CN110711596A - Efficient full-hydrolysis water catalyst IPBAP/Ni2P@MoOx/NF and preparation method thereof - Google Patents
Efficient full-hydrolysis water catalyst IPBAP/Ni2P@MoOx/NF and preparation method thereof Download PDFInfo
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910015711 MoOx Inorganic materials 0.000 title claims abstract description 48
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006460 hydrolysis reaction Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 224
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 92
- 239000000463 material Substances 0.000 claims abstract description 59
- -1 potassium ferricyanide Chemical compound 0.000 claims abstract description 24
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002243 precursor Substances 0.000 claims abstract description 13
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 9
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 8
- 238000011068 loading method Methods 0.000 claims abstract description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 6
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 6
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002131 composite material Substances 0.000 claims abstract description 4
- 229910052573 porcelain Inorganic materials 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 35
- 229910021641 deionized water Inorganic materials 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 29
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 21
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 18
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 18
- 238000002791 soaking Methods 0.000 claims description 17
- 238000005303 weighing Methods 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000007062 hydrolysis Effects 0.000 claims description 10
- 238000009210 therapy by ultrasound Methods 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 32
- 239000001257 hydrogen Substances 0.000 abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 abstract description 28
- 239000001301 oxygen Substances 0.000 abstract description 28
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 27
- 239000006260 foam Substances 0.000 abstract description 23
- 238000005868 electrolysis reaction Methods 0.000 abstract description 10
- 239000010411 electrocatalyst Substances 0.000 abstract description 9
- 238000007598 dipping method Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 8
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 8
- 238000005520 cutting process Methods 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- 239000002135 nanosheet Substances 0.000 description 7
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 7
- 238000011161 development Methods 0.000 description 6
- 238000011066 ex-situ storage Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000012876 topography Methods 0.000 description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- YWMAPNNZOCSAPF-UHFFFAOYSA-N Nickel(1+) Chemical compound [Ni+] YWMAPNNZOCSAPF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940006444 nickel cation Drugs 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
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- B01J35/33—
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- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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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 belongs to the field of new energy materials, and particularly relates to an efficient full-hydrolysis water catalyst IPBAP/Ni2P @ MoOx/NF and a preparation method thereof. The invention relates to a high-efficiency full-electrolysis water catalyst IPBAP/Ni2P @ MoOx/NF is a spherical precursor of a nanometer flower synthesized by a hydrothermal reaction of ammonium molybdate and nickel nitrate in a certain proportion; and then the composite material of in-situ Prussian blue analogue phosphide, nickel phosphide, molybdenum oxide and foam nickel is obtained by low-temperature phosphating after dipping and loading by potassium ferricyanide solution. The catalyst oxidizes molybdenumThe excellent hydrogen evolution performance and the excellent oxygen evolution performance of the Prussian blue analogue are combined, the excellent hydrogen evolution performance is maintained, the oxygen evolution performance is greatly improved, and the electrocatalyst with the efficient full water-splitting performance is obtained.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to an efficient full-hydrolysis water catalyst IPBAP/Ni2P @ MoOx/NF and a preparation method thereof.
Background
With the development of society and the continuous promotion of industrialization process, the global energy demand is increased sharply. At present, the problem of environmental pollution and the shortage of energy are important factors for the urgent development of clean energy form, and the development of a clean, efficient and sustainable new energy system is a fundamental way to solve the increasingly severe energy crisis and environmental pollution in the world today. The hydrogen energy is used as a secondary energy with wide source, green and high efficiency, has the advantages of rich resources, cleanness, high efficiency, high energy density, environmental friendliness and the like, is an ideal renewable energy source, and will certainly become an important component of an energy system in the future. The production and utilization of hydrogen energy is critical to the mitigation of energy and environmental concerns and has attracted considerable attention by researchers. The electrolytic water and hydrogen-oxygen fuel cell is concerned by having unique advantages and application prospects in the preparation and utilization of hydrogen, and the popularization and application of hydrogen production by electrolytic water to consume renewable energy sources such as water and electricity, wind power and photovoltaic power generation with excessive structural property is an important way for optimizing energy consumption structures.
However, the hysteresis of the electrocatalytic reactions such as the oxygen evolution reaction, the hydrogen evolution reaction, and the oxygen reduction reaction, which are involved in the conventional energy conversion devices such as electrolysis water and fuel cells, is one of the important bottlenecks that restrict the development thereof, and the cause of the hysteresis is mainly due to the hysteresis of the catalyst performance. Although the traditional noble metal catalyst has better electrocatalytic performance, the high price and limited reserves thereof hinder the large-scale commercial production thereof and limit the development thereof in the electrocatalytic field. Therefore, the research and development of cheap, abundant and efficient non-noble metal catalysts to replace noble metal catalysts has become a hot area of research. Among them, a full hydrolysis catalyst capable of producing hydrogen and oxygen simultaneously is gaining wide attention.
The molybdenum-based catalyst is a novel high-efficiency hydrogen evolution catalyst, which has excellent electrocatalytic hydrogen evolution performance under acidic, neutral and alkaline conditions, but the oxygen evolution performance of the molybdenum-based catalyst is not excellent. Most of the research is focused on improving the oxygen evolution performance of molybdenum-based catalysts. According to research, the single characteristic of the material can be changed by compounding, and the material has diversified properties, so that a plurality of materials improve the electrocatalytic performance of the material by utilizing a compounding mode at present.
Prussian Blue Analogue (PBA) is a substance formed by coordination interaction of a metal ion center and cyanide, and has multiple valence states and multiple metal ions of multiple coordination ions (such as Fe (CN))6 3-、Fe(CN)6 4-And Co (CN)6 3-) The PBA is given a versatile composition and a controllable morphology. In addition, PBA can be converted into corresponding oxides, selenides, phosphides and the like through interesting and simple heat, so that the PBA derivative has potential application prospects in the aspects of electrocatalysis, energy conversion and storage; meanwhile, the PBA is compounded with other materials, so that the electrocatalytic performance of the material can be obviously improved. Such as Xi et al in Ni (OH)2After a layer of PBA grows on the surface of the PBA, the performance of the generated phosphide is greatly improved compared with the phosphide without PBA, and the analysis shows that the synergy between Fe and Ni and the doping of Ni into Fe atoms2The adsorption energy of O atoms in P can be reduced, and the active sites of the material can be greatly improved by particles formed on the surface (Xi W, Yan G, Lang Z, et al.2018. Oxygen-dot Nickel Ironphosphor Nanocube Arrays Grown Ni Foam for Oxygen evolution analysis. Small [ J W]2018,14: e 1802204.). Hydrothermal formation of Ni (OH) from Ge or the like2Precursor, hydrothermal reaction to produce PBA, and synthesizing Ni2P and Fe3P is a complex product. The material is due to the presence of Ni2P and Fe3The performance of the synergistic effect between P in the aspect of hydrogen evolution is greatly improved (Y, Dong P, Craig S R, equivalent. Transforming Nickel Hydroxide inter 3D Prussian Blue analog Array to Obtain Ni)2P/Fe2P for Efficient Hydrogen Evolution Reaction.Advanced EnergyMaterials[J]:2018,1800484.)。
Therefore, the research on the hydrogen evolution and oxygen evolution performance of the material on the basis of the molybdenum-based catalyst is a problem which needs to be solved urgently at present, the catalyst provided by the invention combines the excellent hydrogen evolution performance of molybdenum oxide and the excellent oxygen evolution performance of a Prussian blue analogue to obtain the electrocatalyst with efficient full water electrolysis performance, and meanwhile, the research on regulating and controlling an electronic structure and manufacturing ion vacancies through ion doping is very important, so that the catalyst has important significance on the development of the full water electrolysis electrocatalyst.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide an efficient full-hydrolysis water catalyst IPBAP/Ni2P @ MoOx/NF, and the catalyst has better hydrogen evolution and oxygen evolution catalytic performances;
the second technical problem to be solved by the invention is to provide the catalyst IPBAP/Ni2A preparation method of P @ MoOx/NF.
In order to solve the technical problems, the invention provides an efficient full-hydrolysis water catalyst IPBAP/Ni2The preparation method of P @ MoOx/NF comprises the following steps:
(1) selecting a porous nickel carrier for pretreatment for later use;
(2) weighing ammonium molybdate, nickel nitrate and acetamide, adding water and mixing uniformly to obtain a load solution;
(3) placing the porous nickel carrier in the loading solution to enable the porous nickel carrier to be completely immersed in the loading solution, obtaining a nanometer flower spherical precursor compounded on the porous nickel carrier through hydrothermal reaction, and washing and drying the nanometer flower spherical precursor for later use;
(4) and completely immersing the dried precursor into a potassium ferricyanide solution for reaction, washing and drying a reaction product, and carrying out low-temperature phosphating treatment to obtain the catalyst.
Specifically, in the step (1), the porous nickel carrier includes foamed nickel.
Specifically, in the step (1), the pretreatment step includes a step of sequentially placing the porous nickel carrier in a dilute hydrochloric acid solution, absolute ethyl alcohol and deionized water for ultrasonic treatment, and a step of vacuum drying at a low temperature.
The concentration of the dilute hydrochloric acid solution used is preferably 3M, while the sonication time in the different solutions is preferably controlled to be 15 min.
