CN117144411B - NiFeHP/MXene/NF self-supporting integral composite electrode and preparation method and application thereof - Google Patents

NiFeHP/MXene/NF self-supporting integral composite electrode and preparation method and application thereof Download PDF

Info

Publication number
CN117144411B
CN117144411B CN202311438406.3A CN202311438406A CN117144411B CN 117144411 B CN117144411 B CN 117144411B CN 202311438406 A CN202311438406 A CN 202311438406A CN 117144411 B CN117144411 B CN 117144411B
Authority
CN
China
Prior art keywords
mxene
nifehp
electrode
self
composite electrode
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
Application number
CN202311438406.3A
Other languages
Chinese (zh)
Other versions
CN117144411A (en
Inventor
杨乃涛
孙苗
孟秀霞
张维民
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.)
Shandong University of Technology
Original Assignee
Shandong University of 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 Shandong University of Technology filed Critical Shandong University of Technology
Priority to CN202311438406.3A priority Critical patent/CN117144411B/en
Publication of CN117144411A publication Critical patent/CN117144411A/en
Application granted granted Critical
Publication of CN117144411B publication Critical patent/CN117144411B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/50—Processes
    • 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
    • C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
    • C25B11/053—Electrodes comprising one or more electrocatalytic coatings on a substrate characterised by multilayer electrocatalytic coatings
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/01—Products
    • C25B3/07—Oxygen containing compounds
    • 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
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/23—Oxidation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention belongs to the technical field of electrolytic processes for producing hydrogen, and particularly relates to a NiFeHP/MXene/NF self-supporting integral composite electrode, and a preparation method and application thereof. Taking pretreated foam nickel as a substrate, taking MXene colloid deposition solution as electrolyte, applying a constant voltage field to promote ordered deposition of MXene on the surface of the foam nickel, performing heat treatment, and then performing freeze drying to obtain an MXene/NF electrode; and (3) taking an MXene/NF electrode as a working electrode, agCl/Ag as a reference electrode, taking a graphite rod as an auxiliary electrode, and adopting an electrosynthesis liquid to perform electrosynthesis, washing and vacuum drying to obtain the NiFeHP/MXene/NF self-supporting integral composite electrode. The invention has high conductivity, super hydrophilicity and corrosion resistance, and has excellent performance in the field of full electrolysis hydrogen production of ethanol coupling seawater.

Description

NiFeHP/MXene/NF self-supporting integral composite electrode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrolytic processes for producing hydrogen, and particularly relates to a NiFeHP/MXene/NF self-supporting integral composite electrode, and a preparation method and application thereof.
Background
Excessive consumption of fossil energy causes problems such as energy shortage and global climate abnormality, and sustainable development of human society is hindered. Therefore, there is an urgent need for human beings to develop clean energy. Hydrogen energy can replace fossil fuel to become a green energy carrier, so that water electrolysis hydrogen production becomes an effective way for solving energy shortage and climate change. Seawater is a rich renewable water resource accounting for 96.5% of the world. Thus, the direct use of seawater for electrolysis to achieve sustainable hydrogen production provides a viable and promising approach; however, the competing reaction kinetics between anodic Oxygen Evolution Reactions (OER) and corrosive chloride ion reactions (CER) make seawater electrolysis very challenging, especially at high current densities. Currently, one of the main considerations in the treatment of chlorides is to maintain an overpotential limit of 480 mV, under conditions that prevent hypochlorite formation in the seawater.
In order to solve the above problems, on the one hand, a novel efficient catalyst is needed to reduce the overpotential required for the anodic oxidation reaction; on the other hand, new approaches to solve the above problems may attempt a new concept of seawater coupled biomass ethanol electrolysis, for example, to utilize thermodynamically favored organic reforming reactions as a substitute for OER to reduce the overpotential required for the anodic oxidation reaction.
Bimetallic phosphides, in particular NiFe phosphine (Ni x Fe y HP z ) Shows the ability to capture hydrogen protons, and can enhance the catalytic activity of Hydrogen Evolution Reaction (HER). An advantage of such a bimetallic phosphide structure is that it is able to effectively catalyze the generation and release of hydrogen ions, thereby promoting the efficiency of the HER process. In addition, the high intrinsic electron conductivity of the catalyst may promote rapid charge transfer during electrocatalysis facilitating the catalytic activity of the Oxygen Evolution Reaction (OER). In recent years, MXene materials have been attracting attention due to its hydrophilicity and high electrical conductivity. MXene is a two-dimensional material with an open layered structure, wherein metal ions are interconnected through chemical bonds formed with carbon and oxygen atoms, and has certain corrosion resistance. Thus, bimetallic phosphinate (e.g., ni x Fe y HP z ) And materials with high conductivity and hydrophilicity (such as MXene) have important application potential in catalyst design.
Chinese patent CN 113684501A discloses a nickel-iron-based phosphide electrocatalytic material, a preparation method and application thereof, wherein a nickel foam material (Ni) modified by nickel phosphide nano-rods is obtained by a high-temperature phosphating method x P/NF) followed by Ni x Uniformly growing amorphous nickel-iron (oxygen) hydroxide (Ni, fe) OOH nano particles on P/NF to obtain (Ni, fe) OOH@Ni x P/NF heterostructure OER electrocatalyst. In the phosphating step, the phosphating temperature is high, expensive argon is needed for phosphating as carrier gas, and the phosphating device is complicated. The product of the patent is not compounded with MXene, and the conductivity and the hydrophilicity of the amorphous metal phosphide per se are still to be improved, so that the adsorption of seawater on the electrode and the transmission of electrons on the conductive matrix are not facilitated; the foam nickel does not have corrosion prevention measures, is easy to erode by seawater, and is only suitable for OER (oxygen evolution reaction) in the seawater.
