CN114672837B - Heterojunction nano array electrode material and preparation method and application thereof - Google Patents
Heterojunction nano array electrode material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114672837B CN114672837B CN202210521647.3A CN202210521647A CN114672837B CN 114672837 B CN114672837 B CN 114672837B CN 202210521647 A CN202210521647 A CN 202210521647A CN 114672837 B CN114672837 B CN 114672837B
- Authority
- CN
- China
- Prior art keywords
- array electrode
- mno
- delta
- feooh
- iron
- 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
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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention belongs to the technical field of electrocatalytic oxygen evolution electrode materials, and particularly relates to a heterojunction nano-array electrode material and a preparation method and application thereof. The method comprises the steps of placing the iron-based current collector in a potassium permanganate aqueous solution, and performing a hydrothermal reaction to obtain the heterojunction nano-array electrode material, wherein the one-step hydrothermal method adopted by the method has the characteristics of economy, rapidness, environment friendliness, simplicity, rapid reaction and mass production; the iron-based current collector is used as a carrier and an iron source, and an array can be grown on the current collector in situ, so that the mechanical stability of an electrode material is improved, and the charge transmission is accelerated. The obtained heterojunction nano-array electrode material has good stability of delta-MnO 2 And the TM-FeOOH is coupled together to construct a heterojunction, so that the electronic structure can be effectively regulated and controlled, the intrinsic activity is improved, the charge transmission is promoted, more active sites can be provided, and the high-performance OER application is realized.
Description
Technical Field
The invention belongs to the technical field of electrocatalytic oxygen evolution electrode materials. More particularly, relates to a heterojunction nano-array electrode material, a preparation method and application thereof.
Background
Hydrogen energy is a 21 st century promising solution to fossil energy crisis and relief ringThe green energy source for environmental pollution problem and the electrocatalytic decomposition of water to produce hydrogen are effective methods for realizing the large-scale production of high-purity hydrogen. Electrolytic in-water anodic oxygen evolution reaction (OER, 4 OH) - →O 2 +2H 2 O+4e - ) Is a multi-electron reaction process, has slow dynamics, needs higher overpotential, and leads to lower electric energy conversion rate. Current IrO 2 And RuO (Ruo) 2 The noble metal-based catalyst exhibits excellent properties in OER, as disclosed in China patent application 2 -RuO 2 The solid solution material has a rutile type crystal structure, cr and Ru atoms are uniformly distributed in the crystal structure, and the solid solution material has good electrochemical catalytic oxygen evolution performance. However, ru belongs to a noble metal catalyst, and the scarcity and high cost of Ru prevent its large-scale practical application. Therefore, it is very necessary to develop a non-noble metal OER catalyst with high activity and good stability based on elements rich in earth reserves.
In recent years, numerous non-noble metal-based OER catalysts have been widely studied. Wherein, delta-MnO 2 Materials are of interest because of their local configuration similar to that of oxygen evolving complexes (Oxygen Evolution Complex) in green plant photosynthesis system II (PS-II); and due to its unique composition structure, delta-MnO 2 Has excellent stability and corrosion resistance, and is especially suitable for OER under severe conditions (such as natural seawater medium). However, previous studies have shown that delta-MnO 2 The electrocatalytic intrinsic activity of the catalyst is limited, the effect can not meet the requirements of the prior art, and the catalyst is prevented from being widely popularized and applied.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the prior delta-MnO 2 The heterojunction nano array electrode material has the defects and defects of limited electrocatalytic intrinsic activity, can effectively regulate and control an electronic structure, improve the intrinsic activity, promote charge transmission and provide more active sites, so that high-performance OER is realized.
The invention aims to provide a preparation method of a heterojunction nano-array electrode material.
The invention also aims to provide application of the heterojunction nano-array electrode material.
The above object of the present invention is achieved by the following technical scheme:
the preparation method of the heterojunction nano-array electrode material is characterized by comprising the following steps of:
placing the iron-based current collector in a potassium permanganate aqueous solution, performing hydrothermal reaction at 80-250 ℃, and performing post-treatment to obtain the composite material;
wherein the iron-based current collector is iron wire, iron net, iron sheet or foam iron.
Preferably, the temperature of the hydrothermal reaction is 100-200 ℃; more preferably, the temperature of the hydrothermal reaction is 150 to 200 ℃.
Further, the potassium permanganate aqueous solution is added with transition metal salt, dissolved into uniform solution, and then subjected to hydrothermal reaction with the iron-based current collector.
Under hydrothermal conditions, the invention provides a method for preparing potassium permanganate (KMnO 4 ) Oxidation-reduction reaction with iron-based current collector, KMnO 4 Is reduced to delta-MnO 2 Fe is oxidized to Fe 3+ Further adding transition metal salt to generate hydrolysis reaction to generate transition metal oxyhydroxide TM-FeOOH and delta-MnO 2 The coupling formation heterojunction grows together in situ on the iron-based current collector. The method solves the problems of the prior art that the method lacks of economic, simple and large-scale mass production preparation technology for constructing delta-MnO 2 The technical problem of coupling TM-FeOOH heterojunction nano array electrodes. The obtained heterojunction nano array electrode solves the problem of delta-MnO 2 The problem of low intrinsic catalytic activity is solved, meanwhile, due to the design of a heterojunction interface, the electronic structure of the obtained material is regulated and controlled, the number of exposed catalytic active sites is increased, and the charge transmission performance is improved, so that OER application with high activity and high stability is realized.
Still further, the transition metal of the transition metal salt is selected from at least one of Sc, ti, V, cr, mn, co, ni, cu, zn, Y, zr, nb, mo, tc, cd, W, ce. Preferably, the transition metal of the transition metal salt is selected from at least one of V, cr, mn, co, ni, cu, zn, zr, cd, ce.
Further, the transition metal salt is selected from one or more of nitrate, acetate, chloride, carbonate and sulfate.
Preferably, the concentration of the transition metal salt is 0.001-5 mol/L; more preferably, the concentration of the transition metal salt is 0.005-0.1 mol/L; specifically, the concentration may be 0.005mol/L, 0.010mol/L, 0.020mol/L, 0.050mol/L, or 0.100mol/L.
Further, the mass ratio of the potassium permanganate to the transition metal salt is (1 to 50): 1. Preferably, the mass ratio of the potassium permanganate to the transition metal salt is (1-20): 1; more preferably, the mass ratio of potassium permanganate to transition metal salt is 1:1, 2:1, 5:1, 10:1 or 20:1.
Further, the hydrothermal reaction time is 1-96 hours. Preferably, the hydrothermal reaction time is 2 to 30 hours.
Further, the post-treatment comprises washing and drying.
Wherein the washed solvent is at least one of deionized water, methanol, ethanol, propanol and N, N-dimethylformamide.
The temperature of the drying is 25-120 ℃, preferably 35-60 ℃; the drying time is 0.5-96 h.
In addition, the invention also claims the heterojunction nano-array electrode material prepared by the preparation method.
Meanwhile, the invention also provides application of the heterojunction nano-array electrode material in oxygen evolution reaction. In particular, the heterojunction nano-array electrode material can be applied to OER under severe conditions, such as natural seawater medium.
The invention has the following beneficial effects:
the method comprises the steps of placing the iron-based current collector in a potassium permanganate aqueous solution, and performing a hydrothermal reaction to obtain the heterojunction nano-array electrode material, wherein the one-step hydrothermal method adopted by the method has the characteristics of economy, rapidness, environment friendliness, simplicity, rapid reaction and mass production; the iron-based current collector is used as a carrier and an iron source, and can realize in-situ growth of an array on the current collector, thereby improving the mechanical stability of the electrode material and accelerating electricityAnd (5) transmitting the load. The obtained heterojunction nano-array electrode material has good stability of delta-MnO 2 And the TM-FeOOH is coupled together to construct a heterojunction, so that the electronic structure can be effectively regulated and controlled, the intrinsic activity is improved, the charge transmission is promoted, more active sites can be provided, and high-performance OER application, especially OER under severe conditions (such as natural seawater medium) can be realized.
Drawings
FIG. 1 shows delta-MnO produced in example 1 2 X-ray powder diffraction pattern of FeOOH heterojunction nano-array electrode.
FIG. 2 shows delta-MnO produced in example 2 2 SEM image of Ni-FeOOH heterojunction nano-array electrode.
FIG. 3 shows delta-MnO produced in example 3 2 SEM image of Zn-FeOOH heterojunction nano-array electrode.
FIG. 4 shows delta-MnO produced in example 4 2 TEM image of Co-FeOOH heterojunction nano-array electrode.
FIG. 5 shows delta-MnO produced in example 5 2 SEM image of Ce-FeOOH heterojunction nano array electrode.
FIG. 6 shows delta-MnO produced in example 6 2 TEM image of Ti-FeOOH heterojunction nano-array electrode.
FIG. 7 shows delta-MnO produced in example 7 2 TEM image of NiCo-FeOOH heterojunction nano-array electrode.
FIG. 8 shows delta-MnO produced in example 8 2 TEM image of MoCu-FeOOH heterojunction nano-array electrode.
FIG. 9 shows delta-MnO produced in example 9 2 SEM image of MnV-FeOOH heterojunction nano-array electrode.
FIG. 10 shows the delta-MnO produced in comparative example 1 2 -X-ray powder diffraction pattern of a 1-nano array electrode.
FIG. 11 is an LSV curve of the electrode catalytic electrolysis of alkaline pure water OER prepared in example 1, comparative example 2.
FIG. 12 is an LSV curve of the electrode catalytic electrolysis of alkaline pure water OER prepared in example 2, comparative example 3, comparative example 4.
FIG. 13 is an LSV curve of the electrode catalytic electrolysis of alkaline seawater OER prepared in example 4, comparative example 5, and comparative example 6.
FIG. 14 shows LSV curves of the electrode catalytic electrolysis of alkaline seawater OER prepared in example 8, comparative example 7, and comparative example 8.
FIG. 15 shows the current density of 500mA cm for the electrode-catalyzed electrolysis of alkaline seawater OER prepared in example 9, comparative example 9 -2 Potential versus time curve of (c).
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
EXAMPLE 1 delta-MnO 2 FeOOH heterojunction nano array electrode
The delta-MnO 2 The preparation method of the FeOOH heterojunction nano-array electrode comprises the following steps:
s1, 0.158g (1 mmol) of potassium permanganate (KMnO 4 ) Dissolving in 30mL of deionized water, and fully stirring on a magnetic stirrer for 0.5h (the rotation speed of the stirrer is 300 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed iron net into a blast drying oven for hydrothermal reaction after sealing, reacting for 7h at 130 ℃, naturally cooling after the reaction is finished, washing for 3 times by using N, N-dimethylformamide, and drying for 2h at 70 ℃ to obtain delta-MnO growing on the iron net 2 FeOOH heterojunction nano-array electrode.
