CN116623225A - Method for improving electrocatalytic stability of nickel-based sulfide catalyst in oxygen evolution reaction - Google Patents
Method for improving electrocatalytic stability of nickel-based sulfide catalyst in oxygen evolution reaction Download PDFInfo
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- CN116623225A CN116623225A CN202310755059.0A CN202310755059A CN116623225A CN 116623225 A CN116623225 A CN 116623225A CN 202310755059 A CN202310755059 A CN 202310755059A CN 116623225 A CN116623225 A CN 116623225A
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- sulfide catalyst
- based sulfide
- oxygen evolution
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 45
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 25
- 239000001301 oxygen Substances 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 33
- 239000002184 metal Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000002798 polar solvent Substances 0.000 claims abstract description 7
- 238000011144 upstream manufacturing Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 20
- 239000004744 fabric Substances 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 238000010306 acid treatment Methods 0.000 claims description 4
- 125000000524 functional group Chemical group 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 238000004073 vulcanization Methods 0.000 claims description 2
- 238000007781 pre-processing Methods 0.000 claims 1
- 229910003160 β-NiOOH Inorganic materials 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 26
- 238000012360 testing method Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000013112 stability test Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000010411 electrocatalyst Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 230000007774 longterm Effects 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 229910006279 γ-NiOOH Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910002640 NiOOH Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 230000003872 anastomosis Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- -1 sulfide ions Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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
- C25B11/091—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
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
- C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- 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)
- Catalysts (AREA)
Abstract
The invention discloses a method for improving electrocatalytic stability of a nickel-based sulfide catalyst in an oxygen evolution reaction, which comprises the steps of mixing a metal nickel source, a low-electronegativity metal element precursor and a high-molecular surfactant in a polar solvent, then using the mixed solution to impregnate or coat a self-supporting conductive substrate, drying, then carrying out heat treatment on the obtained precursor material in a saturated inert atmosphere, and then respectively placing the precursor material and sulfur powder after heat treatment at the downstream and upstream of a tubular furnace, and preparing the nickel-based sulfide catalyst by a chemical vapor deposition method. According to the invention, ni is in an electron-rich state by introducing low electronegativity elements, and beta-NiOOH with higher stability is generated by reconstruction in the OER process, so that the activity and stability of the catalyst are improved.
Description
Technical Field
The invention belongs to the technical field of electrolyzed water catalysts, and particularly relates to a method for improving the electrocatalytic stability of a nickel-based sulfide catalyst in an Oxygen Evolution Reaction (OER).
Background
Electrochemical water dissociation has received great attention over the past few years because it provides a clean energy source, reduces reliance on conventional fossil fuels, and mitigates the effects of climate change. However, the large-scale practical application of electrolyzed water is severely limited by the slow kinetics of the anodic Oxygen Evolution Reaction (OER) and the four electron transfer process, resulting in a great overpotential and energy consumption, increasing the application cost. Therefore, the development of an efficient and low-cost oxygen evolution catalyst is of great significance to the electrolytic aquaculture industry.
Nickel-based sulfides have excellent chemical properties and have received extensive attention and research in recent years due to their abundant crust abundance and low price. Under extensive research, an OER catalytic mechanism for nickel-based sulfides has gradually reached a consensus: under alkaline conditions, nickel-based sulfides gradually reform into the corresponding oxyhydroxide-NiOOH during OER, and this in situ-formed oxyhydroxide is believed to be the active site actually catalyzing OER. However, the reconstructed NiOOH at high current density is liable to form unstable gamma-NiOOH at high voltage, the valence state of Ni ions is greater than trivalent, the structure is more severely distorted, and OH is formed - The "dead phase" with very poor affinity results in a severe decrease in catalytic performance. Thus, the catalytic activity and long-term stability of such materials under high current density electrolysis conditions still need to be further improved to meet the requirements of industrial applications.