Chinese patent CN 113638002A discloses a FeCo LDH/Ti 3 C 2 MXene/NF composite material, preparation method and application thereof, adding LiF powder into HCl solution, and then adding Ti 3 AlC 2 After powder and oil bath stirring and etching, centrifugally washing to obtain multilayer Ti 3 C 2 T x Precipitating; ti is mixed with 3 C 2 T x The precipitate was redispersed in deionized water and the upper exfoliated monolayer of s-Ti was collected by centrifugation 3 C 2 The suspension was then collected by centrifugation for s-Ti 3 C 2 Precipitation to give a exfoliated monolayer of s-Ti 3 C 2 A solid; will s-Ti 3 C 2 The solid is redispersed to form a solution, foam nickel is immersed, and MXene/NF is formed through electrostatic self-assembly; MXene/NF, feCl 3 、CoCl 2 ·6H 2 O and urea undergo one-step hydrothermal reaction, cooling, washing and drying to obtain FeCo LDH/Ti 3 C 2 An MXene/NF composite having a unique sea urchin-like structure. The MXene/NF is formed by self-assembly of charged static electricity of the MXene nano-sheet, and the composite material is only applied to electrocatalytic oxygen evolution. The MXene nano-sheet has limited self-charge, and the MXene nano-sheet has dispersed self-charge and low electric quantity relative to the current field charge of an electrochemical workstation. The patent utilizes MXene nano-meterThe relatively weak charges carried by the sheet self-assemble to form MXene/NF, the bonding force between the MXene and the substrate is limited, and the overall stability of the electrode is not facilitated.
Disclosure of Invention
The invention aims to provide a NiFeHP/MXene/NF self-supporting integral composite electrode which has high conductivity, super hydrophilicity and corrosion resistance and has excellent performance in the field of full-electrolysis hydrogen production of ethanol coupling seawater; the invention also provides a preparation method and application of the NiFeHP/MXene/NF self-supporting integral composite electrode.
The self-supporting integral type composite electrode of NiFeHP/MXene/NF provided by the invention takes NF as a substrate, MXene grows on NF to obtain an MXene/NF electrode, and sea cucumber-shaped NiFeHP grows on the surface of MXene to obtain the self-supporting integral type composite electrode of NiFeHP/MXene/NF; wherein, the surface of the sea cucumber-shaped NiFeHP has a spike-shaped structure.
The preparation method of the NiFeHP/MXene/NF self-supporting integral composite electrode comprises the following steps:
(1) Pretreating foam nickel to obtain pretreated foam nickel;
(2) Preparing MXene colloid deposition solution;
(3) Taking the pretreated foam nickel obtained in the step (1) as a substrate, taking the MXene colloid deposition liquid obtained in the step (2) as an electrolyte, applying a constant voltage field to promote ordered deposition of MXene on the surface of the foam nickel, performing heat treatment, and then performing freeze drying to obtain an MXene/NF electrode;
(4) And (3) taking the MXene/NF electrode obtained in the step (3) as a working electrode, agCl/Ag as a reference electrode, and a graphite rod as an auxiliary electrode, and performing electrosynthesis by adopting electrosynthesis liquid, washing and vacuum drying to obtain the NiFeHP/MXene/NF self-supporting integral composite electrode.
The pretreatment in the step (1) is that foam nickel is sequentially subjected to hydrochloric acid, acetone and ultrapure water cleaning treatment and vacuum drying.
The preparation method of the MXene colloid deposition solution in the step (2) is monolayer Ti 3 C 2 Adding HCl into the MXene suspension to adjust the pH to 3-5 to obtain acidified MXene colloidAnd (3) a deposition solution.
Said single layer Ti 3 C 2 The preparation method of the MXene suspension comprises the following steps:
(1) Adding LiF powder into HCl solution, and then adding Ti 3 AlC 2 After stirring and etching the powder in water bath, centrifugally washing to obtain the multilayer Ti 3 C 2 Tx precipitation;
(2) Multilayer Ti 3 C 2 Adding Tx precipitate into ultrapure water, stirring, and performing ice bath ultrasonic treatment to obtain single-layer Ti 3 C 2 MXene suspension.
The voltage of the constant voltage field in the step (3) is 5-20mV.
The holding time of the constant voltage field in the step (3) is 15-20 seconds.
The heat treatment in the step (3) is vacuum heat treatment, the heat treatment temperature is 25-30 ℃, and the heat treatment time is 3-5 hours.
The freeze-drying temperature in the step (3) is-80 to-60 ℃, and the freeze-drying time is 15 to 20 hours.
The electrosynthetic liquid in the step (4) is Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 2 ·9H 2 O、NaH 2 PO 2 ·H 2 O and a solvent, wherein Ni (NO 3 ) 2 ·6H 2 The mass concentration of O in the electrosynthetic liquid is 1-2% 3 ) 2 ·9H 2 The mass concentration of O in the electrosynthetic liquid is 0.5-1.0% 2 PO 2 ·H 2 The mass concentration of O in the electrosynthetic liquid is 0.3-0.7 per mill; the solvent is a mixed solution of ethanol and deionized water, and the mass ratio of the ethanol to the deionized water is 3:1-9.
The electrosynthesis described in step (4) comprises the steps of:
(1) 3 scans were performed at a scan rate of 5mV/s over a voltage range of-1.5-0.2V;
(2) 3 scans were performed at a scan rate of 1mV/s over a voltage range of-2-0.2V.
The vacuum drying temperature in the step (4) is 80-120 ℃, and the vacuum drying time is 8-12 hours.
The working area of the MXene/NF electrode in the step (4) is 1 multiplied by 1cm 2 。
The electrosynthesis described in step (4) is carried out at ambient temperature and pressure.
The preparation method of the NiFeHP/MXene/NF self-supporting integral composite electrode comprises the following specific steps:
(1) Sequentially cleaning the foam nickel by hydrochloric acid, acetone and ultrapure water, and vacuum drying to obtain pretreated foam nickel;
(2) Single layer Ti 3 C 2 Adding HCl into the MXene suspension to adjust the pH to 3-5 to obtain acidified MXene colloid deposition solution;
(3) Taking the pretreated foam nickel obtained in the step (1) as a substrate, taking the MXene colloid deposition liquid obtained in the step (2) as electrolyte, and applying a constant voltage field of 5-20mV in a double-electrode electrolytic cell, wherein the voltage field exists for 15-20 seconds, so that a single-layer charged MXene nano-sheet is attached to NF under the action of the voltage field; drying the electrode for 3-5 hours under the low-temperature vacuum condition of 25-30 ℃ to slowly remove the moisture in the MXene suspension, so that the MXene forms a relatively dense porous structure; and finally, completely removing water from the electrode by using a freeze dryer to obtain the MXene/NF electrode with the three-dimensional array structure.
(4) And (3) taking the MXene/NF electrode obtained in the step (3) as a working electrode, agCl/Ag as a reference electrode, and a graphite rod as an auxiliary electrode, performing electrosynthesis by adopting electrosynthesis liquid, flushing a sample with deionized water, and vacuum drying to obtain the NiFeHP/MXene/NF self-supporting integral composite electrode with the sea cucumber-shaped porous network.
The invention adopts a mild heat treatment method to lead the combination of the foam nickel surface and the MXene interface to be more compact.
The bottom layer in the NiFeHP/MXene/NF self-supporting integral composite electrode prepared by the invention is NF (foam nickel), the middle layer is three-dimensional porous high-conductivity MXene, and the outermost layer is NiFeHP with a bimetallic active center; wherein, the shape of NiFeHP is sea cucumber, and the surface of the NiFeHP has a spike-shaped structure.
The self-supporting integral type composite electrode of NiFeHP/MXene/NF prepared by the invention takes NF as a substrate, MXene grows on NF to protect NF from seawater erosion, niFeHP grows on the surface of MXene, and the NiFeHP has a rough surface with hydrophilic and hydrophobic properties.
The NiFeHP/MXene/NF self-supporting integral composite electrode prepared by the invention has high conductivity, super hydrophilicity and corrosion resistance, the hydrophilic and hydrophobic surface can improve the exposure degree of an active center and enhance the inherent activity of the active center, the overpotential is reduced, and the self-supporting integral composite electrode shows excellent full-electrolysis electrocatalytic activity in sea water; meanwhile, the composite electrode can form phosphate anions to resist corrosion of chloride ions in seawater in the electrochemical reaction process, and has excellent long-term stability, so that the composite electrode has potential application value in the field of seawater electrolysis.
The composite electrode has a heterostructure of sea cucumber-shaped NiFeHP and three-dimensional porous high-conductivity MXene composite NF, and can improve the exposure degree of an active center and enhance the inherent activity of the active center. The hydrogen phosphate groups can enhance the adsorption energy of oxygen-containing species and can combine highly conductive and hydrophilic MXene. In addition, the porous network structure on the surface of the electrode is provided with a large number of nano cavities, so that the permeation of electrolyte and the release of bubbles can be promoted, the adsorption and desorption of reaction intermediates are promoted, the mass transfer capacity is improved, and more catalytic active sites are exposed. At the heterojunction, a synergistic self-driven electron transfer from NiFeHP to MXene can produce a high carrier density. This will optimize EOR reactions and HER catalytic performance in alkaline seawater, reduce overpotential, avoid hypochlorite formation.
The application of the NiFeHP/MXene/NF self-supporting integral composite electrode is to take a mixed solution of alkali, ethanol and seawater as an electrolyte, and the NiFeHP/MXene/NF self-supporting integral composite electrode is adopted for electrolysis to obtain hydrogen and acetic acid.
The preparation method of the electrolyte comprises the following steps:
(1) Pretreatment of natural seawater: adding alkali into natural seawater and filtering to obtain alkaline seawater;
(2) Preparing an alkali-ethanol-seawater system electrolyte: adding ethanol into the alkaline seawater obtained in the step (1), uniformly stirring and carrying out ultrasonic treatment to obtain an alkaline-ethanol-seawater system electrolyte.
The natural seawater in the step (1) is preferably the seawater of Bohai Bay.
The base in the step (1) is KOH, and the molar concentration of KOH is 1.0M.
The pH of the alkaline seawater in the step (1) is 8.0.
The molar concentration of ethanol described in step (2) was 1.0M.
The ultrasonic time in the step (2) was 5 minutes.
The application of the NiFeHP/MXene/NF self-supporting integral composite electrode is that the mixed solution of alkali, ethanol and seawater is used as electrolyte, two NiFeHP/MXene/NF self-supporting integral composite electrodes are respectively used as an anode and a cathode to carry out full electrolysis reaction, the anode oxidizes the ethanol into acetic acid, the cathode electrolyzes the seawater to generate hydrogen, and the oxidation potential of the full seawater electrolysis is reduced.
The invention uses NiFeHP/MXene/NF heterostructure catalyst electrode in ethanol coupling seawater electrolysis hydrogen production and acetic acid production, and carries out the reaction of producing the hydrogen by the seawater electrolysis and simultaneously carrying out ethanol oxidation in a double-electrode electrolytic cell by LSV technology. After reaction by LSV technique, hydrogen at the cathode was collected by water drainage.
The invention replaces high-potential oxygen evolution reaction with low-potential ethanol oxidation reaction, and the reaction can oxidize ethanol in the seawater into acetic acid with high added value while the ethanol-coupled alkaline seawater shows excellent seawater full-electrolysis hydrogen production performance. The NiFeHP/MXene/NF self-supporting integral composite electrode has excellent long-term stability in the reaction of preparing hydrogen and preparing acetic acid by oxidizing ethanol by an alkali-ethanol-seawater system, so that the NiFeHP/MXene/NF self-supporting integral composite electrode has potential application value in the fields of seawater electrolysis and acetic acid production.
Ethanol is a renewable and cost-effective energy source that is very convenient to obtain, store and transport, while also being environmentally friendly. The production of acetic acid by electrochemical oxidation of ethanol can be considered a more cost-effective process because acetic acid is an important feedstock and solvent for a variety of valuable chemical reactions. The present invention therefore selects the thermodynamically favored oxidation reaction (EOR) of ethanol instead of Oxygen Evolution (OER), reducing the oxidation potential and avoiding hypochlorite formation even at high current densities. Under low potential, the organic biomass ethanol can generate high-value products through oxidation reaction, and the separation of hydrogen and the decomposition of seawater are effectively separated. Thus, this ethanol seawater coupling method not only reduces the energy requirements for hydrogen production, but also produces valuable chemicals. In addition, the method uses carboxylic acid to replace oxygen as anode product, thereby eliminating the risk of mixing hydrogen and oxygen, and being safer and environment-friendly.
The beneficial effects of the invention are as follows:
(1) The sea cucumber-shaped NiFeHP/MXene/NF porous network self-supporting integral composite electrode prepared by the invention has high conductivity, super hydrophilicity and corrosion resistance. The surface roughened sea cucumber-like NiFeHP was grown in situ on a three-dimensional porous MXene/NF substrate. The porous channel structure is favorable for the permeation of electrolyte, the release of bubbles and the adsorption and desorption of reaction intermediates, so that the rapid mass transfer is realized greatly, and the kinetics of the catalytic reaction is improved.
(2) The sea cucumber-shaped NiFeHP/MXene/NF porous network self-supporting integral composite electrode prepared by the invention has a three-metal active center: ni, fe, ti. The unique sea cucumber-like structure increases the contact area with the electrolyte and can provide rich active sites for the electrocatalytic process.
(3) The sea cucumber-shaped NiFeHP/MXene/NF porous network self-supporting integral composite electrode prepared by the invention has excellent catalytic performance and long-term stability in an ethanol coupling seawater full-electrolysis system. Under the same conditions, the ethanol coupling seawater full electrolysis system has better performance than the alkaline seawater full electrolysis system without ethanol.
(4) The invention couples the cathode seawater electrolytic hydrogen production reaction with the anode ethanol oxidation reaction to produce acetic acid, thereby effectively reducing the seawater full hydrolysis hydrogen production potential. In addition, when the cathode generates hydrogen, the anode product oxygen is replaced by carboxylic acid with high added value, so that the danger of mixing hydrogen and oxygen can be avoided, and the system is safer and more environment-friendly.
Drawings
FIG. 1 is a process flow diagram of the invention for preparing a NiFeHP/MXene/NF self-supporting monolithic composite electrode.
FIG. 2 is a scanning electron microscope image of the three-dimensional array structure prepared in example 1 at a scale of 30 μm for the MXene/NF electrodes.
FIG. 3 is a high power scanning electron microscope image at a 2 μm scale of the MXene/NF electrode of the three-dimensional array structure prepared in example 1.
FIG. 4 is a high power scanning electron microscope image at a 1 μm scale of the NiFeHP/MXene/NF self-supporting monolithic composite electrode prepared in example 1.
FIG. 5 is a high power scanning electron microscope image of the NiFeHP/MXene/NF self-supporting monolithic composite electrode prepared in example 1 at a 200nm scale.
FIG. 6 is an X-ray diffraction pattern of the self-supporting monolithic composite electrode of NiFeHP/MXene/NF prepared in example 1, wherein a is an XRD diffraction pattern of the self-supporting monolithic composite electrode of NiFeHP/MXene/NF prepared in example 1, and b is an XRD diffraction pattern of a blank foam nickel substrate.
FIG. 7 is a graph showing the stability of the NiFeHP/MXene/NF self-supporting monolithic composite electrode prepared in example 1 in the production of hydrogen and acetic acid by ethanol-coupled seawater total electrolysis.
FIG. 8 is a schematic diagram showing the use of the NiFeHP/MXene/NF self-supporting monolithic composite electrode prepared in example 1 for 150 hours stability testing before and after ethanol-coupled seawater total electrolysis 1 An H NMR nuclear magnetic spectrum, wherein a is before the full electrolysis stability test of ethanol coupling seawater 1 H NMR nuclear magnetic spectrum, b is the ethanol coupling seawater total electrolysis stability test 1 H NMR nuclear magnetic spectrum.
FIG. 9 is a self-supporting monolithic composite electrode of NiFeHP/MXene/NF prepared in examples 1-3 and Pt/C/NF and RuO prepared in comparative example 1 2 And (3) carrying out comparison graphs of voltage values required by the full electrolysis hydrogen production under different current densities in an ethanol coupling seawater system.
FIG. 10 is a LSV graph of the total electrolysis performed in example 1 and comparative example 1, wherein a is NiFeHP/MXene prepared in example 1LSV curve of/NF self-supporting integral composite electrode for full electrolysis in 1M KOH+1M ethanol+seawater system, b is Pt/C/NF and RuO prepared in comparative example 1 2 The LSV curve of the total electrolysis of/NF was performed in a 1M KOH+1M ethanol+seawater system.
Detailed Description
The invention is further described below with reference to examples.
Example 1
The preparation method of the NiFeHP/MXene/NF self-supporting integral composite electrode comprises the following steps:
(1) The size is 1X 1cm 2 Firstly, ultrasonic cleaning treatment is carried out on the foam nickel sheet by using 2.0M hydrochloric acid for 5 minutes to clean and remove oxides, then acetone is used for cleaning and remove greasy dirt for 5 minutes, and finally ultrasonic cleaning treatment is carried out on the foam nickel sheet by using ultrapure water for 5 minutes; subsequently, the nickel foam is dried in vacuum at 80 ℃ for 10 hours and is preserved in vacuum for standby, so as to obtain the pretreated nickel foam.
(2) In a single layer of Ti 3 C 2 To the MXene suspension (20 mg/ml,20 ml) was added 6M HCl and the pH was adjusted to 3 to give an acidified MXene colloidal sediment.
(3) Taking the pretreated foam nickel obtained in the step (1) as a substrate, taking the MXene colloid deposition liquid obtained in the step (2) as electrolyte, and applying a constant voltage field of 15mV in a double-electrode electrolytic cell, wherein the voltage field exists for 17 seconds, so that a single-layer charged MXene nano-sheet is attached to NF under the action of the voltage field; drying the electrode under vacuum at 27 ℃ for 4 hours, and slowly removing the moisture in the MXene suspension, so that the MXene forms a relatively dense porous structure; and finally, completely removing water from the electrode by using a freeze dryer to obtain the MXene/NF electrode with the three-dimensional array structure.
As shown in FIG. 2, the MXene/NF electrode with the three-dimensional array structure prepared in example 1 shows the form of a section of foam nickel skeleton as a whole, and at a scale of 30 μm, the foam nickel skeleton is seen to be basically covered by a three-dimensional MXene porous network, and a three-dimensional porous MXene nano-sheet network structure which grows on the foam nickel skeleton in a three-dimensional manner is shown.