Characterization of the materials:
the product is identified by an X-ray powder diffractometer, and the crystal phase is delta-MnO 2 And the orthorhombic phase FeOOH, corresponding to PDF card numbers 86-0666 and 18-0639, respectively, see FIG. 1.
EXAMPLE 2 delta-MnO 2 Ni-FeOOH heterojunction nano array electrode
The delta-MnO 2 Ni-FeOOH heterojunction nano array electrodeThe preparation method of the (C) comprises the following steps:
s1, 1.783g (7.5 mmol) of Nickel chloride (NiCl 2 ·6H 2 O) and 11.852g (75 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 150mL deionized water, and fully stirring on a magnetic stirrer for 3h (the rotation speed of the stirrer is 500 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed foam iron into a blast drying oven for hydrothermal reaction after sealing, reacting for 3 hours at 180 ℃, naturally cooling after the reaction is finished, washing for 3 times by ethanol, and drying for 6 hours at 60 ℃ to obtain delta-MnO growing on the foam iron 2 Ni-FeOOH heterojunction nano-array electrode.
Characterization of the materials:
the morphology of the resulting material was characterized by SEM, resulting in fig. 2, which shows that the resulting material is typically ultra-thin nanoplatelets, with individual nanoplatelets having lateral dimensions between 200 and 600 nm.
EXAMPLE 3 delta-MnO 2 Zn-FeOOH heterojunction nano array electrode
The delta-MnO 2 The preparation method of the Zn-FeOOH heterojunction nano-array electrode comprises the following steps:
s1, 2.195g (10 mmol) of zinc acetate (Zn (CH) 3 COO) 2 ·2H 2 O) and 7.901g (50 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 500mL deionized water, and fully stirring on a magnetic stirrer for 3h (the rotation speed of the stirrer is 650 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a plurality of washed iron wires into a blast drying oven for hydrothermal reaction after sealing, reacting for 4 hours at 150 ℃, naturally cooling after the reaction is finished, washing for 3 times by using methanol, and drying for 3 hours at 50 ℃ to obtain delta-MnO growing on the iron wires 2 Zn-FeOOH heterojunction nano-array electrode.
Characterization of the materials:
the morphology of the resulting material was characterized by SEM to give fig. 3, which shows the resulting material as ultra-thin nanoplatelets grown vertically on top of an iron sheet substrate, with individual nanoplatelets having lateral dimensions between 200 and 600 nm.
EXAMPLE 4 delta-MnO 2 Co-FeOOH heterojunction nano array electrode
The delta-MnO 2 The preparation method of the Co-FeOOH heterojunction nano-array electrode comprises the following steps:
s1, 0.996g (4 mmol) of cobalt acetate (Co (CH) 3 COO) 2 ·4H 2 O) and 1.264g (8 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 40mL of deionized water, and fully stirring on a magnetic stirrer for 2h (the rotation speed of the stirrer is 700 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed iron sheet into a blast drying oven for hydrothermal reaction after sealing, reacting for 12h at 120 ℃, naturally cooling after the reaction is finished, washing for 3 times with deionized water, and drying for 8h at 45 ℃ to obtain delta-MnO growing on the iron sheet 2 Co-FeOOH heterojunction nano-array electrode.
Characterization of the materials:
the morphology of the obtained material was characterized by TEM to obtain fig. 4, and it can be seen that the obtained material is an ultrathin nanosheet with wrinkles at the edges.
EXAMPLE 5 delta-MnO 2 Ce-FeOOH heterojunction nano array electrode
The delta-MnO 2 The preparation method of the Ce-FeOOH heterojunction nano array electrode comprises the following steps:
s1, 15.194g (35 mmol) of cerium nitrate (Ce (NO) 3 ) 3 ·6H 2 O) and 16.594g (105 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 35mL of deionized water, and fully stirring on a magnetic stirrer for 10h (the rotation speed of the stirrer is 600 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a plurality of washed iron wires into the kettle, sealing the kettle, putting the kettle into a blast drying box for hydrothermal reaction, reacting for 2 hours at 200 ℃, and naturally cooling the kettle after the reaction is finished, and using N, NAfter 3 washes with dimethylformamide, drying for 24h at 80℃to obtain delta-MnO grown on iron wire 2 A Ce-FeOOH heterojunction nano array electrode.
Characterization of the materials:
the morphology of the resulting material was characterized by SEM, resulting in fig. 5, which shows that the resulting material is typically ultra-thin nanoplatelets, with individual nanoplatelets having lateral dimensions between 200 and 600 nm.
EXAMPLE 6 delta-MnO 2 Ti-FeOOH heterojunction nano array electrode
The delta-MnO 2 The preparation method of the Ti-FeOOH heterojunction nano-array electrode comprises the following steps:
s1, 0.0036g (0.015 mmol) of titanium sulfate (Ti (SO) 4 ) 2 ) And 0.0948g (0.6 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 15mL of deionized water, and fully stirring on a magnetic stirrer for 1h (the rotation speed of the stirrer is 500 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed iron net into a blast drying oven for hydrothermal reaction after sealing, reacting for 6 hours at 100 ℃, naturally cooling after the reaction is finished, washing for 3 times by using propanol, and drying for 48 hours at 35 ℃ to obtain delta-MnO growing on the iron net 2 Ti-FeOOH heterojunction nano-array electrode.
Characterization of the materials:
the morphology of the obtained material was characterized by TEM to obtain fig. 6, and it can be seen that the obtained material is an ultrathin nanosheet with wrinkles at the edges.