Chinese patent CN 110227496a discloses a Fe-doped Ni 3 S 2 The preparation method of the electrocatalyst comprises the step of growing microspherical Fe doped Ni on a conductive foam nickel substrate by utilizing a solvothermal method 3 S 2 A nanostructure. Although the electrode has better OER electrocatalytic performance, the current density of the catalyst can not reach 500 mA cm -2 As described above, in the current density-time test of Oxygen Evolution Reaction (OER), the current density was also only 80 mA cm -2 And a drop in current density occurs only with test 14 h. Therefore, the catalyst still cannot meet the industrial requirements.
Chinese patent CN 112962115a discloses a method for preparing a foam nickel-supported sulfide electrocatalyst, which comprises growing metal simple substance, metal oxide or metal hydroxide nano particles on the surface of foam nickel in situ by using a hydrothermal method, and then immersing the foam nickel after surface reaction in a sulfur-containing solution for room temperature vulcanization to obtain the foam nickel-supported sulfide electrocatalyst. The catalyst has the double-function catalytic effects of both the oxidization of the sulfide ions and the electrolysis of the water, but is also only focused on the research in a small current density range.
In addition, hydrothermal processes can result in a large amount of precursor solution being wasted, which is detrimental to mass production. Therefore, it is important to explore a method which is efficient, economical and easy to produce, and to prepare a catalyst with industrial high-current catalytic performance, and at the same time, to avoid the deactivation of the catalyst in long-term high-current density treatment, and the method is particularly important in the current research.
Disclosure of Invention
The invention aims to provide a method for improving the electrocatalytic stability of nickel-based sulfide in OER.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for improving electrocatalytic stability of nickel-based sulfide catalyst in oxygen evolution reaction is to introduce low electronegativity metal element into nickel-based sulfide catalyst, and utilize electronegativity of low electronegativity metal element to be smaller than Ni element characteristic, make electron migrate from low electronegativity metal element to Ni, thus inhibit Ni from changing to high valence state in OER process, form better stable beta-NiOOH (Ni is less than or equal to +3), in order to improve the electrocatalytic stability of nickel-based sulfide in oxygen evolution reaction effectively; the operation comprises the following steps:
(1) Firstly, pre-treating a self-supporting conductive substrate to remove surface stains and increase oxygen-containing functional groups on the surface;
(2) Mixing a metal nickel source, a low electronegativity metal element precursor and a high molecular surfactant in a polar solvent, then carrying out dipping or coating on the pretreated self-supporting conductive substrate by using the mixed solution, and drying to obtain a precursor material;
(3) And (3) placing the dried precursor material in a tube furnace, performing heat treatment in a saturated inert atmosphere, placing a quartz boat containing sulfur powder at the upstream of the tube furnace, placing the quartz boat containing the precursor material after heat treatment at the downstream of the tube furnace, introducing saturated inert gas from the upstream, and heating the tube furnace in the inert gas atmosphere, so that the precursor material is vulcanized by chemical vapor deposition to prepare the nickel-based sulfide catalyst containing the low-electronegativity metal elements.
Further, in the step (1), the self-supporting conductive substrate is any one of carbon cloth and carbon paper. Preferably, the supporting conductive substrate is carbon cloth with a size of 1-12 cm 2 。
Further, the pretreatment in the step (1) is to clean and remove stains on the surface of the self-supporting conductive substrate by using an organic solvent, and then perform acid treatment to enable the surface of the self-supporting conductive substrate to generate more oxygen-containing functional groups; the acid treatment is to heat the mixture to 95 ℃ in a nitric acid solution with the concentration of 65-68 vol% and reflux the mixture for 6-18 h.
Further, the metallic nickel source in step (2) is a nitrate, hydrochloride, acetate and/or carbonate of nickel. Preferably, the metallic nickel source is Ni (NO 3 ) 2 ·6H 2 O。
Further, the precursor of the low electronegativity metallic element in the step (2) is nitrate, hydrochloride, acetate and/or carbonate of at least one of iron, cobalt, manganese, titanium, molybdenum, zirconium and ruthenium. Preferably, the low electronegativity metallic element precursor is Fe (NO 3 ) 3 •9H 2 O。
Further, the polymer surfactant in the step (2) is any one of polyethyleneimine, polydimethyl amine epichlorohydrin or polyvinylpyrrolidone. Preferably, the molecular surfactant is polyvinylpyrrolidone.
