CN114438545A - Bimetal doped Ni3S2Preparation method of oxygen evolution electrocatalyst - Google Patents
Bimetal doped Ni3S2Preparation method of oxygen evolution electrocatalyst Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 107
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 239000006260 foam Substances 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000758 substrate Substances 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 9
- 150000003681 vanadium Chemical class 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 8
- 239000011593 sulfur Substances 0.000 claims abstract description 8
- 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 abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 238000004073 vulcanization Methods 0.000 claims abstract description 7
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- 238000011065 in-situ storage Methods 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 4
- 229910020516 Co—V Inorganic materials 0.000 claims abstract description 3
- FPVKHBSQESCIEP-JQCXWYLXSA-N pentostatin Chemical compound C1[C@H](O)[C@@H](CO)O[C@H]1N1C(N=CNC[C@H]2O)=C2N=C1 FPVKHBSQESCIEP-JQCXWYLXSA-N 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 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 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 14
- 229910052720 vanadium Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000002019 doping agent Substances 0.000 abstract description 2
- 229910001960 metal nitrate Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001027 hydrothermal synthesis Methods 0.000 abstract 1
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 238000000840 electrochemical analysis Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002803 fossil fuel Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- 229910003206 NH4VO3 Inorganic materials 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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Abstract
The invention relates to a bimetal doped Ni3S2A preparation method of an oxygen evolution electrocatalyst. The method comprises the following steps: (1) immersing the pretreated foam nickel substrate into an aqueous solution containing cobalt salt, vanadium salt, ammonium fluoride and urea, and carrying out hydrothermal reaction to obtain a CoV/NF material growing in situ on the foam nickel substrate; (2) immersing the obtained Co-V precursor material in a second reaction kettle filled with a sulfur source water solution, and carrying out hydrothermal vulcanization to obtain the bimetal doped Ni3S2An oxygen evolution electrocatalyst material. In the catalyst obtained by the invention, Co and V are used as doping agents to synergistically improve Ni3S2The performance of the electrocatalyst in OER; the raw materials required by the preparation process are cheap and harmless chemicals such as metal nitrate, the material cost is reduced, and the subsequent production is facilitated.
Description
The technical field is as follows:
the invention relates to a bimetal doped Ni3S2A preparation method of an oxygen evolution electrocatalyst, belonging to the technical field of electrolytic water catalysis.
The background art comprises the following steps:
with the consumption of fossil fuels, it is of great significance to explore clean renewable energy sources such as solar energy, wind energy, hydrogen energy and the like to replace the fossil fuels, wherein hydrogen is a clean energy carrier capable of replacing the fossil fuels, and has the potential to solve the problem of continuous increase of global energy demand and the environmental protection advantage thereof. The hydrogen production by electrolyzing water is a key for solving the renewable energy at present. However, the Oxygen Evolution Reaction (OER) is a bottleneck to be broken through as water electrolysis is urgent, and the kinetic problem is still a fatal defect. The early most effective electrocatalyst for improving OER performance was RuO2And IrO2. However, their industrial application is severely hampered by the expense and scarcity. Therefore, many attempts have been made to search for economical, efficient and stable non-noble metal electrocatalysts.
At present, the most common non-noble metal OER electrocatalyst is a nano catalyst containing Fe, Co, Ni and other metals, including transition metal oxides, phosphides, sulfides, nitrides and the like. Among them, Transition Metal Sulfide (TMS) having abundant active sites and high conductivity can also exhibit high OER activity. Such as cobalt sulfide, nickel sulfide are the most common OER catalysts. During the electrocatalysis process, the oxidation loss of surface sulfur can induce generation of high-activity MOOH sites, thereby activating the performance of OER.
The porosity of the matrix provides more active sites and surface area, with higher mass transfer for chemical stability due to the highly porous nature. Thus, in situ growth and surface modification of metal substrates is an area of ongoing development in electrocatalytic applications. Under the long-term action of hydrothermal vulcanization, Ni can be caused3S2And a firm bonding is formed between the conductive film and the substrate, so that the conductivity and the stability are improved. However, pure Ni3S2Due to limited catalytic activity, limited active sites and poor electrical conductivity, efforts have been made to design different types of Ni in order to improve catalytic performance in practical applications3S2Based on nanostructures or nanocomposites.
The invention content is as follows:
the present invention is directed to addressing the deficiencies in the prior art,providing a bimetal doped Ni3S2A preparation method of an oxygen evolution electrocatalyst. The method adopts a solvothermal method to dope Co and V with Ni in different proportions3S2In this way, a highly active self-supporting material is obtained. In terms of activity and stability, Co and V are used as doping agents to synergistically improve Ni of the catalyst obtained by the invention3S2The performance of the electrocatalyst in OER; the raw materials required by the preparation process are cheap and harmless chemicals such as metal nitrate, the material cost is reduced, and the subsequent production is facilitated.
The technical scheme adopted by the invention is as follows:
bimetal doped Ni3S2The preparation method of the oxygen evolution electrocatalyst comprises the following steps:
(1) immersing the pretreated foam nickel substrate into the mixed solution, pouring the solution into a first reaction kettle, sealing the reaction kettle, cooling to take out the foam nickel after the reaction is finished, washing the foam nickel with distilled water, drying, and obtaining the CoV/NF material growing in situ on the foam nickel substrate;
wherein the mixed solution is an aqueous solution containing cobalt salt, vanadium salt, ammonium fluoride and urea; the mol ratio of the cobalt salt, the vanadium salt, the ammonium fluoride and the urea is (5-20) to (1), (8-32) to (21-75); the total concentration of the cobalt salt solution and the vanadium salt solution is 0.03mol/L-0.10mol/L, the concentration of the ammonium fluoride solution is 0.05mol/L-0.15mol/L, and the concentration of the urea solution is 0.1mol/L-0.3 mol/L;
(2) immersing the Co-V precursor material obtained in the step (1) in a second reaction kettle filled with a sulfur source water solution, and sealing the reaction kettle, wherein the hydrothermal temperature is 160-180 ℃ and the hydrothermal vulcanization time is 6-8 h; washing and drying after the reaction is finished to obtain CoV-Ni3S2/NF material, i.e. bimetallic doped Ni3S2An oxygen evolution electrocatalyst material.
The pretreatment step in the step (1) is as follows: sequentially carrying out ultrasonic treatment on the foamed nickel in 0.5M-1MHCl solution, deionized water and absolute ethyl alcohol for 20-30min, and drying in vacuum at 50-60 ℃: and (3) pretreating to remove oxides and impurities on the surface of the foamed nickel.
The cobalt salt in the step (1) is cobalt nitrate hexahydrate, and the vanadium salt is ammonium metavanadate;
the volume of the aqueous solution in the step (1) and the step (2) is 60 to 80 percent of the capacity of the polytetrafluoroethylene lining of the hydrothermal kettle;
the washing in the step (1) is carried out for 3-5 times by using deionized water, and the drying is carried out for 10-12h under vacuum at 50-60 ℃.
The sulfur source in the step (2) is NH2CSNH2(ii) a The concentration of the sulfur source solution is 0.05mol/L-0.1 mol/L.
Washing in the step (2) is carried out for 3-5 times by using deionized water and 3-5 times by using absolute ethyl alcohol; drying at 50-60 deg.C under vacuum for 10-12 hr.
The bimetal doped Ni prepared by the method3S2The application of the oxygen evolution electrocatalyst is used for electrocatalytic oxygen evolution reaction.
The invention has the following beneficial effects:
1. the bimetal of the invention is doped with Ni3S2The preparation method of the oxygen evolution electrocatalyst adopts a foam nickel substrate to provide a nickel source, and Co and V are doped into Ni by a hydrothermal vulcanization method3S2The surface appearance of the prepared high-activity OER catalyst becomes rough after vulcanization. The preparation method is simple and easy to operate.
2. The invention is Ni formed by in-situ vulcanization on the basis of foamed nickel3S2Is the true active center of OER, but pure Ni3S2The catalyst is influenced by limited catalytic activity, limited active sites and the like, more active centers can be exposed by doping Co, and the electron density of the active centers can be adjusted by doping V, so that the electrocatalytic activity is improved. Under the synergistic action of the three components, Ni doped with Co and V elements3S2The catalyst becomes an excellent OER electrocatalyst.
3. The oxygen evolution electrocatalyst prepared by the invention is tested in 1M KOH electrolyte, and the current density is 100mA/cm2A low overpotential of 290mV was obtained.
Drawings
FIG. 1 is CoV-Ni prepared in example 13S2The LSV profile of the material for electrocatalysis.
FIG. 2 shows CoV-Ni prepared in example 13S2An ac impedance profile of the material.
FIG. 3 is CoV-Ni prepared in example 13S2XRD pattern of the material.
FIG. 4 shows CoV-Ni prepared in example 13S2SEM image of material.
The specific implementation mode is as follows:
the technical solution of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
(1) The bimetal is doped with Ni3S2The preparation method of the oxygen evolution electrocatalyst comprises the steps of cutting the foamed nickel into the size of 1 x 1.5cm, carrying out ultrasonic cleaning on the cut foamed nickel in 1MHCl, deionized water and absolute ethyl alcohol for 20min respectively once to remove oxides and impurities on the surface of the foamed nickel, and then carrying out vacuum drying at the temperature of 60 ℃ for subsequent use. Firstly, 1.5mmol of Co (NO)3)2·6H2O、0.15mmol NH4VO3、6mmol CO(NH2)2、2.5mmol NH4F is dissolved in 40ml of deionized water, stirred until transparent, the solution is transferred to a polytetrafluoroethylene liner, the treated nickel foam is then immersed in the solution, the liner is transferred to a stainless steel reactor and sealed. Heating at 120 deg.C for 6h, naturally cooling to room temperature, taking out the reaction kettle, washing the obtained product with deionized water for 3-4 times, and drying in a vacuum drying oven at 60 deg.C for 12 h. CoV/NF was obtained.
(2) Dissolving 3mmol of thiourea in 30ml of deionized water, stirring until the solution is transparent, transferring the solution into a polytetrafluoroethylene lining, then immersing the dried material in (1) into the solution, transferring the lining into a stainless steel reaction kettle, and sealing. Heating at 180 deg.C for 8h, naturally cooling to room temperature, taking out the reaction kettle, washing the obtained product with deionized water for 3-4 times, washing with anhydrous ethanol for 3-4 times, and drying in 60 deg.C vacuum drying oven for 12 h. Obtaining CoV-Ni3S2and/NF. I.e. bi-metal doped Ni3S2An oxygen evolution electrocatalyst material.
The resulting self-supporting catalyst material was subjected to electrochemical testing: the electrochemical test adopts Shanghai Hua CHI760E workstation, uses three-electrode test system, the prepared electro-catalyst material is the working electrode, Ag/AgCl electrode is the reference electrode, platinum sheet electrode is the counter electrode, the electrolyte is newly configured 1mol/L KOH, the polarization curve (LSV) graph obtained by linear scanning speed of 10mV/s in the electrolyte is shown in figure 1. It can be seen from the graph that the current density is 100mA/cm2The overpotential of the obtained material is 290mV, and the performance is better. Is significantly lower than that of the commercial noble metal catalyst Ir/C (420 mV).
FIG. 2 shows the AC impedance test of the sample in the apparatus for electrochemical testing, wherein the charge transfer resistance (Rct) is 3.2 Ω/cm according to the AC impedance test result after the equivalent circuit is fitted2The resistance was smaller compared to the material in the comparative example.
Figure 3 is an XRD spectrum of this sample. Can accurately correspond to Ni according to the graph3S2And the peak position of NF, using NF as a substrate results in NF and Ni3S2The XRD peaks of (a) are very strong and are not shown compared to the sulfide peaks obtained after sulfidation of the CoV precursor. Therefore, it is shown that the catalyst prepared finally is indeed CoV-Ni3S2/NF。
Fig. 4 is an SEM image of the catalyst, and it can be seen that the surface morphology of the catalyst is rough, which increases the surface area of the catalyst and is beneficial to increase the catalytic rate.
Example 2
(1) The bimetal is doped with Ni3S2The preparation method of the oxygen evolution electrocatalyst comprises the steps of cutting the foamed nickel into the size of 1 x 1.5cm, carrying out ultrasonic cleaning on the cut foamed nickel in 1MHCl, deionized water and absolute ethyl alcohol for 20min respectively once to remove oxides and impurities on the surface of the foamed nickel, and then carrying out vacuum drying at the temperature of 60 ℃ for subsequent use. Firstly, 1.4mmol of Co (NO)3)2·6H2O、0.28mmol NH4VO3、6mmol CO(NH2)2、2.5mmol NH4F is dissolved in 40ml of deionized water, stirred until transparent, the solution is transferred to a polytetrafluoroethylene liner, the treated nickel foam is then immersed in the solution, the liner is transferred to a stainless steel reaction kettle and sealed. Heating at 120 deg.C for 6h, naturally cooling to room temperature, taking out the reaction kettle, washing the obtained product with deionized water for 3-4 times, and drying in a vacuum drying oven at 60 deg.C for 12 h. CoV/NF was obtained.
(2) Dissolving 3mmol of thiourea in 30ml of deionized water, stirring until the solution is transparent, transferring the solution into a polytetrafluoroethylene lining, then immersing the dried material in (1) into the solution, transferring the lining into a stainless steel reaction kettle, and sealing. Heating at 180 deg.C for 8h, naturally cooling to room temperature, taking out the reaction kettle, washing the obtained product with deionized water for 3-4 times, washing with anhydrous ethanol for 3-4 times, and drying in 60 deg.C vacuum drying oven for 12 h. Obtaining CoV-Ni3S2and/NF. Namely the bimetallic doping of Ni3S2An oxygen evolution electrocatalyst material.
Example 3
(1) The bimetal is doped with Ni3S2The preparation method of the oxygen evolution electrocatalyst comprises the steps of cutting the foamed nickel into the size of 1 x 1.5cm, carrying out ultrasonic cleaning on the cut foamed nickel in 1MHCl, deionized water and absolute ethyl alcohol for 20min respectively once to remove oxides and impurities on the surface of the foamed nickel, and then carrying out vacuum drying at the temperature of 60 ℃ for subsequent use. Firstly, 1.6mmol of Co (NO)3)2·6H2O、0.08mmol NH4VO3、6mmol CO(NH2)2、2.5mmol NH4F is dissolved in 40ml of deionized water, stirred until transparent, the solution is transferred to a polytetrafluoroethylene liner, the treated nickel foam is then immersed in the solution, the liner is transferred to a stainless steel reaction kettle and sealed. Heating at 120 deg.C for 6h, naturally cooling to room temperature, taking out the reaction kettle, washing the obtained product with deionized water for 3-4 times, and drying in a vacuum drying oven at 60 deg.C for 12 h. CoV/NF was obtained.
(2) Dissolving 3mmol of thiourea in 30ml of deionized water, stirring until it is clear, and dissolvingTransferring the solution into a polytetrafluoroethylene lining, then soaking the dried material in the step (1) into the solution, transferring the lining into a stainless steel reaction kettle, and sealing. Heating at 180 deg.C for 8h, naturally cooling to room temperature, taking out the reaction kettle, washing the obtained product with deionized water for 3-4 times, washing with anhydrous ethanol for 3-4 times, and drying in 60 deg.C vacuum drying oven for 12 h. Obtaining CoV-Ni3S2and/NF. Namely the bimetallic doping of Ni3S2An oxygen evolution electrocatalyst material.
Comparative example 1
Omitting NH from example 14VO31.5mmol of Co (NO)3)2·6H2Replacement of O with 1.65mmol Co (NO)3)2·6H2And O. Other conditions or parameters were the same as those in example 1 to obtain Co-Ni3S2and/NF. Using the same electrochemical test conditions as in examples 1 to 3, it was found that the current density was 100mA/cm2The overpotential of the obtained material was 350mV, but CoV-Ni3S2The current density of the/NF material is 100mA/cm2The overpotential at this time was 290 mV. Comparative Co-Ni3S2The overpotential of/NF is higher; according to the test result of the fitted alternating current impedance of the equivalent circuit, the charge transfer resistance (Rct) is 7.35 omega/cm2And there is also room for optimization.
Comparative example 2
Omitting Co (NO) from example 13)2·6H2O, 0.15mmol of NH4VO3Replacement with 1.65mmol NH4VO3. Other conditions or parameters were in accordance with example 1 to obtain V-Ni3S2and/NF. Using the same electrochemical test conditions as in examples 1 to 3, it was found that the current density was 100mA/cm2The overpotential of the obtained material is 420mV, and the current density of the obtained material is 100mA/cm with a commercial noble metal catalyst Ir/C2The overpotential (420mV) is equivalent; according to the test result of the fitted alternating current impedance of the equivalent circuit, the charge transfer resistance (Rct) is 12.52 omega/cm2. Therefore, V-Ni3S2The catalytic performance of/NF is general, and there is optimization space.
Comparative example 3
Step (1) in example 1 was omitted. Other conditions or parameters were the same as in example 1 to obtain Ni3S2and/NF. Using the same electrochemical test conditions as in examples 1 to 3, it was found that the current density was 100mA/cm2The overpotential of the obtained material is 530mV, which is obviously higher than that of a commercial noble metal catalyst Ir/C at the current density of 100mA/cm2Overpotential (420 mV); according to the test result of the fitted alternating current impedance of the equivalent circuit, the charge transfer resistance (Rct) is 39.52 omega/cm2. Ni indicating no doping of bimetal3S2The catalytic performance of/NF is poor.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the technical spirit and principles of the present invention are intended to be included within the scope of the present invention.
The invention is not the best known technology.
Claims (7)
1. Bimetal doped Ni3S2The preparation method of the oxygen evolution electrocatalyst is characterized by comprising the following steps:
(1) immersing the pretreated foam nickel substrate into the mixed solution, pouring the solution into a first reaction kettle, sealing the reaction kettle, cooling to take out the foam nickel after the reaction is finished, washing the foam nickel with distilled water, drying, and obtaining the CoV/NF material growing in situ on the foam nickel substrate;
wherein the mixed solution is an aqueous solution containing cobalt salt, vanadium salt, ammonium fluoride and urea; the mol ratio of the cobalt salt, the vanadium salt, the ammonium fluoride and the urea is (5-20) to (1), (8-32) to (21-75); the total concentration of the cobalt salt solution and the vanadium salt solution is 0.03mol/L-0.10mol/L, the concentration of the ammonium fluoride solution is 0.05mol/L-0.15mol/L, and the concentration of the urea solution is 0.1mol/L-0.3 mol/L;
(2) immersing the Co-V precursor material obtained in the step (1) in a second reaction kettle filled with a sulfur source water solution, and sealing the reaction kettle, wherein the hydrothermal temperature is 160-180 ℃ and the hydrothermal vulcanization time is 6-8 h; after the reaction is finishedWashing and drying after formation to obtain CoV-Ni3S2/NF material, i.e. bimetallic doped Ni3S2An oxygen evolution electrocatalyst material;
the sulfur source is NH2CSNH2(ii) a The concentration of the sulfur source solution is 0.05mol/L-0.1 mol/L.
2. The bi-metal doped Ni of claim 13S2The preparation method of the oxygen evolution electrocatalyst is characterized in that the pretreatment step in the step (1) is as follows: sequentially carrying out ultrasonic treatment on the foamed nickel in 0.5M-1MHCl solution, deionized water and absolute ethyl alcohol for 20-30min, and drying in vacuum at 50-60 ℃: and (3) pretreating to remove oxides and impurities on the surface of the foamed nickel.
3. The bi-metal doped Ni of claim 13S2The preparation method of the oxygen evolution electrocatalyst is characterized in that the cobalt salt in the step (1) is cobalt nitrate hexahydrate, and the vanadium salt is ammonium metavanadate.
4. The bi-metal doped Ni of claim 13S2The preparation method of the oxygen evolution electrocatalyst is characterized in that the volume of the aqueous solution in the steps (1) and (2) is 60-80% of the capacity of the polytetrafluoroethylene lining of the hydrothermal kettle.
5. The bi-metal doped Ni of claim 13S2The preparation method of the oxygen evolution electrocatalyst is characterized in that the washing in the step (1) is 3 to 5 times of washing by using deionized water, and the drying is carried out for 10 to 12 hours in vacuum at the temperature of between 50 and 60 ℃.
6. The bi-metal doped Ni of claim 13S2The preparation method of the oxygen evolution electrocatalyst is characterized in that the washing in the step (2) is washing for 3-5 times by using deionized water and then washing for 3-5 times by using absolute ethyl alcohol; drying at 50-60 deg.C under vacuum for 10-12 hr.
7. The method of claim 1Bimetallic doped Ni prepared by the method3S2The application of the oxygen evolution electrocatalyst is characterized in that the oxygen evolution electrocatalyst is used for electrocatalytic oxygen evolution reaction.
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| CN115029709A (en) * | 2022-05-23 | 2022-09-09 | 常州大学 | Cobalt-nickel metal sulfide bifunctional electrocatalyst and preparation method and application thereof |
| CN115125575A (en) * | 2022-07-11 | 2022-09-30 | 广东工业大学 | Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 Catalyst, preparation method and application thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114774963A (en) * | 2022-05-20 | 2022-07-22 | 澳门大学 | Nitrate radical reduction electrocatalyst and preparation method thereof |
| CN114774963B (en) * | 2022-05-20 | 2024-05-10 | 澳门大学 | Nitrate radical reduction electrocatalyst and preparation method thereof |
| CN115029709A (en) * | 2022-05-23 | 2022-09-09 | 常州大学 | Cobalt-nickel metal sulfide bifunctional electrocatalyst and preparation method and application thereof |
| CN115029709B (en) * | 2022-05-23 | 2023-06-20 | 常州大学 | Cobalt-nickel metal sulfide bifunctional electrocatalyst and preparation method and application thereof |
| CN115125575A (en) * | 2022-07-11 | 2022-09-30 | 广东工业大学 | Sulfur and nitrogen doped carbon coated Co 9 S 8 -Ni 3 S 2 Catalyst, preparation method and application thereof |
| CN115520938A (en) * | 2022-09-30 | 2022-12-27 | 常州工学院 | Preparation method and application of plasma modified iron-doped nickel sulfide |
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