EXAMPLE 7 delta-MnO 2 NiCo-FeOOH heterojunction nano-array electrode
The delta-MnO 2 The preparation method of the NiCo-FeOOH heterojunction nano-array electrode comprises the following steps:
s1, 17.449g (60 mmol) of Nickel nitrate (Ni (NO) 3 ) 2 ·6H 2 O), 4.759g (20 mmol) of cobalt chloride (CoCl) 2 ·6H 2 O) and 12.642g (80 mmol) of potassium permanganate (KMnO) 4 ) Dissolved in 100mL of deionized water, and stirred well on a magnetic stirrer for 5 hours (stirringThe rotation speed of the device is 700 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed iron sheet into a blast drying oven for hydrothermal reaction after sealing, reacting for 5 hours at 160 ℃, naturally cooling after the reaction is finished, washing for 5 times by ethanol, and drying for 5 hours at30 ℃ to obtain delta-MnO growing on the iron sheet 2 A NiCo-FeOOH heterojunction nano-array electrode.
Characterization of the materials:
the morphology of the obtained material was characterized by TEM to obtain fig. 7, and it can be seen that the obtained material is an ultrathin nanosheet with wrinkles at the edge.
EXAMPLE 8 delta-MnO 2 MoCu-FeOOH heterojunction nano array electrode
The delta-MnO 2 The preparation method of the MoCu-FeOOH heterojunction nano-array electrode comprises the following steps:
s1, 1.597g (8 mmol) of copper acetate (Cu (CH) 3 COO) 2 ·4H 2 O), 2.555g (8 mmol) of molybdenum nitrate (Mo (NO) 3 ) 3 ·5H 2 O) and 37.927g (240 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 80mL of deionized water, and fully stirring on a magnetic stirrer for 4 hours (the rotation speed of the stirrer is 500 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed iron sheet into a blast drying oven for hydrothermal reaction after sealing, reacting for 8 hours at 140 ℃, naturally cooling after the reaction is finished, washing for 3 times by using N, N-dimethylformamide, and drying for 30 hours at 65 ℃ to obtain delta-MnO growing on the iron sheet 2 MoCu-FeOOH heterojunction nano-array electrode.
Characterization of the materials:
the morphology of the obtained material was characterized by TEM to obtain fig. 8, and it can be seen that the obtained material is an ultrathin nanosheet with wrinkles at the edges.
EXAMPLE 9 delta-MnO 2 MnV-FeOOH heterojunction nano-array electrode
The delta-MnO 2 /MnV-The preparation method of the FeOOH heterojunction nano-array electrode comprises the following steps:
s1, 0.507g (3 mmol) of manganese sulfate (MnSO 4 ·H 2 O), 0.315g (2 mmol) vanadium chloride (VCl 3 ) And 15.803g (100 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 1000mL of deionized water, and fully stirring on a magnetic stirrer for 10h (the rotation speed of the stirrer is 550 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed foam iron into a blast drying oven for hydrothermal reaction after sealing, reacting for 10 hours at 110 ℃, naturally cooling after the reaction is finished, washing for 3 times by deionized water, and drying for 4 hours at 55 ℃ to obtain delta-MnO growing on the foam iron 2 MnV-FeOOH heterojunction nano-array electrode.
Characterization of the materials:
the morphology of the resulting material was characterized by SEM, resulting in fig. 9, which shows that the resulting material is typically ultra-thin nanoplatelets, with individual nanoplatelets having lateral dimensions between 200 and 600 nm.
Comparative example 1 delta-MnO 2 -1 nanoarray electrode
The delta-MnO 2 The preparation method of the-1 nano array electrode comprises the following steps:
s1, 0.158g (1 mmol) of potassium permanganate (KMnO 4 ) Dissolving in 30mL of deionized water, and fully stirring on a magnetic stirrer for 0.5h (the rotation speed of the stirrer is 300 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed carbon cloth into a blast drying oven for hydrothermal reaction after sealing, reacting for 7 hours at 130 ℃, naturally cooling after the reaction is finished, washing for 3 times by using N, N-dimethylformamide, and drying for 2 hours at the temperature of 70 ℃ to obtain delta-MnO growing on the carbon cloth 2 A nano-array electrode;
in comparison with example 1, comparative example 1 is different in that the iron-based current collector is replaced with carbon cloth, and the occurrence of FeOOH in the product is avoided, thereby achieving single-phase delta-MnO 2 Nano arrayPreparation of column electrodes.
Characterization of materials:
the product is identified by an X-ray powder diffractometer, and the crystal phase is delta-MnO 2 The corresponding PDF card numbers are 86-0666, see in particular fig. 10.
Comparative example 2FeOOH nanoarray electrode
The preparation method of the FeOOH nano array electrode comprises the following steps:
s1, adding 30mL of deionized water into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed iron net into the kettle, sealing the kettle, putting the kettle into a blast drying box for hydrothermal reaction, reacting at 130 ℃ for 7 hours, naturally cooling the kettle after the reaction is finished, washing the kettle with N, N-dimethylformamide for 3 times, and drying the kettle at 70 ℃ for 2 hours to obtain the FeOOH heterojunction nano-array electrode growing on the iron net.
Comparative example 2 differs from example 1 in that KMnO was not added 4 Thereby realizing the preparation of FeOOH nano array electrodes.