Further, in the step (2), the polar solvent is any one of water, methanol, ethanol or dimethylformamide. Preferably, the solvent is dimethylformamide.
Further, the total concentration of metal salts in the mixed solution in the step (2) is 0.5-2 mol/L, wherein the molar ratio of the low electronegativity metal element to nickel is 1:1-1:3, and is preferably 1:2; the molar ratio of the macromolecular surfactant to the metal salt in the mixed solution is 1:1000-1:2000, preferably 1:1500.
Further, the temperature of the heat treatment in the step (3) is 500-700 ℃ and the time is 1-3 h. Preferably, the temperature of the heat treatment is 650 ℃ and the time is 2 h.
Further, the mass ratio of the precursor material to the sulfur powder used in the step (3) is 1:10-30, preferably 1:20; the heating temperature is 300-400 ℃ for 1-3 hours, preferably 350 ℃ for 2 hours; the air flow of the saturated inert gas is 10-30 mL/min, preferably 20 mL/min.
The invention has the beneficial effects that:
(1) According to the invention, the low electronegativity metal element is introduced into the nickel-based sulfide catalyst to form a heterostructure, so that Ni electrons are in an electron-rich state, the reconstruction of Ni into gamma-NiOOH with higher valence state in the OER process is effectively inhibited, the structural distortion is reduced, and the stability of the catalyst in the OER process with high current density is enhanced.
(2) According to the invention, the low electronegativity metal element is introduced into the nickel-based sulfide catalyst to form a heterostructure, so that the electronic conductivity is effectively improved, and the synergistic effect among different components also improves the performance of the nickel-based sulfide in OER. The OER performance of the catalyst is 200 mAcm under the condition of 1M KOH electrolyte -2 The overpotential was 237 mV only at 500 mA cm -2 When the overpotential is only 306 mV, the potential of the electrolytic water meeting the industrial current density is provided.
Drawings
Figure 1 is an XRD pattern of the products prepared in example 1 and comparative example.
Fig. 2 is a high resolution XPS plot of Ni in the products prepared in example 1 and comparative example.
FIG. 3 is an OER polarization graph for the products prepared in example 1 and comparative example.
FIG. 4 is a graph showing stability test of the products prepared in example 1 and comparative example.
Fig. 5 is an SEM image of the products prepared in example 1 and comparative example before and after OER testing.
Fig. 6 is a Raman plot of the products prepared in example 1 and comparative example before and after OER testing.
Fig. 7 is an XRD pattern of the products prepared in example 2 and comparative example.
Fig. 8 is an OER polarization graph of the products prepared in example 2 and comparative example.
FIG. 9 is a graph showing stability test of the products prepared in example 2 and comparative example.
Fig. 10 is an XRD pattern of the products prepared in example 3 and comparative example.
FIG. 11 is an OER polarization graph for the products prepared in example 3 and comparative example.
FIG. 12 is a graph showing stability test of the products prepared in example 3 and comparative example.
Detailed Description
A method for improving electrocatalytic stability of nickel-based sulfide catalyst in oxygen evolution reaction comprises the following operation steps:
(1) Firstly, cleaning a self-supporting conductive substrate by using an organic solvent to remove stains on the surface of the self-supporting conductive substrate, then heating the self-supporting conductive substrate to 95 ℃ in a nitric acid solution with the concentration of 65-68 vol%, and refluxing for 6-18 hours to enable the surface of the self-supporting conductive substrate to generate more oxygen-containing functional groups;
(2) Mixing a metal nickel source, a low electronegativity metal element precursor and a high molecular surfactant in a polar solvent, wherein the total concentration of metal salt in the obtained mixed solution is 0.5-2 mol/L, the molar ratio of the low electronegativity metal element to nickel is 1:1-1:3, and the molar ratio of the high molecular surfactant to the metal salt is 1:1000-1:2000; then, the mixed solution is used for dipping or coating the pretreated self-supporting conductive substrate, and then, the precursor material is obtained through drying;
(3) And (3) placing the dried precursor material in a tube furnace, performing heat treatment for 1-3 hours at 500-700 ℃ in a saturated inert atmosphere, weighing the precursor material and sulfur powder after heat treatment according to a mass ratio of 1:10-30, placing a quartz boat containing the sulfur powder at the upstream of the tube furnace, placing the quartz boat containing the precursor material at the downstream of the tube furnace, introducing saturated inert gas at a gas flow rate of 10-30 mL/min from the upstream, heating the tube furnace to 300-400 ℃ in the inert gas atmosphere, and preserving heat for 1-3 hours to obtain the nickel-based sulfide catalyst containing the low-electronegativity metal element.
