CN117286527A - Preparation method of transition metal sulfide nanosheet catalytic electrode and application of transition metal sulfide nanosheet catalytic electrode in nitrate electrocatalysis - Google Patents
Preparation method of transition metal sulfide nanosheet catalytic electrode and application of transition metal sulfide nanosheet catalytic electrode in nitrate electrocatalysis Download PDFInfo
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- CN117286527A CN117286527A CN202311325622.7A CN202311325622A CN117286527A CN 117286527 A CN117286527 A CN 117286527A CN 202311325622 A CN202311325622 A CN 202311325622A CN 117286527 A CN117286527 A CN 117286527A
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- metal sulfide
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- 229910002651 NO3 Inorganic materials 0.000 title claims abstract description 63
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 46
- -1 transition metal sulfide Chemical class 0.000 title claims abstract description 46
- 239000002135 nanosheet Substances 0.000 title claims abstract description 36
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000000151 deposition Methods 0.000 claims abstract description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 9
- 239000011593 sulfur Substances 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 46
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 239000004744 fabric Substances 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 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
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical class 0.000 claims description 2
- 239000002351 wastewater Substances 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims 1
- 230000001737 promoting effect Effects 0.000 claims 1
- 230000009467 reduction Effects 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 7
- 230000033228 biological regulation Effects 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 9
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 description 8
- 235000011152 sodium sulphate Nutrition 0.000 description 8
- 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 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 239000003115 supporting electrolyte Substances 0.000 description 4
- 229910000314 transition metal oxide Inorganic materials 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002064 nanoplatelet Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 230000001603 reducing effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000009360 aquaculture Methods 0.000 description 1
- 244000144974 aquaculture Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000004172 nitrogen cycle Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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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
- C25B1/27—Ammonia
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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
- C25B11/02—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
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- 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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- 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
- C25B11/065—Carbon
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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Abstract
In order to solve the problems of complex preparation process, limited load regulation and control and the like of the existing nitrate electrocatalytic reduction material, the invention provides a preparation method of a transition metal sulfide nanosheet catalytic electrode, which comprises the following operation steps: dissolving transition metal salt and sulfur source to form solution; immersing the self-supporting electrode carrier subjected to pre-acidification in the solution; and depositing the transition metal sulfide nano-sheet MxS on the self-supporting electrode carrier in a constant current mode by taking the self-supporting electrode carrier as a cathode to obtain the transition metal sulfide nano-sheet catalytic electrode. Meanwhile, the invention also discloses application of the transition metal sulfide nanosheet catalytic electrode in nitrate electrocatalysis. The transition metal sulfide nanosheet catalytic electrode provided by the invention is a novel nitrate electrocatalytic reduction material, has the advantages of short preparation flow, high cycle stability, high nitrogen selectivity, high catalytic activity and the like, and is easy to realize large-scale production and application.
Description
Technical Field
The invention relates to a preparation method of a transition metal sulfide nanosheet catalytic electrode and application of the transition metal sulfide nanosheet catalytic electrode in nitrate electrocatalysis.
Background
With the rapid development of industry, agriculture and aquaculture, nitrate has become one of the most common pollutants in surface water and groundwater, severely disrupting the nitrogen cycle process in nature. Nitrate is used as a non-ligand formed oxyanion, has very high fluidity and is easy to dissolve in water, and is one of important indexes for causing water eutrophication and affecting the drinking water quality. According to the related regulations in the water quality conventional index and the limit value of the national sanitary Standard for Drinking Water GB5749-2006, the nitrate (counted as N) is regulated to be 10mg/L, and the groundwater source is regulated to be 20mg/L. Therefore, how to effectively solve the problem of nitrate pollution has become a hot spot of global interest.
Among the methods for removing nitrate, electrochemical denitrification represented by the electrocatalytic reduction method has the advantages of high efficiency, simple operation, environmental protection and the like, and is considered as one of effective ways for solving nitrate pollution in the future. The electrocatalytic reduction method mainly loads materials with specific catalytic activity on the cathode through externally applied current, achieves the purpose of degrading and converting nitrate, and basically has no harmful residues after treatment. Factors influencing the technical performance of electrocatalytic nitrate reduction mainly include cathode materials, external potential, electrolyte solution, pH value and the like, wherein the cathode materials are one of the most critical factors, and directly influence the reaction efficiency of nitrate.
The conventional metal electrode materials such as Pb, pt, au, ru, cu show good hydrogen adsorption capacity and excellent activity of indirectly reducing nitrate, but have high and poor chemical stability, and particularly in a high chloride ion system (seawater culture tail water), so that the application of the conventional metal electrode materials is greatly limited. Transition metal oxides, e.g. Co 3 O 4 Is widely used for electrochemical hydrogen production, and the catalytic activity and electrochemical durability of the catalyst make the catalyst an ideal cathode electrode material. However, the transition metal oxide itself is less electrically conductive and has fewer catalytically active sites, which hampers the nitrate-reducing properties of the transition metal oxide. The electronic structure and adsorption capacity of the metal oxide can be regulated and controlled through doping of hetero atoms, and the electrocatalytic reduction activity of nitrate can be effectively improved. Gao et al prepared a three-dimensional P-doped Co by hydrothermal coupling high-temperature phosphating method 3 O 4 And an electrode for electrocatalytic reduction of nitrate. The results show that the introduction of P increases Co 3+ Percentage of P doped Co 3 O 4 Higher electrochemically active area and lowerThe interfacial resistance of the material improves the nitrate reducing activity of the material. In addition, compared with the transition metal oxide, the transition metal sulfide has the advantages of better electronic conductivity, high hydrogen evolution activity and the like, and has a larger application prospect in the field of electrocatalytic reduction of nitrate, and the application of the transition metal sulfide as an electrocatalytic reduction nitrate electrode material has not been reported yet. The main synthesis methods of the transition metal sulfide include a hydrothermal method, a pyrolysis method and the like. The hydrothermal and pyrolysis preparation process of the transition metal sulfide is complex in flow, relatively harsh in control conditions, and difficult to control the load.
Disclosure of Invention
Aiming at the problems of complex preparation process, limited load regulation and control and the like of the existing nitrate electrocatalytic reduction material, the invention provides a preparation method of a transition metal sulfide nanosheet catalytic electrode and application of the transition metal sulfide nanosheet catalytic electrode in nitrate electrocatalytic.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the invention provides a preparation method of a transition metal sulfide nanosheet catalytic electrode, which comprises the following operation steps:
dissolving transition metal salt and sulfur source to form solution;
immersing the self-supporting electrode carrier subjected to pre-acidification in the solution;
and depositing a transition metal sulfide nano sheet MxS on the self-supporting electrode carrier in a constant current mode by taking the self-supporting electrode carrier as a cathode, wherein M is a transition metal, taking out after the deposition is finished, washing and drying to obtain the transition metal sulfide nano sheet catalytic electrode.
Further, the transition metal salt is selected from one or more of sulfate, chloride and acetate of nickel, cobalt, iron and copper.
Further, the sulfur source is selected from one or more of thiourea, sodium thiosulfate and thioacetamide, and the concentration of the sulfur source in the solution is 0.6-1.2 mol/L.
Further, the ratio of the amount of the transition metal salt to the amount of the sulfur source substance is 1:10 to 1:50.
Further, the self-supporting electrode carrier is selected from one or more of foam nickel, foam copper, carbon cloth, carbon paper and foam carbon, and the acid adopted in the pre-acidification treatment of the self-supporting electrode carrier is one or more of hydrochloric acid, acetic acid, phosphoric acid and citric acid.
Further, the cathode deposition current is 0.6 mA-0.9 mA, the deposition time is 20-60 min, and the deposition temperature is 10-60 ℃.
The invention also provides application of the transition metal sulfide nanosheet catalytic electrode prepared by the preparation method in nitrate electrocatalysis, the catalytic electrode of the transition metal sulfide nanosheet is used as a cathode, the DSA electrode is used as an anode, and nitrate wastewater is treated under a two-electrode system.
Further, the working conditions of the two-electrode system are as follows: the working current is 2-4 mA/cm 2 The initial nitrate concentration is 10-500 mg/L and the chloride ion concentration is 0-30 g/L.
The transition metal sulfide nanosheet catalytic electrode provided by the invention is based on a constant current deposition method to develop a novel transition metal sulfide electrode material with high-efficiency nitrate catalytic activity and chloride ion corrosion resistance, and compared with a common hydrothermal method, the constant current deposition method can accurately regulate and control the growth rate of transition metal sulfide to obtain an evenly-distributed electrocatalytic material, and the preparation process of the transition metal sulfide nanosheet catalytic electrode is simple, low in energy consumption, relatively friendly to environment and easy to realize large-scale production and application; the catalyst is used as a catalyst for electrocatalytic reduction of nitrate, and has high nitrate removal rate and N 2 The selectivity is high, the reaction byproducts are low, the stability is good, and a certain theoretical reference can be provided for the design of the novel electrochemical nitrate reduction catalyst.
Drawings
FIG. 1 is a NiCo provided in example 1 of the present invention 2 S 4 SEM image of nanoplatelets;
FIG. 2 is a NiCo provided in example 1 of the present invention 2 S 4 (a) XRD and (b) Raman patterns of the nanoplatelets;
FIG. 3 is NiCo prepared in example 1 2 S 4 A comparison graph of nitrate removal performance of the NF electrode (a) and the NF electrode (b);
FIG. 4 is a graph of the effect of Cl-concentration on NiCo of example 1 2 S 4 The nitrate graph is removed by the NF electrode;
FIG. 5 is NiCo prepared in example 1 2 S 4 Repeated use performance graph of NF electrode.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects solved by the invention more clear, the invention is further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment provides a preparation method and application of a nickel-cobalt-based sulfide nitrate electrocatalyst, comprising the following steps:
cutting a selected foam nickel screen (NF) into 2cm, ultrasonically washing the nickel screen for 20min by using acetone, absolute ethyl alcohol, 0.5mol/L hydrochloric acid and deionized water, and then drying in a vacuum drying oven at 50 ℃ to obtain a pretreated nickel screen serving as a sulfide deposition substrate. The pretreated nickel screen is used as a working electrode, the Pt sheet electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, 100mL of mixed solution of nickel nitrate, cobalt nitrate and thiourea is put into the mixed solution, wherein the concentration of the nickel nitrate is 20mmol/L, the concentration of the cobalt nitrate is 25mol/L, the concentration of the thiourea is 0.8mol/L, the mixture is deposited for 30min at room temperature under the current of 0.7mA, and then NiCo grows 2 S 4 Nickel net of nano sheet (NiCo) 2 S 4 (NF) were washed with deionized water and absolute ethyl alcohol in this order, and then dried in a vacuum oven at 50℃for further use, and NiCo prepared in example 1 was obtained 2 S 4 As shown in FIG. 1, SEM image of the obtained NiCo film was observed by electron microscope 2 S 4 In the form of nano-sheet, has larger specific surface area, is beneficial to improving the catalytic effect, and is shown in the figure 2 as NiCo 2 S 4 (a) XRD and (b) Raman patterns. For NiCo 2 S 4 The electrochemical catalytic performance of the NF was tested, and the results were shown in FIGS. 3 to 5. As can be seen from the test results of figure 3,compared to the nickel screen (NF) alone, the NiCo provided in example 1 2 S 4 The NF can effectively improve the removal rate of nitrate in the treated sample, and simultaneously, N is removed in the process of removal 2 The selectivity is high. As can be seen from the test results of FIG. 4, the NiCo provided in example 1 2 S 4 On the premise of having chloride ion interference (10 g/L), the NF still has a good electrocatalytic removal effect of nitrate. As can be seen from the test results of FIG. 5, the NiCo provided in example 1 2 S 4 the/NF has better circulation stability and can be continuously used for a plurality of times.
Comparative example 1
The comparative example provides a preparation method and application of a nickel-cobalt-based sulfide nitrate electrocatalyst, comprising the following steps:
weighing 5mmol of nickel nitrate, 10mmol of cobalt nitrate and 20mmol of urea, mixing and dissolving into 100mL of deionized water, stirring uniformly, transferring into a polytetrafluoroethylene reaction kettle, immersing a pretreated nickel screen part into a reaction liquid, reacting for 4 hours at 120 ℃, cooling and washing to obtain a nickel screen loaded with pink Ni-Co precursor, placing the nickel screen into 100mL of 0.05mol/L sodium sulfide aqueous solution, preserving heat for 8 hours at 170 ℃, cooling, washing and drying to obtain NiCo 2 S 4 NF-SR electrode samples.
Performance testing
NiCo prepared in example 1 and comparative example 1 were respectively prepared 2 S 4 NF electrode or NiCo 2 S 4 The NF-SR electrode is taken as a cathode, the DSA electrode is taken as an anode, and the anode is placed in 100mL of mixed solution of nitrate and sodium sulfate, wherein the concentration of the nitrate is 20mg/L (calculated by N), the concentration of the sodium sulfate is 0.05mol/L (taken as a supporting electrolyte), and the reaction is carried out for 180min under the working current of 4.0 mA; the test results are shown in table 1:
TABLE 1
As can be seen from the test results of Table 1, niCo of example 1 2 S 4 Nitrate removal rate of the/NF electrode is 85.3%, N 2 The selectivity is as high as 94.5%. NiCo 2 S 4 After the/NF electrode is reused for 5 times, the nitrate removal rate and N are higher 2 Selectivity (82.4% and 92.2%). Whereas in comparative example 1 NiCo prepared by hydrothermal coupling vulcanization 2 S 4 NF-SR electrode, corresponding NiCo 2 S 4 The catalyst amount is 6 times of that of electrodeposition, but the reaction is carried out for 180min under the working current of 4.0mA, the nitrate removal rate is only 78.9 percent, and the corresponding N is 2 The selectivity is only 86.1%; after 5 cycles, the nitrate removal rate is reduced to 68.7%, N 2 The selectivity was 78.3%, laterally illustrating the superiority of electrodeposition to prepare MxS.
Example 2
The embodiment provides a preparation method and application of a nickel-based sulfide nitrate electrocatalyst, comprising the following steps:
(1) Cutting the selected foam nickel screen into 2cm, ultrasonically washing the nickel screen for 20min by using acetone, absolute ethyl alcohol, 0.5mol/L acetic acid and deionized water, and then drying the nickel screen in a vacuum drying oven at 50 ℃ to obtain the pretreated nickel screen serving as a sulfide deposition substrate. The pretreated nickel screen is used as a working electrode, the Pt sheet electrode is used as a counter electrode, the Ag/AgCl electrode is used as a reference electrode, the nickel screen is placed into 100mL of nickel sulfate and sodium thiosulfate mixed solution, wherein the concentration of nickel chloride is 30mmol/L, the concentration of thiourea is 1.0mol/L, the nickel screen is deposited for 20min at the temperature of 30 ℃ under the current of 0.6mA, and then the nickel screen (NixS/NF) growing with the NixS nano-sheets is sequentially washed with deionized water and absolute ethyl alcohol for multiple times and then placed into a vacuum drying box at the temperature of 50 ℃ for drying for standby.
(2) The prepared NixS/NF electrode is taken as a cathode and a DSA electrode is taken as an anode, and is placed in 100mL of mixed solution of nitrate and sodium sulfate, wherein the concentration of the nitrate is 20mg/L (calculated by N), the concentration of the sodium sulfate is 0.05mol/L (taken as supporting electrolyte), the concentration of chloride ions is 15g/L, the reaction is carried out for 180min under the working current of 4.0mA, the nitrate removal rate is 82.1 percent, and the N is the same as the concentration of the nitrate 2 The selectivity is as high as 92.1%. After the NixS/NF electrode is reused for 5 times, the nitrate removal rate and the N are still higher 2 Selectivity (80.2% and 90.3%).
Example 3
The embodiment provides a preparation method and application of a cobalt-based sulfide nitrate electrocatalyst, comprising the following steps:
(1) Cutting the selected copper foam into 2cm, ultrasonically washing the copper foam for 20min by using acetone, absolute ethyl alcohol, 0.5mol/L hydrochloric acid and deionized water, and then drying in a vacuum drying oven at 50 ℃ to obtain a pretreated nickel screen serving as a sulfide deposition substrate. The pretreated foamy copper is used as a working electrode, a Pt sheet electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the pretreated foamy copper is placed into 100mL of mixed solution of cobalt acetate and thioacetamide, wherein the concentration of the cobalt acetate is 30mmol/L, the concentration of the thiourea is 0.7mol/L, the pretreated foamy copper is deposited for 30min at room temperature under the current of 0.8mA, and then the foamy copper (CoxS/CF) with the CoxS nano sheet is sequentially washed by deionized water and absolute ethyl alcohol for multiple times and then is placed into a vacuum drying oven at 50 ℃ for drying for standby.
(2) The prepared CoxS/CF electrode is taken as a cathode and a DSA electrode is taken as an anode, and is placed in 100mL of mixed solution of nitrate and sodium sulfate, wherein the concentration of the nitrate is 10mg/L (calculated by N), the concentration of the sodium sulfate is 0.05mol/L (taken as supporting electrolyte), the concentration of chloride ions is 30g/L, the reaction is carried out for 180min under the working current of 3.0mA, the nitrate removal rate is 87.1 percent, and the N is the same as the concentration of the nitrate 2 The selectivity is as high as 93.7%. After the CoxS/CF electrode is reused for 5 times, the electrode still has higher nitrate removal rate and N 2 Selectivity (83.2% and 91.5%).
Example 4
The embodiment provides a preparation method and application of a copper-based sulfide nitrate electrocatalyst, comprising the following steps:
(1) Cutting the selected carbon cloth to 2cm, ultrasonically washing the carbon cloth for 20min by using absolute ethyl alcohol, 0.5mol/L phosphoric acid and deionized water, and then drying in a vacuum drying oven at 50 ℃ to obtain the pretreated carbon cloth serving as a sulfide deposition substrate. The pretreated carbon cloth is used as a working electrode, a Pt sheet electrode is used as a counter electrode, an Ag/AgCl electrode is used as a reference electrode, the pretreated carbon cloth is placed into 100mL of mixed solution of copper acetate and thioacetamide, wherein the concentration of copper acetate is 20mmol/L, the concentration of thiourea is 0.8mol/L, the pretreated carbon cloth is deposited for 30min at the deposition current of 0.9mA and the environmental temperature of 50 ℃, and then the carbon cloth (CuxS/CC) growing with CuxS nano sheets is washed with deionized water and absolute ethyl alcohol for multiple times in sequence and then is placed into a vacuum drying box at 50 ℃ for drying for standby.
(2) The prepared CuxS/CC electrode is taken as a cathode and a DSA electrode is taken as an anode, and is placed in 100mL of mixed solution of nitrate and sodium sulfate, wherein the concentration of the nitrate is 50mg/L (calculated by N), the concentration of the sodium sulfate is 0.05mol/L (taken as a supporting electrolyte), the concentration of chloride ions is 20g/L, the reaction is carried out for 240min under the working current of 5.0mA, the nitrate removal rate is 85.1 percent, and the N is the same as the concentration of the nitrate 2 The selectivity is as high as 91.7%. After the CuxS/NF electrode is repeatedly used for 5 times, the CuxS/NF electrode still has higher nitrate removal rate and N 2 Selectivity (82.2% and 90.1%).
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (8)
1. The preparation method of the transition metal sulfide nanosheet catalytic electrode is characterized by comprising the following operation steps of:
dissolving transition metal salt and sulfur source to form solution;
immersing the self-supporting electrode carrier subjected to pre-acidification in the solution;
and depositing a transition metal sulfide nano sheet MxS on the self-supporting electrode carrier in a constant current mode by taking the self-supporting electrode carrier as a cathode, wherein M is a transition metal, taking out after the deposition is finished, washing and drying to obtain the transition metal sulfide nano sheet catalytic electrode.
2. The method for preparing a catalytic electrode of transition metal sulfide nanosheets according to claim 1, wherein the transition metal salt is selected from one or more of a sulfate, chloride, acetate of nickel, cobalt, iron, copper.
3. The method for preparing a catalytic electrode of a transition metal sulfide nanosheet according to claim 1, wherein the sulfur source is one or more selected from thiourea, sodium thiosulfate and thioacetamide, and the concentration of the sulfur source in the solution is 0.6-1.2 mol/L.
4. The method for preparing a catalytic electrode of transition metal sulfide nanosheets according to claim 3, wherein the ratio of the amounts of the transition metal salt and the sulfur source is 1:10 to 1:50.
5. The method for preparing the transition metal sulfide nanosheet catalytic electrode according to claim 1, wherein the self-supporting electrode carrier is one or more selected from the group consisting of nickel foam, copper foam, carbon cloth, carbon paper and carbon foam, and the acid used for the pre-acidification treatment of the self-supporting electrode carrier is one or more selected from the group consisting of hydrochloric acid, acetic acid, phosphoric acid and citric acid.
6. The method for preparing a catalytic electrode of transition metal sulfide nanosheets according to claim 1, wherein the cathodic deposition current is 0.6mA to 0.9mA, the deposition time is 20 to 60min, and the deposition temperature is 10 to 60 ℃.
7. The application of the transition metal sulfide nanosheet catalytic electrode prepared by the preparation method according to any one of claims 1-6 in nitrate electrocatalysis, wherein the catalytic electrode for promoting transition metal sulfide nanosheet is used as a cathode, a DSA electrode is used as an anode, and nitrate wastewater is treated under a two-electrode system.
8. The use of a transition metal sulfide nanosheet catalytic electrode according to claim 7, wherein the operating conditions of the two electrode system are: the working current is 2-4 mA/cm 2 The initial nitrate concentration is 10-500 mg/L and the chloride ion concentration is 0-30 g/L.
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