CN113856711A - Design synthesis and electrolytic water hydrogen evolution research of high-efficiency nickel-cobalt phosphide heterojunction catalyst - Google Patents
Design synthesis and electrolytic water hydrogen evolution research of high-efficiency nickel-cobalt phosphide heterojunction catalyst Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000001257 hydrogen Substances 0.000 title claims abstract description 66
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 66
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 238000011160 research Methods 0.000 title claims abstract description 5
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000013461 design Methods 0.000 title abstract description 3
- 230000015572 biosynthetic process Effects 0.000 title description 2
- 238000003786 synthesis reaction Methods 0.000 title description 2
- 239000006260 foam Substances 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 18
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 238000002791 soaking Methods 0.000 claims abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims description 14
- 239000011574 phosphorus Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 239000007789 gas Substances 0.000 claims description 9
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 239000010411 electrocatalyst Substances 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 239000003517 fume Substances 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 6
- 229910052786 argon Inorganic materials 0.000 claims 4
- 239000012159 carrier gas Substances 0.000 claims 3
- 230000001681 protective effect Effects 0.000 claims 3
- 239000011943 nanocatalyst Substances 0.000 claims 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 21
- 230000007935 neutral effect Effects 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 229910052759 nickel Inorganic materials 0.000 abstract description 9
- 238000011161 development Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000007605 air drying Methods 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- -1 cobalt and nickel Chemical class 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 9
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
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- 238000012360 testing method Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 241000282414 Homo sapiens Species 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
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- 230000006866 deterioration Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 238000005120 petroleum cracking Methods 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a preparation method of a high-performance nickel cobalt phosphide hydrogen evolution catalyst and efficient electrolytic water hydrogen evolution research, and belongs to the technical field of hydrogen production and new energy through electrolytic water. The key points are as follows: the non-noble metal phosphide Co is prepared by phosphorizing foam metal substrates such as foam cobalt, nickel and the like by a chemical vapor deposition method2P/Ni2P porous conductive skeleton. Soaking the conductive skeleton in solution of metal salt such as cobalt and nickel, air drying, and phosphorizing again to obtain the final productThe obtained non-noble metal phosphide hydrogen evolution catalyst with the nano porous structure has excellent catalytic hydrogen evolution activity and stability in neutral and alkaline environments. The unique structural design greatly exposes active sites of metal phosphide, reduces contact resistance among components of the material, is beneficial to hydrogen adsorption and release, and accelerates charge transfer among interfaces of different components, thereby greatly reducing overpotential of hydrogen reaction and helping the development of hydrogen energy industry and hydrogen fuel cells in China.
Description
Technical Field
The invention relates to the field of application of an electrocatalyst to the research of hydrogen production by water electrolysis, in particular to an M based on surface growth of non-noble metal phosphide materials such as cobalt and nickelxThe preparation method of the P nano-particle catalyst and the application of the P nano-particle catalyst in the electrocatalytic hydrogen evolution reaction in neutral and alkaline solutions, wherein M refers to cheap transition metals such as cobalt, nickel and the like.
Background
The current problems of traditional energy shortage around the world and environmental deterioration caused by the combustion of fuels such as coal and petroleum drive people to search and develop new renewable clean energy. Renewable clean energy sources in various forms such as wind energy, solar energy, geothermal energy and the like are rapidly developed, mainly have the advantages of large energy storage capacity, cleanness, environmental protection, inexhaustibility and the like, and are expected to become mainstream energy sources of future energy requirements of human beings. However, the wind power or solar power generation is greatly influenced by local climate, is difficult to control, and has the problems of seasonality of hydraulic resources, excessive power at night and the like. Due to the fact that new energy layout in China is relatively centralized, renewable energy power supply and local consumption capability are not coordinated, and the renewable power is difficult to be connected to the grid, the problems of wind abandoning, light abandoning and water abandoning in China are serious, and the amount of economic loss caused by the problems is huge. The hydrogen energy is one of clean energy sources, and has high energy density and environmental friendliness, so that the hydrogen energy is possible to become an ideal substitute of the traditional fossil fuel and has wide development prospect and application value. At present, hydrogen produced by using more fossil fuels, namely hydrogen obtained by a water gas method and petroleum cracking, has low purity, consumes a large amount of petroleum fuels and releases a large amount of greenhouse gas CO2It is not favorable for the sustainable development of energy. Therefore, there is a pressing need to improve existing hydrogen production pathways in order to promote energy sustainability and reduce greenhouse gas emissions.
The earth with human living has abundant water resources, such as daily life water, river water, industrial wastewater, seawater, etc., which may be natural hydrogen production raw materials, and the total amount of hydrogen fuel obtained by water decomposition is about 9000 times of fossil fuel on earth. In view of the above, the water electrolysis hydrogen production technology is an ideal hydrogen production scheme, can convert surplus renewable energy power such as photovoltaic, wind power, water power and the like into hydrogen fuel capable of being stored and transported, is expected to occupy a very important position in the future hydrogen production technology, and has extremely high social and economic benefits for the rapid development of hydrogen energy industry in China. However, the industrial water electrolysis technology still has many defects, so that the economic benefit of the technology is not ideal. Taking an alkaline electrolytic cell as an example, an electrocatalytic hydrogen evolution half-reaction is generally carried out by using an inexpensive Ni/C material as a cathode, and an electrocatalytic oxygen evolution half-reaction is carried out by using Ni/Co/Fe as an anode. However, the activity of the non-noble metal catalyst is limited, so that the energy conversion efficiency in the water electrolysis process is low, the electric energy consumption is large, and the cost of hydrogen production is increased. In addition, hydrogen production technology in both alkaline environment and acidic environment faces the problem of electrode corrosion, so people aim at preparing hydrogen in neutral electrolyte, but due to poor activity of the catalyst, the reaction mechanism is unknown, and the like, the hydrogen evolution reaction rate in the neutral environment is far lower than that in the alkaline environment and the acidic environment. Therefore, the development of a cheap and excellent hydrogen evolution catalyst for electrolysis of water becomes slow, and the reports of high-performance non-noble metal hydrogen evolution catalyst suitable for use in neutral or alkaline environment are still few. In the patent, aiming at meeting the commercial factors such as catalyst efficiency, catalyst cost, environmental protection and the like, a high-efficiency low-cost electrolytic water-evolution hydrogen-evolution catalyst produced by a simple two-step chemical vapor deposition technology is designed, and the industrial large-scale hydrogen production application is hopefully realized. The catalyst is a high-efficiency hydrogen evolution electrocatalyst formed by three-dimensional porous non-noble metal (Ni, Co and the like) phosphide nanoparticles, and the main catalytic active sites are derived from phosphide nanoparticles growing on foam metal phosphide. The material has excellent electrocatalytic hydrogen evolution activity in alkaline or neutral electrolyte, and realizes effective hydrogen production reaction by electrolyzing water through a two-electrode full-hydrolysis device constructed by matching with another strong oxygen evolution catalyst (such as NiFeN and the like), thereby converting energy in other forms into hydrogen chemical energy to be stored.
Disclosure of Invention
The invention aims to provide a foam substrate surface growth M based on non-noble metal such as foamed cobalt, nickel or cobaltxThe preparation method of the P nanoparticle (M = Fe, Co or Ni) hydrogen evolution catalyst and the application thereof in the water electrolysis hydrogen evolution reaction in neutral and alkaline solutions, and the catalyst obtained by the chemical vapor deposition method shows excellent electrocatalytic hydrogen evolution activity in neutral and alkaline electrolytes. For example, Co we synthesized2The P/CoNiP hydrogen evolution catalyst greatly reduces the overpotential of the electrocatalytic water hydrogen evolution reaction, and the current density is 10 mA/cm under the neutral environment2The overpotential of (A) is only 65.7 mV, and the corresponding overpotential is reduced to 51 mV in alkaline environment. The performance of the catalyst is better than that of most of non-noble metal hydrogen evolution catalysts reported at present.
The preparation method of the hydrogen evolution catalyst comprises the following steps: (taking foamed cobalt nickel substrates as an example).
Step 1: the foamed cobalt nickel substrate was cut to an area of 15 mm long by 5 mm wide.
Step 2: a CoNiP foam substrate was prepared by the following method: and respectively placing the cut foamed cobalt nickel and 50mg of phosphorus powder at the center positions of temperature areas II and I of the double-temperature-area high-temperature tube furnace for carrying out thermal phosphating reaction, wherein the phosphorus powder is placed at the center of the temperature area I at the upstream of the gas, and the CoNiP foam substrate is placed at the center of the temperature area II at the downstream of the gas. And (3) respectively heating the phosphorus powder and the CoNiP foam substrate from room temperature to 400 ℃ and 450 ℃ at the heating rate of 15 ℃/min, maintaining the temperature, calcining for 1 hour, cooling to room temperature, and taking out to obtain the CoNiP porous foam substrate.
And step 3: growing cobalt phosphide nanoparticles on a CoNiP porous foam substrate by the following method: the CoNiP porous foam substrate is soaked in 0.69M cobalt nitrate DMF solution for a few seconds, then naturally dried in a fume hood, and pushed into a double-temperature-zone high-temperature tube furnace together with 30mg phosphorus powder. Repeating the thermal phosphorization process of the step 2 to obtain Co with a nano porous structure2P/CoNiP electrocatalytic hydrogen evolution catalyst.
The invention is in phase with the existing electrocatalytic materialCompared with the characteristics of the prior art: 1. the invention synthesizes the high-performance hydrogen evolution catalyst based on transition metal elements such as nickel, cobalt, iron and the like, has simple and convenient preparation process and wide raw material sources, and is suitable for macro-quantitative or large-size preparation. 2. According to the invention, cobalt phosphide nano-particles are synthesized on nickel-cobalt-phosphorus foam through a chemical vapor deposition method, and the path promotes the bonding between the metal phosphide foam substrate and the phosphide nano-particles through strong chemical bonds, so that the interface contact resistance is reduced, the interface charge transfer is accelerated, the electronic structure of the catalyst is regulated and controlled, the defect of poor conductivity of a cobalt phosphide material is overcome, a comfortable path is provided for the effective transmission of charges and ions, the hydrogen ion adsorption and hydrogen molecule desorption process in the electrolytic water hydrogen evolution reaction is facilitated, and the hydrogen evolution overpotential is greatly reduced. Current of 10 mA/cm was reached under neutral environment (pH = 6.5)2 The overpotential of (2) needs only 65.7 mV, and the current reaches 500 mA/cm under the alkaline environment (pH is approximately equal to 14)2The overpotential of (A) is 146 mV, which is superior to most of reported non-noble metal hydrogen evolution catalysts, such as cobalt phosphide, nickel phosphide or molybdenum disulfide. 3. The electrocatalytic material of the invention can reach the current of 500 mA/cm in 30 percent KOH in strong alkaline environment2The overpotential of the electrolytic solution only needs 138 mV, can keep the performance stable for more than tens of hours, has simple manufacturing process, energy conservation and compatibility with the commercial alkaline electrolytic tank technology, is expected to realize industrialized application, and is used for large-scale water electrolysis hydrogen production.
Drawings
Fig. 1 is a graph of current-potential polarization of cobalt phosphide nanoparticle hydrogen evolution catalyst in neutral 1M PBS solution initially and after 1000 CV cycles in example 1 of the present invention.
FIG. 2 shows the AC impedance test of the catalyst material of example 1 of the present invention in a neutral 1M PBS solution.
FIG. 3 is a graph of current-potential polarization of cobalt phosphide nanoparticle hydrogen evolution catalyst in alkaline 1M KOH solution initially and after 1000 CV cycles in example 1 of the present invention.
FIG. 4 shows the AC impedance test of the catalyst material of example 1 of the present invention in an alkaline 1M KOH solution.
FIG. 5 is a comparison of the electrocatalytic hydrogen evolution performance of the catalyst material in example 1 of the present invention in KOH solutions of different concentrations.
Fig. 6 is a graph of electrochemical stability testing of catalyst materials in alkaline and neutral electrolytes. It is apparent that the catalyst was operated at a current density of 50 mA/cm2Has good stability.