Comparative example 3 delta-MnO 2 -3 nano-array electrode
The delta-MnO 2 The preparation method of the-3 nano array electrode comprises the following steps:
s1, 11.852g (75 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 150mL deionized water, and fully stirring on a magnetic stirrer for 3h (the rotation speed of the stirrer is 500 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed carbon cloth into a blast drying oven for hydrothermal reaction after sealing, reacting for 3 hours at 180 ℃, naturally cooling after the reaction is finished, washing for 3 times by ethanol, and drying for 6 hours at 60 ℃ to obtain delta-MnO growing on the carbon cloth 2 A nano-array electrode;
compared with example 2, the difference of comparative example 3 is that no transition metal salt is additionally added, and the iron-based current collector is replaced by carbon cloth, so that the occurrence of Ni-FeOOH in the product is avoided, and single-phase delta-MnO is realized 2 And (3) preparing the nano array electrode.
Comparative example 4 Ni-FeOOH nanoarray electrode
The preparation method of the Ni-FeOOH nano array electrode comprises the following steps:
s1, 1.783g (7.5 mmol) of Nickel chloride (NiCl 2 ·6H 2 O) dissolving in 150mL of deionized water, and fully stirring on a magnetic stirrer for 3h (the rotation speed of the stirrer is 500 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed foam iron into a blast drying oven for hydrothermal reaction after sealing, reacting for 3 hours at 180 ℃, naturally cooling after the reaction is finished, washing for 3 times by ethanol, and drying for 6 hours at 60 ℃ to obtain the Ni-FeOOH nano array electrode growing on the foam iron.
Comparative example 4 differs from example 2 in that KMnO was not added 4 Thereby realizing the preparation of the Ni-FeOOH nano array electrode.
Comparative example 5 delta-MnO 2 -5 nm array electrode
The delta-MnO 2 The preparation method of the-5 nano array electrode comprises the following steps:
s1, 1.264g (8 mmol) of potassium permanganate (KMnO) 4 ) Dissolving in 40mL of deionized water, and fully stirring on a magnetic stirrer for 2h (the rotation speed of the stirrer is 700 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed carbon cloth into a blast drying oven for hydrothermal reaction after sealing, reacting for 12 hours at 120 ℃, naturally cooling after the reaction is finished, washing for 3 times with deionized water, and drying for 8 hours at 45 ℃ to obtain delta-MnO growing on the carbon cloth 2 A nano-array electrode;
compared with example 4, the difference of comparative example 5 is that no transition metal salt is additionally added, and the iron-based current collector is replaced by carbon cloth, so that Co-FeOOH is avoided, and single-phase delta-MnO is realized 2 And (3) preparing the nano array electrode.
Comparative example 6 Co-FeOOH nanoarray electrode
The preparation method of the Co-FeOOH nano array electrode comprises the following steps:
s1, 0.996g (4 mmol) of cobalt acetate (Co (CH) 3 COO) 2 ·4H 2 O) dissolving in 40mL of deionized water, and fully stirring on a magnetic stirrer for 2h (the rotation speed of the stirrer is 700 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed iron sheet into a blast drying oven for hydrothermal reaction after sealing, reacting for 12 hours at 120 ℃, naturally cooling after the reaction is finished, washing for 3 times by deionized water, and drying for 8 hours at 45 ℃ to obtain the Co-FeOOH nano array electrode growing on the iron sheet.
Comparative example 6 differs from example 4 in that KMnO was not added 4 Thereby realizing the preparation of the Co-FeOOH nano array electrode.
Comparative example 7 delta-MnO 2 -7 nm array electrode
The delta-MnO 2 The preparation method of the-7 nano array electrode comprises the following steps:
s1, 37.927g (240 mmol) of potassium permanganate (KMnO 4 ) Dissolving in 80mL of deionized water, and fully stirring on a magnetic stirrer for 4 hours (the rotation speed of the stirrer is 500 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed carbon cloth into a blast drying oven for hydrothermal reaction after sealing, reacting for 8 hours at 140 ℃, naturally cooling after the reaction is finished, washing for 3 times by using N, N-dimethylformamide, and drying for 30 hours at 65 ℃ to obtain delta-MnO growing on the carbon cloth 2 A nano-array electrode.
Compared with example 8, the difference of comparative example 7 is that no transition metal salt is additionally added, and the iron-based current collector is replaced by carbon cloth, so that MoCu-FeOOH is avoided, and single-phase delta-MnO is realized 2 And (3) preparing the nano array electrode.
Comparative example 8 MoCu-FeOOH nanoarray electrode
The preparation method of the MoCu-FeOOH nano array electrode comprises the following steps:
s1, 1.597g (8 mmol) of copper acetate (Cu (CH) 3 COO) 2 ·4H 2 O) and 2.555g (8 mmol) of molybdenum nitrate (Mo (NO) 3 ) 3 ·5H 2 O) dissolving in 80mL of deionized water, and fully stirring on a magnetic stirrer for 4 hours (the rotation speed of the stirrer is 500 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a piece of washed iron sheet into a blast drying oven for hydrothermal reaction after sealing, reacting for 8 hours at 140 ℃, naturally cooling after the reaction is finished, washing for 3 times by using N, N-dimethylformamide, and drying for 30 hours at 65 ℃ to obtain the MoCu-FeOOH nano array electrode growing on the iron sheet;
comparative example 8 differs from example 8 in that KMnO was not added 4 Thereby realizing the preparation of the MoCu-FeOOH nano array electrode.
Comparative example 9 delta-MnO 2 -9 nanoarray electrode
The delta-MnO 2 The preparation method of the-9 nano array electrode comprises the following steps:
s1, 15.803g (100 mmol) of potassium permanganate (KMnO 4 ) Dissolving in 1000mL of deionized water, and fully stirring on a magnetic stirrer for 10h (the rotation speed of the stirrer is 550 r/min) to obtain a uniform mixed solution;
s2, transferring the mixed solution obtained in the step S1 into a polytetrafluoroethylene high-pressure reaction kettle, putting a circle of washed carbon cloth, sealing, putting into a blast drying box for hydrothermal reaction, reacting at 110 ℃ for 10 hours, naturally cooling after the reaction is finished, washing with deionized water for 3 times, and drying at 55 ℃ for 4 hours to obtain delta-MnO growing on the carbon cloth 2 A nano-array electrode.
Compared with example 9, the difference of comparative example 9 is that no transition metal salt is additionally added, and the iron-based current collector is replaced by carbon cloth, so that MnV-FeOOH is avoided, and single-phase delta-MnO is realized 2 And (3) preparing the nano array electrode.
Application example 1 Performance test of electrocatalytic alkaline pure water decomposition OER
Electrocatalytic testing was performed using a computer controlled electrochemical workstation (Autolab, PGSTAT 302N) using a standard three electrode system. The main indexes for evaluating the activity of the electrocatalytic material are as follows: the current density reaches 100mA cm -2 Voltage required at the time (E 100 )。
The testing method comprises the following steps: the electrocatalytic performance of the samples was studied in a three electrode system with 1.0M KOH alkaline pure water as electrolyte, and then with the prepared heterojunction nano-array electrode (comparative example nano-array electrode) (size 1cm x 1 cm) as working electrode, pt as counter electrode, hg/HgO (immersed in 1M KOH solution) as reference electrode. According to formula E (RHE) ＝E (Hg/HgO) +0.098+0.0591×pH, potential value E (RHE) From E (Hg/HgO) Converted into the product. Before recording the electrocatalytic activity of the catalyst, the catalyst was activated by CV (0.1V-0.8V vs. Hg/HgO) scanning in an electrolyte under stirring, and after CV scanning was stabilized, LSV curves (0.1V-1.1V vs. Hg/HgO) were tested. Meanwhile, the obtained polarization curve is subjected to iR correction by using 95% of Rs value when data processing is performed, and the solution resistance is compensated.
The alkaline pure water decomposition OER performance of example 1 and comparative example 1, comparative example 2 was tested, and the results thereof are shown in fig. 11.
As can be seen from the graph, for the alkaline pure water decomposition OER performance, delta-MnO 2 FeOOH heterojunction nano-array electrode and delta-MnO 2 -1 nanoarray electrode, feOOH nanoarray electrode, has smaller E 100 Better performance, E 100 RHE is in particular delta-MnO 2 /FeOOH(1.493V)<FeOOH(1.532V)<δ-MnO 2 -1(1.593V)。
Application example 2 Performance test of electrocatalytic alkaline pure water decomposition OER
Electrocatalytic testing was performed using a computer controlled electrochemical workstation (Autolab, PGSTAT 302N) using a standard three electrode system. Main index for evaluating electrocatalytic material activity: the current density reaches 100mA cm -2 Voltage required at the time (E 100 )。
The testing method comprises the following steps: the electrocatalytic performance of the samples was studied in a three electrode system with 1.0M KOH alkaline pure water as electrolyte, and then with the prepared heterojunction nano-array electrode (comparative example nano-array electrode) (size 1cm x 1 cm) as working electrode, pt as counter electrode, hg/HgO (immersed in 1M KOH solution) as reference electrode. According to formula E (RHE) ＝E (Hg/HgO) +0.098+0.0591×pH, potential value E (RHE) From E (Hg/HgO) Converted into the product. Before recording the electrocatalytic activity of the catalyst, the catalyst was activated by CV (0.1V-0.8V vs. Hg/HgO) scanning in an electrolyte under stirring, and after CV scanning was stabilized, LSV curves (0.1V-1.1V vs. Hg/HgO) were tested. Meanwhile, the obtained polarization curve is subjected to iR correction by using 95% of Rs value when data processing is performed, and the solution resistance is compensated.
The alkaline pure water decomposition OER performance of example 2 and comparative examples 3 and 4 was tested, and the results thereof are shown in fig. 12.
As can be seen from the graph, for the alkaline pure water decomposition OER performance, delta-MnO 2 Ni-FeOOH heterojunction nano array electrode and delta-MnO 2 -3 nanoarray electrode, ni-FeOOH nanoarray electrode, has smaller E 100 Better performance, E 100 RHE is in particular delta-MnO 2 /Ni-FeOOH(1.464V)<Ni-FeOOH(1.514V)<δ-MnO 2 -3(1.597V)。
Application example 3 Performance test of electrocatalytic alkaline seawater OER
Electrocatalytic testing was performed using a computer controlled electrochemical workstation (Autolab, PGSTAT 302N) using a standard three electrode system. Main index for evaluating electrocatalytic material activity: the current density reaches 100mA cm -2 Voltage required at the time (E 100 )。
The testing method comprises the following steps: the electrocatalytic performance of the samples was studied in a three electrode system with alkaline seawater containing 1.0M KOH as electrolyte, and then with the prepared heterojunction nano-array electrode (comparative example, nano-array electrode) (size 1cm x 1 cm) as working electrode, pt as counter electrode, hg/HgO (immersed in 1M KOH solution) as reference electrode. According to formula E (RHE) ＝E (Hg/HgO) +0.098+0.0591×pH, potential value E (RHE) From E (Hg/HgO) Converted into the product. Before recording the electrocatalytic activity of the catalyst, the catalyst was activated by CV (0.1V-0.8V vs. Hg/HgO) scanning in an electrolyte under stirring, and after CV scanning was stabilized, LSV curves (0.1V-1.1V vs. Hg/HgO) were tested. Meanwhile, the obtained polarization curve is subjected to iR correction by using 95% of Rs value when data processing is performed, and the solution resistance is compensated.
OER performance in alkaline seawater of example 4 and comparative example 5, comparative example 6 was tested, and the results are shown in fig. 13.
As can be seen from the graph, for OER performance of alkaline seawater, delta-MnO 2 Co-FeOOH heterojunction nano-array electrode and delta-MnO 2 -5 nanoarray electrode, co-FeOOH nanoarray electrode with smaller E 100 Better performance, E 100 RHE is in particular delta-MnO 2 /Co-FeOOH(1.469V)<Co-FeOOH(1.516V)<δ-MnO 2 -5(1.613V)。
Application example 4 Performance test of electrocatalytic alkaline seawater OER
Electrocatalytic testing was performed using a computer controlled electrochemical workstation (Autolab, PGSTAT 302N) using a standard three electrode system. Main index for evaluating electrocatalytic material activity: the current density reaches 100mA cm -2 Voltage required at the time (E 100 )。
The electrocatalytic performance of the samples was studied in a three electrode system with alkaline seawater containing 1.0M KOH as electrolyte, and then with the prepared heterojunction nano-array electrode (comparative example, nano-array electrode) (size 1cm x 1 cm) as working electrode, pt as counter electrode, hg/HgO (immersed in 1M KOH solution) as reference electrode. According to formula E (RHE) ＝E (Hg/HgO) +0.098+0.0591×pH, potential value E (RHE) From E (Hg/HgO) Converted into the product. Before recording the electrocatalytic activity of the catalyst, the catalyst was activated by CV (0.1V-0.8V vs. Hg/HgO) scanning in an electrolyte under stirring, and after CV scanning was stabilized, LSV curves (0.1V-1.1V vs. Hg/HgO) were tested. At the same time, the obtained polarization curves are 95% used in data processingAnd (3) performing iR correction on the Rs value of the resistor, and compensating the solution resistance.
OER performance of example 8 and comparative examples 7 and 8 in alkaline seawater was tested, and the results are shown in fig. 14.
As can be seen from the graph, for OER performance of alkaline seawater, delta-MnO 2 MoCu-FeOOH heterojunction nano array electrode and delta-MnO 2 -7 nanoarray electrode, moCu-FeOOH nanoarray electrode with smaller E 100 Better performance, E 100 RHE is in particular delta-MnO 2 /MoCu-FeOOH(1.461V)<MoCu-FeOOH(1.513V)<δ-MnO 2 -7(1.612V)。
Application example 5 Performance test of electrocatalytic alkaline seawater OER
Electrocatalytic testing was performed using a computer controlled electrochemical workstation (Autolab, PGSTAT 302N) using a standard three electrode system. Main index for evaluating stability of electrocatalytic material: the current density reaches 500mA cm -2 Voltage required at the time (E 500 ) Is a stable degree of (c).
The electrocatalytic performance of the samples was studied in a three electrode system with alkaline seawater containing 1.0M KOH as electrolyte, and then with the prepared heterojunction nano-array electrode (comparative example, nano-array electrode) (size 1cm x 1 cm) as working electrode, pt as counter electrode, hg/HgO (immersed in 1M KOH solution) as reference electrode. According to formula E (RHE) ＝E (Hg/HgO) +0.098+0.0591×pH, potential value E (RHE) From E (Hg/HgO) Converted into the product. Before recording the electrocatalytic activity of the catalyst, the catalyst was activated by CV (0.1V-0.8V vs. Hg/HgO) scanning in an electrolyte under stirring, and after CV scanning was stabilized, LSV curves (0.1V-1.1V vs. Hg/HgO) were tested. Meanwhile, the obtained polarization curve is subjected to iR correction by using 95% of Rs value when data processing is performed, and the solution resistance is compensated.
OER stability in alkaline seawater was tested for example 9 and comparative example 9, the results of which are shown in fig. 15.
As can be seen from the graph, the OER stability for alkaline seawater was at 500mA cm -2 delta-MnO at current density 2 -9 nanoarraysThe required potential for the column electrode was 1.783V vs. RHE, but after 120h of operation the potential increased by nearly 60mV, while the delta-MnO 2 The required potential of the MnV-FeOOH heterojunction nano-array electrode is 1.510V vs. RHE, the potential is increased to less than 10mV after 120 hours of operation, the catalytic activity is higher, and the stability is better.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the heterojunction nano-array electrode material is characterized by comprising the following steps of:
adding transition metal salt into a potassium permanganate aqueous solution, dissolving to obtain a uniform solution, placing an iron-based current collector into the uniform solution, performing hydrothermal reaction at 80-250 ℃, wherein the hydrothermal reaction time is 1-96 h, and performing post-treatment to obtain the composite material;
wherein the iron-based current collector is iron wire, iron net, iron sheet or foam iron;
the transition metal of the transition metal salt is selected from at least one of Sc, ti, V, cr, mn, co, ni, cu, zn, Y, zr, nb, mo, tc, cd, W, ce; the mass ratio of the potassium permanganate to the transition metal salt is (1-50): 1;
the heterojunction nano-array electrode material is delta-MnO 2 And coupling a TM-FeOOH heterojunction nano-array electrode, wherein TM is the transition metal.
2. The method according to claim 1, wherein the transition metal of the transition metal salt is at least one selected from V, cr, mn, co, ni, cu, zn, zr, cd, ce.
3. The method according to claim 1, wherein the transition metal salt is one or more selected from the group consisting of nitrate, acetate, chloride, carbonate and sulfate.
4. The method according to claim 1, wherein the hydrothermal reaction is performed at a temperature of 100 to 200 ℃.
5. The heterojunction nano-array electrode material prepared by the preparation method of any one of claims 1-4.
6. The use of the heterojunction nano-array electrode material of claim 5 in oxygen evolution reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210521647.3A CN114672837B (en) | 2022-05-13 | 2022-05-13 | Heterojunction nano array electrode material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210521647.3A CN114672837B (en) | 2022-05-13 | 2022-05-13 | Heterojunction nano array electrode material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114672837A CN114672837A (en) | 2022-06-28 |
| CN114672837B true CN114672837B (en) | 2023-09-19 |
Family
ID=82079751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210521647.3A Active CN114672837B (en) | 2022-05-13 | 2022-05-13 | Heterojunction nano array electrode material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114672837B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113416980B (en) * | 2021-06-09 | 2023-03-21 | 江西理工大学 | Efficient full-hydrolysis water catalyst MoO 2 -CeO x /NF and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110723755A (en) * | 2019-10-25 | 2020-01-24 | 北京化工大学 | Fe7S8alpha-FeOOH/iron-based electrode material and preparation method and application thereof |
| CN110947374A (en) * | 2019-12-16 | 2020-04-03 | 佛山职业技术学院 | Hydroxyl metal oxide nano catalyst and preparation method thereof |
-
2022
- 2022-05-13 CN CN202210521647.3A patent/CN114672837B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110723755A (en) * | 2019-10-25 | 2020-01-24 | 北京化工大学 | Fe7S8alpha-FeOOH/iron-based electrode material and preparation method and application thereof |
| CN110947374A (en) * | 2019-12-16 | 2020-04-03 | 佛山职业技术学院 | Hydroxyl metal oxide nano catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| Cheng, Bo 等.Accelerating water oxidation kinetics via synergistic in-layer modification and interlayer reconstruction over hetero-epitaxial Fe-Mn-O nanosheets.Chemical Engineering Journal.2022,第441卷第136122页. * |
| Sanjit Saha等.In-situ hydrothermal synthesis of MnO2/NiO@Ni hetero structrure electrode for hydrogen evolution reaction and high energy asymmetric supercapacitor applications.Journal of Energy Storage.2016,第22-31页. * |
| 罗娟.过渡金属氧化物纳米复合材料的制备及其电催化裂解水性能研究.中国优秀硕士学位论文全文数据库-工程科技I辑.2022,(1),第B015-177页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114672837A (en) | 2022-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111229232B (en) | Foam nickel-based porous NiFe hydrotalcite nano-sheet and preparation and application thereof | |
| CN110055557B (en) | Three-dimensional nickel-doped iron-based oxygen evolution catalyst and preparation method and application thereof | |
| CN108396329B (en) | Iron-doped two-phase nickel sulfide nano array material, preparation method and application thereof | |
| CN110639534B (en) | Oxygen evolution electrocatalytic material and preparation method and application thereof | |
| CN111282582A (en) | Preparation method of foam nickel-based catalyst for hydrogen production by water electrolysis | |
| CN113373476B (en) | Phosphorus-doped bimetallic selenide electrocatalyst material with single metal element and adjustable electronic structure as well as preparation method and application thereof | |
| CN110947374A (en) | Hydroxyl metal oxide nano catalyst and preparation method thereof | |
| CN109999845B (en) | All-iron-based oxygen evolution catalyst and preparation method and application thereof | |
| CN109354056B (en) | Iron-doped copper sulfide nanosheet material with abundant defects and preparation method and application thereof | |
| CN113481534A (en) | Preparation method of zirconium-doped cobalt-iron layered double hydroxide with low crystallinity and application of zirconium-doped cobalt-iron layered double hydroxide in hydrogen production by water electrolysis | |
| CN114672837B (en) | Heterojunction nano array electrode material and preparation method and application thereof | |
| CN114540831A (en) | Nickel-iron bimetal coordination polymer catalyst for water electrolysis and preparation method thereof | |
| CN111777102A (en) | Metal oxide-based bifunctional water decomposition nano material and preparation method thereof | |
| CN113457689A (en) | Three-dimensional structure iron-doped cobalt-molybdenum oxide composite material and preparation method and application thereof | |
| CN116180128A (en) | Self-supporting non-noble metal electrocatalyst material, and preparation method and application thereof | |
| CN111905818A (en) | MOF-based two-dimensional ultrathin electrocatalyst and preparation method and application thereof | |
| CN116219490A (en) | Preparation and application of high-performance low-noble metal electrode for electrolyzed water | |
| CN115522216A (en) | Phosphorus-doped pentlandite electrocatalyst and preparation method thereof | |
| CN113293407B (en) | Iron-rich nanobelt oxygen evolution electrocatalyst and preparation method thereof | |
| CN113388860B (en) | Preparation method of ferric oxide/CuCo-MOF/carbon cloth oxygen evolution composite electrocatalytic film | |
| CN115323392B (en) | Preparation of efficient Co/NiCoP/CC heterogeneous nanoparticle hydrogen evolution reaction electrocatalyst | |
| CN114990627B (en) | NiFe LDHs-NiFe alloy gradient transition catalytic material and application thereof | |
| CN115110113B (en) | Rod-shaped Co 2 C-MoN composite material and preparation method and application thereof | |
| CN115784327B (en) | Mid-entropy sulfide material with MOF structure and preparation method thereof | |
| CN114990619B (en) | Amorphous NiOOH/Ni 3 S 2 Nickel-based composite catalyst with heterojunction structure, 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 |