CN116676626A - Dual-function OER/HER water electrolysis catalyst, preparation method and application thereof - Google Patents

Dual-function OER/HER water electrolysis catalyst, preparation method and application thereof Download PDF

Info

Publication number
CN116676626A
CN116676626A CN202310672726.9A CN202310672726A CN116676626A CN 116676626 A CN116676626 A CN 116676626A CN 202310672726 A CN202310672726 A CN 202310672726A CN 116676626 A CN116676626 A CN 116676626A
Authority
CN
China
Prior art keywords
catalyst
nio
foam
dimensional
oer
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.)
Pending
Application number
CN202310672726.9A
Other languages
Chinese (zh)
Inventor
刘敏敏
徐欢
章丹
张久俊
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.)
University of Shanghai for Science and Technology
Original Assignee
University of Shanghai for Science and Technology
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 University of Shanghai for Science and Technology filed Critical University of Shanghai for Science and Technology
Priority to CN202310672726.9A priority Critical patent/CN116676626A/en
Publication of CN116676626A publication Critical patent/CN116676626A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • 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
    • C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
    • C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
    • C25B11/031—Porous electrodes
    • 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
    • C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
    • 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
    • C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
    • C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
    • C25B11/065—Carbon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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

Abstract

The application belongs to the technical field of nano materials and electrochemistry, and discloses a difunctional OER/HER water electrolysis catalyst, a preparation method and application thereof, wherein the electrocatalyst is prepared by loading transition metal oxide Co by three-dimensional self-supporting foam carbon 3 O 4 Core-shell structure of nanowire @ NiO nanosheets (NiO-NS@Co) 3 O 4 -NW/CF). The catalyst material has rich active site and surface area, co 3 O 4 Synergistic effect between nanowires and NiO nanoplatelets and NiO@Co 3 O 4 The interaction between the core-shell structure and the three-dimensional foam carbon carrier has the advantages that the core-shell structure and the three-dimensional foam carbon carrier show high catalytic activity in the aspects of electrocatalytic hydrogen evolution and oxygen evolution, and the assembled electrolytic water full cell also has the characteristics of low overpotential and high stability. The three-dimensional self-supporting transition metal-based core-shell structure catalyst prepared by the application provides a new thought for designing and synthesizing the low-cost and high-activity bifunctional electrolyzed water catalyst.

Description

Dual-function OER/HER water electrolysis catalyst, preparation method and application thereof
Technical Field
The application belongs to the technical field of nano materials and electrochemistry, and relates to a bifunctional OER/HER water electrolysis catalyst for water electrolysis, a preparation method and application thereof.
Background
The hydrogen energy has the advantages of high heat value, good combustion performance, cleanness, no pollution, diversified production, storage and use modes and the like, is a clean energy with great development prospect, and has important significance for realizing sustainable and coordinated development of energy source environment. In the prior main hydrogen production mode, electrolyzed water is an important method for preparing hydrogen, and is paid attention to because of the advantages of simple preparation method, wide raw material source, high product purity and the like. There are two half reactions of electrolyzed water, namely the cathodic Hydrogen Evolution Reaction (HER) and the anodic Oxygen Evolution Reaction (OER). Because HER and OER present their own higher activation barriers, which are thermodynamically less likely to occur, water baths typically need to operate at higher voltages of 1.8-2.0V under alkaline conditions, whereas the theoretical limit voltage of electrolyzed water is only 1.23V.
In the prior art, noble metal-based catalysts such as RuO 2 Pt/C, etc. can effectively catalyze oxygen evolution and hydrogen evolution reactions, respectively, but are expensive and scarce, severely limiting their large-scale application and commercial popularization. Notably, generally good OER catalysts may exhibit poor HER activity and vice versa. Furthermore, in the same electrolyte solution, the pH ranges of the two electrocatalysts for OER and HER, respectively, tend not to match in the steady and most active state, which results in poor overall cell performance. The use of a highly efficient OER/HER bi-functional electrocatalyst can improve the kinetics of the reaction retardation and reduce the OER and HER overpotential, thereby improving the overall performance of the system. Thus, for non-noble OER/HER bi-functional catalystsThe method has very important significance for developing stable and efficient electrolyzed water catalysts.
The transition metal has a unique d electronic structure due to rich reserves and low price, and becomes a potential substitute of the noble metal catalyst. Transition metal-based compounds such as oxides, hydroxides, sulfides, phosphides, nitrides, and alloys have been intensively studied for catalyzing hydrogen evolution and oxygen evolution. Among them, the unique redox properties, the diverse structures and the variable valence states of the transition metal oxides promote their excellent OER catalytic performance under alkaline conditions. However, single transition metal oxides tend to exhibit poor HER performance, and therefore, the construction and synthesis of bifunctional catalysts capable of simultaneously catalyzing hydrogen evolution and oxygen evolution reactions with high efficiency is of great significance for the application of electrolyzed water.
Disclosure of Invention
Aiming at the problems existing in the prior art, the application provides a bifunctional OER/HER water electrolysis catalyst, a preparation method and application thereof, and the three-dimensional self-supporting non-noble metal-based OER/HER bifunctional water electrolysis catalyst NiO-NS@Co with a core-shell structure is prepared through a novel conception 3 O 4 NW/CF (hereinafter abbreviated as NiO@Co 3 O 4 and/CF) the catalyst has high-efficiency catalytic activity and stability of hydrogen evolution and oxygen evolution under alkaline conditions.
In order to achieve the above purpose, the application adopts the following technical scheme:
the double-function OER/HER water electrolysis catalyst is characterized by being a three-dimensional self-supporting transition metal-based OER/HER catalyst, which consists of two transition metal oxides and a conductive carrier, wherein the composite metal oxide is in-situ loaded on conductive three-dimensional foam carbon through a solvothermal method and heat treatment to form a three-dimensional self-supporting hierarchical porous nano composite material with a core-shell heterostructure.
The dual-function OER/HER water electrolysis catalyst is characterized by being three-dimensional self-supporting NiO@Co 3 O 4 The catalyst is NiO@Co with a core-shell structure and a transition metal-based oxide by taking three-dimensional carbon foam as a carrier 3 O 4 Three-dimensional self-supporting hierarchical porous nano composite material NiO@Co obtained by compounding 3 O 4 a/CF; wherein NiO@Co with core-shell structure 3 O 4 Is made of Co 3 O 4 Is nuclear and is in Co 3 O 4 Shell layer formed by uniformly loading NiO nano-sheets on in-situ and coating Co 3 O 4 Nano wire to obtain NiO@Co with core-shell structure 3 O 4 The core-shell structure is an active component in the catalyst.
The preparation method of the dual-function OER/HER water electrolysis catalyst is characterized by comprising the following steps:
s1: preparing a three-dimensional foam carbon carrier by carbonized melamine foam: at 100mLmin -1 Heating Melamine Foam (MF) to 700 ℃ according to a heating program, preserving heat for 1 hour, and cooling to room temperature to obtain black three-dimensional Carbon Foam (CF);
s2: preparing a carbon foam loaded with a nickel@cobalt precursor: dissolving appropriate amount of cobalt salt, urea and CTAB in water, and performing ultrasonic treatment for 5-10 min to obtain transparent solution with size of 2×2cm 2 The foam carbon is immersed in the solution and then is transferred into a hydrothermal reaction kettle for a first-step hydrothermal reaction to obtain the foam carbon loaded with cobalt precursor, and the foam carbon is immersed into an ethanol solution containing nickel salt and urea after being washed and is integrally transferred into the reaction kettle for a second-step hydrothermal reaction; cooling to room temperature, and washing to obtain the foam carbon loaded with the nickel-cobalt precursor;
s3: preparing a catalyst: placing the foam carbon loaded with the nickel@cobalt precursor in a tube furnace, calcining at 350 ℃ and preserving heat for 1 hour, and cooling to room temperature to obtain NiO@Co 3 O 4 A CF catalyst.
The application has the advantages that:
1. the application reasonably designs the components and the structure of the self-supporting non-noble metal-based catalyst, which is a three-dimensional self-supporting hierarchical porous nano composite material, is favorable for transportation and charge storage of electrolyte in the catalytic process, and increases the surface area of the catalyst. Compared with single metal oxide, the synthesized NiO@Co 3 O 4 the/CF has richOxygen vacancies, co thereof 3 O 4 The synergistic effect between the NW core layer and the NiO-NS shell layer and the interaction between the whole core-shell structure and the three-dimensional foam carbon can cause the change of the surface electronic structure of the catalyst, and improve the catalytic activity on hydrogen evolution and oxygen evolution; in addition, three-dimensional carbon foam with high conductivity and porosity is selected as a substrate, so that electron transfer can be improved, and release of generated hydrogen and oxygen bubbles can be promoted.
2. The application adopts a two-step hydrothermal method and a subsequent calcination method to prepare the core-shell structure (NiO@Co) of the cobalt oxide nanowire@nickel oxide nanosheet grown in situ on the three-dimensional Carbon Foam (CF) 3 O 4 CF) as a bifunctional catalyst for the electrolysis of water under alkaline conditions. Wherein the NiO-NS shell layer and Co 3 O 4 The synergistic effect between NW core layers and the interaction with the three-dimensional carbon foam can effectively improve the catalytic performance of hydrogen evolution and oxygen evolution. NiO@Co with unique core-shell structure and rich oxygen vacancies 3 O 4 The composite material is beneficial to exposing more active sites and increasing the electrochemical active area; compared with a powdery catalyst, the self-supporting catalyst taking the three-dimensional carbon foam as the conductive substrate also avoids the adverse effect of the binder on the catalyst, and is more beneficial to improving the catalytic activity and chemical stability of the catalyst; the metal oxide composite material has low cost, simple and feasible synthesis process, and can be used as a cathode and an anode to electrolyze water in the same electrolyte.
3. The preparation method of the application has strong operability, abundant raw material sources and low price. The method has the advantages of simple and feasible operation, low raw material cost and rich content.
4. The catalyst prepared by the application can efficiently catalyze hydrogen evolution reaction and oxygen evolution reaction in alkaline medium. And can be used as a cathode and an anode to electrolyze water in the same electrolyte at the same time, and has good stability.
The present application will be described in further detail with reference to the accompanying drawings and detailed description.
Drawings
In FIG. 1, (a) and (b) are NiO@Co obtained in example 1 of the present application 3 O 4 Sweep of/CFAnd (5) drawing an electron microscope image.
FIG. 2 shows NiO@Co obtained in example 1 of the present application 3 O 4 Transmission electron microscope image (a) of/CF, high resolution transmission electron microscope image (b).
FIG. 3 is NiO@Co obtained in example 1 of the present application 3 O 4 X-ray energy spectrum (EDS) of/CF.
FIG. 4 (a) shows NiO@Co obtained in example 1 of the present application 3 O 4 CF and comparative example 1 (Co 3 O 4 Comparative example 2 (NiO/CF), oxygen evolution polarization curve comparison plot of pure foam nickel catalyst under 1.0m koh alkaline condition;
FIG. 4 (b) shows NiO@Co obtained in example 1 of the present application 3 O 4 CF and comparative example 1 (Co 3 O 4 Comparative example 2 (NiO/CF), and a polarization curve comparison plot of hydrogen evolution reaction of a pure foam nickel catalyst under alkaline conditions of 1.0 MKOH.
FIG. 5 shows NiO@Co obtained in example 1 of the present application 3 O 4 Water electrolysis device composed of anode and cathode simultaneously by/CF and NiO@Co 3 O 4 /CF (-) //NiO@Co 3 O 4 /CF (+) Is a full hydrolytic polarization curve (a) and a stability test curve (b).
Detailed Description
The following detailed description of preferred embodiments of the application is made in connection with the accompanying drawings, which form a part hereof, and together with the description of the embodiments of the application, are used to explain the principles of the application and are not intended to limit the scope of the application.
Examples
The dual-function OER/HER water electrolysis catalyst provided by the embodiment is a three-dimensional self-supporting transition metal-based OER/HER catalyst, which consists of two transition metal oxides and a conductive carrier, wherein the composite metal oxide is in-situ loaded on conductive three-dimensional foam carbon through solvothermal method and heat treatment to form a three-dimensional self-supporting hierarchical porous nano composite material with a core-shell heterostructure.
The dual-function OER/HER water electrolysis catalyst is three-dimensional self-supporting NiO@Co 3 O 4 Catalyst for use in CFThe catalyst is NiO@Co with a transition metal base oxide and a core-shell structure by taking three-dimensional foam carbon as a carrier 3 O 4 Three-dimensional self-supporting hierarchical porous nano composite material NiO@Co obtained by compounding 3 O 4 a/CF; wherein NiO@Co with core-shell structure 3 O 4 Is made of Co 3 O 4 Is nuclear and is in Co 3 O 4 Shell layer formed by uniformly loading NiO nano-sheets on in-situ and coating Co 3 O 4 Nano wire to obtain NiO@Co with core-shell structure 3 O 4 The core-shell structure is an active component in the catalyst.
The catalyst is prepared by loading transition metal oxide Co by three-dimensional self-supporting foam carbon 3 O 4 Nanowire @ NiO nanosheets, wherein Co is selected from the group consisting of 3 O 4 The core layer has a nanowire structure, the length of the nanowire structure is 3-5 mu m, the diameter of the nanowire structure is 100-200nm, and the nanowire structure is uniformly distributed on the framework of the carrier three-dimensional foam carbon.
The NiO shell layer has the shape of a nano sheet, the average size is 200-500nm, and the thickness is 10-50nm.
The preparation method of the dual-function OER/HER water electrolysis catalyst comprises the following steps:
s1: preparing a three-dimensional foam carbon carrier by carbonized melamine foam: at 100mLmin -1 Heating Melamine Foam (MF) to 700 ℃ according to a heating program, preserving heat for 1 hour, and cooling to room temperature to obtain black three-dimensional Carbon Foam (CF);
s2: preparing a carbon foam loaded with a nickel@cobalt precursor: dissolving appropriate amount of cobalt salt, urea and CTAB in water, and performing ultrasonic treatment for 5-10 min to obtain transparent solution with size of 2×2cm 2 The foam carbon is immersed in the solution and then is transferred into a hydrothermal reaction kettle for a first-step hydrothermal reaction to obtain the foam carbon loaded with cobalt precursor, and the foam carbon is immersed into an ethanol solution containing nickel salt and urea after being washed and is integrally transferred into the reaction kettle for a second-step hydrothermal reaction; cooling to room temperature, and washing to obtain the foam carbon loaded with the nickel-cobalt precursor; cobalt salt is Co (NO) 3 ) 2 ·6H 2 O, ni salt is Ni (NO) 3 ) 2 ·6H 2 O；
S3: preparing a catalyst: placing the foam carbon loaded with the nickel@cobalt precursor in a tube furnace, calcining at 350 ℃ and preserving heat for 1 hour, and cooling to room temperature to obtain NiO@Co 3 O 4 a/CF catalyst; wherein the hydrothermal condition of the cobalt nanowire in-situ grown on the carbon foam is 160 ℃ for 1 hour. The hydrothermal condition for the formation of the nickel nano-sheets is 90 ℃ for 10 hours.
Application of dual-function OER/HER (organic electronic equipment/HER) electrolyzed water catalyst in electrolyzed water reaction, wherein the dual-function OER/HER electrolyzed water catalyst is specifically three-dimensional self-supporting NiO@Co 3 O 4 A CF catalyst.
The three-dimensional self-supporting NiO@Co 3 O 4 the/CF catalyst has the dual functions of electrolysis of water, and oxygen evolution reaction and hydrogen evolution reaction reach 10mAcm under alkaline condition -2 The overpotential required for the current density of (2) is 195mV and 103mV, respectively.
The three-dimensional self-supporting NiO@Co 3 O 4 the/CF catalyst has the double functions of water electrolysis, and when water electrolysis is carried out by respectively serving as a cathode electrode and an anode electrode in the same alkaline electrolytic cell, 10mAcm can be realized at the voltage of 1.53V -2 And can be stably operated.
More specifically, the preparation method of the dual-function OER/HER water electrolysis catalyst comprises the following steps:
at 100mLmin -1 Carbonized Melamine Foam (MF) to produce Carbon Foam (CF). Initially at 5℃for min -1 Is heated in a tube furnace to 300 ℃ and is kept for 5 minutes. Then at 1 ℃ for min -1 The temperature was continued to rise until the temperature reached 400℃and the temperature was maintained for 5 minutes. Finally, the temperature is 2 ℃ for min -1 Further heating to 700 ℃ and preserving heat for 1 hour to obtain carbonized black three-dimensional foam carbon.
Adding proper amount of Co (NO) into 35mL deionized water in turn 3 ) 2 ·6H 2 O、CO(NH 2 ) 2 And CTAB, ultrasonic treatment for 5 minutes gave a clear pink solution a.
About 6mg of carbon foam is immersed in the solution A, then the system is transferred into a 50mL hydrothermal reaction kettle, heated to a proper temperature and kept for a proper time, and then cooled to room temperature;
the obtained foam carbon loaded Co nanowire precursor is respectively washed for 3-5 times by water and ethanol to remove redundant surfactant and free ions.
Adding appropriate amount of Ni (NO) into 35mL ethanol solution sequentially 3 ) 2 ·6H 2 O、CO(NH 2 ) 2 After 5 minutes of ultrasonic treatment, a transparent pale green solution B was obtained.
The carbon foam loaded with the Co nanowire precursor is immersed in the solution B, the system is transferred into a 50mL hydrothermal reaction kettle, heated to a proper temperature and kept for a proper time, and then cooled to room temperature.
The resulting carbon foam loaded with cobalt @ nickel species was washed 3-5 times with water and ethanol, respectively, and then dried in an oven at 60 ℃.
Placing the dried foam carbon loaded with cobalt@nickel substances in a tubular furnace, and introducing inert gas nitrogen for 5 ℃ for min -1 Heating to proper temperature and preserving heat for proper time, and then cooling the system to room temperature to obtain the final product NiO@Co 3 O 4 A CF catalyst.
Example 1
Referring to fig. 1-5, on the basis of the foregoing embodiment, the efficient OER/HER dual-function electrolyzed water catalyst (nio@co) provided in this embodiment 3 O 4 /CF) and its preparation method are as follows:
0.0873g of Co (NO) was added sequentially to 35mL of deionized water 3 ) 2 ·6H 2 O、0.06gCO(NH 2 ) 2 And 0.225g CTAB, a clear pink solution A was obtained after 5 minutes of sonication.
Will be 2X 2cm in size 2 The carbon foam of (2) was immersed in solution A, then the system was transferred to a 50mL hydrothermal reaction vessel, heated to 160℃and incubated for 1h. The system was then cooled to room temperature.
The obtained carbon foam loaded with the Co nanowire precursor is washed with water and ethanol for 3 times respectively to remove redundant surfactant and free ions.
0.0967gNi (NO) was added sequentially to 35mL of ethanol solution 3 ) 2 ·6H 2 O、0.06gCO(NH 2 ) 2 After 5 minutes of ultrasonic treatment, a transparent pale green solution B was obtained.
The carbon foam loaded with the Co nanowire precursor is immersed in the solution B, then the system is transferred into a 50mL hydrothermal reaction kettle, the temperature is raised to 90 ℃ and kept for 10 hours, and then the system is cooled to room temperature.
The resulting carbon foam loaded with cobalt nickel species was washed 3 times with water and ethanol, respectively, and then dried in an oven at 60 ℃ overnight.
Placing the dried foam carbon loaded with cobalt-nickel substances in a tube furnace, introducing inert gas nitrogen, and heating to 5 ℃ for min -1 Heating to 350 ℃ and preserving heat for 1h, and then cooling the system to room temperature to obtain the final product NiO@Co 3 O 4 /CF。
NiO@Co prepared in this example and taking carbon foam as substrate 3 O 4 The microstructure of the/CF catalyst is shown in FIGS. 1 and 2.
As can be seen from the accompanying figures 1 and 2, niO@Co successfully and uniformly grows on the framework of the three-dimensional foam carbon 3 O 4 A core-shell structure. The EDS of FIG. 3 clearly shows the presence of Co, ni, and Co to Ni atomic ratio of 13:5. FIG. 4 (a) shows NiO@Co 3 O 4 when/CF catalyzes OER in alkaline medium, the current density is 10 and 100mAcm -2 At this time, the overpotential was as low as 195 and 283mV, indicating that the catalyst had excellent OER performance. Exhibits excellent OER activity. In FIG. 4 (b), it is shown that at NiO@Co 3 O 4 when/CF catalyzes HER in alkaline medium, the current density is 10mA cm -2 When the overpotential was only 103mV, this catalyst showed excellent HER performance. When NiO@Co 3 O 4 the/CF catalyst is simultaneously used as the anode and the cathode of the water electrolysis device to be assembled into NiO@Co 3 O 4 /CF (-) //NiO@Co 3 O 4 /CF (+) The polarization curve of FIG. 5 (a) shows that the full cell can achieve 10mAcm with only 1.53V -2 And can be run stably for more than 42 hours (b in fig. 5).
In other embodiments of the present application, the two-step hydrothermal method and the subsequent calcination method are adopted to prepare the core-shell structure NiO-NS@Co of the cobalt oxide nanowire@nickel oxide nanosheets grown in situ on the three-dimensional Carbon Foam (CF) 3 O 4 -NW (abbreviated as NiO@Co 3 O 4 A CF catalyst) as a bifunctional catalyst for electrolysis of water under alkaline conditions.
Comparative example 1
Comparative example A similar Co was prepared 3 O 4 NW/CF catalyst and compare it to example 1.
0.0873g of Co (NO) was added sequentially to 35mL of deionized water 3 ) 2 ·6H 2 O、0.06gCO(NH 2 ) 2 And 0.225g CTAB, a clear pink solution A was obtained after 5 minutes of sonication.
Will be 2X 2cm in size 2 Is immersed in solution a, then the system is transferred to a 50mL hydrothermal reaction vessel, heated to 160 ℃ and incubated for 1h, then the system is cooled to room temperature.
The resulting carbon foam loaded with the Co nanowire precursor was washed 3 times with water and ethanol, respectively, and then dried in an oven at 60 ℃ overnight.
Placing the dried carbon foam loaded with the cobalt nanowire precursor in a tube furnace, introducing inert gas nitrogen, and standing at 5 ℃ for min -1 Heating to 350 ℃ at a heating rate and preserving heat for 1h, and then cooling the system to room temperature to obtain a final product Co 3 O 4 -NW/CF。
Comparative example 2
A similar NiO-NS/CF catalyst was prepared and compared to example 1.
0.0967gNi (NO) was added sequentially to 35mL of ethanol solution 3 ) 2 ·6H 2 O、0.06gCO(NH 2 ) 2 After 5 minutes of ultrasonic treatment, a transparent pale green solution B was obtained.
Will be 2X 2cm in size 2 Is immersed in solution BThe system was then transferred to a 50mL hydrothermal reaction kettle, heated to 90 ℃ and incubated for 10h, and then cooled to room temperature.
The obtained carbon foam loaded with the Ni nano-sheet precursor was washed with water and ethanol respectively 3 times, and then dried in an oven at 60℃overnight.
Placing the dried foam carbon loaded with the Ni nano-sheet precursor in a tube furnace, introducing inert gas nitrogen, and heating to 5 ℃ for min -1 The temperature is raised to 350 ℃ at a temperature rising rate and is kept for 1h, and then the system is cooled to room temperature, so as to obtain the final product NiO-NS/CF.
The bifunctional electrocatalyst prepared in the above embodiment of the application is prepared by three-dimensional self-supporting foam carbon-supported transition metal oxide Co with high conductivity 3 O 4 Core-shell structure of nanowire@NiO nanosheets (NiO@Co) 3 O 4 ) Composition is prepared. The catalyst material has rich active site and surface area, co 3 O 4 Synergistic effect between nanowires and NiO nanoplatelets and NiO@Co 3 O 4 The interaction between the core-shell structure and the three-dimensional foam carbon carrier has the advantages that the core-shell structure and the three-dimensional foam carbon carrier show high catalytic activity in the aspects of electrocatalytic hydrogen evolution and oxygen evolution, and the assembled electrolytic water full cell also has the characteristics of low overpotential and high stability. The three-dimensional self-supporting transition metal-based core-shell structure catalyst prepared by the application provides a new technical idea for designing and synthesizing the low-cost and high-activity bifunctional electrolyzed water catalyst.
The application provides a double-function OER/HER water electrolysis catalyst and application thereof in water electrolysis reaction, which consists of two transition metal oxides and a conductive carrier through combining the structure and components of the double-function OER/HER water electrolysis catalyst, wherein the composite metal oxides form a core-shell heterostructure through solvothermal method and heat treatment, and are loaded on conductive three-dimensional foam carbon in situ, so that the double-function OER/HER water electrolysis catalyst has double functions of catalyzing oxygen evolution reaction and hydrogen evolution reaction in water electrolysis reaction, and is specifically three-dimensional self-supporting NiO@Co 3 O 4 A CF catalyst.
Through practical tests, the three-dimensional self-supporting NiO@Co provided by the application 3 O 4 the/CF catalyst hasThe double functions of catalyzing oxygen evolution reaction and hydrogen evolution reaction in the electrolytic water reaction reach 10mA cm under alkaline condition -2 The overpotential required by the current density of (2) is 195mV and 103mV respectively, and when the electrolysis is carried out in the same alkaline electrolytic cell as the cathode and anode respectively, the 10mAcm can be realized by only 1.53V voltage -2 And can be run stably for more than 42 hours.
It should be noted that, within the scope of the present application described above, other OER/HER dual-function water electrolysis catalysts obtained by selecting other components, ratios and preparation processes can all implement the technical effects of the present application, and therefore, they are not listed one by one.
The above description is only of the preferred embodiment of the present application and is not intended to limit the present application in any way. Any person skilled in the art can make many possible variations or modifications of the technical solution of the present application within the scope described in the present application without departing from the technical solution of the present application as equivalent embodiments. Therefore, all equivalent modifications made according to the structure, construction and principle of the present application are intended to be included within the scope of the present application.

Claims (9)

1. The double-function OER/HER water electrolysis catalyst is characterized by being a three-dimensional self-supporting transition metal-based OER/HER catalyst, which consists of two transition metal oxides and a conductive carrier, wherein the composite metal oxide is in-situ loaded on conductive three-dimensional foam carbon through a solvothermal method and heat treatment to form a three-dimensional self-supporting hierarchical porous nano composite material with a core-shell heterostructure.
2. The dual function OER/HER electrolyzed water catalyst of claim 1 characterized in that it is a three-dimensional self-supporting NiO-ns@co 3 O 4 -NW/CF catalyst, abbreviated nio@co 3 O 4 The catalyst is NiO@Co with a core-shell structure and a transition metal-based oxide by taking three-dimensional carbon foam as a carrier 3 O 4 Three-dimensional self-supporting hierarchical porous nano composite material NiO@Co obtained by compounding 3 O 4 a/CF; wherein NiO@Co with core-shell structure 3 O 4 Is made of Co 3 O 4 Is nuclear and is in Co 3 O 4 Shell layer formed by uniformly loading NiO nano-sheets on in-situ and coating Co 3 O 4 Nano wire to obtain NiO@Co with core-shell structure 3 O 4 The core-shell structure is an active component in the catalyst.
3. The dual function OER/HER electrolyzed water catalyst of claim 2 wherein the catalyst is a three-dimensional self-supporting carbon foam supported transition metal oxide Co 3 O 4 Nanowire @ NiO nanosheets, wherein Co is selected from the group consisting of 3 O 4 The core layer has a nanowire structure, the length of the nanowire structure is 3-5 mu m, the diameter of the nanowire structure is 100-200nm, and the nanowire structure is uniformly distributed on the framework of the carrier three-dimensional foam carbon.
4. The dual-function OER/HER water electrolysis catalyst according to claim 2, wherein the NiO shell has the morphology of nanosheets with an average size of 200-500nm and a thickness of 10-50nm.
5. A method of preparing a dual function OER/HER water electrolysis catalyst according to any one of claims 1 to 4, comprising the steps of:
s1: preparing a three-dimensional foam carbon carrier by carbonized melamine foam: at 100mLmin -1 Heating Melamine Foam (MF) to 700 ℃ according to a heating program, preserving heat for 1 hour, and cooling to room temperature to obtain black three-dimensional Carbon Foam (CF);
s2: preparing a carbon foam loaded with a nickel@cobalt precursor: dissolving appropriate amount of cobalt salt, urea and CTAB in water, and performing ultrasonic treatment for 5-10 min to obtain transparent solution with size of 2×2cm 2 The foam carbon is immersed in the solution and then is transferred into a hydrothermal reaction kettle for the first step of hydrothermal reaction, so as to obtain the foam carbon loaded with cobalt precursor, and the foam carbon is immersed in the solution containing nickel salt and urea after washingThe mixture is integrally transferred into a reaction kettle to carry out a second-step hydrothermal reaction; cooling to room temperature, and washing to obtain the foam carbon loaded with the nickel-cobalt precursor;
s3: preparing a catalyst: placing the foam carbon loaded with the nickel@cobalt precursor in a tube furnace, calcining at 350 ℃ and preserving heat for 1 hour, and cooling to room temperature to obtain NiO@Co 3 O 4 A CF catalyst.
6. The method according to claim 5, wherein,
the cobalt salt in the step S2 is Co (NO 3 ) 2 ·6H 2 O, ni salt is Ni (NO) 3 ) 2 ·6H 2 O。
7. Use of a dual function OER/HER electrolyzed water catalyst as defined in claims 1 to 4 in an electrolyzed water reaction having dual functions of catalyzing an oxygen evolution reaction and a hydrogen evolution reaction in the electrolyzed water reaction.
8. The use according to claim 7, wherein the catalyst is three-dimensional self-supporting nio@co 3 O 4 The oxygen evolution reaction and the hydrogen evolution reaction reach 10mAcm under the alkaline condition of the/CF catalyst -2 The overpotential required for the current density of (2) is 195mV and 103mV, respectively.
9. The use according to claim 8, wherein the catalyst is capable of obtaining 10mAcm at a voltage of 1.53V when used as cathode and anode respectively for electrolysis of water in the same alkaline cell -2 And can be stably operated.
CN202310672726.9A 2023-06-08 2023-06-08 Dual-function OER/HER water electrolysis catalyst, preparation method and application thereof Pending CN116676626A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310672726.9A CN116676626A (en) 2023-06-08 2023-06-08 Dual-function OER/HER water electrolysis catalyst, preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310672726.9A CN116676626A (en) 2023-06-08 2023-06-08 Dual-function OER/HER water electrolysis catalyst, preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN116676626A true CN116676626A (en) 2023-09-01

Family

ID=87783313

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310672726.9A Pending CN116676626A (en) 2023-06-08 2023-06-08 Dual-function OER/HER water electrolysis catalyst, preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN116676626A (en)

Similar Documents

Publication Publication Date Title
CN109954503B (en) Nickel selenide and ternary nickel-iron selenide composite electrocatalyst, preparation method and application
CN111672514A (en) Bifunctional electrocatalytic material and preparation method and application thereof
CN110639534B (en) Oxygen evolution electrocatalytic material and preparation method and application thereof
CN110474057A (en) A kind of preparation method and application of the oxygen reduction electro-catalyst based on lignocellulose-like biomass carbon
CN112439459B (en) Ultrathin nanosheet material with coexisting crystal and amorphous interface and application thereof in water electrolysis
CN112080759B (en) Preparation method of bismuth-doped bimetallic sulfide electrode for electrocatalytic oxidation of urea
CN111939947B (en) Preparation method of nanosheet array electrocatalyst
CN113667993A (en) Oxygen vacancy-rich cobalt monoxide/cobalt ferrite nanosheet array structure catalyst and preparation and application thereof
CN114836779A (en) Layered double hydroxide/nitrogen-doped carbon composite material and preparation method and application thereof
CN110230072B (en) Preparation method and application of N-NiZnCu LDH/rGO nanosheet array material on foamed nickel
CN109097788B (en) Double-carbon coupling transition metal nickel-based quantum dot electrocatalyst and preparation method thereof
CN113774425B (en) Preparation method and application of Ru-modified FeCo @ NF electrocatalyst
CN115770621A (en) Preparation method and application of bimetallic MOF (metal organic framework) anchored Pt nanocluster catalyst
WO2023279406A1 (en) Method for preparing supported catalyst and application thereof
CN116676626A (en) Dual-function OER/HER water electrolysis catalyst, preparation method and application thereof
CN114214636B (en) Method for preparing cobalt-based nanosheet self-supporting electrode by selenium-containing ligand and application of cobalt-based nanosheet self-supporting electrode
CN115110113B (en) Rod-shaped Co 2 C-MoN composite material and preparation method and application thereof
CN115449693B (en) Preparation method and application of high-entropy alloy oxygen evolution catalyst with frame structure
CN113215616B (en) IrCoFe @ MXene composite catalyst and preparation method and application thereof
CN115125578B (en) Preparation method of B-S co-doped nickel-cobalt-based electrolytic water oxygen evolution catalyst
CN113955728B (en) Preparation of cobalt phosphide/cobalt manganese phosphide with hollow grade structure and application of electrolytic water
CN117904672A (en) Cerium-vanadium bimetal hollow nano-pillar array type electrocatalytic material and preparation method and application thereof
Liu et al. Self‐supported bimetallic array superstructures for high‐performance coupling electrosynthesis of formate and adipate
CN117488354A (en) Ru monoatomic doped Ni (OH) 2 Preparation method of coupling FeOOH and application of coupling FeOOH in electrolysis of water under industrial current density
CN117661020A (en) Co (cobalt) 3 (PO 4 ) 2 -Mo 8 P 5 Preparation method and application of/NF full hydrolysis catalyst

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