Specifically, in the step (2):
controlling the mol ratio of molybdenum to nickel in the ammonium molybdate and the nickel nitrate to be 9: 1-8: 7;
controlling the molar ratio of acetamide to ammonium molybdate to be 10-30: 1.
and as for the amount of water in the supporting solution, it is preferable to use an amount sufficient to dissolve the above-mentioned substances with the purpose of dissolving ammonium molybdate, nickel nitrate and acetamide, and to use an amount sufficient to completely impregnate the support.
Specifically, in the step (3), the temperature of the hydrothermal reaction is controlled to be 150 ℃ and 240 ℃, and the reaction time is 16-32 h.
Specifically, in the step (4), the concentration of the potassium ferricyanide solution is controlled to be 0.01M-0.04M, the soaking time is controlled to be 1-32h, and the volume of the potassium ferricyanide solution is preferably used for complete soaking.
Specifically, in the step (4), the low-temperature phosphating step is performed in a tube furnace, and specifically includes the steps of placing a porcelain boat containing sodium hypophosphite at the air inlet end of the tube furnace, and placing porcelain boats containing the porous nickel material at positions 2cm apart.
Specifically, in the step (4), the firing temperature of the low-temperature phosphating step is controlled to be 300-.
Specifically, in the step (3) and/or (4), the washing step is deionized water washing, and the drying step is drying at 40-60 ℃ for 10-15 h.
The invention also discloses the high-efficiency full-hydrolysis water catalyst IPBAP/Ni prepared by the method2P @ MoOx/NF, wherein the catalyst is a composite material of in-situ Prussian blue analogue phosphide, nickel phosphide, molybdenum oxide and porous nickel.
The invention relates to a high-efficiency full-electrolysis water catalyst IPBAP/Ni2P @ MoOx/NF is a spherical precursor of a nanometer flower synthesized by a hydrothermal reaction of ammonium molybdate and nickel nitrate in a certain proportion; and then the composite material of in-situ Prussian blue analogue phosphide, nickel phosphide, molybdenum oxide and foam nickel is obtained by low-temperature phosphating after dipping and loading by potassium ferricyanide solution. The catalystDue to the reaction of nickel ions and potassium ferricyanide, the Prussian blue analogue grows on the molybdenum nickel-based precursor nano flower ball in situ, and meanwhile, a large number of nickel cation vacancies are left in the material, so that the intrinsic activity of the material is improved, and meanwhile, the active sites of the material are further increased; the Prussian blue analogue generated in situ and the nickel-based material in the precursor are phosphated by low-temperature phosphating to generate in-situ Prussian blue analogue phosphide and nickel phosphide, the excellent hydrogen evolution performance of molybdenum oxide and the excellent oxygen evolution performance of the Prussian blue analogue phosphide are combined, the oxygen evolution performance is greatly improved while the excellent hydrogen evolution performance is maintained, and the electrocatalyst with efficient full water-soluble performance is obtained. Meanwhile, the preparation method of the whole catalyst is simple and feasible, and is suitable for industrial popularization.
Drawings
In order that the present invention may be more readily and clearly understood, the following detailed description of the present invention is provided according to specific embodiment 1 of the present invention, taken in conjunction with the accompanying drawings, in which,
FIG. 1 is an SEM topography of a precursor obtained after soaking in a potassium ferricyanide solution in example 1;
FIG. 2 shows the IPBAP/Ni obtained in example 12SEM topography of P @ MoOx/NF;
FIG. 3 shows IPBAP/Ni obtained in example 12XRD pattern of P @ MoOx/NF;
FIG. 4 shows IPBAP/Ni obtained in example 12LSV, Tafel slope diagram and current density versus time diagram of P @ MoOx/NF material;
FIG. 5 shows IPBAP/Ni obtained in example 12The hydrogen evolution performance and oxygen evolution performance of the P @ MoOx/NF material are compared with those of other materials.
Detailed Description
Example 1
The full hydrolysis electrocatalyst IPBAP/Ni described in this example2The preparation method of P @ MoOx/NF comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 0.1mmol of ammonium molybdate tetrahydrate, 0.26mmol of nickel nitrate hexahydrate and 2mmol of acetamide, adding 60ml of deionized water, and stirring for 2 hours to obtain a load solution;
(3) transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into an oven at 180 ℃ for reaction for 24 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) soaking dried foam nickel in 0.01M potassium ferricyanide for 24h, taking out, washing with deionized water for 3 times, placing in a 60 ℃ oven, and drying for 12h to obtain the required precursor, wherein the SEM topography is shown in figure 1;
weighing 2g of sodium hypophosphite, putting the sodium hypophosphite into a porcelain boat, putting the porcelain boat into an air inlet of a tube furnace, putting dried foamed nickel into another porcelain boat at a distance of 2cm from the former porcelain boat, carrying out low-temperature phosphorization at 400 ℃, and carrying out heat preservation for 2h to finally obtain IPBAP/Ni2The SEM topography of the P @ MoOx/NF high-efficiency full-electrolysis water electro-catalytic material is shown in figure 2, and the XRD spectrum is shown in figure 3.
As shown in fig. 1, as can be seen from (1) in fig. 1, the structure of the nanosheet sphere is uniformly and closely attached to the foamed nickel, so that a large number of active sites can be provided for the material; as can be seen from (2) in fig. 1, the diameter of the nanosheet sphere can be estimated approximately to be about 10 microns; as can be seen from (3) in fig. 1, the nanosheets of the nanosheet sphere are distributed crosswise and vertically to form a sphere-like shape, which has an extremely high surface area and a stable structure; as can be seen from (4) in fig. 1, it can be seen from fig. 1 to 4 that after the potassium ferricyanide is soaked, the surface of the material has a plurality of protrusions with similar sizes and uniform distribution, and the protrusions are prussian blue analogues generated after the nickel ions react with the potassium ferricyanide.
As shown in fig. 2, (1) in fig. 2, it can be seen that the material after phosphating still maintains the structure of the nanosheet sphere, and thus it can be seen that the microstructure of the material is not changed by low-temperature phosphating; it can be seen from (2) in fig. 2 that which protrusions disappeared before the phosphating did not appear, because these prussian blue analogues shrunk in volume after the phosphating.
As shown in FIG. 3, Fe is present in the material2P、Ni2P、Mo4O11And Mo8O23. Wherein, Fe2P is derived from the product of the Prussian blue analogue after phosphorization, Ni2P is respectively from the product of prussian blue analogue after phosphorization and the product of NiO in the nano-sheet ball after phosphorization, Mo4O11And Mo8O23Mainly a composition of nano-sheet spheres.
IPBAP/Ni obtained in this example2The LSV and Tafel slope diagram and the current density-time relationship diagram of the P @ MoOx/NF material are shown in figure 4; wherein the content of the first and second substances,
FIG. 4 (1) is a LSV graph of hydrogen evolution of the material, from which it can be seen that the hydrogen evolution performance of the material is 61mV at 10 mA/cm;
FIG. 4 (2) is a Tafel slope diagram converted from the LSV diagram of hydrogen evolution of the material, from which it can be seen that the Tafel slope of hydrogen evolution of the material is 67 mA/dec;
FIG. 4 (3) is the LSV diagram of oxygen evolution of the material, from which it can be seen that the oxygen evolution performance of the material is 100mA/cm2267mV at the time of (1);
FIG. 4 (4) is a Tafel slope diagram converted from the LSV diagram of oxygen evolution of the material, from which it can be seen that the Tafel slope of oxygen evolution of the material is 27/mA/dec;
in FIG. 4, (5) shows the hydrogen evolution cycle of the material, which can be seen at 50mA/cm2The current density can be kept for 80 hours without obvious change, so that the hydrogen evolution catalyst has good hydrogen evolution cycle performance;
FIG. 4 (6) shows the oxygen evolution cycle of the material, which is shown to be at 100mA/cm2The current density can be kept for 80h without obvious change, so that the oxygen evolution cycle performance is good.
Example 2
The full hydrolysis electrocatalyst IPBAP/Ni described in this example2The preparation method of P @ MoOx/NF comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) 0.1mmol of ammonium molybdate tetrahydrate, 0.35mmol of nickel nitrate hexahydrate and 2mmol of acetamide are weighed, 60ml of deionized water is added, and stirring is carried out for 2 hours, so as to obtain a load solution;
(3) transferring the obtained load solution into a reaction kettle, adding the treated foamed nickel, sealing, and putting into an oven at 180 ℃ for reaction for 24 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) soaking the dried foam nickel in 0.03M potassium ferricyanide for 24h, taking out, washing with deionized water for 3 times, and drying in an oven at 60 ℃ for 12 h; weighing 4g of sodium hypophosphite, putting the sodium hypophosphite into a porcelain boat, putting the porcelain boat into an air inlet of a tube furnace, putting dried foamed nickel into another porcelain boat at a distance of 2cm from the former porcelain boat, carrying out low-temperature phosphorization at 400 ℃, and carrying out heat preservation for 2h to finally obtain IPBAP/Ni2P @ MoOx/NF high-efficiency full-electrolysis water electro-catalytic material.
The electrocatalytic material obtained in the example was determined to have a current density of 10mA/cm2When the hydrogen evolution overpotential is 93mV, the Tafel slope is 112 mV/dec; the current density is 100mA/cm2When the oxygen evolution overpotential is 353mV, the Tafel slope is 42 mV/dec; meanwhile, under constant voltage, the current density can still be kept stable after 80 h.
