CN110773210A - Self-supporting rod-shaped phosphorus-doped CoMoO 3Oxygen evolution electrocatalyst and preparation method thereof - Google Patents
Self-supporting rod-shaped phosphorus-doped CoMoO 3Oxygen evolution electrocatalyst and preparation method thereof Download PDFInfo
- Publication number
- CN110773210A CN110773210A CN201911181676.4A CN201911181676A CN110773210A CN 110773210 A CN110773210 A CN 110773210A CN 201911181676 A CN201911181676 A CN 201911181676A CN 110773210 A CN110773210 A CN 110773210A
- Authority
- CN
- China
- Prior art keywords
- comoo
- oxygen evolution
- doped
- foamed nickel
- self
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 219
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 110
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 80
- 239000001301 oxygen Substances 0.000 claims abstract description 80
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 80
- 238000010438 heat treatment Methods 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 32
- 239000006260 foam Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 31
- 229910052698 phosphorus Inorganic materials 0.000 claims description 31
- 239000011574 phosphorus Substances 0.000 claims description 31
- 238000001035 drying Methods 0.000 claims description 22
- 238000004140 cleaning Methods 0.000 claims description 21
- -1 cobalt fluorohydroxide Chemical compound 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 20
- 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 19
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- 238000001291 vacuum drying Methods 0.000 claims description 12
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 9
- 229940010552 ammonium molybdate Drugs 0.000 claims description 9
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 9
- 239000011609 ammonium molybdate Substances 0.000 claims description 9
- 239000004202 carbamide Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 238000003411 electrode reaction Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 34
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
Self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst and a preparation method thereof belong to the field of electrocatalytic materials, and particularly relate to an oxygen evolution electrocatalyst and a preparation method thereof. The invention aims to solve the problems of large overpotential of electrode reaction, slow reaction kinetics process and high cost of the existing oxygen evolution electrocatalyst. Self-supporting rod-shaped phosphorus-doped CoMoO
3The oxygen evolution electrocatalyst takes foam nickel as a framework to grow rodlike CoMoO
3And is doped with P. The preparation method comprises the following steps: firstly, preparing a primary heat treatment solution; secondly, carrying out primary hydrothermal treatment; thirdly, preparing a secondary heat treatment solution; fourthly, secondary hydrothermal treatment; and fifthly, phosphating. The advantages are that: at 10mA cm
‑2When the process is carried out, the overpotential is only 267mV, the electrocatalyst can stably operate for 40h, and the cost is low. The method is mainly used for preparing the self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to an oxygen evolution electrocatalyst and a preparation method thereof.
Background
Electrocatalytic decomposition of water is an important form of energy storage and conversion. Oxygen evolution half reactions (OERs) remain the bottleneck for water splitting due to the complex four electron conversion process and high overpotentials. The OER reaction currently uses mainly noble metal oxides (RuO)
2/IrO
2) Catalysis is carried out, but the high price and low reserves limit the large-scale application in industry. Therefore, the development of non-noble metal OER catalysts is urgent. Abundant transition metals have become the focus of research as potential substitutes for noble metal catalysts. In recent years, studies have shown that binary metal oxides exhibit performance comparable to that of noble metal catalysts in electrocatalytic oxygen evolution reactions and are receiving much attention. Of these non-noble metal catalysts, cobalt molybdate-based materials have been proven by theoretical calculations and experimental results to be better oxygen evolution electrocatalysts. The binary metal Co/Mo interaction enables the cobalt molybdate-based material to show more than single Co
3O
4Or MoO
3More excellent OER performance. However, the existing materials still have the problems of slow reaction kinetic process, large electrode reaction overpotential and the like. When the current density is 10mA cm
-2At times, the overpotential is typically over 300mV, and much work remains to be done to develop high performance oxygen evolution electrocatalysts.
Disclosure of Invention
The invention aims to solve the problems of larger overpotential of electrode reaction, slower reaction kinetic process and overhigh cost of the existing oxygen evolution electrocatalyst, and provides the self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst and a preparation method thereof.
Self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electro-catalyst is prepared by taking foamed nickel as a framework, cobalt nitrate, ammonium fluoride and urea as raw materials and deionized water as a solvent to prepare a primary heat treatment solution, obtaining foamed nickel for growing a cobalt fluorohydroxide precursor through the primary heat treatment solution, then taking ammonium molybdate as a raw material and taking the deionized water as a solvent to prepare the oxygen evolution electro-catalystPerforming secondary heat treatment on the solution to obtain the CoMoO in a growing rod shape through secondary hydrothermal treatment
4·H
2Foam nickel of O, and finally, taking sodium hypophosphite as a phosphorus source to carry out phosphating treatment and doping P to obtain the self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst.