FIG. 7 is a surface topography under a scanning electron microscope of a low power of the catalyst material in example 1 of the present invention.
FIG. 8 is a surface topography under a high-power scanning electron microscope of the catalyst material in example 1 of the present invention.
FIG. 9 is an X-ray diffraction chart of a cobalt-based hydrogen evolution catalyst in example 1 of the present invention, which shows the main components constituting the catalyst.
Detailed Description
The foregoing will provide further details of the invention in order to provide a better understanding of the nature of the patent, but is not to be construed as limiting the invention.
The scope of the present invention is not limited to the following examples, and any techniques based on the above implementations of the present invention are within the scope of the present invention.
An example of a preparation method of a transition metal phosphide-based high-efficiency hydrogen evolution catalyst such as nickel and cobalt and an electrolytic water hydrogen evolution reaction in a neutral and alkaline solution thereof is as follows.
Example 1: co2Preparation of P/CoNiP nano-porous catalyst and electrocatalytic hydrogen evolution test thereof in 1M PBS, 1M KOH and 30% KOH environment.
Step 1: the foam cobalt nickel base substrate was cut to an area of 15 mm long by 5 mm wide.
Step 2: a CoNiP foam substrate was prepared by the following method: and pushing the cut foam cobalt nickel and 50mg of phosphorus powder into a double-temperature-zone high-temperature tube furnace together for carrying out a phosphating reaction, wherein the phosphorus powder is placed in the center of a temperature zone at the upstream of the gas, and a CoNiP foam substrate is placed in the center of a temperature zone at the downstream of the gas. And (3) respectively heating the phosphorus powder and the CoNiP foam substrate from room temperature to 400 ℃ and 450 ℃ at the heating rate of 15 ℃/min, maintaining the temperature, calcining for 1 hour, cooling to room temperature, and taking out to obtain the CoNiP foam substrate.
And step 3: the method for growing cobalt phosphide nano-particles on cobalt phosphide nickel foam comprises the following steps: cobalt nickel phosphide foam is soaked in 0.69M cobalt nitrate DMF solution for a few seconds and then dried, and is pushed into a double-temperature-zone high-temperature tube furnace together with 30mg phosphorus powder. The CoNiP foam substrate and the phosphorus powder of the modified precursor solution are respectively heated from room temperature to 450 ℃ and 400 ℃ at the heating rate of 15 ℃/min, the temperature is maintained for calcining for 1 hour, then the temperature is reduced to room temperature, and the Co foam substrate and the phosphorus powder are taken out, so that the Co with high catalytic performance can be obtained2P/CoNiP electrolyzes the water to separate out the hydrogen reaction catalyst.
The electrocatalytic hydrogen evolution performance test mainly adopts an American GARY Reference 3000 electrochemical workstation and adopts a standard three-electrode system (a working electrode, a counter electrode and a Reference electrode) for testing. Wherein the three-electrode system has Co2P/CoNiP is used as a working electrode, a saturated calomel electrode imported by Gamry manufacturers is used as a reference electrode in a neutral environment, a graphite rod is used as a counter electrode, a Hg/HgO electrode imported by Gamry manufacturers is used as a reference electrode in an alkaline environment, a platinum wire is used as a counter electrode, 1M PBS and 1M KOH solution are respectively used as electrolyte solutions, and the electro-catalysis performance test results are shown in figures 1, 2, 3, 4, 5 and 6, and Co is used for the test of the electro-catalysis performance of the lead-free lithium ion battery2The topography of P/CoNiP is shown in FIG. 7, Co2The composition of the main components of P/CoNiP is shown in FIG. 8.
The above examples illustrate the basic processes and applications of the present invention in the field of hydrogen production from electrolyzed water, and it will be understood by those skilled in the art that the present invention is not limited by the above examples, which are provided in the description for illustrating the principles and processes of the present invention, and that various changes and modifications may be made without departing from the scope of the principles and processes of the present invention and within the scope of the invention.
Claims (4)
1. The invention takes the preparation of high-performance non-noble metal cobalt phosphide nano-catalyst as an example to illustrate the preparation process of the cheap hydrogen evolution catalytic material and the application research in the aspect of electrolytic water hydrogen evolution reaction; non-noble metal phosphide Co2P/CoNiP hydrogen evolution catalystThe preparation method comprises the following steps: step 1: cutting the foam cobalt-nickel substrate, wherein the cutting area is 15 mm long by 5 mm wide; step 2: placing a foamed cobalt-nickel substrate at the center of a downstream temperature zone II of a double-temperature-zone tubular furnace, taking phosphorus powder as a phosphorus source at the center of a temperature zone I above an airflow, taking high-purity argon as a carrier gas and a protective gas, setting the temperature of the temperature zone II at 450 ℃, the temperature of the temperature zone I at 400 ℃, keeping the temperature for 1 h, and performing first thermal phosphating treatment to obtain a CoNiP porous foam substrate; and step 3: adding proper amount of Co (NO)3)2·6H2Dissolving O powder in a dimethylformamide solution to serve as a precursor solution, soaking the prepared CoNiP foam substrate in the precursor solution for a few seconds, and naturally airing in a fume hood; and 4, step 4: placing the CoNiP foam substrate soaked with the precursor solution at the central position of a double-temperature-zone tubular furnace temperature zone II, placing phosphorus powder serving as a phosphorus source at the central position of a temperature zone I, still using high-purity argon gas as a carrier gas and a protective gas, setting the temperature of the temperature zone II to be 450 ℃, the temperature of the temperature zone I to be 400 ℃, keeping the temperature for 1 h, and carrying out secondary thermal phosphating treatment to obtain Co with a nano porous structure2P/CoNiP electrocatalyst.
2. A non-noble metal phosphide Co as claimed in claim 12The preparation method of the P/CoNiP hydrogen evolution catalyst comprises the following steps: the method is characterized in that the flow rate of argon in the step 2 and the step 4 'with high-purity argon as a carrier gas and a protective gas' is 10 sccm.
3. A non-noble metal phosphide Co as claimed in claim 12The preparation method of the P/CoNiP hydrogen evolution catalyst comprises the following steps: characterized in that, said step 3' Co (NO) of appropriate concentration3)2·6H2DMF solution of O "Co (NO)3)2·6H2The proportioning mode of the O precursor solution is 1 g Co (NO)3)2·6H2O, dissolved well in 5 mL dimethylformamide solution and sonicated for more than 5 minutes.
4. A non-noble metal phosphide Co as claimed in claim 12The preparation method of the P/CoNiP hydrogen evolution catalyst comprises the following steps: the method is characterized in that in the step 2 and the step 4, the temperature of the temperature zone II (downstream) is set to be 450 ℃, the temperature of the temperature zone I (upstream) is set to be 400 ℃, and the required heating rate in the constant temperature 1 h is 10 ℃/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114394580A (en) * | 2022-01-25 | 2022-04-26 | 中南大学 | Self-supporting cobalt phosphide nanowire electrode and preparation method and application thereof |
| CN114808012A (en) * | 2022-04-19 | 2022-07-29 | 湖南师范大学 | Phosphide/binary metal nitride nano porous heterojunction electrocatalyst and preparation method and application thereof |
| CN114950502A (en) * | 2022-06-21 | 2022-08-30 | 青岛大学 | Preparation method of nanorod red phosphorescent catalyst with efficient photocatalytic hydrogen evolution activity and stability |
| CN115010220A (en) * | 2022-06-17 | 2022-09-06 | 南通大学 | Electrode with phosphide and hydroxide heterostructure and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140150332A1 (en) * | 2009-04-01 | 2014-06-05 | Sk Energy Co., Ltd. | Metal phosphorus compound for preparing biodiesel and method for preparing biodiesel using the same |
| CN104630822A (en) * | 2015-01-14 | 2015-05-20 | 太原理工大学 | Foam transition-metal solid (gas) phosphated self-support hydrogen evolution electrode and preparation method thereof |
| CN105152149A (en) * | 2015-07-09 | 2015-12-16 | 中国科学技术大学 | Nickel-cobalt-phosphorus crystal, and preparation method and application thereof |
| CN105839131A (en) * | 2016-06-13 | 2016-08-10 | 成都玖奇新材料科技有限公司 | Water electrolytic hydrogen production catalytic electrode of self-supporting metal-doped cobalt phosphide nano structure |
| CN106807416A (en) * | 2017-01-12 | 2017-06-09 | 南开大学 | A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof |
| CN108525685A (en) * | 2017-03-01 | 2018-09-14 | 中国科学院理化技术研究所 | The phosphorous metallic compound of a kind of monodisperse or support type releases hydrogen system as the hydrogen storage material hydrolysis of catalyst |
| CN108671948A (en) * | 2018-05-17 | 2018-10-19 | 上海理工大学 | A kind of preparation method of the flower-shaped nickel cobalt phosphide electrocatalysis material of self-assembling ultrathin |
| CN109759099A (en) * | 2019-03-04 | 2019-05-17 | 河南城建学院 | A kind of photochemical catalyst and preparation method thereof, application |
-
2020
- 2020-06-30 CN CN202010607258.3A patent/CN113856711B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140150332A1 (en) * | 2009-04-01 | 2014-06-05 | Sk Energy Co., Ltd. | Metal phosphorus compound for preparing biodiesel and method for preparing biodiesel using the same |
| CN104630822A (en) * | 2015-01-14 | 2015-05-20 | 太原理工大学 | Foam transition-metal solid (gas) phosphated self-support hydrogen evolution electrode and preparation method thereof |
| CN105152149A (en) * | 2015-07-09 | 2015-12-16 | 中国科学技术大学 | Nickel-cobalt-phosphorus crystal, and preparation method and application thereof |
| CN105839131A (en) * | 2016-06-13 | 2016-08-10 | 成都玖奇新材料科技有限公司 | Water electrolytic hydrogen production catalytic electrode of self-supporting metal-doped cobalt phosphide nano structure |
| CN106807416A (en) * | 2017-01-12 | 2017-06-09 | 南开大学 | A kind of self-supporting nickel phosphide nanometer sheet material of electrocatalytic decomposition water hydrogen manufacturing and preparation method thereof |
| CN108525685A (en) * | 2017-03-01 | 2018-09-14 | 中国科学院理化技术研究所 | The phosphorous metallic compound of a kind of monodisperse or support type releases hydrogen system as the hydrogen storage material hydrolysis of catalyst |
| CN108671948A (en) * | 2018-05-17 | 2018-10-19 | 上海理工大学 | A kind of preparation method of the flower-shaped nickel cobalt phosphide electrocatalysis material of self-assembling ultrathin |
| CN109759099A (en) * | 2019-03-04 | 2019-05-17 | 河南城建学院 | A kind of photochemical catalyst and preparation method thereof, application |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114394580A (en) * | 2022-01-25 | 2022-04-26 | 中南大学 | Self-supporting cobalt phosphide nanowire electrode and preparation method and application thereof |
| CN114808012A (en) * | 2022-04-19 | 2022-07-29 | 湖南师范大学 | Phosphide/binary metal nitride nano porous heterojunction electrocatalyst and preparation method and application thereof |
| CN114808012B (en) * | 2022-04-19 | 2023-12-22 | 湖南师范大学 | Phosphide/binary metal nitride nano-porous heterojunction electrocatalyst and preparation method and application thereof |
| CN115010220A (en) * | 2022-06-17 | 2022-09-06 | 南通大学 | Electrode with phosphide and hydroxide heterostructure and preparation method thereof |
| CN115010220B (en) * | 2022-06-17 | 2023-12-01 | 南通大学 | Electrode with phosphide synergistic hydroxide heterostructure and preparation method thereof |
| CN114950502A (en) * | 2022-06-21 | 2022-08-30 | 青岛大学 | Preparation method of nanorod red phosphorescent catalyst with efficient photocatalytic hydrogen evolution activity and stability |
| CN114950502B (en) * | 2022-06-21 | 2024-01-16 | 青岛大学 | Preparation method of nano rod-shaped red phosphorus photocatalyst with photocatalytic hydrogen evolution activity and stability |
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