Example 3
The full hydrolysis electrocatalyst IPBAP/Ni described in this example2The preparation method of P @ MoOx/NF comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) 0.1mmol of ammonium molybdate tetrahydrate, 0.175mmol of nickel nitrate hexahydrate and 2mmol of acetamide are weighed, 60ml of deionized water is added, and stirring is carried out for 2 hours, so as to obtain a load solution;
(3) transferring the obtained load solution into a reaction kettle, adding the treated foamed nickel, sealing, and putting into an oven at 180 ℃ for reaction for 24 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) soaking the dried foam nickel in 0.02M potassium ferricyanide for 24h, taking out, washing with deionized water for 3 times, and drying in an oven at 60 ℃ for 12 h; weighing 2g of sodium hypophosphite, putting the sodium hypophosphite into a porcelain boat, putting the porcelain boat into an air inlet of a tube furnace, putting dried foamed nickel into another porcelain boat at a distance of 2cm from the former porcelain boat, carrying out low-temperature phosphorization at 400 ℃, and carrying out heat preservation for 2h to finally obtain IPBAP/Ni2P @ MoOx/NF high-efficiency full-electrolysis water electro-catalytic material.
The electrocatalytic material obtained in the example was determined to have a current density of 10mA/cm2When the hydrogen evolution overpotential is 69mV, the Tafel slope is 72 mV/dec; the current density is 100mA/cm2When the oxygen evolution overpotential is 383mV, the Tafel slope is 52 mV/dec; meanwhile, under constant voltage, the current density can still be kept stable after 80 h.
Example 4
The full hydrolysis electrocatalyst IPBAP/Ni described in this example2The preparation method of P @ MoOx/NF comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 0.1mmol of ammonium molybdate tetrahydrate, 0.26mmol of nickel nitrate hexahydrate and 1.5mmol of acetamide, adding 60ml of deionized water, and stirring for 2h to obtain a load solution;
(3) transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into an oven at 180 ℃ for reaction for 24 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) soaking dried foam nickel in 0.02M potassium ferricyanide for 16h, taking out, washing with deionized water for 3 timesDrying in 60 deg.C oven for 12 hr; weighing 2g of sodium hypophosphite, putting the sodium hypophosphite into a porcelain boat, putting the porcelain boat into an air inlet of a tube furnace, putting dried foamed nickel into another porcelain boat at a distance of 2cm from the former porcelain boat, carrying out low-temperature phosphorization at 400 ℃, and carrying out heat preservation for 2h to finally obtain IPBAP/Ni2P @ MoOx/NF high-efficiency full-electrolysis water electro-catalytic material.
The electrocatalytic material obtained in the example was determined to have a current density of 10mA/cm2When the hydrogen evolution overpotential is 89mV, the Tafel slope is 103 mV/dec; the current density is 100mA/cm2When the oxygen evolution overpotential is 0.351mV, the Tafel slope is 45 mV/dec; meanwhile, under constant voltage, the current density can still be kept stable after 80 h.
Example 5
The full hydrolysis electrocatalyst IPBAP/Ni described in this example2P@MoOXThe preparation method of/NF comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 0.1mmol of ammonium molybdate tetrahydrate, 0.26mmol of nickel nitrate hexahydrate and 1.8mmol of acetamide, adding 60ml of deionized water, and stirring for 2h to obtain a load solution;
(3) transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into an oven at 180 ℃ for reaction for 24 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) soaking the dried foam nickel in 0.01M potassium ferricyanide for 32h, taking out, washing with deionized water for 3 times, and drying in an oven at 60 ℃ for 12 h; weighing 2g of sodium hypophosphite, putting the sodium hypophosphite into a porcelain boat, putting the porcelain boat into an air inlet of a tube furnace, putting dried foamed nickel into another porcelain boat at a distance of 2cm from the former porcelain boat, carrying out low-temperature phosphorization at 400 ℃, and carrying out heat preservation for 2h to finally obtain IPBAP/Ni2P @ MoOx/NF high-efficiency full-electrolysis water electro-catalytic material.
Determined byThe electrocatalytic material obtained in this example had a current density of 10mA/cm2When the hydrogen evolution overpotential is 66mV, the Tafel slope is 97 mV/dec; the current density is 100mA/cm2When the oxygen evolution overpotential is 353mV, the Tafel slope is 49 mV/dec; meanwhile, under constant voltage, the current density can still be kept stable after 80 h.
Comparative example 1
The material of the comparative example is an ex-situ grown prussian blue analog (noted as PBAP/MoOx/NF), and the specific preparation process is as follows:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 0.1mmol of ammonium molybdate tetrahydrate and 2.0mmol of acetamide, adding 60ml of deionized water, and stirring for 2h to obtain a load solution;
(3) transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into an oven at 180 ℃ for reaction for 24 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 9.0mmol of sodium citrate and 6.0mmol of nickel nitrate hexahydrate, and dissolving in 200ml of deionized water to form a solution A; 4.0mmol of potassium ferricyanide is weighed and dissolved in 200ml of deionized water to form a solution B;
(5) mixing the solution A and the solution B into a solution C, stirring for 15 minutes, soaking the dried foamed nickel after the hydrothermal reaction in the solution C, carrying out water bath at 40 ℃ for 1 hour, keeping the temperature at room temperature for 10 hours, taking out, and drying in an oven at 60 ℃ for 12 hours;
(6) weighing 2g of sodium hypophosphite, putting the sodium hypophosphite into a porcelain boat, putting the porcelain boat into an air inlet of a tube furnace, putting dried foamed nickel into another porcelain boat at a distance of 2cm from the former porcelain boat, carrying out low-temperature phosphorization at 400 ℃, and carrying out heat preservation for 2h to finally obtain the PBAP/MoOx/NF comparison scheme electrocatalysis material.
Comparative example 2
The material of the comparative example scheme is a material (marked as P-S-0) without soaking potassium ferricyanide, and the specific preparation process comprises the following steps:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 0.1mmol of ammonium molybdate tetrahydrate, 0.26mmol of nickel nitrate hexahydrate and 2.0mmol of acetamide, adding 60ml of deionized water, and stirring for 2h to obtain a load solution;
(3) transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into an oven at 180 ℃ for reaction for 24 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 2g of sodium hypophosphite, putting the sodium hypophosphite into a porcelain boat, putting the porcelain boat into an air inlet of a tube furnace, putting the dried foamed nickel into another porcelain boat at a distance of 2cm from the former porcelain boat, carrying out low-temperature phosphorization at 400 ℃, and carrying out heat preservation for 2h to finally obtain the P-S-0 comparative scheme electro-catalytic material.
Comparative example 3
The material of the comparative example is a material without nickel doping and soaking (noted as MoOx/NF), and the specific preparation process is as follows:
(1) cutting commercial foam nickel into the size of 10mm x 20mm, sequentially performing ultrasonic treatment in 3M dilute hydrochloric acid, absolute ethyl alcohol and deionized water for 15min, and then performing vacuum drying at 60 ℃ for 12h for later use;
(2) weighing 0.1mmol of ammonium molybdate tetrahydrate and 2.0mmol of acetamide, adding 60ml of deionized water, and stirring for 2h to obtain a load solution;
(3) transferring the obtained load solution into a reaction kettle, adding the previously treated foamed nickel, sealing, and placing into an oven at 180 ℃ for reaction for 24 hours; when the reaction kettle is cooled to room temperature, taking out the foamed nickel, washing the foamed nickel for 3 times by using deionized water, and putting the foamed nickel into a 60 ℃ drying oven for drying for 12 hours;
(4) weighing 2g of sodium hypophosphite, putting the sodium hypophosphite into a porcelain boat, putting the porcelain boat into an air inlet of a tube furnace, putting dried foamed nickel into another porcelain boat at a distance of 2cm from the former porcelain boat, carrying out low-temperature phosphorization at 400 ℃, and carrying out heat preservation for 2h to finally obtain the MoOx/NF contrast scheme electrocatalysis material.
The catalytic material prepared in example 1 (noted as P-S-24), the ex-situ grown Prussian blue analogue prepared in comparative example 1 (noted as PBAP/MoOx/NF), the material prepared in comparative example 2 without soaking potassium ferricyanide (P-S-0), the material prepared in comparative example 3 without nickel doping and soaking (MoOx/NF), and the pure nickel foam (noted as NF), the commercial platinum carbon (noted as Pt/C)/the commercial ruthenium oxide (noted as RuO), were used respectively2) The performance difference comparison was performed and the results are shown in figure 5. FIG. 5 (1) is a comparison between the hydrogen evolution performance of the materials, and it can be seen that pure Nickel Foam (NF) has the worst performance, because the nickel foam is the matrix material, and the hydrogen evolution performance of the nickel foam can be ignored; instead of growing Prussian blue analogues (PBAP/MoOx/NF) in situ, no soaked potassium ferricyanide (P-S-0), no nickel doping and soaking (MoOx/NF) and commercial platinum carbon (Pt/C) at 10mA/cm2The values of the time intervals are 177mV, 91mV, 90mV and 27mV respectively.
FIG. 5 (2) is the Tafel slope corresponding to the data in FIG. 5 (1), from which it can be seen that the Tafel slopes of ex situ grown Prussian blue analog (PBAP/MoOx/NF), without soaking potassium ferricyanide (P-S-0), without nickel doping and soaking (MoOx/NF), and commercial platinum carbon (Pt/C) are 171mV/dec, 105mV/dec, 98mV/dec, and 54mV/dec, respectively.