Wherein, the self-supporting conductive substrate is any one of carbon cloth and carbon paper.
The metallic nickel source is nitrate, hydrochloride, acetate and/or carbonate of nickel.
The low electronegativity metal element precursor is nitrate, hydrochloride, acetate and/or carbonate of at least one of iron, cobalt, manganese, titanium, molybdenum, zirconium and ruthenium.
The high molecular surfactant is any one of polyethyleneimine, polydimethyl amine epichlorohydrin or polyvinylpyrrolidone.
The polar solvent is any one of water, methanol, ethanol or dimethylformamide.
In order to make the contents of the present invention more easily understood, the technical scheme of the present invention will be further described with reference to the specific embodiments, but the present invention is not limited thereto.
The carbon cloth used in the following examples and comparative examples was WOS1009, 0.33mm thick and 2X 3 cm in specification 2 Purchased from taiwan carbon energy technology company (CeTech). Electrochemical testing used the CHI 660E electrochemical workstation.
Example 1
The preparation of the nickel-based sulfide electrocatalyst of this example comprises the steps of:
1) Respectively soaking the carbon cloth by using acetone, ethanol and deionized water, and performing ultrasonic treatment for 30 minutes to remove surface impurities; then placing the carbon cloth into 65-68 vol% nitric acid solution, heating to 95 ℃, refluxing for 12 hours to increase polar groups on the surface of the carbon cloth and enhance the hydrophilicity of the carbon cloth, and then repeatedly cleaning with deionized water and drying;
2) Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 3 •9H 2 O and polyvinylpyrrolidone (PVP) in dimethylformamideDMF), wherein the molar ratio of Ni to Fe is 2:1, the total concentration of metal salts is 1.5. 1.5M, and the molar ratio of metal ions to PVP is about 1500:1;
3) Immersing the carbon cloth pretreated in the step 1) into the precursor solution obtained in the step 2), and standing for 6 h after ultrasonic treatment for 30 min; then taking out the carbon cloth, removing superfluous solution on the surface by using experimental absorbent paper, and then putting the carbon cloth into a vacuum oven at 60 ℃ for drying 8 h;
4) Arranging the dried carbon in the step 3) at the middle position of a tube furnace, introducing high-purity nitrogen for half an hour until the nitrogen in the tube is saturated, then heating to 650 ℃ at a rate of 5 ℃ per minute, preserving heat for 2 hours, after the reaction is finished (the mass of carbon cloth is increased by 10 mg), moving a quartz boat filled with carbon cloth to the lower air port of the tube furnace, placing the quartz boat filled with sublimed sulfur powder at the upper air port of the tube furnace (the mass ratio of the carbon cloth to the sublimed sulfur powder is 1:20), introducing high-purity nitrogen from the upper air port for half an hour at an air flow rate of 20 mL/min until the nitrogen in the tube is saturated, then heating to 350 ℃ at a rate of 5 ℃/min, preserving heat for 2 hours to obtain FeS 2 @NiS 2 /CC。
Comparative example
In step 2), fe (NO) is not added 3 ) 3 •9H 2 O, other operations are the same as in example 1 to give NiS 2 /CC。
Figure 1 is an XRD pattern of the products prepared in example 1 and comparative example. As can be seen from the figure, feS is compared with the standard map 2 @NiS 2 Diffraction peak of/CC and FeS 2 (PDF # 79-0617) and NiS 2 Standard card anastomosis of (PDF # 65-3325), proving FeS 2 @NiS 2 Successful formation of heterostructures. Whereas NiS 2 /CC NiS only 2 Is a diffraction peak of (2).
