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 PDF

Info

Publication number
CN111437837A
CN111437837A CN202010162136.8A CN202010162136A CN111437837A CN 111437837 A CN111437837 A CN 111437837A CN 202010162136 A CN202010162136 A CN 202010162136A CN 111437837 A CN111437837 A CN 111437837A
Authority
CN
China
Prior art keywords
transition metal
solution
catalyst
copper sulfide
alanine
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.)
Granted
Application number
CN202010162136.8A
Other languages
Chinese (zh)
Other versions
CN111437837B (en
Inventor
饶德伟
杨欢
颜晓红
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu University
Original Assignee
Jiangsu University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu University filed Critical Jiangsu University
Priority to CN202010162136.8A priority Critical patent/CN111437837B/en
Publication of CN111437837A publication Critical patent/CN111437837A/en
Application granted granted Critical
Publication of CN111437837B publication Critical patent/CN111437837B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04Sulfides
    • B01J27/043Sulfides with iron group metals or platinum group metals
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33Electric or magnetic properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091Electrodes 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen 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-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

Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof
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.
CN202010162136.8A 2020-03-10 2020-03-10 Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof Active CN111437837B (en)

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 true CN111437837A (en) 2020-07-24
CN111437837B 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)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Title
ALI MANSOURI AND NATALIA SEMAGINA: "Promotion of Niobium Oxide Sulfidation by Copper and Its Effects on Hydrodesulfurization Catalysis", 《ACS CATALYSIS》 *
AMRITA GHOSH等: "Efficient charge separation in mixed phase Cu7S4-CuO thin film: Enhanced photocatalytic reduction of aqueous Ni (II) under visible-light", 《THIN SOLID FILMS》 *
DOUDOU REN等: "Highly efficient visible-light photocatalytic H2 evolution over 2D–2D CdS/Cu7S4 layered heterojunctions", 《CHINESE JOURNAL OF CATALYSIS》 *
QUN LI等: "Electronic Modulation of Electrocatalytically Active Center of Cu7S4 Nanodisks by Cobalt-Doping for Highly Efficient Oxygen Evolution Reaction", 《ACS NANO》 *
谭亮 等: "Cu7S4/CuO微纳米异质结构的同步合成及光催化性能研究", 《化工新型材料》 *

Also Published As

Publication number Publication date
CN111437837B (en) 2023-02-17

Similar Documents

Publication Publication Date Title
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
CN110354876B (en) Hollow Ni2P/Co2P/Fe2Preparation method of P nano composite electrocatalyst
Nai et al. Electrochemistry: Efficient Electrocatalytic Water Oxidation by Using Amorphous Ni–Co Double Hydroxides Nanocages (Adv. Energy Mater. 10/2015)
Man et al. Tailored transition metal-doped nickel phosphide nanoparticles for the electrochemical oxygen evolution reaction (OER)
CN108704649B (en) Non-noble metal-based electrolytic water oxygen evolution reaction electrocatalyst and preparation method thereof
Li et al. Enhanced OER performance of composite Co–Fe-based MOF catalysts via a one-pot ultrasonic-assisted synthetic approach
Jiang et al. Atomically dispersed Fe-NSC anchored on pomegranate-shaped carbon spheres for oxygen reduction reaction and all-solid-state zinc-air battery
Dai et al. Controlled synthesis of NiCo2O4@ Ni-MOF on Ni foam as efficient electrocatalyst for urea oxidation reaction and oxygen evolution reaction
CN109847778A (en) A kind of cobalt disulfide for being electrolysed elutriation oxygen/carbon nitrogen composite material and its synthetic method
Zhang et al. Carbon-based material-supported single-atom catalysts for energy conversion
Yuan et al. A MOF-derived CuCo (O)@ carbon–nitrogen framework as an efficient synergistic catalyst for the hydrolysis of ammonia borane
CN113699553B (en) Supported porous N-doped carbon nanomaterial and preparation method and application thereof
Deng et al. One-dimensional nitrogen-doped carbon frameworks embedded with zinc-cobalt nanoparticles for efficient overall water splitting
Liu et al. Co-CoO/ZnFe2O4 encapsulated in carbon nanowires derived from MOFs as electrocatalysts for hydrogen evolution
Yang et al. Prussian blue analogue assisted formation of iron doped CoNiSe2 nanosheet arrays for efficient oxygen evolution reaction
Lv et al. Heterostructured ultrafine metal oxides nanoparticles anchored on Co-MOF nanosheets obtained by partial pyrolysis for promoted oxygen evolution reaction
CN110013855B (en) High-efficiency cobalt nickel oxide/nickel hydroxide compound electrocatalyst and preparation method and application thereof
CN109234762B (en) Catalyst, preparation method and application thereof, and water decomposition system
Ding et al. Ni-B-Co nanoparticles based on ZIF-67 as efficient electrocatalyst for oxygen evolution reaction
CN111495368B (en) Co cluster/SiO 2 Composite material, preparation method and application
CN113659154A (en) Carbon catalyst for cathode of alkaline fuel cell and preparation method thereof
Wang et al. Multivariate indium–organic frameworks for highly efficient carbon dioxide capture and electrocatalytic conversion
CN111437837B (en) Oxygen precipitation transition metal base heterojunction catalyst and preparation method thereof
CN111957315A (en) One-step method for preparing high-performance trimetal hydroxide electrocatalyst
CN114232009B (en) Bimetallic MOF derived catalyst and preparation method and application thereof

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