FIG. 5 (3) is a comparison between the oxygen evolution performance of the materials, and it can be seen that the pure Nickel Foam (NF) has the worst performance, because the nickel foam is the matrix material, and the oxygen evolution performance of the nickel foam is negligible; ex situ growth of Prussian blue analogues (PBAP/MoOx/NF), no immersion potassium ferricyanide (P-S-0), no nickel doping and immersion (MoOx/NF), and commercial ruthenium oxide (RuO)2) At 100mA/cm2383mV, 371mV, 442mV and 457mV respectively.
FIG. 5 (4) is the Tafel slope corresponding to the data in FIG. 5 (3), from which it can be seen that Prussian blue analog (PBAP/MoOx/NF) is grown ex situ, potassium ferricyanide is not soaked (P-S-0), nickel-doped and soaked (MoOx/NF), and commercial ruthenium oxide (RuO)2) Respectively having a Tafel slope of 52mVdec, 54mV/dec, 81mV/dec, and 85 mV/dec.
Therefore, the catalyst material has excellent hydrogen evolution performance and oxygen evolution performance and has electrocatalysis performance of high-efficiency full water decomposition performance.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. Efficient full-hydrolysis water catalyst IPBAP/Ni2The preparation method of P @ MoOx/NF is characterized by comprising the following steps:
(1) selecting a porous nickel carrier for pretreatment for later use;
(2) weighing ammonium molybdate, nickel nitrate and acetamide, adding water and mixing uniformly to obtain a load solution;
(3) placing the porous nickel carrier in the loading solution to enable the porous nickel carrier to be completely immersed in the loading solution, obtaining a nanometer flower spherical precursor compounded on the porous nickel carrier through hydrothermal reaction, and washing and drying the nanometer flower spherical precursor for later use;
(4) and completely immersing the dried precursor into a potassium ferricyanide solution for reaction, washing and drying a reaction product, and carrying out low-temperature phosphating treatment to obtain the catalyst.
2. The high-efficiency full-hydrolysis hydro-catalyst IPBAP/Ni as claimed in claim 12The preparation method of P @ MoOx/NF is characterized in that in the step (1), the porous nickel carrier comprises foamed nickel.
3. The high efficiency full hydrolysis hydro-catalyst IPBAP/Ni as claimed in claim 1 or 22The preparation method of P @ MoOx/NF is characterized in that in the step (1), the pretreatment step comprises the step of loading the porous nickel on a carrierThe method comprises the steps of sequentially placing the body in dilute hydrochloric acid solution, absolute ethyl alcohol and deionized water for ultrasonic treatment, and vacuum drying at low temperature.
4. A high efficiency full hydrolysis hydro-catalyst IPBAP/Ni as claimed in any one of claims 1 to 32The preparation method of P @ MoOx/NF is characterized in that in the step (2):
controlling the mol ratio of molybdenum to nickel in the ammonium molybdate and the nickel nitrate to be 9: 1-8: 7;
controlling the molar ratio of acetamide to ammonium molybdate to be 10-30: 1.
5. the high efficiency total decomposition hydro-electric catalyst IPBAP/Ni according to any one of claims 1-42The preparation method of P @ MoOx/NF is characterized in that in the step (3), the temperature of the hydrothermal reaction is controlled to be 150-240 ℃, and the reaction time is controlled to be 16-32 h.
6. The high efficiency total decomposition hydro-electric catalyst IPBAP/Ni according to any one of claims 1-52The preparation method of P @ MoOx/NF is characterized in that in the step (4), the concentration of the potassium ferricyanide solution is controlled to be 0.01-0.04M, and the soaking time is controlled to be 1-32 h.
7. The high efficiency full hydrolysis hydro-catalyst IPBAP/Ni as defined in any one of claims 1-62The preparation method of P @ MoOx/NF is characterized in that in the step (4), the low-temperature phosphating step is carried out in a tube furnace, and specifically comprises the steps of placing a porcelain boat containing sodium hypophosphite at the air inlet end of the tube furnace and placing porcelain boats containing the porous nickel material at intervals of 2 cm.
8. The high-efficiency full-hydrolysis hydro-catalyst IPBAP/Ni as claimed in claim 72The preparation method of P @ MoOx/NF is characterized in that in the step (4), the firing temperature of the low-temperature phosphating step is controlled to be 300-400 ℃, and the heat preservation time is 1-6 h.
9. The high efficiency total decomposition hydro-electric catalyst IPBAP/Ni according to any one of claims 1-82The preparation method of P @ MoOx/NF is characterized in that in the step (3) and/or (4), the washing step is washing by deionized water, and the drying step is drying at 40-60 ℃ for 10-15 h.
10. High efficiency full hydrolysis hydro-catalyst IPBAP/Ni prepared by the method of any one of claims 1 to 92P @ MoOx/NF, characterized in that the catalyst is a composite of in-situ Prussian blue analog phosphide, nickel phosphide, molybdenum oxide and porous nickel.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112877727A (en) * | 2021-01-17 | 2021-06-01 | 大连理工大学 | Preparation method and application of efficient seawater full-electrolysis hydrogen production phosphide catalyst |
| CN112916028A (en) * | 2021-01-12 | 2021-06-08 | 安徽理工大学 | Benzene ring structure-like bimetal composite material and preparation and application thereof |
| CN113026049A (en) * | 2021-02-22 | 2021-06-25 | 江苏大学 | Two-step solvothermal method for preparing NiFe (CN)5NO-Ni3S2-NF composite catalyst and application thereof |
| CN113275027A (en) * | 2021-07-07 | 2021-08-20 | 西北师范大学 | Preparation and application of bimetallic phosphide derived from prussian blue analogue as template and growing on foamed nickel |
| CN113428847A (en) * | 2021-06-11 | 2021-09-24 | 上海大学 | Nickel-molybdenum-copper ternary metal phosphide, preparation method and application thereof |
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| CN113772644A (en) * | 2020-06-09 | 2021-12-10 | 东莞理工学院 | Bimetallic phosphide and preparation method and application thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988536A (en) * | 2015-08-04 | 2015-10-21 | 重庆大学 | Method for preparing high-performance molybdenum-based hydrogen evolution electrode by phosphatizing molybdate precursor |
| CN107159293A (en) * | 2017-05-12 | 2017-09-15 | 华南理工大学 | A kind of NiFe3N/NF electrochemical catalysts and preparation method and application |
| CN108654658A (en) * | 2018-05-28 | 2018-10-16 | 北京工业大学 | A kind of efficient water decomposition bifunctional electrocatalyst NiCoP and preparation method thereof |
| CN108855159A (en) * | 2018-06-27 | 2018-11-23 | 广东工业大学 | A kind of phosphatization cobalt and its preparation method and application with the synthesis of Prussian blue derivative |
| CN110227549A (en) * | 2019-06-28 | 2019-09-13 | 陕西科技大学 | A kind of hollow cube structure anode catalyst and preparation method thereof |
| CN110354876A (en) * | 2019-07-19 | 2019-10-22 | 南京理工大学 | A kind of hollow Ni2P/Co2P/Fe2The preparation method of the nano combined elctro-catalyst of P |
-
2019
- 2019-10-24 CN CN201911015721.9A patent/CN110711596B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104988536A (en) * | 2015-08-04 | 2015-10-21 | 重庆大学 | Method for preparing high-performance molybdenum-based hydrogen evolution electrode by phosphatizing molybdate precursor |
| CN107159293A (en) * | 2017-05-12 | 2017-09-15 | 华南理工大学 | A kind of NiFe3N/NF electrochemical catalysts and preparation method and application |
| CN108654658A (en) * | 2018-05-28 | 2018-10-16 | 北京工业大学 | A kind of efficient water decomposition bifunctional electrocatalyst NiCoP and preparation method thereof |
| CN108855159A (en) * | 2018-06-27 | 2018-11-23 | 广东工业大学 | A kind of phosphatization cobalt and its preparation method and application with the synthesis of Prussian blue derivative |
| CN110227549A (en) * | 2019-06-28 | 2019-09-13 | 陕西科技大学 | A kind of hollow cube structure anode catalyst and preparation method thereof |
| CN110354876A (en) * | 2019-07-19 | 2019-10-22 | 南京理工大学 | A kind of hollow Ni2P/Co2P/Fe2The preparation method of the nano combined elctro-catalyst of P |
Non-Patent Citations (2)
| Title |
|---|
| WEI HUA ET AL: "Self-Supported Ni(P, O)x MoOx Nanowire Array on Nickel Foam as an Efficient and Durable Electrocatalyst for Alkaline Hydrogen Evolution", 《NANOMATERIALS》 * |
| YUANCAI GE ET AL: "Transforming Nickel Hydroxide into 3D Prussian Blue Analogue Array to Obtain Ni2P/Fe2P for Efficient Hydrogen Evolution Reaction", 《ADV. ENERGY MATER. 》 * |
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| CN113772644A (en) * | 2020-06-09 | 2021-12-10 | 东莞理工学院 | Bimetallic phosphide and preparation method and application thereof |
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| CN112916028A (en) * | 2021-01-12 | 2021-06-08 | 安徽理工大学 | Benzene ring structure-like bimetal composite material and preparation and application thereof |
| CN112877727A (en) * | 2021-01-17 | 2021-06-01 | 大连理工大学 | Preparation method and application of efficient seawater full-electrolysis hydrogen production phosphide catalyst |
| CN112877727B (en) * | 2021-01-17 | 2022-05-10 | 大连理工大学 | Preparation method and application of efficient seawater full-electrolysis hydrogen production phosphide catalyst |
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