Fig. 2 is a high resolution XPS plot of Ni in the products prepared in example 1 and comparative example. As can be seen from the figure, feS 2 @NiS 2 Characteristic peak of/CC relative to NiS 2 The overall/CC shift toward low binding energy, proving that Ni gets electrons and valence state decreases.
FIG. 3 shows the basicity O of the products prepared in example 1 and comparative exampleER polarization curve. As can be seen from the figure, feS 2 @NiS 2 CC shows more excellent oxygen evolution performance, indicating that successful construction of the heterojunction can improve the performance of the catalyst.
FIG. 4 is a graph showing stability test of the products prepared in example 1 and comparative example. As can be seen, feS 2 @NiS 2 CC at 100 mA/cm 2 The current density can stably run 10 h in a chronopotentiometric test; whereas NiS 2 The CC shows a large performance decay after 10 h.
FeS 2 @NiS 2 CC shows a ratio of NiS in both redox stability and long-term steady-state testing 2 The higher stability of/CC indicates that the low electronegativity Fe element and NiS are introduced 2 Constructed FeS 2 @NiS 2 The heterostructure can effectively improve OER electrocatalytic stability.
FIG. 5 is an SEM image of the product of example 1 and comparative example before and after OER test, wherein a and b are NiS 2 SEM image of CC before OER, c, d are NiS 2 SEM image of CC after OER, e, f are FeS 2 @NiS 2 SEM image of CC before OER, g, h are FeS 2 @NiS 2 SEM image of CC after OER. As can be seen from the figure, niS after the reaction 2 The surface morphology of/CC is more varied and the original morphology is completely lost; and FeS 2 @NiS 2 CC shows less morphology change and still maintains a richer porosity.
Fig. 6 is a Raman plot of the products prepared in example 1 and comparative example before and after OER testing. As can be seen from the figure, feS after OER test 2 @NiS 2 The phase after reconstruction is beta-NiOOH@FeOOH heterostructure, and NiS 2 The reconstructed phase was then gamma-NiOOH, which further confirmed FeS 2 @NiS 2 Ratio of/CC NiS 2 the/CC has stronger stability, and the heterostructure can effectively enhance OER performance.
Example 2
Fe (NO) used in step 2) 3 ) 3 •9H 2 O is replaced by Co (NO) 3 ) 2 •6H 2 O, which isIt was operated as in example 1 to give CoS 2 @NiS 2 /CC。
Fig. 7 is an XRD pattern of the products prepared in example 2 and comparative example. As can be seen, coS is compared with the standard spectrum 2 @NiS 2 Diffraction peak of/CC and CoS 2 (PDF#41-1471) and NiS 2 Standard card anastomosis of (PDF # 65-3325), proving CoS 2 @NiS 2 Successful formation of heterostructures.
Fig. 8 is an OER polarization graph of example 2 and comparative example. As shown, coS constructed with Co was introduced 2 @NiS 2 the/CC catalyst shows more excellent oxygen evolution performance.
FIG. 9 is a graph showing stability test of the products prepared in example 2 and comparative example. As can be seen from the figure, compared to NiS 2 And the stability of the catalyst is effectively improved after Co is introduced.
Example 3
Fe (NO) used in step 2) 3 ) 3 •9H 2 O is replaced by Mn (NO) 3 ) 2 •4H 2 O, other operations are the same as in example 1 to give Mn-NiS 2 /CC。
Fig. 10 is an XRD pattern of the products prepared in example 3 and comparative example. As can be seen from the figure, mn-NiS is caused by the fact that Mn has a larger atomic radius than Ni 2 XRD characteristic peaks of/CC are shifted to low angles.
Fig. 11 is an OER polarization graph of example 3 and comparative example. As shown in the figure, mn-NiS prepared after Mn is introduced 2 CC compared to NiS 2 The OER performance of/CC is improved.
FIG. 12 is a graph showing stability test of the products prepared in example 3 and comparative example. As shown in the figure, mn-NiS 2 Performance decay of/CC compared to NiS 2 CC is slower.
The foregoing description is only of the preferred embodiments of the invention, and all changes and modifications that come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (10)
1. A method for improving the electrocatalytic stability of a nickel-based sulfide catalyst in an oxygen evolution reaction is characterized in that a low electronegativity metal element is introduced into the nickel-based sulfide catalyst to effectively improve the electrocatalytic stability of the nickel-based sulfide in the oxygen evolution reaction.
2. The method for improving the electrocatalytic stability of a nickel based sulfide catalyst in an oxygen evolution reaction according to claim 1, wherein the operation thereof comprises the steps of:
(1) Firstly, preprocessing a self-supporting conductive substrate;
(2) Mixing a metal nickel source, a low electronegativity metal element precursor and a high molecular surfactant in a polar solvent, then carrying out dipping or coating on the pretreated self-supporting conductive substrate by using the mixed solution, and drying to obtain a precursor material;
(3) And (3) carrying out heat treatment on the dried precursor material in a saturated inert atmosphere, and then carrying out chemical vapor deposition on the precursor material by utilizing sulfur powder to prepare the nickel-based sulfide catalyst containing the low electronegative metal element.
3. The method for improving the electrocatalytic stability of a nickel-based sulfide catalyst in an oxygen evolution reaction according to claim 2, wherein the self-supporting conductive substrate in the step (1) is any one of carbon cloth and carbon paper.
4. The method for improving the electrocatalytic stability of a nickel-based sulfide catalyst in an oxygen evolution reaction according to claim 2, wherein the pretreatment in step (1) is to clean and remove stains on the surface of the self-supporting conductive substrate by using an organic solvent, and then to perform acid treatment to generate more oxygen-containing functional groups on the surface; the acid treatment is to heat the mixture to 95 ℃ in a nitric acid solution with the concentration of 65-68 vol% and reflux the mixture for 6-18 h.
5. The method for improving the electrocatalytic stability of a nickel base sulfide catalyst in an oxygen evolution reaction according to claim 2, wherein the metallic nickel source in step (2) is a nitrate, hydrochloride, acetate and/or carbonate of nickel;
the low electronegativity metal element precursor is nitrate, hydrochloride, acetate and/or carbonate of at least one of iron, cobalt, manganese, titanium, molybdenum, zirconium and ruthenium;
the high molecular surfactant is any one of polyethyleneimine, polydimethyl amine epichlorohydrin or polyvinylpyrrolidone; the polar solvent is any one of water, methanol, ethanol or dimethylformamide.
6. The method for improving the electrocatalytic stability of a nickel-based sulfide catalyst in an oxygen evolution reaction according to claim 2, wherein the total concentration of metal salts in the mixed solution in the step (2) is 0.5-2 mol/L, and the molar ratio of low electronegativity metal elements to nickel is 1:1-1:3; the molar ratio of the high molecular surfactant to the metal salt in the mixed solution is 1:1000-1:2000.
7. The method for improving the electrocatalytic stability of a nickel-based sulfide catalyst in an oxygen evolution reaction according to claim 2, wherein the temperature of the heat treatment in the step (3) is 500-700 ℃ and the time is 1-3 h.
8. The method for improving the electrocatalytic stability of a nickel-based sulfide catalyst as claimed in claim 2, wherein in the chemical vapor deposition in the step (3), the precursor material after heat treatment and sulfur powder are respectively placed at the downstream and upstream of a tube furnace, and then saturated inert gas is introduced from the upstream and the tube furnace is heated to realize the vulcanization of the precursor material at the downstream.
9. The method for improving the electrocatalytic stability of a nickel-based sulfide catalyst in an oxygen evolution reaction according to claim 8, wherein the mass ratio of the used precursor material to sulfur powder is 1:10-30; the heating temperature is 300-400 ℃ and the heating time is 1-3 hours; the air flow of the saturated inert gas is 10-30 mL/min.
10. A nickel-based sulfide catalyst containing a low electronegative metal element having high electrocatalytic stability, obtainable by the process of any one of claims 1 to 9.
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