As shown in FIG. 3, a high power scanning electron microscope image at a 2 μm scale of the MXene/NF electrode of the three-dimensional array structure prepared in example 1 shows that vertical MXene nanoplatelets are uniformly deposited and grown on the nickel foam, and the structure provides a three-dimensional porous and highly conductive substrate for the growth of NiFeHP. Sufficient gaps exist between the MXene nanoplatelets to facilitate transport of the reactants. This morphology can significantly increase the specific surface area of the electrode, thereby promoting the adsorption of reactants at the electrode surface.
(4) The MXene/NF electrode obtained in the step (3) (working area of electrode sheet 1X 1 cm) 2 ) The electrode is a working electrode, agCl/Ag is a reference electrode, a graphite rod is an auxiliary electrode, and electrosynthesis is carried out by adopting an electrosynthesis liquid, wherein the electrosynthesis liquid is prepared from 0.15g of Ni (NO) 3 ) 2 ·6H 2 O、0.07g Fe(NO 3 ) 2 ·9H 2 O and 0.05g NaH 2 PO 2 ·H 2 O and solvent; wherein the solvent is 100g of mixed solution of ethanol and deionized water, and the mass ratio of the ethanol to the deionized water is 3:1. The electrosynthesis process comprises the steps of: first, 3 scans were performed at a scan rate of 5mV/s in a voltage range of-1.5 to-0.2V, and then, 3 scans were performed at a scan rate of 1mV/s in a voltage range of-2 to 0.2V. And washing the sample with deionized water, and carrying out vacuum drying at 80 ℃ for 12 hours to obtain the NiFeHP/MXene/NF self-supporting integral composite electrode with the sea cucumber-like porous network.
As shown in FIG. 4, a high-power scanning electron microscope image of the NiFeHP/MXene/NF self-supporting integral composite electrode prepared in example 1 at a 1 μm scale shows that after NiFeHP is electrodeposited on a three-dimensional MXene nano-sheet, a sea cucumber-shaped NiFeHP nano-rod is grown on the MXene nano-sheet and wound to form a porous network. The porous network structure has a large number of nano cavities, and can promote the permeation of electrolyte and the release of bubbles, thereby promoting the adsorption and desorption of reaction intermediates, improving the mass transfer capacity and exposing more catalytic active sites.
As shown in FIG. 5, the high-power scanning electron microscope image of the NiFeHP/MXene/NF self-supporting integral composite electrode prepared in the embodiment 1 under the 200nm scale clearly shows the appearance of the NiFeHP sea cucumber-like nanorod, and the surface of the NiFeHP sea cucumber-like nanorod has a spike-like structure and is similar to the appearance of sea cucumber. These roughened structures increase the active contact sites between the catalytic electrode and the electrolyte.
As shown in FIG. 6, the X-ray diffraction pattern of the self-supporting monolithic composite electrode of NiFeHP/MXene/NF prepared in example 1 demonstrates the heterostructure of NiFeHP/MXene/NF. The characteristic peak of MXene was shown at 7.5 DEG, which is characterized by a (002) crystal plane and an interlayer spacing of 1.18nm, which resulted in an increase in the interlayer spacing of the original MXene sheet. Diffraction peaks at 23.5 °, 34.7 °, 44.8 °, 51.5 °, 55.2 ° and 75.9 ° of NiFeHP/MXene/NF correspond to Ni, except for the original foam nickel and MXene characteristic peaks 3 The (100), (110), (111), (200), (210) and (220) crystal planes of Fe. In addition, diffraction peaks at 34.1 °, 45.5 °, 55.5 °, and 79.5 ° correspond to Ti, respectively 4 P 3 The (220), (321), (420) and (611) planes. XRD patterns of NiFeHP/MXene/NF also indicate the presence of Fe-P groups (Fe 2P) in the material. Interface Ti 4 P 3 And Fe (Fe) 2 The interaction of P enhances the exposure of the active site, and the heterogeneous structure provides rich grain boundaries and ion diffusion channels for NiFeHP/MXene/NF, which is beneficial to catalytic reaction.
The application of the NiFeHP/MXene/NF self-supporting integral composite electrode is as follows:
(1) Pretreatment of natural seawater: adding 1M KOH into natural seawater from Bohai Bay, and filtering to remove precipitate to obtain alkaline seawater with pH of 8.0;
(2) Preparing an alkali-ethanol-seawater system electrolyte: adding 1M ethanol into the alkaline seawater obtained in the step (1), uniformly stirring and carrying out ultrasonic treatment for 5 minutes to obtain an alkaline-ethanol-seawater system electrolyte;
(3) And (3) adopting the alkali-ethanol-seawater system electrolyte obtained in the step (2), taking two NiFeHP/MXene/NF self-supporting integral composite electrodes as an anode and a cathode respectively, carrying out full electrolysis reaction in a double-electrode electrolytic cell through an LSV technology, oxidizing ethanol into acetic acid by the anode, electrolyzing seawater by the cathode to generate hydrogen, and collecting the hydrogen of the cathode by a drainage method.
As shown in fig. 7, the stability curve of the NiFeHP/MXene/NF self-supporting integral composite electrode applied to ethanol-coupled seawater full-electrolysis hydrogen production and acetic acid production in the electrolytic cell of the 1M koh+1m ethanol+seawater system shows that the NiFeHP/MXene/NF self-supporting integral composite electrode shows excellent durability in the electrolyte of the 1M koh+ M ethanol+seawater, and the current curve does not significantly drop after 150 hours of operation. This indicates that this electrode has excellent electrochemical stability in the presence of organic molecules.
As shown in FIG. 8, the NiFeHP/MXene/NF self-supporting integral composite electrode prepared in example 1 is used before and after ethanol coupling seawater total electrolysis 1 The H NMR nuclear magnetic spectrum shows that the signal peak of ethanol in the electrolyte (1M KOH+1M ethanol+seawater) before seawater full electrolysis is stronger. After 150 hours of electrolytic reaction, the signal corresponding to acetic acid (1.78 ppm) was detected, while the signal of ethanol was decreased. This confirms that ethanol is consumed and converted to an economically high value added acetic acid product.
Example 2
The preparation method of the NiFeHP/MXene/NF self-supporting integral composite electrode comprises the following steps:
(1) The nickel foam pretreatment procedure was the same as in example 1.
(2) In a single layer of Ti 3 C 2 To the MXene suspension (20 mg/ml,20 ml) was added 6M HCl and the pH was adjusted to 5 to give an acidified MXene colloidal sediment.
