3), pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, preserving the temperature at 90 ℃ for 12h, taking out the carbon cloth, placing the carbon cloth in the deionized water, ultrasonically cleaning for 5min, and drying the carbon cloth in the oven for later use; taking the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode, putting the carbon cloth and the carbon rod into a prepared nickel acetate electrolyte solution, and depositing for 3600s at a constant voltage of-3V by using a workstation to obtain a precursor material; placing the deposited precursor material in a prepared ammonium molybdate electrolyte solution, and depositing for 1800s at a constant voltage of-2V by using a work station; and (3) washing the deposited nickel-molybdenum oxide quantum dots by absolute ethyl alcohol, drying the nickel-molybdenum oxide quantum dots in an oven at 60 ℃ and keeping the temperature for 16h to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nanosheets.
FIG. 1 is a scanning electron microscope image of a nickel oxide nanosheet loaded with a nickel-molybdenum oxide quantum dot material prepared by the present invention, showing that the nanosheet structure is uniformly loaded on a carbon rod.
FIG. 2 is a transmission electron microscope image of a nickel oxide nano-sheet loaded with a nickel-molybdenum oxide quantum dot material prepared in the present invention, which shows that the surface of the synthesized nano-sheet is loaded with uniform nano-particles, the diameter of the particles is about 3-4nm, and the structure facilitates the exposure of active sites and is beneficial to the promotion of electrochemical performance; as shown in fig. 11, the nickel oxide forms a nanosheet morphology.
FIG. 3 is an XRD spectrum of a material loaded with nickel-molybdenum oxide quantum dots on nickel oxide nano-sheets prepared in the invention, which shows that the material contains metallic nickel besides the standard peak of carbon cloth, and has no peaks of nickel oxide and molybdenum oxide in JCPDS standard card No.04-0805, because nickel oxide is amorphous and molybdenum oxide content is too small.
FIG. 4 shows XPS spectra of a nickel-molybdenum oxide quantum dot loaded on nickel oxide nanosheets prepared in the present invention, indicating that the material contains zero-valent nickel and divalent nickel, as well as tetravalent and hexavalent molybdenum, indicating that the sample consists of nickel oxide, nickel and molybdenum oxide (composite molybdenum oxide).
FIG. 5 is an LSV diagram of HER of the nickel oxide nano-sheet loaded with nickel-molybdenum oxide quantum dot material in 1M KOH electrolyte, wherein the hydrogen evolution overpotential can be reduced to below 96mV, and the additional energy consumption can be effectively reduced.
FIG. 6 is a long-period HER stability test result of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared in the invention in a 1M KOH electrolyte, and the material can still maintain a low overpotential after continuously catalyzing hydrogen evolution in an alkaline environment for 20h, which shows that the material has good stability.
FIG. 7 is an LSV diagram of OER of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared in the invention in 1M KOH electrolyte, compared with noble metal IrO2More excellent, hydrogen evolution over potential (100 mA/cm)2) And the additional energy consumption is effectively reduced by less than 347 mV.
FIG. 8 is a long-period OER stability test result of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared in the invention in 1M KOH electrolyte, and the material can still maintain a low overpotential after continuous catalytic oxygen evolution for 20h in an alkaline environment, which shows that the material has good stability.
FIG. 9 is an LSV diagram of the total water decomposition of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared in the invention in a 1M KOH electrolyte, and the water electrolysis of the material can reduce the hydrogen evolution overpotential to below 1.62V, thereby effectively reducing the extra energy consumption.
Fig. 10 is a long-period full-hydrolysis stability test result diagram of the nickel oxide nano-sheet loaded nickel-molybdenum oxide quantum dot material prepared in the invention in 1M KOH electrolyte, and the material can continuously catalyze full-hydrolysis in an alkaline environment for 20 hours and then can still maintain a low overpotential, which shows that the material has good stability.
Fig. 12 is a high-power transmission electron microscope photograph of the nickel and molybdenum oxide quantum dots in the nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the present invention, and the quantum dots having metallic nickel and molybdenum oxide can be known from lattice measurement data.
Example 2
Respectively weighing nickel nitrate and ammonium molybdate, and dissolving in deionized water to obtain 1g/L nickel acetate electrolyte solution and 5g/L ammonium molybdate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 24h at 60 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; placing the carbon cloth with the activated surface as a working electrode and the carbon rod as a counter electrode in a prepared nickel nitrate electrolyte solution, and depositing for 14400s under constant voltage by using a work station-1V to obtain a precursor material; placing the deposited precursor material in a prepared ammonium molybdate electrolyte solution, and depositing for 10800s at a constant voltage of-1V by using a workstation; and washing the deposited nickel-molybdenum oxide quantum dots by absolute ethyl alcohol, and keeping the temperature in an oven at 50 ℃ for 12h for drying to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nano-sheets.
The nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nano-sheet can be obtained by utilizing the characterization results of scanning, transmission electron microscope, XRD, XPS and Raman on the morphology and structure of the nickel-molybdenum oxide quantum dot material. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the embodiment is composed of three phases, namely nickel oxide, simple substance nickel and composite molybdenum oxide, the quantum dot size is about 5nm, the quantum dots are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth.
Example 3
Respectively weighing nickel sulfate and ammonium molybdate, and dissolving in deionized water to obtain 20g/L nickel sulfate electrolyte solution and 0.1g/L ammonium molybdate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 5h at 120 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; taking the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode, placing the carbon cloth and the carbon rod into a prepared nickel sulfate electrolyte solution, and depositing for 600s at a constant voltage of-6V by using a work station to obtain a precursor material; placing the deposited precursor material in a prepared ammonium molybdate electrolyte solution, and depositing for 600s at constant voltage of-5V by using a workstation; and (4) washing the deposited nickel-molybdenum oxide quantum dots by absolute ethyl alcohol, drying the nickel-molybdenum oxide quantum dots in an oven at 80 ℃ and keeping the temperature for 6 hours to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nanosheets.
The nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nano-sheet can be obtained by utilizing the characterization results of scanning, transmission electron microscope, XRD, XPS and Raman on the morphology and structure of the nickel-molybdenum oxide quantum dot material. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the embodiment is composed of three phases, namely nickel oxide, simple substance nickel and composite molybdenum oxide, the quantum dot size is about 20nm, the quantum dots are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth.
Example 4
Respectively weighing nickel chloride and ammonium molybdate, and dissolving in deionized water to obtain 10g/L nickel chloride electrolyte solution and 2g/L ammonium molybdate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 5h at 120 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; taking the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode, placing the carbon cloth and the carbon rod into a prepared nickel chloride electrolyte solution, and depositing for 1200s at a constant voltage of-4V by using a workstation to obtain a precursor material; putting the deposited precursor material into a prepared ammonium molybdate electrolyte solution, and depositing for 600s at a working station under the constant pressure of-4V; and (4) washing the deposited nickel-molybdenum oxide quantum dots by absolute ethyl alcohol, drying the nickel-molybdenum oxide quantum dots in an oven at 80 ℃ and keeping the temperature for 6 hours to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nanosheets.
The nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nano-sheet can be obtained by utilizing the characterization results of scanning, transmission electron microscope, XRD, XPS and Raman on the morphology and structure of the nickel-molybdenum oxide quantum dot material. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the embodiment is composed of three phases, namely nickel oxide, simple substance nickel and composite molybdenum oxide, the quantum dot size is about 10nm, the quantum dots are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth.
Example 5
Respectively weighing nickel sulfate and sodium molybdate, and dissolving the nickel sulfate and the sodium molybdate in deionized water to obtain 10g/L nickel sulfate electrolyte solution and 2.55g/L sodium molybdate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 15h at 90 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; taking the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode, placing the carbon cloth and the carbon rod into a prepared nickel sulfate electrolyte solution, and depositing for 7200s at a constant voltage of-4V by using a workstation to obtain a precursor material; placing the deposited precursor material in a prepared sodium molybdate electrolyte solution, and depositing for 5400s at constant voltage of-3V by using a workstation; and (4) washing the deposited nickel-molybdenum oxide quantum dots by absolute ethyl alcohol, drying the nickel-molybdenum oxide quantum dots in an oven at 700 ℃, and keeping the temperature for 9 hours to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nanosheets.
The nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nano-sheet can be obtained by utilizing the characterization results of scanning, transmission electron microscope, XRD, XPS and Raman on the morphology and structure of the nickel-molybdenum oxide quantum dot material. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the embodiment is composed of three phases, namely nickel oxide, simple substance nickel and composite molybdenum oxide, the quantum dot size is about 15nm, the quantum dots are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth.
Example 6
Respectively weighing nickel nitrate and sodium molybdate, and dissolving the nickel nitrate and the sodium molybdate in deionized water to obtain 5g/L nickel nitrate electrolyte solution and 1.25g/L sodium molybdate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature at 75 ℃ for 16h, placing the reaction kettle in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; taking the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode, putting the carbon cloth and the carbon rod into a prepared nickel nitrate electrolyte solution, and depositing for 4800s at a constant voltage of-5V by using a work station to obtain a precursor material; putting the deposited precursor material into a prepared sodium molybdate electrolyte solution, and depositing for 6400s at a constant voltage of-4V by using a workstation; and (4) washing the deposited nickel-molybdenum oxide quantum dots by absolute ethyl alcohol, drying the nickel-molybdenum oxide quantum dots in an oven at 60 ℃ and keeping the temperature for 9 hours to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nanosheets.
The nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nano-sheet can be obtained by utilizing the characterization results of scanning, transmission electron microscope, XRD, XPS and Raman on the morphology and structure of the nickel-molybdenum oxide quantum dot material. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the embodiment is composed of three phases, namely nickel oxide, simple substance nickel and composite molybdenum oxide, the quantum dot size is about 2nm, the quantum dots are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth.
Example 7
Respectively weighing nickel chloride and sodium molybdate, and dissolving in deionized water to obtain 20g/L of nickel chloride electrolyte solution and 7.5g/L of sodium molybdate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 5h at 80 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; taking the carbon cloth with the activated surface as a working electrode and a carbon rod as a counter electrode, putting the carbon cloth and the carbon rod into a prepared nickel chloride electrolyte solution, and depositing for 8000s at a constant voltage of-2.5V by using a workstation to obtain a precursor material; placing the deposited precursor material in a prepared sodium molybdate electrolyte solution, and depositing for 12000s at a constant voltage of-1V by using a work station; and washing the deposited nickel-molybdenum oxide quantum dots by absolute ethyl alcohol, drying the nickel-molybdenum oxide quantum dots in an oven at 70 ℃ and keeping the temperature for 18h to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nanosheets.
The nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nano-sheet can be obtained by utilizing the characterization results of scanning, transmission electron microscope, XRD, XPS and Raman on the morphology and structure of the nickel-molybdenum oxide quantum dot material. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the embodiment is composed of three phases, namely nickel oxide, simple substance nickel and composite molybdenum oxide, the quantum dot size is about 12nm, the quantum dots are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth.
Example 8
Respectively weighing nickel acetate and sodium molybdate, and dissolving the nickel acetate and the sodium molybdate in deionized water to obtain 15g/L nickel acetate electrolyte solution and 3.75g/L sodium molybdate electrolyte solution; activating the surface of carbon cloth, placing the carbon cloth in acetone, alcohol and deionized water in sequence, ultrasonically cleaning for 10min, taking out the carbon cloth, placing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in an oven, activating the carbon cloth, keeping the temperature for 5h at 80 ℃, placing the carbon cloth in the deionized water after taking out, ultrasonically cleaning for 5min, and drying in the oven for later use; placing the carbon cloth with the activated surface as a working electrode and the carbon rod as a counter electrode in a prepared nickel acetate electrolyte solution, and depositing for 12000s at a constant voltage of-2V by using a working station to obtain a precursor material; placing the deposited precursor material in a prepared sodium molybdate electrolyte solution, and depositing for 8000s at constant voltage of-1V by using a workstation; and washing the deposited nickel-molybdenum oxide quantum dots by absolute ethyl alcohol, drying the nickel-molybdenum oxide quantum dots in an oven at 70 ℃ and keeping the temperature for 18h to obtain the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nanosheets.
The nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nano-sheet can be obtained by utilizing the characterization results of scanning, transmission electron microscope, XRD, XPS and Raman on the morphology and structure of the nickel-molybdenum oxide quantum dot material. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material prepared in the embodiment is composed of three phases, namely nickel oxide, simple substance nickel and composite molybdenum oxide, the quantum dot size is about 20nm, the quantum dots are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth.
The preparation of the composite material can be realized by adjusting the process parameters according to the content of the invention, and the composite material shows the performance basically consistent with the invention. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The nickel oxide nanosheet is loaded with a nickel-molybdenum oxide quantum dot material and is characterized by consisting of three phases of nickel oxide, elemental nickel and molybdenum oxide, wherein the size of nickel quantum dots is 2-20 nm, the size of molybdenum oxide quantum dots is 2-20 nm, the nickel quantum dots and the molybdenum oxide quantum dots are uniformly distributed on the nickel oxide nanosheet, and the nickel oxide nanosheet is uniformly distributed on carbon cloth; molybdenum oxide contains tetravalent and hexavalent molybdenum.
2. The nickel oxide nanosheet supported nickel-molybdenum oxide quantum dot material of claim 1, wherein the elemental nickel is zero-valent nickel and the nickel oxide is divalent nickel.
3. The nickel oxide nanosheet loaded nickel-molybdenum oxide quantum dot material of claim 1 or 2, wherein the nickel quantum dots are 5-12 nm in size; the size of the molybdenum oxide quantum dots is 6-15 nm.
4. The method for preparing the nickel oxide nano-sheet loaded with the nickel-molybdenum oxide quantum dots by the electrodeposition method is characterized by comprising the following steps:
step 1, activating the surface of the carbon cloth
Placing the carbon cloth in acetone, alcohol and deionized water in sequence for ultrasonic cleaning, taking out the carbon cloth after ultrasonic cleaning, immersing the carbon cloth in an acid solution, pouring the carbon cloth into a reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle in a drying oven, carrying out activation treatment on the carbon cloth, taking out the carbon cloth, placing the carbon cloth in deionized water for ultrasonic cleaning, and drying the carbon cloth for later use; the temperature of the activation reaction is set to be 60-120 ℃, and the time of the activation treatment is set to be 5-24 hours;
step 2, nickel source deposition
Placing the carbon cloth treated in the step 1 as a working electrode and a carbon rod as a counter electrode in a prepared nickel source electrolyte solution, and performing constant-voltage deposition by using a workstation to uniformly distribute nickel oxide-nickel materials in the carbon cloth, wherein the concentration of nickel ions in the nickel source electrolyte solution is 1-20 g/L, the nickel source is nickel acetate, nickel chloride, nickel nitrate or nickel sulfate, the electrodeposition voltage is-1 to-6V, and the deposition time is 600-14400 s;
step 3, molybdenum source deposition
And (3) placing the carbon cloth treated in the step (2) as a working electrode and a carbon rod as a counter electrode in a prepared molybdenum source electrolyte solution, and performing constant-voltage deposition by using a workstation, wherein in the molybdenum source electrolyte solution, the concentration of molybdenum ions is 0.1-5 g/L, the nickel source is ammonium molybdate or sodium molybdate, the electrodeposition voltage is-1 to-5V, and the deposition time is 600-10800 s.
5. The electrodeposition method for preparing nickel-molybdenum oxide quantum dots loaded on nickel oxide nano-sheets according to claim 4, wherein in step 1, the acid solution is a mixed solution of nitric acid and water, and 65-68 wt% of concentrated nitric acid and water are used according to a volume ratio of 1: 3, preparing; the temperature of the activation reaction is 80-100 ℃, and the time of the activation treatment is 10-20 h.
6. The method for preparing the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nano-sheets by the electrodeposition method according to claim 4, wherein in the step 1, the carbon cloth is taken and sequentially placed in acetone, alcohol and deionized water for ultrasonic cleaning, and the cleaning time is 10-20 min; after activation treatment, placing the mixture in deionized water for ultrasonic cleaning for 5-10 min; and drying by using a drying oven, wherein the drying temperature is set to be 60-90 ℃, and the drying time is 10-24 h.
7. The method for preparing the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nano-sheets by the electrodeposition method according to claim 4, wherein in the step 2, the concentration of nickel ions is 5-10 g/L; the electro-deposition voltage is-3 to-6V, and the deposition time is 3600 to 12000 s.
8. The method for preparing the nickel-molybdenum oxide quantum dots loaded on the nickel oxide nanosheets by the electrodeposition method according to claim 4, wherein in step 3, the concentration of molybdenum ions is 1-5 g/L; the electro-deposition voltage is-2 to-3V, and the deposition time is 3600 to 10800 s.
9. The use of the nickel oxide nanosheets loaded with a nickel-molybdenum oxide quantum dot material as claimed in any one of claims 1 to 3 in electrode catalysis.
10. The application of the nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nanosheets in electrode catalysis is characterized in that the nickel-molybdenum oxide quantum dot material loaded on the nickel oxide nanosheets is used as a negative working electrode and a positive working electrode simultaneously in electrode catalysis, the application comprises a full-hydrolytic or dye battery, and 1.0mol/L KOH or sodium hydroxide aqueous solution is used as electrolyte.
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| CN104894595A (en) * | 2015-05-19 | 2015-09-09 | 派新（上海）能源技术有限公司 | High-catalytic-activity amorphous metal oxide hydrogen evolution electrode and preparation method thereof |
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