CN111437837B - 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
- Publication number
- CN111437837B CN111437837B CN202010162136.8A CN202010162136A CN111437837B CN 111437837 B CN111437837 B CN 111437837B CN 202010162136 A CN202010162136 A CN 202010162136A CN 111437837 B CN111437837 B CN 111437837B
- Authority
- CN
- China
- Prior art keywords
- transition metal
- solution
- copper sulfide
- alanine
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 30
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 16
- 239000001301 oxygen Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000001556 precipitation Methods 0.000 title claims abstract description 9
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 50
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims abstract description 22
- 235000004279 alanine Nutrition 0.000 claims abstract description 22
- 229910000314 transition metal oxide Inorganic materials 0.000 claims abstract description 15
- 239000002243 precursor Substances 0.000 claims abstract description 11
- 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
- 238000003756 stirring Methods 0.000 claims description 19
- 238000005303 weighing Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 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 9
- -1 polytetrafluoroethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- 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
- 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 7
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 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 55
- 238000012360 testing method Methods 0.000 description 16
- 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
- 230000002194 synthesizing effect Effects 0.000 description 9
- 239000011259 mixed solution Substances 0.000 description 8
- 239000011734 sodium 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
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 7
- 229910021397 glassy carbon Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 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
- 239000010949 copper Substances 0.000 description 6
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 6
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 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
- 238000011056 performance test Methods 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
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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
- 238000010317 ablation therapy Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013170 computed tomography imaging Methods 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- 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
- C25B11/073—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of electrocatalysis, and relates to an oxygen precipitation transition metal base 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) Preparation of copper sulfide according to the method reported in the literature (M.Zhou, R.Zhang, M.Huang, W.Lu, S.Song, M.P.Melanocon, M.Tian, D.Liang and C.Li.A. chemical-free multifunctional [ ], ] 64 Cu]-CuS nanoparticle platform for simultaneous micro-PET/CT imaging and photothermal ablation 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 Na 2 S·9H 2 O aqueous solution, followed by adding Na 2 S·9H 2 Quickly adding an O aqueous solution into a light blue solution, and magnetically stirring at room temperature for reaction until the mixed solution turns into dark brown; and transferring the mixed solution into a constant-temperature water bath kettle, heating in a water bath to 90 ℃, reacting to obtain a dark green copper sulfide nanoparticle solution, cooling in an ice-water bath, and finally placing the solution in a refrigerator for later use.
In the light blue solution, the ratio of copper chloride dihydrate, trisodium citrate dihydrate and deionized water is 0.2mmol:0.136mmol:180mL.
The Na is 2 S·9H 2 The volume ratio of the O aqueous solution to the light blue solution is 1 2 S·9H 2 The concentration of the O aqueous solution was 10mmol/L.
The reaction time was 5min with magnetic stirring at room temperature.
The water bath is heated to 90 ℃ for reaction for 15min.
The refrigerator temperature was 4 ℃.
(2) Weighing alanine, dissolving the alanine into the nano copper sulfide solution, and magnetically stirring the solution uniformly 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) 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 mol 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; the magnetic stirring was continued at room temperature for 10min.
In the step (5), the product is washed 3-5 times by water and ethanol respectively, and is dried for 24 hours in vacuum at room temperature.
The invention provides a simple and universal method for preparing different transition metal (Fe, co and Ni) base heterojunctions, and a one-step hydrothermal method is used for directly synthesizing CuS/double transition metalThe two components of the oxide heterojunction both contain transition metal Cu, so that the electronic structure of the heterojunction is effectively adjusted, the two components can play a better synergistic catalytic effect, and the catalyst is endowed with excellent OER catalytic activity. Tests show that the prepared different transition metal oxide/copper sulfide heterostructure materials have OER catalytic performance close to or even far beyond commercial RuO 2 The OER performance of the catalyst is hopeful 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 (LSV) of copper sulfide/different transition metal-based oxide heterojunction catalysts prepared in specific 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 indication.
Cupric chloride dihydrate (CuCl) 2 ·2H 2 O), sodium sulfide nonahydrate (Na) 2 S·9H 2 O), trisodium citrate dihydrate (C) 6 H 5 Na 3 O 7 ·2H 2 O), alanine, cobalt chloride hexahydrate (CoCl) 2 ·6H 2 O), ferrous sulfate heptahydrate (FeSO) 4 ·7H 2 O), nickel chloride hexahydrate (NiCl) 2 ·6H 2 O), potassium hydroxide (KOH) used for electrochemical tests is analytically pure and purchased from national pharmaceutical group chemical reagents, inc.; carbon powderAnhydrous ruthenium oxide (RuO) 2 99.9% metals basis, alfa Aesar), nafion perfluorinated resin solution (5 wt%, sigma Aldrich).
Analytical balance (Precisa, XJ 220A), centrifuge (hunan xiang instrument, TG 16-WS), air-blast drying cabinet (shanghai jing macros, DFG-9076A), vacuum drying cabinet (shanghai jing macros, DZF-6090), electrochemical workstation (shanghai chen hua, CHI 760E), rotating disk ring electrode device (pone company, usa).
Electrochemical testing: the electrochemical oxygen evolution performance test adopts a Chenghua electrochemical workstation and a three-electrode test system, a glassy carbon electrode loaded with a catalyst is used as a working electrode, and a reversible hydrogen reference electrode and a graphite rod electrode are respectively used as a reference electrode and a counter electrode. Mixing a catalyst and carbon powder according to a mass ratio of 1 2 Electrochemical OER performance was tested in saturated 1M KOH solutions to give an LSV curve 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) Synthesizing a nano copper sulfide aqueous solution: transferring 180mL of deionized water into a 250mL round-bottom flask, respectively weighing 34mg of copper chloride dihydrate (0.2 mmol) and 40mg of trisodium citrate dihydrate (0.136 mmol) and adding the mixture into the flask, and magnetically stirring the mixture uniformly at room temperature to form a light blue solution; 0.1201g of sodium sulfide nonahydrate was weighed,deionized water was added to dissolve and fix the volume in a 50mL volumetric flask (sodium sulfide nonahydrate concentration 10 mmol/L), followed by 20mL of Na 2 S·9H 2 Dropwise 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 ℃, continuously heating for continuous reaction for 15min to finally obtain dark green copper sulfide nanoparticle solution, cooling in an ice water bath, and storing the solution in a refrigerator at 4 ℃ for later use.
(2) Synthesizing copper sulfide/Co-containing transition metal oxide heterojunction catalyst: measuring 40mL of nano CuS solution (containing 0.04mmol of nano copper sulfide) into a 100mL beaker, weighing 0.0445g of alanine (0.5 mmol) and adding the alanine into the beaker, magnetically stirring the solution at room temperature for 10mm, weighing 0.1189g of cobalt chloride hexahydrate (0.5 mmol) and adding the cobalt chloride hexahydrate into the solution, and continuously magnetically stirring the solution at room temperature for 10min to obtain a uniformly dissolved solution; transferring the solution into a 100mL polytetrafluoroethylene lining, putting the lining into a stainless steel reaction kettle, heating to 150 ℃, and carrying out hydrothermal reaction for 10h. After the reaction was complete, the solution was centrifuged, the product was washed 5 times with water and ethanol, respectively, and vacuum dried at room temperature for 24h.
(3) Electrochemical OER performance testing: the test adopts a standard three-electrode test, a Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, a graphite rod is selected as a counter electrode, and a Glassy Carbon (GC) disk electrode is selected as a working electrode. 3mg of the catalyst and 3mg of the carbon powder were weighed and dispersed in 1mL of a solution (water: ethanol: 5wt% nafion volume ratio 40. At O 2 Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
As shown by the XRD test results in FIG. 1, the copper sulfide/Co-containing transition metal oxide heterostructure catalyst prepared in example 1 was prepared from Cu 7 S 4 And Cu 0.76 Co 2.24 O 4 The composition and the morphology thereof are shown in FIG. 2. The results of the OER performance test of the catalyst are shown in FIG. 3, at a current density of 10mA/cm 2 The overpotential of (A) is 280mV, far exceeding that of commercial RuO 2 OER catalytic performance of(10mA/cm 2 The overpotential at (b) is 321 mV).
Example 2 (preferably, copper sulfide/iron-based oxide heterojunction)
(1) Synthesizing a nano copper sulfide aqueous solution: transferring 180mL of deionized water into a 250mL round-bottom flask, respectively weighing 34mg of copper chloride dihydrate (0.2 mmol) and 40mg of trisodium citrate dihydrate (0.136 mmol) and adding the mixture into the flask, and magnetically stirring the mixture uniformly at room temperature to form a light blue solution; 0.1201g of sodium sulfide nonahydrate is weighed, dissolved in deionized water and added to a 50mL volumetric flask (the concentration of sodium sulfide nonahydrate is 10 mmol/L), and then 20mL of Na is added 2 S·9H 2 Dropwise 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) Synthesizing a copper sulfide/Fe-containing transition metal oxide heterojunction catalyst: weighing 40mL of nano CuS solution (containing 0.04mmol of nano copper sulfide) into a 100mL beaker, weighing 0.0445g of alanine (0.5 mmol) and adding the alanine into the beaker, magnetically stirring the solution at room temperature for 10mm, weighing 0.1390g of ferrous sulfate heptahydrate (0.5 mmol) and adding the ferrous sulfate heptahydrate into the solution, and continuously magnetically stirring the solution at room temperature for 10min to obtain a uniformly dissolved solution; transferring the solution into a 100mL polytetrafluoroethylene lining, putting the lining into a stainless steel reaction kettle, heating to 150 ℃, and carrying out hydrothermal reaction for 10h. After the reaction was complete, the solution was centrifuged, the product was washed 5 times with water and ethanol, respectively, and vacuum dried at room temperature for 24h.
(3) Electrochemical OER performance testing: the test adopts a standard three-electrode test, a Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, a graphite rod is selected as a counter electrode, and a Glassy Carbon (GC) disk electrode is selected as a working electrode. 3mg of the catalyst and 3mg of carbon powder were weighed and dispersed in 1mL of a solution (water: ethanol: 5wt% Nafion volume ratio 40. At O 2 Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR replenishmentAnd (6) obtaining the compensation test.
Example 2 preparation of copper sulfide/Fe-containing transition metal oxide heterostructure catalyst from Cu 7 S 4 And CuFeO 2 The results of OER performance test of the catalyst are shown in FIG. 3, at a current density of 10mA/cm 2 At an overpotential of 370mV, close to that of commercial RuO 2 OER catalytic performance (10 mA/cm) 2 The overpotential at (b) is 321 mV).
Example 3 (preferred, copper sulfide/Nickel-based oxide heterojunction)
(1) Synthesizing a nano copper sulfide aqueous solution: transferring 180mL of deionized water into a 250mL round-bottom flask, respectively weighing 34mg of copper chloride dihydrate (0.2 mmol) and 40mg of trisodium citrate dihydrate (0.136 mmol) and adding the mixture into the flask, and magnetically stirring the mixture uniformly at room temperature to form a light blue solution; 0.1201g of sodium sulfide nonahydrate is weighed, dissolved in deionized water and added to a 50mL volumetric flask (the concentration of sodium sulfide nonahydrate is 10 mmol/L), and then 20mL of Na is added 2 S·9H 2 Dropwise 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 ℃, continuously heating for continuous reaction for 15min to finally obtain dark green copper sulfide nanoparticle solution, cooling in an ice water bath, and storing the solution in a refrigerator at 4 ℃ for later use.
(2) Synthesizing copper sulfide/Ni-containing transition metal oxide heterojunction catalyst: measuring 40mL of nano CuS solution (containing 0.04mmol of nano copper sulfide) into a 100mL beaker, weighing 0.0445g of alanine (0.5 mmol) and adding the alanine into the beaker, magnetically stirring the solution at room temperature for 10mm, weighing 0.1188g of nickel chloride hexahydrate (0.5 mmol) and adding the nickel chloride hexahydrate into the solution, and continuously magnetically stirring the solution at room temperature for 10min to obtain a uniformly dissolved solution; transferring the solution into a 100mL polytetrafluoroethylene lining, putting the lining into a stainless steel reaction kettle, heating to 150 ℃, and carrying out hydrothermal reaction for 10h. After the reaction was complete, the solution was centrifuged, the product was washed 5 times with water and ethanol, respectively, and vacuum dried at room temperature for 24h.
(3) Electrochemical OER performance testing: the test adopts a standard three-electrode test, a Reversible Hydrogen Electrode (RHE) is selected as a reference electrode, a graphite rod is selected as a counter electrode, and glassy carbon is adopted(GC) a disk electrode as the working electrode. 3mg of catalyst and 3mg of carbon powder were weighed and dispersed in 1mL of solution (water: ethanol: 5wt% nafion volume ratio 40. At O 2 Electrochemical OER performance was tested in saturated 1M KOH electrolyte solution and all data were obtained without iR compensation testing.
Example 3 preparation of a copper sulfide/Fe containing transition Metal oxide heterostructure catalyst from Cu 7 S 4 And CuNiO 2 The results of OER performance test of the catalyst are shown in FIG. 3, at a current density of 20mA/cm 2 Over-potential of 353mV, exceeding that of commercial RuO 2 OER catalytic performance (20 mA/cm) 2 The 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 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 preparation method of the oxygen precipitation transition metal base heterojunction catalyst comprises the following steps:
(1) Weighing alanine, dissolving the alanine into the nano copper sulfide solution, and uniformly stirring the alanine and the nano copper sulfide solution at room temperature by using 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;
(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.
2. The method for preparing an oxygen evolving transition metal based heterojunction catalyst according to claim 1, comprising the following specific 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;
(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 10min.
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 10min.
5. The method for preparing an oxygen evolution transition metal based heterojunction catalyst as claimed in claim 2, wherein in the step (4), the product is washed 3-5 times with water and ethanol respectively, and vacuum dried for 24h at room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010162136.8A CN111437837B (en) | 2020-03-10 | 2020-03-10 | Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010162136.8A CN111437837B (en) | 2020-03-10 | 2020-03-10 | Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111437837A CN111437837A (en) | 2020-07-24 |
| CN111437837B true CN111437837B (en) | 2023-02-17 |
Family
ID=71627337
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010162136.8A Active CN111437837B (en) | 2020-03-10 | 2020-03-10 | Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111437837B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107890873A (en) * | 2017-11-06 | 2018-04-10 | 许昌学院 | A kind of hollow shape platinoid cobalt ternary-alloy nano particle analogue enztme and its preparation and application |
| CN110227478A (en) * | 2019-07-10 | 2019-09-13 | 西北师范大学 | Cobalt/cobalt oxide/pucherite composite material method is prepared by spin coating calcining |
-
2020
- 2020-03-10 CN CN202010162136.8A patent/CN111437837B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107890873A (en) * | 2017-11-06 | 2018-04-10 | 许昌学院 | A kind of hollow shape platinoid cobalt ternary-alloy nano particle analogue enztme and its preparation and application |
| CN110227478A (en) * | 2019-07-10 | 2019-09-13 | 西北师范大学 | Cobalt/cobalt oxide/pucherite composite material method is prepared by spin coating calcining |
Non-Patent Citations (5)
| Title |
|---|
| Cu7S4/CuO微纳米异质结构的同步合成及光催化性能研究;谭亮 等;《化工新型材料》;20200131;第48卷(第1期);全文 * |
| Efficient charge separation in mixed phase Cu7S4-CuO thin film: Enhanced photocatalytic reduction of aqueous Ni (II) under visible-light;Amrita Ghosh等;《Thin Solid Films》;20170302;第628卷;全文 * |
| Electronic Modulation of Electrocatalytically Active Center of Cu7S4 Nanodisks by Cobalt-Doping for Highly Efficient Oxygen Evolution Reaction;Qun Li等;《ACS Nano》;20171127;第11卷;第12230-12239页 * |
| Highly efficient visible-light photocatalytic H2 evolution over 2D–2D CdS/Cu7S4 layered heterojunctions;Doudou Ren等;《Chinese Journal of Catalysis》;20200105;第41卷(第1期);全文 * |
| Promotion of Niobium Oxide Sulfidation by Copper and Its Effects on Hydrodesulfurization Catalysis;Ali Mansouri and Natalia Semagina;《ACS Catalysis》;20180710;第8卷;全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111437837A (en) | 2020-07-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cao et al. | Prussian blue analogues and their derived nanomaterials for electrocatalytic water splitting | |
| CN110354876B (en) | Hollow Ni2P/Co2P/Fe2Preparation method of P nano composite electrocatalyst | |
| Yi et al. | Co-CoO-Co3O4/N-doped carbon derived from metal-organic framework: The addition of carbon black for boosting oxygen electrocatalysis and Zn-Air battery | |
| Man et al. | Tailored transition metal-doped nickel phosphide nanoparticles for the electrochemical oxygen evolution reaction (OER) | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN112481653B (en) | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof | |
| Jiang et al. | Atomically dispersed Fe-NSC anchored on pomegranate-shaped carbon spheres for oxygen reduction reaction and all-solid-state zinc-air battery | |
| Yang et al. | Copper-involved highly efficient oxygen reduction reaction in both alkaline and acidic media | |
| CN113699553B (en) | Supported porous N-doped carbon nanomaterial and preparation method and application thereof | |
| CN110639565A (en) | Carbon-bimetal phosphide composite material and preparation method thereof | |
| CN109908969A (en) | A kind of Ni of V doping2The preparation method of P elctro-catalyst | |
| Yang et al. | Prussian blue analogue assisted formation of iron doped CoNiSe2 nanosheet arrays for efficient oxygen evolution reaction | |
| Li et al. | CoP-anchored high N-doped carbon@ graphene sheet as bifunctional electrocatalyst for efficient overall water splitting | |
| CN112691688A (en) | High-activity Co-Ni-Fe Co-embedded non-noble metal catalyst and preparation method and application thereof | |
| CN112354549A (en) | Preparation method of metal composite porous nanosheet | |
| Lv et al. | Heterostructured ultrafine metal oxides nanoparticles anchored on Co-MOF nanosheets obtained by partial pyrolysis for promoted oxygen evolution reaction | |
| CN111495368B (en) | Co cluster/SiO 2 Composite material, preparation method and application | |
| CN110013855B (en) | High-efficiency cobalt nickel oxide/nickel hydroxide compound electrocatalyst and preparation method and application thereof | |
| Lyu et al. | Interface and cation dual-engineering promoting Ce-Co (OH) 2/CoP/NF as bifunctional electrocatalyst toward overall water splitting coupling with oxidation of organic compounds | |
| Lei et al. | Porous FeP/CoP heterogeneous materials as efficient alkaline oxygen evolution reaction (OER) catalysts | |
| CN112592484B (en) | MOF material constructed by taking 5-mercapto-1-phenyl-1H-tetrazole as ligand and preparation method and application of derivative thereof | |
| Yuan et al. | Single atom iron implanted polydopamine-modified hollow leaf-like N-doped carbon catalyst for improving oxygen reduction reaction and zinc-air batteries | |
| CN111437837B (en) | Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof | |
| Jiang et al. | Ru-optimized geometric sites of cations in CoFe/CoFe2O4 electrocatalysts with graphitic carbon shells for boosting water oxidation | |
| Wang et al. | Multivariate indium–organic frameworks for highly efficient carbon dioxide capture and electrocatalytic conversion |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |