CN115466979A - Preparation method of nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution - Google Patents
Preparation method of nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution Download PDFInfo
- Publication number
- CN115466979A CN115466979A CN202211100988.XA CN202211100988A CN115466979A CN 115466979 A CN115466979 A CN 115466979A CN 202211100988 A CN202211100988 A CN 202211100988A CN 115466979 A CN115466979 A CN 115466979A
- Authority
- CN
- China
- Prior art keywords
- nickel
- phosphorus
- cobalt
- electrocatalyst
- electrode
- 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 50
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000005868 electrolysis reaction Methods 0.000 title claims description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 29
- 239000006262 metallic foam Substances 0.000 claims abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000004140 cleaning Methods 0.000 claims description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 13
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000002484 cyclic voltammetry Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 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 4
- 238000004070 electrodeposition Methods 0.000 claims description 4
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 abstract description 28
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 abstract description 5
- 239000010941 cobalt Substances 0.000 abstract description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003792 electrolyte Substances 0.000 abstract description 5
- 238000002848 electrochemical method Methods 0.000 abstract description 4
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 239000006260 foam Substances 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000010453 quartz Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 238000004506 ultrasonic cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 241000080590 Niso Species 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000012159 carrier gas Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000002386 leaching Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- IVZIWCDZLYTGNL-UHFFFAOYSA-N [Co].[Ni].[P].[Ni] Chemical compound [Co].[Ni].[P].[Ni] IVZIWCDZLYTGNL-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
-
- 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)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention discloses a preparation method of a nickel-cobalt-phosphorus electrocatalyst for efficiently electrolyzing water to separate hydrogen. The preparation method comprises the following steps: metal foam is used as substrate, pretreated and used as working electrode, ni is used 2+ 、Co 2+ And PO 2 3‑ The mixed solution is an electrolyte solution, nickel, cobalt and phosphorus are deposited through electrochemical cycle scanning in a three-electrode system, and then the nickel, cobalt and phosphorus electrocatalyst is prepared through low-temperature phosphorization. The invention adopts a method combining an electrochemical method and low-temperature phosphorization, can further increase the electrochemical performance of the electrocatalyst in the alkaline electrolyte, improves the conductivity and stability of the electrocatalyst, and increases the electron transmission rate.The catalytic electrode catalyst prepared by the invention is firmly combined with a substrate, and has good catalytic activity and electrochemical stability and long service life.
Description
Technical Field
The invention relates to a preparation method of a nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution, belonging to the technical field of water electrolysis hydrogen evolution.
Background
Nowadays, social energy and climate problems are becoming more and more serious, and countries in the world are seeking ways to solve the current problems. Hydrogen energy is considered to be one of the issues to solve the above problems, and is playing an increasingly important role. For the electrolytic water hydrogen evolution reaction, the most effective is the catalyst synthesized based on the noble metal platinum, but the large-scale application of the material is limited due to the problems of low reserves and high cost. Therefore, it is important to develop a non-noble metal hydrogen evolution catalyst which is efficient, stable and cheap as a substitute. The transition metal phosphide has the characteristics of abundant raw material reserves, low cost and relatively good catalytic hydrogen evolution performance, and is widely concerned. But the transition metal phosphide also has the problems of relatively poor stability, complex preparation process of part of materials, relatively high synthesis cost and the like. Wherein, nickel cobalt metal is a transition metal element commonly used for preparing the electrolytic water catalyst at present. Therefore, the preparation of the nickel-cobalt-phosphorus hydrogen evolution electrocatalyst which is efficient, cheap and stable has important practical significance for the industrial development in the field.
Disclosure of Invention
The purpose of the invention is: aiming at the problems of large overpotential and poor stability of the existing nickel-cobalt-phosphorus hydrogen evolution electrocatalyst, a method for preparing the hydrogen evolution electrocatalyst with high stability and low overpotential by combining an electrochemical method and low-temperature phosphorization is provided.