Self-supporting rod-shaped phosphorus-doped CoMoO
3The preparation method of the oxygen evolution electrocatalyst is specifically completed according to the following steps:
firstly, preparing a primary heat treatment solution: dissolving cobalt nitrate, ammonium fluoride and urea in deionized water, and uniformly stirring to obtain a primary heat treatment solution;
secondly, primary hydrothermal treatment: placing the primary heat treatment solution in a reaction kettle, obliquely soaking the foamed nickel in the primary heat treatment solution, then placing the reaction kettle in an air-blowing drying oven for heating reaction, taking out the reaction kettle to obtain foamed nickel subjected to primary hydrothermal treatment, ultrasonically cleaning the foamed nickel subjected to primary hydrothermal treatment by using deionized water, and then placing the cleaned foamed nickel in a vacuum drying oven for drying to obtain foamed nickel for growing the cobalt fluorohydroxide precursor;
thirdly, preparing a secondary heat treatment solution: dissolving ammonium molybdate in deionized water, and uniformly stirring to obtain a secondary heat treatment solution;
fourthly, secondary hydrothermal treatment: placing the secondary heat treatment solution into a reaction kettle, obliquely soaking the foamed nickel for growing the cobalt fluorohydroxide precursor into the secondary heat treatment solution, then placing the reaction kettle into a forced air drying oven for heating reaction, taking out the reaction kettle to obtain the foamed nickel subjected to secondary hydrothermal treatment, ultrasonically cleaning the foamed nickel subjected to secondary hydrothermal treatment by using deionized water, and then placing the cleaned foamed nickel into a vacuum drying oven for drying to obtain the growing rod-shaped CoMoO
4·H
2Nickel foam of O;
fifthly, phosphating treatment: taking sodium hypophosphite as a phosphorus source, and growing rodlike CoMoO
4·H
2Respectively placing foamed nickel of O and sodium hypophosphite in a tubular furnace, and carrying out phosphating treatment in a nitrogen atmosphere by taking nitrogen as protective gas to obtain self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst.
The invention has the advantages that: firstly, the self-supporting prepared by the inventionRod-supporting type phosphorus-doped CoMoO
3The electrode of the oxygen evolution electrocatalyst is 10mA cm
-2When the overpotential is 267mV, the activity of the electrode surface can be increased by the unique rod-shaped structure after doping, so that the transfer of electrons is easier, and the reaction kinetic process is accelerated. Secondly, the self-supporting phosphorus-doped CoMoO prepared by the invention
3A large number of rod-shaped structures grow on the surface of the foamed nickel, more active sites are exposed, more electrolytic active centers are provided, the catalytic activity is high, and the problem of slow reaction kinetics is effectively solved; thirdly, the invention self-supporting rod-shaped phosphorus-doped CoMoO
3The oxygen evolution electrocatalyst has the advantages of simple preparation process, no precious metal contained in raw materials, low cost and good repeatability.
Drawings
FIG. 1 is a scanning electron microscope image of the nickel foam for growing cobalt fluorohydroxide precursor obtained in step two of example 1;
FIG. 2 shows CoMoO in the form of a growing rod obtained in step four of example 1
4·H
2Scanning electron micrographs of nickel foam of O;
FIG. 3 is a phosphorus-doped CoMoO rod in a free-standing rod shape obtained in step five of example 1
3Scanning electron micrographs of oxygen evolution electrocatalysts;
FIG. 4 shows an X-ray diffraction pattern, in which A represents the phosphorus-doped CoMoO in a free-standing rod form obtained in step five of example 1
3X-ray diffraction spectrum of oxygen evolution electrocatalyst, ◆ represents characteristic peak of Ni, B represents CoMoO
3The standard card of (1);
FIG. 5 is a graph of oxygen evolution performance, wherein ● shows phosphorus doped CoMoO in the form of a free standing rod obtained by the fifth step of example 1
3Graph of oxygen evolution performance of oxygen evolution electrocatalyst as working electrode, ▲ shows phosphorus doped CoMoO in self-supporting rod shape obtained by step five of example 2
3An oxygen evolution performance curve chart when the oxygen evolution electrocatalyst is used as a working electrode,
shows CoMoO in the form of a growing rod obtained in step four of example 1
4·H
2Oxygen evolution performance curve of O-based nickel foam as working electrode, ★ shows the procedure of example 1Obtaining an oxygen evolution performance curve when the foamed nickel of the grown cobalt fluorohydroxide precursor is used as a working electrode in the second step;
FIG. 6 is an oxygen evolution stability curve;
FIG. 7 is a phosphorus-doped CoMoO rod in a free-standing rod form obtained in step five of example 1
3EDS energy spectrum of oxygen evolution electrocatalyst.
Detailed Description
The first embodiment is as follows: the present embodiment is a self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electro-catalyst is prepared by taking foamed nickel as a framework, cobalt nitrate, ammonium fluoride and urea as raw materials and deionized water as a solvent to prepare a primary heat treatment solution, obtaining foamed nickel for growing a cobalt fluorohydroxide precursor through the primary heat treatment solution, then taking ammonium molybdate as a raw material, preparing a secondary heat treatment solution by taking the deionized water as a solvent, and obtaining rodlike CoMoO through secondary hydro-thermal treatment
4·H
2Foam nickel of O, and finally, taking sodium hypophosphite as a phosphorus source to carry out phosphating treatment and doping P to obtain the self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst.
The second embodiment is as follows: the present embodiment is a self-supporting rod-shaped phosphorus-doped CoMoO
3The preparation method of the oxygen evolution electrocatalyst is specifically completed according to the following steps:
firstly, preparing a primary heat treatment solution: dissolving cobalt nitrate, ammonium fluoride and urea in deionized water, and uniformly stirring to obtain a primary heat treatment solution;
secondly, primary hydrothermal treatment: placing the primary heat treatment solution in a reaction kettle, obliquely soaking the foamed nickel in the primary heat treatment solution, then placing the reaction kettle in an air-blowing drying oven for heating reaction, taking out the reaction kettle to obtain foamed nickel subjected to primary hydrothermal treatment, ultrasonically cleaning the foamed nickel subjected to primary hydrothermal treatment by using deionized water, and then placing the cleaned foamed nickel in a vacuum drying oven for drying to obtain foamed nickel for growing the cobalt fluorohydroxide precursor;
thirdly, preparing a secondary heat treatment solution: dissolving ammonium molybdate in deionized water, and uniformly stirring to obtain a secondary heat treatment solution;
fourthly, secondary hydrothermal treatment: heat treatment for the second timePlacing the conditioning solution into a reaction kettle, obliquely soaking the foamed nickel of the cobalt fluorohydroxide precursor growing in the secondary heat treatment solution, then placing the reaction kettle into a forced air drying oven for heating reaction, taking out the reaction kettle to obtain the foamed nickel subjected to secondary hydrothermal treatment, ultrasonically cleaning the foamed nickel subjected to secondary hydrothermal treatment by using deionized water, and then placing the cleaned foamed nickel into a vacuum drying oven for drying to obtain the rodlike CoMoO
4·H
2Nickel foam of O;
fifthly, phosphating treatment: taking sodium hypophosphite as a phosphorus source, and growing rodlike CoMoO
4·H
2Respectively placing foamed nickel of O and sodium hypophosphite in a tubular furnace, and carrying out phosphating treatment in a nitrogen atmosphere by taking nitrogen as protective gas to obtain self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst.
And proper heteroatom doping is carried out to improve the OER performance of the cobalt molybdate based material. Phosphorus doped CoMoO
3The OER catalytic performance of the nickel foam can be improved by directly growing the nickel foam on the nickel foam. Self-supporting rod-shaped phosphorus-doped CoMoO prepared by the embodiment
3The oxygen evolution electrocatalyst has the advantages of unique rod-like structure, large surface area, high electron conductivity and high stability, and can improve and enhance charge transfer. The embodiment prepares the CoMoO in a growing rod shape by a simple two-step solvothermal reaction
4·H
2Foamed nickel of O by growing CoMoO in stick form
4·H
2Further phosphating of foamed nickel of O to form phosphorus doped CoMoO
3So as to improve the OER catalytic performance of the material and reduce the overpotential of the material.
The third concrete implementation mode: the present embodiment is different from the second embodiment in that: in the second step, before the foam nickel is immersed in the primary heat treatment solution, cleaning treatment is carried out, and the specific process is as follows:
firstly ultrasonically cleaning the foamed nickel in acetone for 5-30 min, then ultrasonically cleaning in ethanol for 5-30 min, finally ultrasonically cleaning in deionized water for 5-30 min, and then drying to finish the cleaning treatment of the foamed nickel.
The rest is the same as the second embodiment.
The fourth concrete implementation mode: the present embodiment differs from the second or third embodiment in that: in the first step, the molar ratio of cobalt nitrate to ammonium fluoride in the solution subjected to primary heat treatment is 0.5-2: 2-6, the molar ratio of cobalt nitrate to urea is 0.5-2: 4-8, and the volume ratio of the amount of cobalt nitrate to deionized water is (1-10) mmol (10-100) mL. The other embodiments are the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: in the third step, the volume ratio of the ammonium molybdate substance in the secondary heat treatment solution to the deionized water is (0.2-0.8) mmol (10-100) mL. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is as follows: and step two, placing the reaction kettle into a blast drying oven, preserving heat for 2-10 h at the temperature of 80-160 ℃, taking out to obtain primary hydrothermal treatment-carried foamed nickel, ultrasonically cleaning the primary hydrothermal treatment-carried foamed nickel for 3-10 min by using deionized water, then placing into a vacuum drying oven, and drying for 5-10 h at the temperature of 60 ℃ to obtain the foamed nickel for growing the cobalt fluorohydroxide precursor. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: putting the reaction kettle into a blast drying oven, keeping the temperature at 80-160 ℃ for 2-10 h, taking out to obtain secondary hydrothermally treated foamed nickel, ultrasonically cleaning the secondary hydrothermally treated foamed nickel for 3-10 min by using deionized water, then putting the cleaned secondary hydrothermally treated foamed nickel into a vacuum drying oven, and drying the cleaned secondary hydrothermally treated foamed nickel for 5-10 h at 60 ℃ to obtain the growing rod-shaped CoMoO
4·H
2Nickel foam of O. The rest is the same as the first to sixth embodiments.
The specific implementation mode is eight: the difference between this embodiment and one of the first to seventh embodiments is: growing the rod-shaped CoMoO in the step five
4·H
2The mass ratio of the foamed nickel of O to the sodium hypophosphite is 1-5: 1. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: this embodiment is different from the first to eighth embodimentsThe same points are that: in the fifth step, sodium hypophosphite and the CoMoO in the shape of a growing rod are mixed along the flowing direction of nitrogen
4·H
2The foamed nickel of O is placed in a tube furnace in sequence, and sodium hypophosphite and growing rod-shaped CoMoO
4·H
2The interval of the O foam nickel is 10 cm-30 cm. The others are the same as the first to eighth embodiments.
The detailed implementation mode is ten: the difference between this embodiment and one of the first to ninth embodiments is as follows: in the fifth step, the specific process of the phosphating treatment in the nitrogen atmosphere is as follows: heating the temperature in the tubular furnace from room temperature to 450-600 ℃ at a heating rate of 1-10 ℃/min under a nitrogen atmosphere, then preserving the heat for 100-200 min under the conditions of the nitrogen atmosphere and the temperature of 450-600 ℃, cooling the temperature to 100 ℃ within 20-30 h, and opening the tubular furnace to cool to the room temperature along with the furnace. The rest is the same as the first to ninth embodiments.
The invention is not limited to the above embodiments, and one or a combination of several embodiments may also achieve the object of the invention.
The following tests were carried out to confirm the effects of the present invention
Example 1: self-supporting rod-shaped phosphorus-doped CoMoO
3The preparation method of the oxygen evolution electrocatalyst is specifically completed according to the following steps:
firstly, preparing a primary heat treatment solution: dissolving 2mmol of cobalt nitrate, 8mmol of ammonium fluoride and 10mmol of urea in 36mL of deionized water, and uniformly stirring to obtain a primary heat treatment solution;
secondly, primary hydrothermal treatment: placing the primary heat treatment solution in a reaction kettle, obliquely soaking the foamed nickel in the primary heat treatment solution, then placing the reaction kettle in an air-blast drying box, preserving heat for 6 hours at the temperature of 100 ℃, taking out the reaction kettle to obtain the foamed nickel subjected to the primary hydrothermal treatment, ultrasonically cleaning the foamed nickel subjected to the primary hydrothermal treatment for 3 minutes by using deionized water, then placing the cleaned foamed nickel in a vacuum drying box, and drying the cleaned foamed nickel for 8 hours at the temperature of 60 ℃ to obtain the foamed nickel for growing the cobalt fluorohydroxide precursor;
thirdly, preparing a secondary heat treatment solution: dissolving 0.48mmol of ammonium molybdate in 40mL of deionized water, and uniformly stirring to obtain a secondary heat treatment solution;
fourthly, secondary hydrothermal treatment: placing the secondary heat treatment solution in a reaction kettle, obliquely soaking the foamed nickel for growing the cobalt fluorohydroxide precursor in the secondary heat treatment solution, then placing the reaction kettle in a blast drying box, preserving heat for 4 hours at the temperature of 140 ℃, taking out the reaction kettle to obtain the foamed nickel subjected to secondary hydrothermal treatment, ultrasonically cleaning the foamed nickel subjected to secondary hydrothermal treatment for 3 minutes by using deionized water, then placing the cleaned foamed nickel into a vacuum drying box, and drying the cleaned foamed nickel for 8 hours at the temperature of 60 ℃ to obtain the rodlike grown CoMoO
4·H
2Nickel foam of O;
fifthly, phosphating treatment: sodium hypophosphite is used as a phosphorus source, and the sodium hypophosphite and the CoMoO in a growing rod shape are mixed along the flowing direction of nitrogen
4·H
2The foamed nickel of O is placed in a tube furnace in sequence, and sodium hypophosphite and growing rod-shaped CoMoO
4·H
2The interval of O foamed nickel is 10-30 cm, nitrogen is used as protective gas, the temperature in the tube furnace is firstly increased from room temperature to 450 ℃ at the temperature increase rate of 2 ℃/min under the nitrogen atmosphere, then the temperature is kept for 120min under the conditions of the nitrogen atmosphere and the temperature of 450 ℃, the temperature is reduced to 100 ℃ under 20h, then the tube furnace is opened and cooled to room temperature along with the furnace, and the self-supporting rod-shaped phosphorus-doped CoMoO is obtained
3An oxygen evolution electrocatalyst; the growing rod-shaped CoMoO
4·H
2The mass ratio of the foamed nickel of O to the sodium hypophosphite is 3: 1.
In the second step of this embodiment, before the nickel foam is immersed in the first heat treatment solution, a cleaning process is performed, specifically, the process is as follows:
cutting the foamed Nickel (NF) into a rectangle with the length, width and height of 4cm multiplied by 2cm multiplied by 0.1cm, firstly carrying out ultrasonic cleaning in acetone for 10min, then carrying out ultrasonic cleaning in ethanol for 10min, finally carrying out ultrasonic cleaning in deionized water for 10min, and then drying to finish the foamed nickel cleaning treatment.
For the nickel foam for growing the cobalt fluorohydroxide precursor obtained in the second step of the example 1 and the CoMoO in the shape of a growing rod obtained in the fourth step of the example 1
4·H
2Foamed nickel of O and phosphorus doped CoMoO in free-standing stick form obtained in step five of example 1
3Scanning electron microscope with oxygen evolution electrocatalystDescribing, as shown in fig. 1-3, fig. 1 is a scanning electron microscope image of the nickel foam for growing the cobalt fluorohydroxide precursor obtained in step two of example 1; FIG. 2 shows CoMoO in the form of a growing rod obtained in step four of example 1
4·H
2Scanning electron micrographs of nickel foam of O; FIG. 3 is a free standing rod of phosphorus doped CoMoO prepared in step five of example 1
3Scanning electron micrographs of oxygen evolution electrocatalysts; from fig. 1, it can be known that the foamed nickel obtained in the second step of example 1 and used for growing the cobalt fluorohydroxide precursor presents a saw-toothed morphology; FIG. 2 shows that CoMoO in the form of a growing rod is obtained in the fourth step of example 1
4·H
2Foam nickel of O has a rod-like structure, and a self-supporting rod-like phosphorus-doped CoMoO is obtained in the fifth step of example 1 after phosphating
3The oxygen evolution electrocatalyst can still keep the original rod-shaped appearance, but small particles are generated on the surface of the oxygen evolution electrocatalyst.
FIG. 4 shows an X-ray diffraction pattern, in which A represents the phosphorus-doped CoMoO in a free-standing rod form obtained in step five of example 1
3X-ray diffraction spectrum of oxygen evolution electrocatalyst, ◆ represents characteristic peak of Ni, B represents CoMoO
3The standard card of (1); from FIG. 4, it can be seen that the phosphorus-doped CoMoO in the shape of a free-standing rod is obtained in step five of example 1
3All diffraction peaks of the oxygen evolution electrocatalyst can be matched with a standard map JCPDS (CoMoO) 21-869
3Standard card of (c) to match.
Example 2: the present embodiment differs from embodiment 1 in that: in the fifth step, the temperature in the tubular furnace is firstly increased from room temperature to 500 ℃ at the heating rate of 2 ℃/min under the nitrogen atmosphere, then the temperature is preserved for 120min under the conditions of the nitrogen atmosphere and the temperature of 500 ℃, the temperature is reduced to 100 ℃ under 30h, then the tubular furnace is opened and cooled to the room temperature along with the furnace, and the self-supporting rod-shaped phosphorus-doped CoMoO is obtained
3An oxygen evolution electrocatalyst. The rest is the same as in example 1.
The foamed nickel of the cobalt fluorohydroxide precursor obtained in the second step of the example 1 and the CoMoO of the growing rod shape obtained in the fourth step of the example 1 are respectively used
4·H
2Foamed nickel of O, phosphorus doped CoMoO in free-standing stick form obtained in step five of example 1
3Oxygen evolution electrocatalyst and example 2 step five obtained phosphorus doped Co in free standing stick formMoO
3Oxygen evolution electrocatalyst as working electrode, oxygen evolution performance test was performed in KOH aqueous solution with concentration of 1mol/mL, as shown in FIG. 5, FIG. 5 is oxygen evolution performance graph, wherein ● represents phosphorus doped CoMoO in self-supporting rod shape obtained by step five of example 1
3Graph of oxygen evolution performance of oxygen evolution electrocatalyst as working electrode, ▲ shows phosphorus doped CoMoO in self-supporting rod shape obtained by step five of example 2
3An oxygen evolution performance curve chart when the oxygen evolution electrocatalyst is used as a working electrode,
shows CoMoO in the form of a growing rod obtained in step four of example 1
4·H
2FIG. 5 shows the oxygen evolution performance curve of the working electrode made of nickel foam of O, ★ shows the oxygen evolution performance curve of the working electrode made of nickel foam of cobalt fluorohydroxide precursor grown in the second step of example 1, and FIG. 5 shows that the self-supporting rod-shaped phosphorus-doped CoMoO is obtained in the fifth step of example 1
3When the oxygen evolution electrocatalyst is used as a working electrode, the current density is 10mA cm
-2When the oxygen evolution overpotential is 267 mV. Phosphorus doped CoMoO in free-standing rod form obtained in step five of example 2
3When the oxygen evolution electrocatalyst is used as a working electrode, the current density is 10mA cm
-2When the oxygen evolution overpotential is 285 mV; thus the self-supporting rod-shaped phosphorus-doped CoMoO prepared by the invention
3The oxygen evolution electrocatalyst has better oxygen evolution catalytic performance.
Phosphorus doped CoMoO in free-standing rods was obtained as in step five of example 1
3The oxygen evolution electrocatalyst was used as a working electrode, and the oxygen evolution stability test was performed in KOH aqueous solution with a concentration of 1mol/mL, as shown in FIG. 6, FIG. 6 is an oxygen evolution stability curve, and it can be seen from FIG. 6 that the phosphorus doped CoMoO in the form of a self-supporting rod obtained in step five of example 1
3The oxygen evolution electrocatalyst maintains good stability.
FIG. 7 is a phosphorus-doped CoMoO rod in a free-standing rod form obtained in step five of example 1
3EDS energy spectrum of oxygen evolution electrocatalyst, and from FIG. 7, it can be seen that the phosphorus doped CoMoO with self-supporting rod shape is obtained in the fifth step of example 1
3The oxygen evolution electrocatalyst has phosphorus element.
The invention produces phosphorus doped CoMoO in the form of free-standing rods, combining examples 1 and 2
3The oxygen evolution electrocatalyst has the advantages of increased specific surface area, increased active sites, improved catalytic activity, simple preparation process and suitability for large-scale production.
Claims (10)
1. Self-supporting rod-shaped phosphorus-doped CoMoO
3Oxygen evolution electrocatalyst characterized in that said self-supporting rod-like phosphorus doped CoMoO
3The oxygen evolution electrocatalyst uses foam nickel as a framework, cobalt nitrate, ammonium fluoride and urea as raw materials, deionized water as a solvent to prepare a primary heat treatment solution, the primary heat treatment solution is used for obtaining foam nickel for growing a cobalt fluorohydroxide precursor, ammonium molybdate is used as a raw material, deionized water is used as a solvent to prepare a secondary heat treatment solution, and the secondary hydrothermal treatment is used for obtaining rodlike CoMoO
4·H
2Foam nickel of O, and finally, taking sodium hypophosphite as a phosphorus source to carry out phosphating treatment and doping P to obtain the self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst.
2. The self-supporting rod-shaped phosphorus-doped CoMoO of claim 1
3The preparation method of the oxygen evolution electrocatalyst is characterized by comprising the following steps of:
firstly, preparing a primary heat treatment solution: dissolving cobalt nitrate, ammonium fluoride and urea in deionized water, and uniformly stirring to obtain a primary heat treatment solution;
secondly, primary hydrothermal treatment: placing the primary heat treatment solution in a reaction kettle, obliquely soaking the foamed nickel in the primary heat treatment solution, then placing the reaction kettle in an air-blowing drying oven for heating reaction, taking out the reaction kettle to obtain foamed nickel subjected to primary hydrothermal treatment, ultrasonically cleaning the foamed nickel subjected to primary hydrothermal treatment by using deionized water, and then placing the cleaned foamed nickel in a vacuum drying oven for drying to obtain foamed nickel for growing the cobalt fluorohydroxide precursor;
thirdly, preparing a secondary heat treatment solution: dissolving ammonium molybdate in deionized water, and uniformly stirring to obtain a secondary heat treatment solution;
four and two water heating partsProcessing: placing the secondary heat treatment solution into a reaction kettle, obliquely soaking the foamed nickel for growing the cobalt fluorohydroxide precursor into the secondary heat treatment solution, then placing the reaction kettle into a forced air drying oven for heating reaction, taking out the reaction kettle to obtain the foamed nickel subjected to secondary hydrothermal treatment, ultrasonically cleaning the foamed nickel subjected to secondary hydrothermal treatment by using deionized water, and then placing the cleaned foamed nickel into a vacuum drying oven for drying to obtain the growing rod-shaped CoMoO
4·H
2Nickel foam of O;
fifthly, phosphating treatment: taking sodium hypophosphite as a phosphorus source, and growing rodlike CoMoO
4·H
2Respectively placing foamed nickel of O and sodium hypophosphite in a tubular furnace, and carrying out phosphating treatment in a nitrogen atmosphere by taking nitrogen as protective gas to obtain self-supporting rod-shaped phosphorus-doped CoMoO
3An oxygen evolution electrocatalyst.
3. Self-supporting rod-like phosphorus doped CoMoO according to claim 2
3The preparation method of the oxygen evolution electrocatalyst is characterized in that in the second step, the foamed nickel is cleaned before being immersed into the primary heat treatment solution, and the specific process is as follows:
firstly ultrasonically cleaning the foamed nickel in acetone for 5-30 min, then ultrasonically cleaning in ethanol for 5-30 min, finally ultrasonically cleaning in deionized water for 5-30 min, and then drying to finish the cleaning treatment of the foamed nickel.
4. Self-supporting rod-like phosphorus doped CoMoO according to claim 2
3The preparation method of the oxygen evolution electrocatalyst is characterized in that in the step one, the molar ratio of cobalt nitrate to ammonium fluoride in the primary heat treatment solution is 0.5-2: 2-6, the molar ratio of cobalt nitrate to urea is 0.5-2: 4-8, and the volume ratio of the amount of cobalt nitrate to deionized water is (1-10) mmol (10-100) mL.
5. Self-supporting rod-like phosphorus doped CoMoO according to claim 2
3The preparation method of the oxygen evolution electrocatalyst is characterized in that the volume ratio of the amount of ammonium molybdate substances in the secondary heat treatment solution to deionized water in the third step is (0.2-0.8))mmol:(10~100)mL。
6. Self-supporting rod-like phosphorus doped CoMoO according to claim 2
3And the preparation method of the oxygen evolution electrocatalyst is characterized in that in the second step, the reaction kettle is placed in an air-blast drying oven, the temperature is kept at 80-160 ℃ for 2-10 h, the reaction kettle is taken out to obtain the foamed nickel after primary hydrothermal treatment, the foamed nickel after primary hydrothermal treatment is ultrasonically cleaned for 3-10 min by deionized water, and then the foamed nickel is placed in a vacuum drying oven and dried at 60 ℃ for 5-10 h to obtain the foamed nickel for growing the cobalt fluorohydroxide precursor.
7. Self-supporting rod-like phosphorus doped CoMoO according to claim 2
3The preparation method of the oxygen evolution electrocatalyst is characterized in that in the fourth step, a reaction kettle is placed in a blast drying oven, the temperature is kept at 80-160 ℃ for 2-10 h, the reaction kettle is taken out to obtain secondary nickel foam after hydrothermal treatment, the secondary nickel foam after hydrothermal treatment is ultrasonically cleaned for 3-10 min by deionized water, and then the reaction kettle is placed in a vacuum drying oven and dried at 60 ℃ for 5-10 h to obtain rodlike CoMoO
4·H
2Nickel foam of O.
8. Self-supporting rod-like phosphorus doped CoMoO according to claim 2
3The preparation method of the oxygen evolution electrocatalyst is characterized in that the rodlike CoMoO grows in the step five
4·H
2The mass ratio of the foamed nickel of O to the sodium hypophosphite is 1-5: 1.
9. Self-supporting rod-like phosphorus doped CoMoO according to claim 8
3The preparation method of the oxygen evolution electrocatalyst is characterized in that sodium hypophosphite and rodlike CoMoO are added along the flowing direction of nitrogen in the fifth step
4·H
2The foamed nickel of O is placed in a tube furnace in sequence, and sodium hypophosphite and growing rod-shaped CoMoO
4·H
2The interval of the O foam nickel is 10 cm-30 cm.
10. The method of claim 2 or 9Self-supporting rod-shaped phosphorus-doped CoMoO
3The preparation method of the oxygen evolution electrocatalyst is characterized in that the phosphating treatment is carried out in the nitrogen atmosphere in the step five, and the specific process is as follows: heating the temperature in the tubular furnace from room temperature to 450-600 ℃ at a heating rate of 1-10 ℃/min under a nitrogen atmosphere, then preserving the heat for 100-200 min under the conditions of the nitrogen atmosphere and the temperature of 450-600 ℃, cooling the temperature to 100 ℃ within 20-30 h, and opening the tubular furnace to cool to the room temperature along with the furnace.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911181676.4A CN110773210B (en) | 2019-11-27 | 2019-11-27 | Self-supporting rod-shaped phosphorus-doped CoMoO3Oxygen evolution electrocatalyst and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201911181676.4A CN110773210B (en) | 2019-11-27 | 2019-11-27 | Self-supporting rod-shaped phosphorus-doped CoMoO3Oxygen evolution electrocatalyst and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN110773210A true CN110773210A (en) | 2020-02-11 |
CN110773210B CN110773210B (en) | 2022-06-17 |
Family
ID=69392809
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201911181676.4A Active CN110773210B (en) | 2019-11-27 | 2019-11-27 | Self-supporting rod-shaped phosphorus-doped CoMoO3Oxygen evolution electrocatalyst and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110773210B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114289043A (en) * | 2020-09-22 | 2022-04-08 | 新疆大学 | Preparation method and application of self-supporting porous nano-plate cobalt-nickel phosphide catalyst |
CN114855215A (en) * | 2022-05-30 | 2022-08-05 | 清华大学 | Catalyst for high-efficiency electrocatalytic synthesis of ammonia and preparation method thereof |
CN114855187A (en) * | 2022-05-27 | 2022-08-05 | 浙江大学 | Catalyst for preparing hydrogen by water decomposition under heavy current electrocatalysis and preparation method and application thereof |
CN115172782A (en) * | 2022-08-10 | 2022-10-11 | 山东大学 | Radial hollow rod-shaped P-Cu 2 MoS 4 And preparation method and application thereof |
Citations (7)
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 |
CN105448543A (en) * | 2015-12-29 | 2016-03-30 | 东华大学 | Preparation method for CoMoO4 nanostructure supercapacitor electrode material taking foam nickel as substrate |
CN107626322A (en) * | 2017-09-06 | 2018-01-26 | 河海大学 | A kind of preparation method of heterogeneous catalysis and its application in degradation of dye waste water |
CN108314092A (en) * | 2017-12-29 | 2018-07-24 | 安泰科技股份有限公司 | A kind of foamed nickel supported nano bar-shape cobalt molybdate and its preparation method and application |
CN108380229A (en) * | 2018-04-25 | 2018-08-10 | 华中农业大学 | A kind of preparation method and products thereof of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent |
CN110195235A (en) * | 2019-06-21 | 2019-09-03 | 盐城工学院 | A kind of phosphorus doping cobalt acid nickel/foam nickel electrode and its preparation method and application |
CN110344078A (en) * | 2019-07-03 | 2019-10-18 | 湖北大学 | A kind of nickel foam@cobalt molybdenum phosphide/ferronickel double-hydroxide electrode and the preparation method and application thereof |
-
2019
- 2019-11-27 CN CN201911181676.4A patent/CN110773210B/en active Active
Patent Citations (7)
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 |
CN105448543A (en) * | 2015-12-29 | 2016-03-30 | 东华大学 | Preparation method for CoMoO4 nanostructure supercapacitor electrode material taking foam nickel as substrate |
CN107626322A (en) * | 2017-09-06 | 2018-01-26 | 河海大学 | A kind of preparation method of heterogeneous catalysis and its application in degradation of dye waste water |
CN108314092A (en) * | 2017-12-29 | 2018-07-24 | 安泰科技股份有限公司 | A kind of foamed nickel supported nano bar-shape cobalt molybdate and its preparation method and application |
CN108380229A (en) * | 2018-04-25 | 2018-08-10 | 华中农业大学 | A kind of preparation method and products thereof of phosphorus doping cobalt molybdate Electrocatalytic Activity for Hydrogen Evolution Reaction agent |
CN110195235A (en) * | 2019-06-21 | 2019-09-03 | 盐城工学院 | A kind of phosphorus doping cobalt acid nickel/foam nickel electrode and its preparation method and application |
CN110344078A (en) * | 2019-07-03 | 2019-10-18 | 湖北大学 | A kind of nickel foam@cobalt molybdenum phosphide/ferronickel double-hydroxide electrode and the preparation method and application thereof |
Non-Patent Citations (4)
Title |
---|
LEI YU等: ""Cobalt/Molybdenum Phosphide and Oxide Heterostructures Encapsulated in N Doped Carbon Nanocomposite for Overall Water Splitting in Alkaline Media"", 《APPL.MATER.INTERFACES》 * |
LINXIA FANG等: ""Hierarchical CoMoO4 nanoneedle electrodes for advanced supercapacitors and electrocatalytic oxygen evolution"", 《ELECTROCHIMICA ACTA》 * |
XUNHANG LIU等: ""Mo-Doped Cobalt Phosphide Nanosheets for EfficientHydrogen Generation in an Alkaline Media"", 《ENERGY TECHNOL》 * |
刘欢欢: ""纳米结构钴基电催化材料的制备及析氢性能研究"", 《万方硕士论文数据库》 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114289043A (en) * | 2020-09-22 | 2022-04-08 | 新疆大学 | Preparation method and application of self-supporting porous nano-plate cobalt-nickel phosphide catalyst |
CN114855187A (en) * | 2022-05-27 | 2022-08-05 | 浙江大学 | Catalyst for preparing hydrogen by water decomposition under heavy current electrocatalysis and preparation method and application thereof |
CN114855187B (en) * | 2022-05-27 | 2024-01-16 | 浙江大学 | Catalyst for high-current electrocatalytic water splitting hydrogen production and preparation method and application thereof |
CN114855215A (en) * | 2022-05-30 | 2022-08-05 | 清华大学 | Catalyst for high-efficiency electrocatalytic synthesis of ammonia and preparation method thereof |
CN114855215B (en) * | 2022-05-30 | 2023-11-21 | 清华大学 | Catalyst for high-efficiency electrocatalytic synthesis of ammonia and preparation method thereof |
CN115172782A (en) * | 2022-08-10 | 2022-10-11 | 山东大学 | Radial hollow rod-shaped P-Cu 2 MoS 4 And preparation method and application thereof |
Also Published As
Publication number | Publication date |
---|---|
CN110773210B (en) | 2022-06-17 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN110773210B (en) | Self-supporting rod-shaped phosphorus-doped CoMoO3Oxygen evolution electrocatalyst and preparation method thereof | |
JP2020082079A (en) | Ruthenium-based catalyst for hydrogen production from ammonia decomposition, preparation method therefor and application thereof | |
CN108325539B (en) | Rod-like vanadium modified Ni self-assembled into flower ball shape3S2Synthesis method of electrocatalyst | |
CN107252700B (en) | Multi-metal phosphide nanotube catalyst with uniformly distributed catalytic centers and low-temperature preparation method | |
CN108940328B (en) | Nano sheet-nano rod coupled three-dimensional composite material Ni-Co modified molybdenum carbide electro-catalysis hydrogen production catalyst and preparation method thereof | |
CN106048650B (en) | The preparation method of 3D porous electrodes and its application in electrochemistry evolving hydrogen reaction | |
CN111883773B (en) | Preparation method of Ni/Co-CNT/NHPC lithium-sulfur battery positive electrode material | |
CN112076761B (en) | Copper oxide nanowire loaded silver particle composite electrode, preparation method and application | |
CN112774704A (en) | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof | |
CN112058296B (en) | Preparation method and application of carbonized wood-loaded cobalt and nitrogen co-doped carbon nanotube composite material | |
CN107999105B (en) | Preparation method of molybdenum phosphide hydrogen evolution catalyst with rod-shaped porous morphology structure | |
CN108889314B (en) | Foamed cobalt in-situ vulcanized nanometer flower ball-shaped Co4S3@ Co hydrogen evolution material and preparation method thereof | |
CN111889128A (en) | Preparation method of cage-shaped ferronickel bimetallic phosphide loaded nitrogen-doped porous carbon material | |
CN110846680B (en) | Preparation method of multi-defect and active site electrocatalyst | |
CN110938831A (en) | Foam alloy-based iron-doped NiSe microsphere electrocatalytic material and preparation method thereof | |
CN111495399B (en) | S-doped WP 2 Nanosheet array electrocatalyst and preparation method thereof | |
CN111215104A (en) | Phosphorus-doped carbon-loaded molybdenum-tungsten carbide catalyst, and preparation and application thereof | |
CN110935480A (en) | Vanadium-doped cobalt phosphide nano-thorn catalytic material for full-hydrolytic reaction | |
CN114182287A (en) | Nickel-molybdenum nickel nitride composite catalyst and preparation method and application thereof | |
CN113502503A (en) | Self-supporting transition metal nitride composite material, preparation method and application of self-supporting transition metal nitride composite material in electrocatalytic hydrogen evolution | |
CN112657521A (en) | Preparation method of chromium-doped cobalt phosphide nanorod array grown on carbon cloth in situ | |
CN113652698B (en) | Tungsten-doped nickel phosphide dual-functional catalytic material with crossed nano-sheet structure | |
CN113089014B (en) | Super-hydrophilic super-gas-dredging efficient hydrogen evolution catalyst with core-shell structure and preparation method thereof | |
CN110961136B (en) | Fe with three-dimensional continuous structure3N-coated FeNCN compound and preparation method thereof | |
CN107715883A (en) | A kind of Ni3The preparation method of FeN@graphenes/marine alga aeroge elctro-catalyst |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |