CN112126951A - Preparation method of oxygen evolution reaction electrocatalyst - Google Patents

Preparation method of oxygen evolution reaction electrocatalyst Download PDF

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Publication number
CN112126951A
CN112126951A CN201910552225.0A CN201910552225A CN112126951A CN 112126951 A CN112126951 A CN 112126951A CN 201910552225 A CN201910552225 A CN 201910552225A CN 112126951 A CN112126951 A CN 112126951A
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mol
oxygen evolution
evolution reaction
carbon paper
iron
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刘海鹏
朱胜利
梁砚琴
崔振铎
吴水林
李朝阳
杨贤金
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Tianjin University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron
    • 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
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • 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

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Abstract

The invention discloses a preparation method of an oxygen evolution reaction electrocatalyst, which comprises the following steps of treating carbon paper under the condition of concentrated sulfuric acid; according to Na3C6H5O7·2H2O、NiSO4·6H2O、Na2MoO4·2H2O、Na2WO4·2H2O, boric acid, ascorbic acid and FeSO4·7H2Dissolving the reagents in deionized water in the order of O to obtain a standby plating solution; then placing the carbon paper in plating solution for constant potential deposition, and obtaining a sample after the reaction is finished by using deionized water and absolute ethyl alcoholWashing and drying with cold air to obtain the iron-based alloy oxygen evolution reaction electrocatalyst. Low implementation cost, stable structure, simple and convenient operation and short preparation period, and is a high-efficiency and economic synthesis method.

Description

Preparation method of oxygen evolution reaction electrocatalyst
Technical Field
The invention relates to the technical field of iron-based alloy oxygen evolution reaction electrocatalysts, in particular to a preparation method of an iron-based alloy oxygen evolution reaction electrocatalysts and application of the iron-based alloy oxygen evolution reaction electrocatalysts in an alkaline solution.
Background
Conventional fossil fuels are not renewable for a short period of time and present a series of environmental problems after use. Hydrogen energy is a renewable clean energy source and is expected to become an alternative energy source of fossil fuels. The hydrogen production by electrolyzing water is an effective way for preparing hydrogen. The hydrogen production by water electrolysis comprises two half reactions: the cathodic hydrogen evolution and anodic oxygen evolution, because the oxygen evolution reaction needs to go through the four electron transfer process, the kinetic process is slower, becoming the bottleneck limiting the efficiency of water electrolysis. Noble metal compounds such as ruthenium, iridium and the like are the most efficient oxygen evolution catalysts at present, and the application and popularization of the noble metal compounds are limited by overhigh cost and resource shortage, so that the development of a cheap, energy-saving and low-overpotential oxygen evolution catalyst is urgently needed. The high specific surface area and the synergistic effect among elements are beneficial to improving the catalytic performance of the material, and the electrodeposition method is simple and easy to operate and is convenient for realizing industrial production. The iron-based alloy oxygen evolution electrocatalyst with high specific surface area prepared by the electrodeposition method improves the oxygen evolution catalytic performance by utilizing the synergistic effect among elements, and the elements are base metals and are cheap and easy to obtain. Therefore, research on the preparation of the iron-based alloy oxygen evolution electrocatalyst by the electrodeposition method is necessary and reasonable.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of an oxygen evolution reaction electrocatalyst, which has the advantages of low cost, simple preparation process, low implementation cost and simple and convenient operation.
The technical purpose of the invention is realized by the following technical scheme.
A preparation method of an oxygen evolution reaction electrocatalyst is carried out according to the following steps:
taking carbon paper as a working electrode, and carrying out constant potential deposition in a plating solution by using a three-electrode system to obtain an oxygen evolution reaction electrocatalyst on the carbon paper; the deposition potential range is-1.0V to-1.5V vs SCE, and the deposition time is 10-40 min; deionized water is used as a solvent in the plating solution, and the concentration of each solute is 0.2-0.6 mol.L of sodium citrate-10.1 to 0.4 mol/L of iron sulfate-10.1 to 0.4 mol/L of nickel sulfate-10.01 to 0.1 mol/L of sodium molybdate-10.01 to 0.1 mol/L sodium tungstate-10.2 to 0.5 mol/L boric acid-1And ascorbic acid 0.1 to 0.3 mol.L-1The pH value is 4-7.
In the technical scheme, the deposition potential range is-1.0V to-1.3V vs SCE, the deposition time is 10-30 min, and the deposition temperature is 20-25 ℃.
In the technical scheme, a platinum mesh counter electrode and a saturated calomel electrode are used as reference electrodes.
In the technical scheme, after constant potential deposition, the obtained product is cleaned by deionized water and alcohol and then dried by cold air, and the iron-based alloy oxygen evolution reaction electrocatalyst is obtained.
In the technical scheme, the concentration of each solute in the plating solution is 0.3-0.5 mol.L of sodium citrate-10.1 to 0.3 mol/L of iron sulfate-10.2 to 0.4 mol/L of nickel sulfate-10.04 to 0.07 mol/L sodium molybdate-10.05-0.08 mol/L sodium tungstate-10.3 to 0.5 mol/L boric acid-1And ascorbic acid 0.1 to 0.2 mol.L-1。
In the above technical scheme, according to Na3C6H5O7·2H2O、NiSO4·6H2O、Na2MoO4·2H2O、Na2WO4·2H2O, boric acid, ascorbic acid and FeSO4·7H2Dissolving the reagents into a 200ml beaker according to the requirements of the order and the concentration of O, fixing the volume of deionized water to 200ml, fully stirring and dissolving, standing for 2 hours, and preparingAnd (4) plating the solution.
In the technical scheme, the carbon paper is hydrophilic carbon paper, the carbon paper is placed in concentrated sulfuric acid for treatment so as to improve the hydrophilicity of the carbon paper and enable the surface of the carbon paper to form hydroxyl, carboxyl or aldehyde functional groups, the used concentrated sulfuric acid is 95-98 wt% of sulfuric acid, the treatment time is 5-8 hours, and the treatment temperature is 20-50 ℃.
The invention also discloses the iron-based alloy oxygen evolution reaction electrocatalyst obtained by the method and application thereof in water electrolysis oxygen generation.
Compared with the prior art, the invention has the following beneficial effects: the iron-based alloy oxygen evolution reaction electrocatalyst has high electrocatalytic oxygen evolution activity and stability; the synthesis method adopts an electrodeposition method to obtain the iron-based alloy oxygen evolution reaction electrocatalyst, and the method has the advantages of simple process, mild conditions, short reaction time, good reproducibility, safe operation and high yield, and can be suitable for large-scale production.
Drawings
FIG. 1 is an SEM photograph of an iron-based alloy oxygen evolution reaction electrocatalyst prepared in example 1 of the present invention.
FIG. 2 is an EDS-XRD spectrum diagram showing the morphology of the iron-based alloy oxygen evolution reaction electrocatalyst prepared in example 1 of the present invention, wherein a is a SEM photograph of the sample; b is a STEM picture of the sample; c is HRSEM picture of sample; d is sample SAED pattern; e is the sample transmission EDS spectrum; f is sample element surface distribution; g is the sample and blank carbon paper structure (XRD).
FIG. 3 is a graph showing the electrochemical performance test of the Fe-based alloy oxygen evolution catalyst prepared in example 1 of the present invention, wherein a is 1 mol. L-1In KOH solution at a sweep rate of 10/20/40/60/80/100/120/140/160/180/200mV · s-1The cyclic voltammogram of the sweep (in the direction of the arrow in the figure), b is the capacitive current versus sweep rate.
FIG. 4 shows the oxygen evolution rate of the iron-based alloy catalyst at 1 mol. L prepared in example 1 of the present invention -12 mV. s in KOH solution-1Linear sweep voltammogram of the sweep.
FIG. 5 is the present inventionIllustrating the stability test graph of the iron-based alloy oxygen evolution catalyst prepared in example 1, wherein a is the concentration of the iron-based alloy oxygen evolution catalyst at 1 mol.L-1In KOH solution at 100 mV. s-1A scanning stability test curve chart, b is that the iron-based alloy precipitation catalyst is at 10mA cm-1Lower constant current stability test graph.
Detailed Description
The process of the present invention is further illustrated below with reference to specific examples. Adopting a three-electrode system, wherein a working electrode is Japanese Dongli TGP-H-060 type hydrophilic carbon paper, a counter electrode is a platinum net, a reference electrode is a Saturated Calomel Electrode (SCE), and depositing is carried out in a constant potential mode; the material characterization uses a scanning electron microscope of Japanese Hitachi S-4800 type and a transmission electron microscope of Japanese electronic 2100F type to observe the appearance of a sample; detecting a sample phase structure by using a MiniFlex 600X-ray diffractometer in Japan; the deposition process and the oxygen evolution performance test both adopt a United states Gamry Interface 1000 electrochemical workstation.
Example 1:
the preparation method of the iron-based alloy oxygen evolution reaction electrocatalyst comprises the following preparation steps:
step one, heating carbon paper in concentrated sulfuric acid to 40 ℃ for 8 h;
step two, according to Na3C6H5O7·2H2O、NiSO4·6H2O、Na2MoO4·2H2O、Na2WO4·2H2O, boric acid, ascorbic acid and FeSO4·7H2Dissolving the reagents in a 200ml beaker in the order of O, keeping the volume of the deionized water to 200ml, fully stirring and dissolving the reagents, standing the solution for 2 hours, and adding 0.5 mol.L of sodium citrate-10.3 mol/L of ferric sulfate-10.1 mol. L of nickel sulfate-1Sodium molybdate 0.05 mol.L-1Sodium tungstate 0.05 mol. L-1Boric acid 0.5 mol. L-1Ascorbic acid 0.1 mol. L-1(ii) a The pH value of the plating solution is 6;
step three, taking the carbon paper treated in the step one as a working electrode, a platinum mesh counter electrode and a saturated calomel electrode as a reference electrode, depositing the carbon paper in the plating solution obtained in the step two by using a three-electrode system constant potential, and cleaning and drying the product deionized water and alcohol by cold air to obtain the iron-based alloy oxygen evolution reaction electrocatalyst, wherein the deposition potential is-1.3V vs SCE; the deposition time was 20 min.
Example 2:
the preparation process is basically the same as that of example 1, and the difference is only that: in the second step, the deposition potential was-1.2V vs SCE.
Example 3:
the preparation process is basically the same as that of example 1, and the difference is only that: in the first step, Na3C6H5O7·2H2O 0.4mol·L-1The deposition potential was-1.1V vs SCE.
Example 4:
the preparation process is basically the same as that of example 1, and the difference is only that: in step one, the deposition potential is-1.0V vs SCE. As can be seen from fig. 1 and 2a, the FeNiMoW alloy uniformly grows on the surface of the carbon fiber in a sheet structure, as can be seen from fig. 2b, the FeNiMoW sheet structure is fully wrinkled, as can be seen from fig. 2c, the FeNiMoW alloy is a nanocrystal with 4-6 nm distributed on an amorphous matrix, the XRD result shows an amorphous state (fig. 2g), the selective electron diffraction pattern amorphous halo is distributed with a few diffraction spots (fig. 2d) which are mutually verified, as can be seen from the energy spectrum result of fig. 2e, the four elements of iron, nickel, molybdenum and tungsten really exist the surface alloy deposition success, and as can be seen from fig. 2f, the four elements are uniformly distributed in the sample. From FIG. 3b, the slope was 73.21mF cm when the electrochemical activity specific surface area of the sample was measured by the cyclic voltammogram of FIG. 3-2It is shown that the sample has more active sites for electrochemical reaction, and the sample is 10mA cm in FIG. 4-1The overpotential of the oxygen evolution reaction is 299.14 mV under the current density, the curve difference between the first circle and the 5000 th circle of the 5000-circle linear scanning volt-ampere stability test is very small as can be seen from the graph in fig. 5a, which shows that the oxygen evolution stability of the sample is good, and the curve difference between the first circle and the 5000 th circle of the 5000-circle linear scanning volt-ampere stability test is 10 mA.cm.-1The current density is continuous to separate oxygen, the potential change of the sample oxygen separating electrode is less than 0.01 millivolt, and the stability is good.
The preparation of the catalyst can be realized by adjusting the process parameters according to the content of the invention, andshows the performance basically consistent with the invention, the obtained iron-based alloy oxygen evolution reaction electrocatalyst electrolyzed water has small oxygen overpotential of 10mA cm-1The overpotential of the oxygen evolution reaction under the current density can be 298-302 millivolts, which indicates that the prepared material has good application prospect in the field of water electrolysis. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (9)

1. The preparation method of the oxygen evolution reaction electrocatalyst is characterized by comprising the following steps of:
taking carbon paper as a working electrode, and carrying out constant potential deposition in a plating solution by using a three-electrode system to obtain an oxygen evolution reaction electrocatalyst on the carbon paper; the deposition potential range is-1.0V to-1.5V vs SCE, and the deposition time is 10-40 min; deionized water is used as a solvent in the plating solution, and the concentration of each solute is 0.2-0.6 mol.L of sodium citrate-10.1 to 0.4 mol/L of iron sulfate-10.1 to 0.4 mol/L of nickel sulfate-10.01 to 0.1 mol/L of sodium molybdate-10.01 to 0.1 mol/L sodium tungstate-10.2 to 0.5 mol/L boric acid-1And ascorbic acid 0.1 to 0.3 mol.L-1The pH value is 4-7.
2. The method of claim 1, wherein the concentration of each solute in the plating solution is 0.3-0.5 mol.L sodium citrate-10.1 to 0.3 mol/L of iron sulfate-10.2 to 0.4 mol/L of nickel sulfate-10.04 to 0.07 mol/L sodium molybdate-10.05-0.08 mol/L sodium tungstate-10.3 to 0.5 mol/L boric acid-1And ascorbic acid 0.1 to 0.2 mol.L-1。
3. The method for preparing the oxygen evolution reaction electrocatalyst according to claim 1 or 2, wherein the deposition potential range is-1.0V to-1.3V vs SCE, the deposition time is 10 to 30min, and the deposition temperature is 20 to 25 ℃ at room temperature.
4. The method for preparing an oxygen evolution reaction electrocatalyst according to claim 1 or 2, wherein a platinum mesh counter electrode and a saturated calomel electrode are used as reference electrodes.
5. The method of claim 1 or 2, wherein the carbon paper is hydrophilic carbon paper.
6. The method of claim 5, wherein the carbon paper is treated in concentrated sulfuric acid to improve hydrophilicity of the carbon paper and form hydroxyl, carboxyl or aldehyde functional groups on the surface of the carbon paper, the concentrated sulfuric acid is 95-98 wt% sulfuric acid, the treatment time is 5-8 hours, and the treatment temperature is 20-50 ℃.
7. An iron-based alloy oxygen evolution reaction electrocatalyst obtained by the method for preparing an oxygen evolution reaction electrocatalyst according to claim 1 or 2.
8. The iron-based alloy oxygen evolution reaction electrocatalyst according to claim 7, wherein the FeNiMoW alloy uniformly grows on the surface of the carbon fiber in a sheet structure, four elements of Fe, Ni, Mo and W are uniformly distributed, the FeNiMoW sheet structure is fully folded, and 4-6 nm of nanocrystals are distributed on an amorphous matrix of the FeNiMoW alloy.
9. The use of the iron-based alloy oxygen evolution reaction electrocatalyst obtained by the method for preparing an oxygen evolution reaction electrocatalyst according to claim 1 or 2, for electrolysis of water to produce oxygen, characterized in that it is used at 10 mA-cm-1The overpotential of oxygen evolution reaction under current density can be 298-302 millivolts.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114808008A (en) * 2022-04-26 2022-07-29 华东理工大学 Electrodeposition synthesis method of high-performance oxygen evolution reaction electrocatalyst

Citations (1)

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Publication number Priority date Publication date Assignee Title
US6200450B1 (en) * 1998-03-30 2001-03-13 Wen Hua Hui Method and apparatus for depositing Ni-Fe-W-P alloys

Patent Citations (1)

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Publication number Priority date Publication date Assignee Title
US6200450B1 (en) * 1998-03-30 2001-03-13 Wen Hua Hui Method and apparatus for depositing Ni-Fe-W-P alloys

Non-Patent Citations (3)

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Title
FAN QIN ET. AL: "Trimetallic NiFeMo for Overall Electrochemical Water Splitting with a Low Cell Voltage", 《ACS ENERGY LETT.》 *
MAHDI ALLAM ET. AL.: "Electrodeposition and characterization of NiMoW alloy as electrode material for hydrogen evolution in alkaline water electrolysis", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 *
苏小山: "掺杂Mo(Ⅵ)、W(Ⅵ)的镍铁氢氧化物纳米薄膜的制备及电催化析氧反应的研究", 《中国优秀博硕士学位论文全文数据库(硕士)工程科技Ⅰ辑》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114808008A (en) * 2022-04-26 2022-07-29 华东理工大学 Electrodeposition synthesis method of high-performance oxygen evolution reaction electrocatalyst
CN114808008B (en) * 2022-04-26 2024-09-13 华东理工大学 Electrodeposition synthesis method of high-performance oxygen evolution reaction electrocatalyst

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