In order to achieve the purpose, the invention provides a preparation method of a nickel-cobalt-phosphorus electrocatalyst for efficiently electrolyzing water to separate hydrogen, which comprises the following steps of:
step 1: pretreating the metal foam substrate;
step 2: preparation of Ni-containing alloy 2+ 、Co 2+ And PO 2 3- The mixed solution of (1);
and step 3: taking the metal foam base pretreated in the step 1 as a working electrode, taking the mixed solution prepared in the step 2 as an electrolyte solution, and performing electrochemical deposition in a three-electrode system to obtain a metal foam electrode deposited with a nickel-cobalt-phosphorus electrocatalyst, namely a nickel-cobalt-phosphorus metal foam electrode;
and 4, step 4: and (4) placing a phosphorus source and the nickel cobalt phosphorus metal foam electrode obtained in the step (3) in the same container and separately placing, and then carrying out a phosphating reaction in an inert atmosphere at a temperature lower than 400 ℃ to obtain the nickel cobalt phosphorus metal foam electrode after low-temperature phosphating.
Preferably, the pretreatment in step 1 comprises removing oxide on the surface of the metal foam substrate by acid washing, acetone cleaning, ethanol cleaning, deionized water cleaning and drying in sequence.
Preferably, ni in said step 2 2+ 、Co 2+ And PO 2 3- In a molar ratio of 7:3:6 of the Ni 2+ The molar concentration of the active carbon is 0.035 to 0.14M.
Preferably, the three-electrode system in step 3 uses carbon paper as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode.
Preferably, the electrochemical deposition in the step 3 adopts cyclic voltammetry, the scanning range of the cyclic voltammetry is-0.5V to-1.2V (relative to an Ag/AgCl reference electrode), the scanning speed is 0.01V/s, and the scanning cycle number is 25 to 200.
Preferably, the phosphorus source in step 4 is sodium hypophosphite or its hydrate, and the dosage of the sodium hypophosphite or its hydrate is the same as that of PO in step 2 2 3- Is calculated from 10% to 70% of the molar amount of (A).
Preferably, the temperature of the phosphating reaction in the step 4 is 300-350 ℃ and the time is 1-3 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) The method combines an electrochemical method and low-temperature phosphorization, and can further increase the electrochemical performance of the electrocatalyst in alkaline electrolyte after low-temperature phosphorization, improve the conductivity and stability of the electrocatalyst, and increase the electron transmission rate; thus preparing the high-efficiency electrolysis hydrogen evolution catalyst, reducing the overpotential of the alkaline electrolysis water catalyst, improving the current density, and improving and enhancing the catalytic activity and stability of the hydrogen evolution reaction of the existing electrolysis water hydrogen evolution catalyst in the alkaline electrolyte;
(2) The catalytic electrode catalyst prepared by the invention is firmly combined with a matrix, has good catalytic activity and electrochemical stability and long service life, and in addition, the preparation process is simple, the raw materials are cheap and easy to obtain, the industrialization is easy, and the catalytic electrode catalyst has a large-scale application prospect in the field of hydrogen evolution by electrolyzing water.
Drawings
FIG. 1 is an XRD pattern of nickel foam (Ni Form), nickel phosphide foam (NiP) of comparative example 1, niCoP/NF of comparative example 2, niCoP/NF anealine of comparative example 3, and low temperature nickel cobalt phosphide metal foam electrode prepared in example 1;
FIG. 2 is a full cell hydrogen evolution polarization curve for NiCoP nickel foam electrodes under different electrochemical cycle deposition conditions;
FIG. 3 is a stability test of NiCoP nickel foam electrode prepared in example 1;
FIG. 4 is a comparison of the performance of NiCoP nickel foam electrodes prepared in example 1 before and after 240h stability testing;
fig. 5 is a comparison of the performance of the NiCoP nickel foam electrode prepared in example 1 before and after 1000 cycles of electrochemical testing.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
Example 1
The preparation method of the nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
(1) The commercially available nickel foam is cleaned, and the cleaning process comprises acid washing, acetone cleaning and ethanol cleaning. 5% preparation method of HCl washing solution: 33% concentrated hydrochloric acid: deionized water =1:5.6, ultrasonic cleaning is carried out for 10min at room temperature, deionized water is needed for washing after acid cleaning, then acetone, ethanol and deionized water are respectively used for ultrasonic cleaning for 10min, and vacuum drying is carried out at 50 ℃ for later use.
(2) 1.84g of NiSO 4 ·6H 2 O、0.84g CoSO 4 ·7H 2 O、6.36g NaH 2 PO 2 ·H 2 Adding O into a 250mL beaker, adding 100mL of deionized water, stirring for 30min to fully dissolve the O, immersing the treated nickel foam into the prepared plating solution to be used as a working electrode, taking carbon paper as an auxiliary electrode, and using Ag/AgCl electricityThe electrode was used as a reference electrode, and the catalyst preparation was carried out using CHI760E electrochemical workstation. And (2) using a cyclic voltammetry, scanning the electrode at a scanning range of-0.5V to-1.2V (relative to an Ag/AgCl reference electrode) at a scanning speed of 0.01V/s, performing 100 cycles of scanning cycle times to synthesize a nickel-cobalt-phosphorus electrocatalyst, finally, soaking the electrode in deionized water for 10min, leaching with absolute ethyl alcohol, and drying to obtain the nickel-cobalt-phosphorus metal foam electrode.
(3) One containing 2.0g of NaH 2 PO 2 ·H 2 Placing the small-sized quartz boat of O at one end of a large-sized quartz crucible, placing the obtained electrodeposited nickel cobalt phosphorus metal foam electrode at the other side of the large-sized quartz crucible, then covering the quartz crucible, wrapping the quartz crucible by using aluminum foil paper, and placing the quartz crucible in a tubular furnace. By using N 2 And (3) taking the mixture as a reaction carrier gas, heating to 300 ℃ at the heating rate of 1 ℃/min, maintaining the reaction for 2 hours, stopping heating after the reaction is finished, and naturally cooling to room temperature to obtain the nickel-cobalt-phosphorus metal foam electrode subjected to low-temperature phosphorization.
Comparative example 1
Preparation of phosphated nickel foam (NiP/NF):
(1) The commercially available nickel foam is cleaned, and the cleaning process comprises acid washing, acetone cleaning and ethanol cleaning. 5% preparation method of HCl washing solution: 33% concentrated hydrochloric acid: deionized water =1:5.6, ultrasonic cleaning is carried out for 10min at room temperature, deionized water is needed to wash after acid cleaning, then acetone, ethanol and deionized water are respectively used for ultrasonic cleaning for 10min, and vacuum drying is carried out for standby at 50 ℃.
(2) One containing 2.0g of NaH 2 PO 2 ·H 2 Placing a small-size quartz boat of O at one end of a large-size quartz crucible, placing the foamed nickel obtained in the step 1 at the other side of the large-size quartz crucible, then covering the quartz crucible, wrapping the quartz crucible by using aluminum foil paper, and placing the quartz crucible in a tube furnace. By using N 2 And (3) taking the reaction carrier gas, heating to 300 ℃ at the heating rate of 1 ℃/min, maintaining the reaction for 2h, stopping heating after the reaction is finished, and naturally cooling to room temperature to obtain the phosphorized Foam nickel (NiP/NF), wherein NF represents nickel Foam (Ni Foam).
Comparative example 2
Preparation of non-phosphated NiCoP foam Nickel electrode (NiCoP/NF):
(1) The commercially available nickel foam is cleaned, and the cleaning process comprises acid washing, acetone cleaning and ethanol cleaning. 5% preparation method of HCl washing solution: 33% concentrated hydrochloric acid: deionized water =1:5.6, ultrasonic cleaning is carried out for 10min at room temperature, deionized water is needed for washing after acid cleaning, then acetone, ethanol and deionized water are respectively used for ultrasonic cleaning for 10min, and vacuum drying is carried out at 50 ℃ for later use.
(2) 1.84g of NiSO 4 ·6H 2 O、0.84g CoSO 4 ·7H 2 O、6.36g NaH 2 PO 2 ·H 2 And adding O into a 250mL beaker, adding 100mL of deionized water, stirring for 30min to fully dissolve the O, soaking the treated nickel foam into the prepared plating solution to be used as a working electrode, using carbon paper as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode, and preparing the catalyst by adopting a CHI760E electrochemical workstation. And (2) scanning at the scanning speed of 0.01V/s in a scanning range of-0.5V to-1.2V (relative to an Ag/AgCl reference electrode) by using a cyclic voltammetry, performing scanning cycle times of 100 cycles to synthesize a nickel-cobalt-phosphorus electrocatalyst, finally soaking the electrode in deionized water for 10min, leaching with absolute ethyl alcohol, and drying to obtain a nickel-cobalt-phosphorus metal foam electrode (NiCoP/NF).
Comparative example 3
Preparation of a Heat annealed NiCoP foam Nickel electrode (NiCoP/NF Annealing):
(1) And cleaning the commercially available nickel foam, wherein the cleaning process comprises acid washing, acetone cleaning and ethanol cleaning. 5% preparation method of HCl washing solution: 33% concentrated hydrochloric acid: deionized water =1:5.6, ultrasonic cleaning is carried out for 10min at room temperature, deionized water is needed for washing after acid cleaning, then acetone, ethanol and deionized water are respectively used for ultrasonic cleaning for 10min, and vacuum drying is carried out at 50 ℃ for later use.
(2) 1.84g of NiSO 4 ·6H 2 O、0.84g CoSO 4 ·7H 2 O、6.36g NaH 2 PO 2 ·H 2 Adding O into a 250mL beaker, adding 100mL of deionized water, stirring for 30min to fully dissolve the O, immersing the treated nickel foam into the prepared plating solution to be used as a working electrode, using carbon paper as an auxiliary electrode, and using an Ag/AgCl electrode as a reference electrodeElectrode, catalyst preparation was performed using CHI760E electrochemical workstation. And (2) using a cyclic voltammetry, scanning at a speed of 0.01V/s in a scanning range of-0.5V to-1.2V (relative to an Ag/AgCl reference electrode), performing scanning cycle times of 100 cycles to synthesize a nickel-cobalt-phosphorus electrocatalyst, finally placing the electrode in deionized water to soak for 10min, leaching with absolute ethyl alcohol, and drying to obtain the nickel-cobalt-phosphorus metal foam electrode.
(3) The obtained electrodeposited nickel cobalt phosphorus metal foam electrode is placed in a tube furnace. By the use of N 2 And (3) taking the mixture as a reaction carrier gas, heating the mixture to 300 ℃ at the heating rate of 1 ℃/min, maintaining the reaction for 2 hours, stopping heating after the reaction is finished, and naturally cooling the mixture to room temperature to obtain the nickel-cobalt-phosphorus metal foam electrode (NiCoP/NF annealing) for heating annealing.
The materials prepared in the above examples and comparative examples were confirmed and confirmed by XRD test, as shown in fig. 1.
Example 2
The preparation method of the nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
the procedure of this example was the same as in example 1, except that the number of scanning cycles in step (2) was changed to 25 cycles, and the process parameters were the same as in example 1.
Example 3
A preparation method of a nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
the preparation procedure of this example is the same as that of example 1, except that the number of scanning cycles in step (2) is changed to 50 cycles, and the other process parameters are the same as those of example 1.
Example 4
The preparation method of the nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
the preparation procedure of this example is the same as that of example 1, except that the number of scanning cycles in step (2) is changed to 200 cycles, and the other process parameters are the same as those of example 1.
Example 5
A preparation method of a nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
this implementationExample the preparation procedure was the same as in example 1 except that NaH was added in step (3) in the difference from example 1 2 PO 2 ·H 2 The mass of O was changed to 1.0g, and the remaining process parameters were the same as in example 1.
Example 6
The preparation method of the nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
the procedure of this example was the same as in example 1 except that NaH was added in step (3) as in example 1 2 PO 2 ·H 2 The mass of O was changed to 4.0g, and the other process parameters were the same as in example 1.
Example 7
The preparation method of the nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
the procedure of this example was the same as in example 1, except that in step (3), the temperature of the low-temperature phosphating was changed to 350 ℃ in the case of the low-temperature phosphating, and the process parameters were the same as in example 1.
Example 8
A preparation method of a nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
the preparation steps in this example are the same as example 1, except that in step (2), nickel nitrate hexahydrate is used as a nickel source, the weighed mass is 2.03g, cobalt nitrate hexahydrate is used as a cobalt source, the weighed mass is 0.87g, and the rest of the process parameters are the same as example 1.
Example 9
The preparation method of the nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution comprises the following steps:
the preparation procedure of this example is the same as example 1, except that in step (2), nickel chloride hexahydrate is used as a nickel source, the weighed mass is 1.66g, cobalt chloride hexahydrate is used as a cobalt source, the weighed mass is 0.71g, and the rest of the process parameters are the same as example 1.
The materials were tested for electrohydrodesorption hydrogen as follows:
the electrochemical measurement is carried out by using a CHI760E electrochemical workstation, the test temperature is room temperature, and an electrode system is a three-electrode configuration, wherein nickel and cobalt are contained in the electrochemical workstationThe phosphorus foam nickel electrode is a working electrode, the platinum mesh is an auxiliary electrode, and the Hg/HgO electrode is a reference electrode; clamping the synthesized nickel-cobalt-phosphorus foam nickel electrode by a platinum sheet electrode clamp, wherein the platinum sheet electrode clamp is not contacted with the electrolyte in the reaction tank, and the area of the platinum sheet electrode clamp penetrating into the electrolyte is 1cm 2 Recording linear sweep voltammograms in 30% KOH solution at a sweep rate of 10mV s 1 (ii) a In addition, a nickel-cobalt-phosphorus foam nickel electrode and a platinum mesh electrode are combined to form a full cell, and the full cell is subjected to a full cell linear scanning voltammetry test, wherein the scanning speed is 10mV s 1 . FIG. 2 is a full cell hydrogen evolution polarization curve of NiCoP nickel foam electrodes under different electrochemical cycle deposition conditions; table 1 shows the hydrogen evolution overpotential of the different electrodes in 30% KOH solution. The results showed that the nickel-cobalt-phosphorus nickel foam electrode prepared in example 1 had better performance of hydrogen evolution from electrolyzed water at a current density of 10mA cm KOH as an electrolyte solution under the test conditions of 30% -2 When the voltage is constant, the overpotential is 45mV, the Tafel slope is 89.4mV dec -1 Has better hydrogen evolution catalytic activity at 100mA cm -2 The stability test of 240h under the current still can keep the overpotential not to change greatly, which shows that the electrode has better stability, as shown in figures 3-4, in addition, the NiCoP foam nickel electrode of low-temperature phosphorization has long service life, and the performance is basically kept unchanged before and after 1000 cycles of electrochemical test, as shown in figure 5.
TABLE 1 overpotential of hydrogen evolution of different electrodes in 30% KOH solution
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way and substantially, it should be noted that those skilled in the art may make several modifications and additions without departing from the scope of the present invention, which should also be construed as a protection scope of the present invention.
Claims (9)
1. A preparation method of a nickel-cobalt-phosphorus electrocatalyst for efficient water electrolysis hydrogen evolution is characterized by comprising the following steps:
step 1: pretreating the metal foam substrate;
and 2, step: preparation of a composition containing Ni 2+ 、Co 2+ And PO 2 3- The mixed solution of (1);
and step 3: taking the metal foam base pretreated in the step 1 as a working electrode, taking the mixed solution prepared in the step 2 as an electrolyte solution, and performing electrochemical deposition in a three-electrode system to obtain a metal foam electrode deposited with a nickel-cobalt-phosphorus electrocatalyst, namely a nickel-cobalt-phosphorus metal foam electrode;
and 4, step 4: and (4) placing a phosphorus source and the nickel cobalt phosphorus metal foam electrode obtained in the step (3) in the same container and separately placing, and then carrying out a phosphating reaction in an inert atmosphere at a temperature lower than 400 ℃ to obtain the nickel cobalt phosphorus metal foam electrode after low-temperature phosphating.
2. The method for preparing the nickel-cobalt-phosphorus electrocatalyst for efficient electrolysis of water for hydrogen evolution as claimed in claim 1, wherein the pretreatment in step 1 comprises removing oxide on the surface of the metal foam substrate by acid washing, acetone cleaning, ethanol cleaning, deionized water cleaning and drying sequentially.
3. The method for preparing the nickel-cobalt-phosphorus electrocatalyst for efficient electrolysis of water for hydrogen evolution as claimed in claim 1, wherein Ni in step 2 is Ni 2+ 、Co 2+ And PO 2 3- In a molar ratio of 7:3:6, the Ni 2+ The molar concentration of the active ingredients is 0.035-0.14M.
4. The method for preparing the nickel-cobalt-phosphorus electrocatalyst for high-efficiency electrolysis of water for hydrogen evolution according to claim 1, wherein the three-electrode system in step 3 uses carbon paper as an auxiliary electrode and an Ag/AgCl electrode as a reference electrode.
5. The method for preparing the nickel-cobalt-phosphorus electrocatalyst for high-efficiency electrolysis of water for hydrogen evolution according to claim 1, wherein the electrochemical deposition in step 3 is cyclic voltammetry, which scans in the range of-0.5V to-1.2V (relative to Ag/AgCl reference electrode), scans at 0.01V/s, and scans for 25-200 cycles.
6. The method for preparing the nickel cobalt phosphorus electrocatalyst for high efficiency electrolytic water evolution of hydrogen as claimed in claim 1, wherein the phosphorus source in step 4 is sodium hypophosphite or its hydrate, and the dosage of the sodium hypophosphite or its hydrate is according to PO in step 2 2 3- Is calculated from 10% to 70% of the molar amount of (A).
7. The method for preparing the nickel-cobalt-phosphorus electrocatalyst for efficient electrolysis of water for hydrogen evolution as claimed in claim 1, wherein the temperature of the phosphating reaction in step 4 is 300-350 ℃ for 1-3 h.
8. The nickel cobalt phosphorus electrocatalyst for efficient electrolysis of water for hydrogen evolution prepared by the method of any one of claims 1 to 7.
9. Use of the nickel cobalt phosphorus electrocatalyst according to claim 8 for electrolysis of water for hydrogen evolution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211100988.XA CN115466979B (en) | 2022-09-09 | 2022-09-09 | Preparation method of nickel-cobalt-phosphorus electrocatalyst for high-efficiency electrolysis of water to hydrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211100988.XA CN115466979B (en) | 2022-09-09 | 2022-09-09 | Preparation method of nickel-cobalt-phosphorus electrocatalyst for high-efficiency electrolysis of water to hydrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115466979A true CN115466979A (en) | 2022-12-13 |
| CN115466979B CN115466979B (en) | 2024-04-12 |
Family
ID=84368531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211100988.XA Active CN115466979B (en) | 2022-09-09 | 2022-09-09 | Preparation method of nickel-cobalt-phosphorus electrocatalyst for high-efficiency electrolysis of water to hydrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115466979B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115058735A (en) * | 2022-07-08 | 2022-09-16 | 东北大学 | Porous catalyst with high hydrogen evolution performance by external magnetic field and preparation and use methods thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105826573A (en) * | 2016-05-12 | 2016-08-03 | 湖北大学 | Surface treatment method for improving electro-catalysis hydrogen production performance |
| CN105951123A (en) * | 2016-05-06 | 2016-09-21 | 湖北大学 | Preparation method for NiCoP nanowire electro-catalytic electrode |
| CN108654658A (en) * | 2018-05-28 | 2018-10-16 | 北京工业大学 | A kind of efficient water decomposition bifunctional electrocatalyst NiCoP and preparation method thereof |
| CN110354905A (en) * | 2019-08-13 | 2019-10-22 | 哈尔滨理工大学 | A kind of electrolysis water liberation of hydrogen catalyst n iCoP/NF@PANI composite material and preparation method |
| CN113278988A (en) * | 2021-05-24 | 2021-08-20 | 哈尔滨工业大学 | Preparation method of O-doped NiCoP high-efficiency hydrogen evolution electrode |
| CN113684493A (en) * | 2021-08-20 | 2021-11-23 | 中国科学院过程工程研究所 | Method for preparing efficient electrolytic water hydrogen evolution catalyst by chemical plating method |
| US20230002921A1 (en) * | 2021-07-02 | 2023-01-05 | S-Oil Corporation | Coral reef-like nickel phosphide-tungsten oxide nanocomposite, method for preparing the coral reef-like nickel phosphide-tungsten oxide nanocomposite and catalyst for electrochemical water splitting including the coral reef-like nickel phosphide-tungsten oxide nanocomposite |
-
2022
- 2022-09-09 CN CN202211100988.XA patent/CN115466979B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105951123A (en) * | 2016-05-06 | 2016-09-21 | 湖北大学 | Preparation method for NiCoP nanowire electro-catalytic electrode |
| CN105826573A (en) * | 2016-05-12 | 2016-08-03 | 湖北大学 | Surface treatment method for improving electro-catalysis hydrogen production performance |
| CN108654658A (en) * | 2018-05-28 | 2018-10-16 | 北京工业大学 | A kind of efficient water decomposition bifunctional electrocatalyst NiCoP and preparation method thereof |
| CN110354905A (en) * | 2019-08-13 | 2019-10-22 | 哈尔滨理工大学 | A kind of electrolysis water liberation of hydrogen catalyst n iCoP/NF@PANI composite material and preparation method |
| CN113278988A (en) * | 2021-05-24 | 2021-08-20 | 哈尔滨工业大学 | Preparation method of O-doped NiCoP high-efficiency hydrogen evolution electrode |
| US20230002921A1 (en) * | 2021-07-02 | 2023-01-05 | S-Oil Corporation | Coral reef-like nickel phosphide-tungsten oxide nanocomposite, method for preparing the coral reef-like nickel phosphide-tungsten oxide nanocomposite and catalyst for electrochemical water splitting including the coral reef-like nickel phosphide-tungsten oxide nanocomposite |
| CN113684493A (en) * | 2021-08-20 | 2021-11-23 | 中国科学院过程工程研究所 | Method for preparing efficient electrolytic water hydrogen evolution catalyst by chemical plating method |
Non-Patent Citations (3)
| Title |
|---|
| CAO, YANPENG等: ""One-step synthesis of amorphous NiCoP nanoparticles by electrodeposition as highly efficient electrocatalyst for hydrogen evolution reaction in alkaline solution"", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 896, pages 163103 * |
| YE, FENG等: ""In-situ porous flake heterostructured NiCoP/Ni foam as electrocatalyst for hydrogen evolution reaction"", 《ELECTROCHIMICA ACTA》, vol. 423, pages 2 * |
| 王云龙 等: ""循环伏安法电沉积镍-钴-磷/泡沫镍电极及其析氢催化活性研究"", 《电镀与涂饰》, pages 1 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115058735A (en) * | 2022-07-08 | 2022-09-16 | 东北大学 | Porous catalyst with high hydrogen evolution performance by external magnetic field and preparation and use methods thereof |
| CN115058735B (en) * | 2022-07-08 | 2024-02-27 | 东北大学 | Porous catalyst with high hydrogen evolution performance by externally applied magnetic field and preparation and use methods thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115466979B (en) | 2024-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108796535B (en) | Copper-cobalt-molybdenum/nickel foam porous electrode material with trimetal, and preparation method and application thereof | |
| CN110331414B (en) | MOF (Metal organic framework) composite copper-based nanorod array @ foam copper-based composite electrode material as well as preparation method and application thereof | |
| CN110484934B (en) | Preparation method of nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material | |
| CN112439459B (en) | Ultrathin nanosheet material with coexisting crystal and amorphous interface and application thereof in water electrolysis | |
| CN112080759B (en) | Preparation method of bismuth-doped bimetallic sulfide electrode for electrocatalytic oxidation of urea | |
| CN111939947B (en) | Preparation method of nanosheet array electrocatalyst | |
| CN111686743A (en) | La/NF hydrogen evolution material and preparation method and application thereof | |
| CN113637997A (en) | Co2P/CuP2Preparation method of/NF hydrogen evolution and oxygen evolution electrocatalyst | |
| CN114438545A (en) | Bimetal doped Ni3S2Preparation method of oxygen evolution electrocatalyst | |
| CN112647092A (en) | Supported nickel-based composite hydrogen evolution catalyst and preparation method and application thereof | |
| CN115466979B (en) | Preparation method of nickel-cobalt-phosphorus electrocatalyst for high-efficiency electrolysis of water to hydrogen | |
| CN110820011A (en) | Ni for electrolyzing water3S2Electrode material and preparation method thereof | |
| CN116445972A (en) | Cerium dioxide-transition metal phosphide composite self-supporting electrode material and preparation method and application thereof | |
| CN105047884A (en) | Three-dimensional oxygen-evolution electrode anode material, and preparation method and application thereof | |
| CN115928135A (en) | Iron-doped nickel hydroxide composite nickel selenide material and preparation method and application thereof | |
| CN113684493A (en) | Method for preparing efficient electrolytic water hydrogen evolution catalyst by chemical plating method | |
| CN110735152B (en) | Ni-Cu-C electrocatalyst and preparation method and application thereof | |
| CN115044920B (en) | Preparation method of self-supporting ultralow-crystallinity nano-array electrocatalyst for hydrogen production by water electrolysis | |
| CN113136586B (en) | Electrocatalysis composite electrode material, preparation method and application thereof | |
| CN117230480B (en) | High-entropy alloy dual-function electrocatalytic film and preparation method and application thereof | |
| CN113584512B (en) | Preparation method of cobalt/cobalt oxide/molybdenum oxide in-situ electrode | |
| CN115094469B (en) | Preparation method of trace Cu doped porous NiFe oxygen evolution electrocatalyst | |
| CN116463667A (en) | Lanthanum-copper doped nickel-molybdenum/nickel phosphide self-supporting electrode, and preparation method and application thereof | |
| CN116575055A (en) | CeO doped with foam nickel load 2 Nickel-phosphorus composite hydrogen production electrode, and preparation and application thereof | |
| CN118186473A (en) | B-Co2Preparation method of P/CoP full-water-dissolving dual-function electrode plate |
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 |