CN111437837A - Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof - Google Patents
Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 27
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 17
- 239000001301 oxygen Substances 0.000 title claims abstract description 17
- 238000001556 precipitation Methods 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title abstract description 12
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims abstract description 21
- 235000004279 alanine Nutrition 0.000 claims abstract description 21
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 18
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical group O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 230000000536 complexating effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 70
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 8
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 8
- 239000010949 copper Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 description 6
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000005457 ice water Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000002441 reversible effect Effects 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910016514 CuFeO2 Inorganic materials 0.000 description 1
- 238000012879 PET imaging Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013170 computed tomography imaging Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
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Abstract
The invention belongs to the field of electrocatalysis, and relates to an oxygen precipitation transition metal-based heterojunction catalyst and a preparation method thereof. According to the invention, copper sulfide is introduced, and alanine is used for complexing with Fe/Co/Ni transition metal precursors respectively to form different heterostructure catalytic materials, and the catalyst shows excellent oxygen precipitation reaction activity due to the unique electronic structures of the double transition metal oxide and CuS and the synergistic catalytic action of the two components.
Description
Technical Field
The invention belongs to the field of electrocatalysis, relates to an oxygen precipitation transition metal-based heterojunction catalyst and a preparation method thereof, and particularly relates to a copper sulfide/transition metal-based oxide heterojunction composite material for an anode OER and a preparation method thereof.
Background
Oxygen Evolution Reaction (OER) is used as a key half-reaction of energy conversion devices such as hydrogen production by electrolysis of water and metal-air batteries, so that at present, expensive noble metal-based catalysts are mainly used to reduce overpotentials thereof to improve the overall energy conversion efficiency, and the search for alternative catalysts with low cost and high activity is crucial to the commercialization of the energy conversion devices.
In recent years, transition metal-based heterojunction catalysts are widely researched due to unique electronic structures and synergistic catalytic action among two components, however, methods for synthesizing such catalysts by electrodeposition and the like generally require severe experimental conditions, catalytic activity also needs to be further improved, and development of a uniform method for synthesizing different transition metal-based heterojunction catalysts has important significance for reducing catalyst cost.
Aiming at the problems, the invention discloses a simple universal preparation method, copper sulfide is introduced, and is respectively complexed with Fe/Co/Ni transition metal precursors through alanine to form different heterostructure catalytic materials, and the catalyst shows excellent oxygen precipitation reaction activity through the unique electronic structure of double transition metal oxide and CuS and the synergistic catalytic action of the two components.
Disclosure of Invention
The invention aims to provide a universal preparation method of a transition metal-based heterojunction material with excellent OER catalytic performance. In order to solve the problems, the specific technical scheme is as follows:
a universal preparation method of a copper sulfide/transition metal oxide heterojunction OER catalyst comprises the following steps:
(1) the copper sulfide was prepared according to the method reported in the literature (M.Zhou, R.Zhang, M.Huang, W. L u, S.Song, M.P.Melanocon, M.Tian, D. L iang and C. L i.A chemical-free multifunctionality [, ], [ 2 ]64Cu]-CuSnanoparticle platform for simultaneous micro-PET/CT imaging and photothermalablation therapy.J.Am.Chem.Soc.,2010,132,15351-15358.)。
The adopted specific technical scheme is as follows:
weighing copper chloride dihydrate and trisodium citrate dihydrate, adding deionized water, and magnetically stirring at room temperature to dissolve the copper chloride dihydrate and the trisodium citrate dihydrate into a uniform light blue solution; weighing sodium sulfide nonahydrate, and adding deionized water to prepare Na2S·9H2O aqueous solution, followed by adding Na2S·9H2Quickly adding the O aqueous solution into the light blue solution, and magnetically stirring at room temperature for reaction until the mixed solution turns into dark brown; transferring the mixed solution into a constant-temperature water bath kettle, heating in water bath to raise the temperatureReacting at 90 ℃ to obtain dark green copper sulfide nanoparticle solution, cooling in ice water bath, and finally placing the solution in a refrigerator for later use overnight.
In the light blue solution, the ratio of copper chloride dihydrate, trisodium citrate dihydrate and deionized water is 0.2 mmol: 0.136 mmol: 180m L.
The Na is2S·9H2The volume ratio of the O aqueous solution to the light blue solution is 1:9, and Na2S·9H2The concentration of the O aqueous solution was 10 mmol/L.
The reaction time was 5min with magnetic stirring at room temperature.
The water bath is heated to 90 ℃ for reaction for 15 min.
The refrigerator temperature was 4 ℃.
(2) Weighing alanine, dissolving the alanine into the nano copper sulfide solution, and magnetically stirring the solution at room temperature to obtain a solution 1;
(3) weighing a certain amount of transition metal precursor, adding the transition metal precursor into the solution 1 prepared in the step (2), and continuously performing magnetic stirring at room temperature to obtain a uniformly dissolved solution 2;
(4) and (4) transferring the solution 2 prepared in the step (3) into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120-180 ℃, and carrying out hydrothermal reaction for 10 hours.
(5) And (4) after the reaction is finished, centrifuging the solution obtained in the step (4), washing a product with water and ethanol, and drying in vacuum to obtain the copper sulfide/transition metal oxide heterojunction OER catalyst.
In the step (2), the molar ratio of alanine to nano copper sulfide of the nano copper sulfide solution is 25: 2, stirring for 10min at room temperature.
In the step (3), the transition metal precursor is ferrous sulfate heptahydrate, cobalt chloride hexahydrate or nickel chloride hexahydrate; the molar ratio of the ferrous sulfate heptahydrate to the alanine is 1:1, the molar ratio of the cobalt chloride hexahydrate to the alanine is 1:1, and the molar ratio of the nickel chloride hexahydrate to the alanine is 1: 1; the magnetic stirring was continued at room temperature for 10 min.
And (5) washing the product with water and ethanol for 3-5 times respectively, and performing vacuum drying at room temperature for 24 hours.
The invention provides a simple and universal method for preparing different transition metal (Fe, Co and Ni) base heterojunctions, a CuS/double transition metal oxide heterojunctions are directly synthesized by a one-step hydrothermal method, both components contain transition metal Cu, the electronic structure of the heterojunctions is effectively adjusted, a double-component plays a better synergistic catalytic action, and excellent OER catalytic activity of a catalyst is endowed. Tests show that the prepared different transition metal oxide/copper sulfide heterostructure materials have OER catalytic performance close to or even far beyond commercial RuO2The OER performance of the catalyst is expected to replace the application of a noble metal-based catalyst in electrocatalytic water decomposition.
The preparation method is one-step hydrothermal reaction, has universality and simple preparation process, can effectively reduce the synthesis cost of the catalyst, has wide sources of synthesis raw materials and no toxicity, and the prepared transition metal-based heterojunction catalyst has high-efficiency OER catalytic performance and has potential application value in the field of replacing the traditional noble metal-based catalyst in the future.
Drawings
Fig. 1 is an XRD pattern of the copper sulfide/Co-containing transition metal oxide heterojunction catalyst prepared in specific example 1.
FIG. 2 is a TEM image of the copper sulfide/Co-containing transition metal oxide heterojunction catalyst prepared in specific example 1.
FIG. 3 is a graph of Oxygen Evolution Reaction (OER) linear sweep (L SV) of copper sulfide/different transition metal based oxide heterojunction catalysts prepared in examples 1-3 in alkaline electrolyte.
Detailed Description
Reagents and instrumentation: the reagents used in the invention are all analytically pure, and the reagents are directly applied without any special treatment without special description.
Cupric chloride dihydrate (CuCl)2·2H2O), sodium sulfide nonahydrate (Na)2S·9H2O), trisodium citrate dihydrate (C)6H5Na3O7·2H2O), alanine, cobalt chloride hexahydrate (CoCl)2·6H2O), ferrous sulfate heptahydrate (FeSO)4·7H2O), hexahydrateNickel chloride (NiCl)2·6H2O), potassium hydroxide (KOH) used for electrochemical tests is analytically pure and purchased from national pharmaceutical group chemical reagents, Inc.; carbon powder, anhydrous ruthenium oxide (RuO)299.9% metals basis, Alfa Aesar), Nafion perfluorinated resin solution (5 wt%, Sigma Aldrich).
Analytical balance (Precisa, XJ220A), centrifuge (hunan xiang instrument, TG16-WS), air-blast drying cabinet (shanghai sperm macro, DFG-9076A), vacuum drying cabinet (shanghai sperm macro, DZF-6090), electrochemical workstation (shanghai chenhua, CHI760E), rotating disk ring electrode device (pone corporation, usa).
Electrochemical test, namely performing electrochemical oxygen evolution performance test by adopting a Chenghua electrochemical workstation and a three-electrode test system, wherein a glassy carbon electrode loaded with a catalyst is used as a working electrode, a reversible hydrogen reference electrode and a graphite rod electrode are respectively used as a reference electrode and a counter electrode, the catalyst and carbon powder are mixed according to the mass ratio of 1:1 and added into a prepared membrane solution (the volume ratio of water to ethanol to 5 wt% Nafion is 40: 10: 1), the mixture is ultrasonically dispersed into a catalyst solution of 3mg/m L, 10 mu L solution is dripped on the glassy carbon electrode with the diameter of 5mm each time, the mixture is naturally dried and dripped twice, and O is added on the glassy carbon electrode2Electrochemical OER performance was tested in saturated 1M KOH solution and gave L SV curves at a sweep rate of 5 mV/s.
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings of the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the described embodiments of the invention without any inventive step, are within the scope of protection of the invention.
The present invention will be described in detail with reference to specific examples.
Example 1 (preferably, copper sulfide/cobalt-based oxide heterojunction)
(1) Synthesis of aqueous solution of Nano copper sulfide by transferring 180m L deionized water to 250m L round-bottomed flask, weighing 34mg chlorine dihydrateAdding copper (0.2mmol) and 40mg trisodium citrate dihydrate (0.136mmol), magnetically stirring at room temperature to obtain light blue solution, weighing 0.1201g sodium sulfide nonahydrate, dissolving in deionized water, and placing in 50m L volumetric flask (the concentration of sodium sulfide nonahydrate is 10 mmol/L), and adding 20m L Na2S·9H2Dropwise adding an O aqueous solution into the solution, and continuously magnetically stirring at room temperature for 5min to obtain a reaction mixed solution which is dark brown; and (3) moving the mixed solution into a constant-temperature water bath kettle, heating to 90 ℃, continuing to heat for continuous reaction for 15min to finally obtain dark green copper sulfide nanoparticle solution, cooling in an ice water bath, storing the solution in a refrigerator at 4 ℃ and keeping the solution for later use overnight.
(2) The copper sulfide/Co-containing transition metal oxide heterojunction catalyst is synthesized by the steps of weighing 40m L nanometer CuS solution (containing 0.04mmol of nanometer copper sulfide) into a 100m L beaker, weighing 0.0445g of alanine (0.5mmol) and adding the alanine, magnetically stirring the solution at room temperature for 10mm, weighing 0.1189g of cobalt chloride hexahydrate (0.5mmol) and adding the cobalt chloride hexahydrate into the solution, magnetically stirring the solution at room temperature for 10min to obtain a uniformly dissolved solution, transferring the solution into a 100m L polytetrafluoroethylene lining, putting the solution into a stainless steel reaction kettle, heating the solution to 150 ℃, carrying out hydrothermal reaction for 10h, centrifuging the solution after the reaction is finished, washing the product with water and ethanol for 5 times respectively, and carrying out vacuum drying at room temperature for 24 h.
(3) Electrochemical OER performance test adopts standard three-electrode test, Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, graphite rod is taken as a counter electrode, Glassy Carbon (GC) disc electrode is taken as a working electrode, 3mg of catalyst and 3mg of carbon powder are respectively weighed and dispersed in 1m L solution (water: ethanol: 5 wt% Nafion volume ratio is 40: 10: 1) to prepare 3mg/m L solution, ultrasonic dispersion is carried out for 30min, 10 mu L is dropped on the GC electrode for 2 times, drying is carried out at room temperature, and O is added2Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
As shown in the XRD test results of FIG. 1, the copper sulfide/Co-containing transition metal oxide heterostructure catalyst prepared in example 1 was prepared from Cu7S4And Cu0.76Co2.24O4The composition and the appearance thereof are shown in FIG. 2. The catalystThe results of the OER performance test of the oxidizing agent are shown in FIG. 3, at a current density of 10mA/cm2The overpotential of (A) is 280mV, far exceeding that of commercial RuO2OER catalytic performance (10 mA/cm)2The overpotential at (b) is 321 mV).
Example 2 (preferably, copper sulfide/iron-based oxide heterojunction)
(1) Synthesis of aqueous solution of Nano copper sulfide by transferring 180m L deionized water to 250m L round bottom flask, separately weighing 34mg copper chloride dihydrate (0.2mmol) and 40mg trisodium citrate dihydrate (0.136mmol) and adding them, magnetically stirring them uniformly at room temperature to give light blue solution, weighing 0.1201g sodium sulfide nonahydrate, adding deionized water to dissolve and fix it in 50m L volumetric flask (concentration of sodium sulfide nonahydrate is 10 mmol/L), then adding 20m L Na2S·9H2Dropwise adding an O aqueous solution into the solution, and continuously magnetically stirring at room temperature for 5min to obtain a reaction mixed solution which is dark brown; and (3) moving the mixed solution into a constant-temperature water bath kettle, heating to 90 ℃, continuing to heat for continuous reaction for 15min to finally obtain dark green copper sulfide nanoparticle solution, cooling in an ice water bath, storing the solution in a refrigerator at 4 ℃ and keeping the solution for later use overnight.
(2) The copper sulfide/Fe-containing transition metal oxide heterojunction catalyst is synthesized by the steps of weighing 40m L nanometer CuS solution (containing 0.04mmol of nanometer copper sulfide) into a 100m L beaker, weighing 0.0445g of alanine (0.5mmol) and adding the alanine, magnetically stirring the solution at room temperature for 10mm, weighing 0.1390g of ferrous sulfate heptahydrate (0.5mmol) and adding the ferrous sulfate heptahydrate into the solution, magnetically stirring the solution at room temperature for 10min to obtain a uniformly dissolved solution, transferring the solution into a 100m L polytetrafluoroethylene lining, putting the solution into a stainless steel reaction kettle, heating the solution to 150 ℃, carrying out hydrothermal reaction for 10h, centrifuging the solution after the reaction is finished, washing the product with water and ethanol for 5 times respectively, and carrying out vacuum drying at room temperature for 24 h.
(3) Electrochemical OER performance test adopts standard three-electrode test, a Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, a graphite rod is used as a counter electrode, a Glassy Carbon (GC) disk electrode is used as a working electrode, 3mg of catalyst and 3mg of carbon powder are weighed and dispersed in 1m L solution (the volume ratio of water to ethanol to 5 wt% of Nafion is 40: 10: 1) to prepare 3mg/m L solution, ultrasonic dispersion is carried out for 30min, and 10 mu m of solution is takenL dropping on GC electrode for 2 times, drying at room temperature, and drying in O2Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
Example 2 preparation of copper sulfide/Fe-containing transition metal oxide heterostructure catalyst from Cu7S4And CuFeO2The results of OER performance test of the catalyst are shown in FIG. 3, at a current density of 10mA/cm2At an overpotential of 370mV, close to that of commercial RuO2OER catalytic performance (10 mA/cm)2The overpotential at (b) is 321 mV).
Example 3 (preferably, copper sulfide/Nickel-based oxide heterojunction)
(1) Synthesis of aqueous solution of Nano copper sulfide by transferring 180m L deionized water to 250m L round bottom flask, separately weighing 34mg copper chloride dihydrate (0.2mmol) and 40mg trisodium citrate dihydrate (0.136mmol) and adding them, magnetically stirring them uniformly at room temperature to give light blue solution, weighing 0.1201g sodium sulfide nonahydrate, adding deionized water to dissolve and fix it in 50m L volumetric flask (concentration of sodium sulfide nonahydrate is 10 mmol/L), then adding 20m L Na2S·9H2Dropwise adding an O aqueous solution into the solution, and continuously magnetically stirring at room temperature for 5min to obtain a reaction mixed solution which is dark brown; and (3) moving the mixed solution into a constant-temperature water bath kettle, heating to 90 ℃, continuing to heat for continuous reaction for 15min to finally obtain dark green copper sulfide nanoparticle solution, cooling in an ice water bath, storing the solution in a refrigerator at 4 ℃ and keeping the solution for later use overnight.
(2) The copper sulfide/Ni-containing transition metal oxide heterojunction catalyst is synthesized by weighing 40m L nanometer CuS solution (containing 0.04mmol of nanometer copper sulfide) into a 100m L beaker, weighing 0.0445g of alanine (0.5mmol) and adding the alanine, magnetically stirring the solution at room temperature for 10mm, weighing 0.1188g of nickel chloride hexahydrate (0.5mmol) and adding the nickel chloride hexahydrate into the solution, magnetically stirring the solution at room temperature for 10min to obtain a uniformly dissolved solution, transferring the solution into a 100m L polytetrafluoroethylene lining, putting the solution into a stainless steel reaction kettle, heating the solution to 150 ℃, carrying out hydrothermal reaction for 10h, centrifuging the solution after the reaction is finished, washing the product with water and ethanol for 5 times respectively, and carrying out vacuum drying at room temperature for 24 h.
(3) Electrochemical OER performance test adopts standard three-electrode test, Reversible Hydrogen Electrode (RHE) is selected as reference electrode, graphite rod is taken as counter electrode, Glassy Carbon (GC) disk electrode is taken as working electrode, 3mg of catalyst and 3mg of carbon powder are weighed and dispersed in 1m L solution (water: ethanol: 5 wt% Nafion volume ratio is 40: 10: 1) to prepare 3mg/m L solution, ultrasonic dispersion is carried out for 30min, 10 mu L is dropped on GC electrode for 2 times, drying at room temperature, O is added2Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
Example 3 preparation of copper sulfide/Fe-containing transition metal oxide heterostructure catalyst from Cu7S4And CuNiO2The results of OER performance test of the catalyst are shown in FIG. 3, at a current density of 20mA/cm2The overpotential of (1) is 353mV over the commercial RuO2OER catalytic performance (20 mA/cm)2The overpotential at (b) was 361 mV).
It should be understood that while the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein, and any combination of the various embodiments may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (5)
1. The oxygen precipitation transition metal-based heterojunction catalyst is characterized in that the oxygen precipitation transition metal-based heterojunction catalyst is a copper sulfide/cobalt-based oxide heterojunction, or a copper sulfide/iron-based oxide heterojunction or a copper sulfide/nickel-based oxide heterojunction; the oxygen precipitation transition metal-based heterojunction catalyst is used as a catalyst and loaded on a glassy carbon electrode to serve as a working electrode, and is used for efficiently catalyzing oxygen precipitation reaction.
2. The method for preparing the oxygen evolution transition metal based heterojunction catalyst as claimed in claim 1, comprising the following steps:
(1) weighing alanine, dissolving the alanine into the nano copper sulfide solution, and uniformly stirring the solution at room temperature by magnetic force to obtain a solution 1, wherein the molar ratio of the alanine to the nano copper sulfide of the nano copper sulfide solution is 25: 2;
(2) weighing a certain amount of transition metal precursor, adding the transition metal precursor into the solution 1 prepared in the step (1), and continuously performing magnetic stirring at room temperature to obtain a uniformly dissolved solution 2, wherein the transition metal precursor is ferrous sulfate heptahydrate, cobalt chloride hexahydrate or nickel chloride hexahydrate; the molar ratio of the ferrous sulfate heptahydrate to the alanine is 1:1, the molar ratio of the cobalt chloride hexahydrate to the alanine is 1:1, and the molar ratio of the nickel chloride hexahydrate to the alanine is 1: 1;
(3) transferring the solution 2 prepared in the step (2) into a polytetrafluoroethylene lining, putting the polytetrafluoroethylene lining into a stainless steel reaction kettle, heating to 120-180 ℃, and carrying out hydrothermal reaction for 10 hours;
(4) and (4) after the reaction is finished, centrifuging the solution obtained in the step (3), washing a product with water and ethanol, and drying in vacuum to obtain the copper sulfide/transition metal oxide heterojunction OER catalyst.
3. The method for preparing an oxygen evolution transition metal based heterojunction catalyst as claimed in claim 2, wherein in the step (1), the stirring time at room temperature is 10 min.
4. The method for preparing an oxygen evolution transition metal based heterojunction catalyst as claimed in claim 2, wherein in the step (2), the magnetic stirring is continued at room temperature for 10 min.
5. The method for preparing the oxygen evolution transition metal based heterojunction catalyst as claimed in claim 2, wherein in the step (4), the product is washed with water and ethanol for 3-5 times respectively, and vacuum-dried for 24 hours at room temperature.
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