(3) Taking the pretreated foam nickel obtained in the step (1) as a substrate, taking the MXene colloid deposition liquid obtained in the step (2) as electrolyte, and applying a constant voltage field of 5mV in a double-electrode electrolytic cell, wherein the voltage field exists for 20 seconds, so that a single-layer charged MXene nano-sheet is attached to NF under the action of the voltage field; drying the electrode under vacuum at 25 ℃ for 5 hours, and slowly removing the moisture in the MXene suspension, so that the MXene forms a relatively dense porous structure; and finally, completely removing water from the electrode by using a freeze dryer to obtain the MXene/NF electrode with the three-dimensional array structure.
(4) The MXene/NF electrode obtained in the step (3) (working area of electrode sheet 1X 1 cm) 2 ) The electrode is a working electrode, agCl/Ag is a reference electrode, a graphite rod is an auxiliary electrode, and electrosynthesis is carried out by adopting an electrosynthesis liquid, wherein the electrosynthesis liquid is prepared from 0.1g of Ni (NO) 3 ) 2 ·6H 2 O、0.1g Fe(NO 3 ) 2 ·9H 2 O and 0.03g NaH 2 PO 2 ·H 2 O and solvent; wherein the solvent is 100g of mixed solution of ethanol and deionized water, and the mass ratio of the ethanol to the deionized water is 3:6. The electrosynthesis process comprises the steps of: first, 3 scans were performed at a scan rate of 5mV/s in a voltage range of-1.5 to-0.2V, and then, 3 scans were performed at a scan rate of 1mV/s in a voltage range of-2 to 0.2V. Washing a sample with deionized water, and vacuum drying at 100 ℃ for 10 hours to obtain the NiFeHP/MXene/NF self-supporting integral composite electrode of the sea cucumber-shaped porous network.
The application of the NiFeHP/MXene/NF self-supporting monolithic composite electrode was the same as in example 1.
Example 3
The preparation method of the NiFeHP/MXene/NF self-supporting integral composite electrode comprises the following steps:
(1) The nickel foam pretreatment procedure was the same as in example 1.
(2) In a single layer of Ti 3 C 2 To the MXene suspension (20 mg/ml,20 ml) was added 6M HCl and the pH was adjusted to 4 to give an acidified MXene colloidal sediment.
(3) Taking the pretreated foam nickel obtained in the step (1) as a substrate, taking the MXene colloid deposition liquid obtained in the step (2) as electrolyte, and applying a constant voltage field of 20mV in a double-electrode electrolytic cell, wherein the voltage field exists for 15 seconds, so that a single-layer charged MXene nano-sheet is attached to NF under the action of the voltage field; drying the electrode under vacuum at 30 ℃ for 3 hours, and slowly removing the moisture in the MXene suspension, so that the MXene forms a relatively dense porous structure; and finally, completely removing water from the electrode by using a freeze dryer to obtain the MXene/NF electrode with the three-dimensional array structure.
(4) The MXene/NF electrode obtained in the step (3) (working area of electrode sheet 1X 1 cm) 2 ) The electrode is a working electrode, agCl/Ag is a reference electrode, a graphite rod is an auxiliary electrode, and electrosynthesis is carried out by adopting an electrosynthesis liquid, wherein the electrosynthesis liquid is prepared from 0.2g of Ni (NO) 3 ) 2 ·6H 2 O、0.05g Fe(NO 3 ) 2 ·9H 2 O and 0.07g NaH 2 PO 2 ·H 2 O and solvent; wherein the solvent is 100g of mixed solution of ethanol and deionized water, and the mass ratio of the ethanol to the deionized water is 1:3. The electrosynthesis process comprises the steps of: first, 3 scans were performed at a scan rate of 5mV/s in a voltage range of-1.5 to-0.2V, and then, 3 scans were performed at a scan rate of 1mV/s in a voltage range of-2 to 0.2V. And washing the sample with deionized water, and carrying out vacuum drying at 120 ℃ for 8 hours to obtain the NiFeHP/MXene/NF self-supporting integral composite electrode with the sea cucumber-like porous network.
The application of the NiFeHP/MXene/NF self-supporting monolithic composite electrode was the same as in example 1.
Comparative example 1
Pt/C/NF and RuO 2 The preparation method of the NF electrocatalytic electrode comprises the following steps:
(1) The nickel foam pretreatment procedure was the same as in example 1.
(2) 5mg of a commercial 20% Pt/C catalyst and 5mg of RuO were added 2 The catalyst was dissolved and dispersed in 400. Mu.l of deionized water, 540. Mu.l of ethanol, and 60. Mu.l of Nafion solution, respectively, to obtain a mixture.
(3) The mixture was then sonicated for 2 hours to form two uniform catalyst inks.
(4) Depositing the catalyst ink on a clean NF and drying overnight at room temperature to obtain NF-supported Pt/C/NF and NF-supported RuO 2 Electrode RuO 2 /NF。
Pt/C/NF is respectively taken as a cathode and RuO is respectively adopted 2 The procedure of example 1 is followed except that hydrogen is produced by total electrolysis of hydrogen at anode in 1M KOH+1M ethanol+seawater.
FIG. 9 is a self-supporting monolithic composite electrode of NiFeHP/MXene/NF prepared in examples 1-3 and Pt/C/NF and RuO prepared in comparative example 1 2 And (3) carrying out comparison graphs of voltage values required by the full electrolysis hydrogen production under different current densities in an ethanol coupling seawater system.
As shown in FIG. 9, the values were respectively 10 mA.cm -2 、100mA·cm -2 、300mA·cm -2 And 500mA cm -2 The voltage values required by the NiFeHP/MXene/NF self-supporting integral composite electrode prepared in the embodiment 1 for full-electrolytic hydrogen production in the ethanol-coupled seawater system are lower than those of the comparative example 1, which shows that the performance of the embodiment 1 for full-electrolytic hydrogen production in the ethanol-coupled seawater system is superior to that of the comparative example 1.
Respectively at 10mA cm -2 And 500mA cm -2 The voltage values required by the NiFeHP/MXene/NF self-supporting integral composite electrode prepared in example 2 for full-electrolysis hydrogen production in an ethanol-coupled seawater system are lower than those of comparative example 1, which shows that the voltage values are all lower than those of comparative example 1, namely the voltage values are equal to 10mA cm -2 And 500mA cm -2 The performance of example 2 for full electrolysis hydrogen production in an ethanol-coupled seawater system is superior to that of comparative example 1. Respectively at 100mA cm -2 And 300mA cm -2 The voltage values required by the NiFeHP/MXene/NF self-supporting integral composite electrode prepared in the example 2 for full-electrolysis hydrogen production in an ethanol coupling seawater system are slightly higher than those of the comparative example 1, which shows that the voltage values are 100mA cm -2 And 300mA cm -2 Example 2 performed full electrolysis hydrogen production in an ethanol coupled seawater system at a hydrogen evolution current density approaching the level of comparative example 1.
Respectively at 10mA cm -2 、100mA·cm -2 、300mA·cm -2 And 500mA cm -2 The voltage values required by the NiFeHP/MXene/NF self-supporting integral composite electrode prepared in the embodiment 3 for full-electrolysis hydrogen production in an ethanol-coupled seawater system are slightly higher than those of the comparative example 1, which shows that the performance of the embodiment 3 for full-electrolysis hydrogen production in the ethanol-coupled seawater system is close to the level of the comparative example 1.
As shown in FIG. 10, a is an LSV curve of the NiFeHP/MXene/NF self-supporting monolithic composite electrode prepared in example 1 for full electrolysis in a 1M KOH+1M ethanol+seawater system. The NiFeHP/MXene/NF self-supporting integral composite electrode prepared in example 1 can reach 100mA cm in a 1M KOH+1M ethanol+seawater system only by 1.34V and 1.60V respectively -2 And 500mA cm -2 The current density of the self-supporting integrated NiFeHP/MXene/NF composite electrode prepared in the embodiment 1 can produce hydrogen by seawater full electrolysis in a lower potential in an ethanol coupling seawater system, and electric energy and fresh water resources are saved.
b is Pt/C/NF and RuO prepared in comparative example 1 2 The LSV curve of the total electrolysis of/NF was performed in a 1M KOH+1M ethanol+seawater system. a is compared with b, and the hydrogen evolution current is 500mA cm -2 When the voltage required for comparative example 1 was higher than that required for example 1, it was shown that example 1 can perform seawater full electrolysis at a lower potential in an ethanol-coupled seawater system, and the performance was superior to that of the commercial electrode of comparative document 1.

Claims (7)

1. A self-supporting integral composite electrode of NiFeHP/MXene/NF is characterized by using NF as substrate, MXene growing on NF, MXene being made of single-layer Ti 3 C 2 The MXene suspension is prepared to obtain an MXene/NF electrode, and the sea cucumber-shaped NiFeHP grows on the surface of the MXene to obtain the NiFeHP/MXene/NF self-supporting integral composite electrode; wherein, the surface of the sea cucumber-shaped NiFeHP has a spike-shaped structure; the diffraction peak of NiFeHP/MXene/NF corresponds to Ni 3 Crystal face and Ti of Fe 4 P 3 Fe is present in NiFeHP/MXene/NF 2 P。
2. A method for preparing a NiFeHP/MXene/NF self-supporting monolithic composite electrode of claim 1, comprising the steps of:
(1) Pretreating foam nickel to obtain pretreated foam nickel;
(2) Preparing MXene colloid deposition solution;
(3) Taking the pretreated foam nickel obtained in the step (1) as a substrate, taking the MXene colloid deposition liquid obtained in the step (2) as an electrolyte, applying a constant voltage field to promote ordered deposition of MXene on the surface of the foam nickel, performing heat treatment, and then performing freeze drying to obtain an MXene/NF electrode;
(4) Taking the MXene/NF electrode obtained in the step (3) as a working electrode, agCl/Ag as a reference electrode, and a graphite rod as an auxiliary electrode, performing electrosynthesis by adopting electrosynthesis liquid, washing, and vacuum drying to obtain the NiFeHP/MXene/NF self-supporting integral composite electrode;
the preparation method of the MXene colloid deposition solution in the step (2) is monolayer Ti 3 C 2 Adding HCl into the MXene suspension to adjust the pH to 3-5 to obtain acidified MXene colloid deposition solution;
the electrosynthesis liquid in the step (4) is Ni (NO) 3 ) 2 ·6H 2 O、Fe(NO 3 ) 2 ·9H 2 O、NaH 2 PO 2 ·H 2 O and a solvent, wherein Ni (NO 3 ) 2 ·6H 2 The mass concentration of O in the electrosynthetic liquid is 1-2% 3 ) 2 ·9H 2 The mass concentration of O in the electrosynthetic liquid is 0.5-1.0% 2 PO 2 ·H 2 The mass concentration of O in the electrosynthetic liquid is 0.3-0.7 per mill; the solvent is a mixed solution of ethanol and deionized water, and the mass ratio of the ethanol to the deionized water is 3:1-9;
the electrosynthesis in step (4) comprises the steps of:
(1) 3 scans were performed at a scan rate of 5mV/s over a voltage range of-1.5-0.2V;
(2) 3 scans were performed at a scan rate of 1mV/s over a voltage range of-2-0.2V.
3. The method for preparing the NiFeHP/MXene/NF self-supporting monolithic composite electrode according to claim 2, wherein the constant voltage field in the step (3) has a voltage of 5-20mV.
4. The method for preparing the self-supporting monolithic composite electrode of NiFeHP/MXene/NF as claimed in claim 2, wherein the holding time of the constant voltage field in the step (3) is 15-20 seconds.
5. The method for preparing the NiFeHP/MXene/NF self-supporting integral composite electrode according to claim 2, wherein the heat treatment in the step (3) is vacuum heat treatment, the heat treatment temperature is 25-30 ℃, and the heat treatment time is 3-5 hours.
6. The method for preparing the NiFeHP/MXene/NF self-supporting integral composite electrode according to claim 2, wherein the vacuum drying temperature in the step (4) is 80-120 ℃, and the vacuum drying time is 8-12 hours.
7. The application of the NiFeHP/MXene/NF self-supporting integral composite electrode as claimed in claim 1, which is characterized in that a mixed solution of alkali, ethanol and seawater is used as an electrolyte, and the NiFeHP/MXene/NF self-supporting integral composite electrode is used for electrolysis to obtain hydrogen and acetic acid.
CN202311438406.3A 2023-11-01 2023-11-01 NiFeHP/MXene/NF self-supporting integral composite electrode and preparation method and application thereof Active CN117144411B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202311438406.3A CN117144411B (en) 2023-11-01 2023-11-01 NiFeHP/MXene/NF self-supporting integral composite electrode and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202311438406.3A CN117144411B (en) 2023-11-01 2023-11-01 NiFeHP/MXene/NF self-supporting integral composite electrode and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN117144411A CN117144411A (en) 2023-12-01
CN117144411B true CN117144411B (en) 2024-01-09

Family

ID=88910559

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202311438406.3A Active CN117144411B (en) 2023-11-01 2023-11-01 NiFeHP/MXene/NF self-supporting integral composite electrode and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN117144411B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113096972A (en) * 2021-04-12 2021-07-09 上海理工大学 Preparation method of MXene/NiCoP/NF composite material
CN113638002A (en) * 2021-07-14 2021-11-12 上海应用技术大学 FeCo LDH/Ti3C2MXene/NF composite material and preparation method and application thereof
CN113684501A (en) * 2021-07-19 2021-11-23 中国海洋大学 Nickel-iron-based phosphide electrocatalytic material and preparation method and application thereof
CN115094456A (en) * 2022-06-02 2022-09-23 吉林大学 Preparation method and application of cerium dioxide nano particle/nickel-iron bimetal phosphide/foamed nickel composite electrode
CN116815224A (en) * 2023-04-18 2023-09-29 中国科学院合肥物质科学研究院 Ferronickel phosphide nanoflower@MXene integrated electrode and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113096972A (en) * 2021-04-12 2021-07-09 上海理工大学 Preparation method of MXene/NiCoP/NF composite material
CN113638002A (en) * 2021-07-14 2021-11-12 上海应用技术大学 FeCo LDH/Ti3C2MXene/NF composite material and preparation method and application thereof
CN113684501A (en) * 2021-07-19 2021-11-23 中国海洋大学 Nickel-iron-based phosphide electrocatalytic material and preparation method and application thereof
CN115094456A (en) * 2022-06-02 2022-09-23 吉林大学 Preparation method and application of cerium dioxide nano particle/nickel-iron bimetal phosphide/foamed nickel composite electrode
CN116815224A (en) * 2023-04-18 2023-09-29 中国科学院合肥物质科学研究院 Ferronickel phosphide nanoflower@MXene integrated electrode and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
In-situ derived Mo-doped NiCoP and MXene to form Mott-Schottky heterojunction with tunable surface electron density to promote overall water splitting;Jibo Jiang et al.;Composites Part B: Engineering;第263卷;第(110834)1-17页 *
Rational design of Schottky heterojunction with modulating surface electron density for high-performance overall water splitting;Lequan Deng et al.;Applied Catalysis B: Environmental;第299卷;第(120660)1-9页 *

Also Published As

Publication number Publication date
CN117144411A (en) 2023-12-01

Similar Documents

Publication Publication Date Title
Yang et al. Molybdenum selenide nanosheets surrounding nickel selenides sub-microislands on nickel foam as high-performance bifunctional electrocatalysts for water splitting
Luo et al. Manganese oxide with different morphology as efficient electrocatalyst for oxygen evolution reaction
CN113638002B (en) FeCo LDH/Ti 3 C 2 MXene/NF composite material, and preparation method and application thereof
CN104549242A (en) Preparation method of nanometer palladium-graphene three-dimensional porous composite electrocatalyst
CN112791736A (en) WP2/Cu3Application of P composite nano-structure catalyst in aspect of hydrogen production by electrolyzing water
CN110820006B (en) MoS2Nanoribbon embedded VS2Micro-flower self-supporting electrode and preparation method and application thereof
Du et al. Vanadium doped cobalt phosphide nanorods array as a bifunctional electrode catalyst for efficient and stable overall water splitting
CN110983361B (en) Tantalum nitride carbon nano film integrated electrode for limited-area growth of cobalt nanoparticles and preparation method and application thereof
CN113019398B (en) High-activity self-supporting OER electrocatalyst material and preparation method and application thereof
Feng et al. Engineering cobalt molybdate nanosheet arrays with phosphorus-modified nickel as heterogeneous electrodes for highly-active energy-saving water splitting
CN114351165B (en) Preparation method and application of three-dimensional core-shell structure bifunctional seawater electrolysis catalyst
CN113637986B (en) Biphase nickel selenide double-function electrolytic water catalyst, preparation method and application thereof
CN111790416A (en) High-efficiency oxygen evolution electrocatalyst and preparation method thereof
Zhan et al. Petal-like NiCoP sheets on 3D nitrogen-doped carbon nanofiber network as a robust bifunctional electrocatalyst for water splitting
CN114250486A (en) Preparation method of surface nano-porous NiMoCu catalyst
CN112909271A (en) Integral transition metal phosphide electrocatalyst with sea urchin-shaped morphology and preparation method and application thereof
CN109097788B (en) Double-carbon coupling transition metal nickel-based quantum dot electrocatalyst and preparation method thereof
CN117144411B (en) NiFeHP/MXene/NF self-supporting integral composite electrode and preparation method and application thereof
Zhao et al. Hollow spherical LaNiO3 perovskite with superior multifunctional performances and durability for urea-assisted Zn-air batteries
Guo et al. Research progress of aqueous Zn–CO2 battery: design principle and development strategy of a multifunctional catalyst
Bi et al. Controllable synthesis and super electrochemical stability of copper phosphide (Cu3P) nanosheets catalyst in nearly neutral electrolyte
CN110420649B (en) Metal phase MoS2-CoNi(OH)2Nano composite material and preparation method and application thereof
CN110227467B (en) Three-layer coaxial oxygen production electrocatalyst and preparation method thereof
Butt et al. Recent Advancement in Manganese-based Electrocatalyst for Green Hydrogen Production
CN117144410B (en) Ni 5 FeCuCrS 3 MXene/NF electrocatalytic composite electrode, and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant