CN114892181A - Preparation method and application of gold-doped copper-based electrode for alkaline electrolyzed water - Google Patents
Preparation method and application of gold-doped copper-based electrode for alkaline electrolyzed water Download PDFInfo
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- 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
- C25B11/055—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
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- 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
- C25B11/093—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 at least one noble metal or noble metal oxide and at least one non-noble metal oxide
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- 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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- 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
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
A preparation method and application of a gold-doped copper-based electrode for alkaline electrolyzed water belong to the technical field of electrochemical energy storage materials. Oxidizing the foam copper in a tubular furnace, doping gold by a sodium chloroaurate solution, and finally washing and drying to obtain the gold-doped copper-based electrode. In a standard three-electrode system, a gold-doped copper-based electrode directly serves as a working electrode and is placed in 1M Na 2 CO 3 In the electrolyte, electrocatalytic oxygen evolution reaction under alkaline condition is carried out. The preparation method is simple and easy to operate, does not need subsequent high-temperature treatment, and is easy for large-scale production. The gold-doped copper-based electrode has excellent OER activity and good cycle stability, has obvious advantages in electrocatalytic oxygen evolution reaction and energy conversion, has smaller overpotential in the OER process and has excellent performanceElectrochemical stability of (3).
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage materials, and relates to a preparation and post-treatment method of a copper oxide nanocube.
Background
With the rapid development of human society, the number of people has rapidly increased, and the demand for energy has greatly increased in countries around the world. The traditional fossil energy belongs to non-renewable resources, is almost exhausted in a large number of mining processes, and cannot support the requirements of human society. At the same time, the consumption of large quantities of fossil fuels severely pollutes the environment, and has prompted significant research interest in the search for clean, renewable and sustainable alternatives. Hydrogen energy is considered one of the most potential energy carriers for fossil energy. Electrochemical water splitting is a promising strategy for producing new clean hydrogen fuels. Currently, ruthenium and iridium based catalysts have been identified as the most efficient water decomposition electrocatalysts, but their scarcity, high cost and low stability severely limit their application. Therefore, the development of a novel electrocatalyst is of great significance for realizing large-scale commercialization of water electrolysis technology.
In order to alleviate global energy and environmental crisis, there is a great demand for the replacement of fossil energy with renewable energy. Hydrogen, a clean and renewable energy source, is of great interest and can be generated by photolysis or electrolysis of water. The electrolytic reaction of water involves two half-reactions: hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER). Due to its central role in water splitting, OER electrocatalysis has been extensively studied in recent years. Since oxygen molecules are generated by several proton/electron couplings, OER involves a slow kinetic process. Therefore, renewable energy sources have great demand for the development of efficient catalysts for OER. In recent years, OER catalysts of metal oxides and hydroxides such as iron, cobalt, nickel, etc. have been widely studied. Compared with iron, cobalt and nickel-based OER catalysts, the copper-based material is a promising OER catalyst, but has lower catalytic activity. It is reported that doping an inert noble metal such as gold into a transition metal oxide can improve the OER catalytic performance of the transition metal oxide due to an electronic interaction between gold and the transition metal oxide.
Disclosure of Invention
In light of the above-mentioned technical problems, the present invention aims to develop a novel gold-doped copper-based self-supporting electrode with cheap and easily available raw materials and with industrial development prospects.
The technical scheme adopted by the invention is as follows: a gold-doped copper-based self-supporting electrode for alkaline electrolysis of water is prepared through electrochemical displacement reaction to grow Au-CuO on foam copper substrate x Nanocubes, the size of which is 0.1um-1um, Au in Au-CuO x In the center of the nanocubes, the ratio of Au on the surface of the electrode is 3-8%.
The electrode sequentially oxidizes a foam copper substrate through two-step reaction, and Au-CuO grows on the surface of the foam copper through electrochemical displacement reaction x Nano-cubic block.
A preparation method of a gold-doped copper-based self-supporting electrode for alkaline electrolysis of water specifically comprises the following steps:
(1) pretreating the foam copper, and drying for later use;
(2) placing the foamy copper in a tube furnace, oxidizing at the temperature of 280-350 ℃, cooling after oxidizing, and taking out;
(3) adding the sodium chloroaurate aqueous solution into the ethanol and the aqueous solution which are mixed in the same volume, and performing ultrasonic treatment to obtain a sodium chloroaurate solution; placing the sodium chloroaurate solution in a reaction container, vertically placing the copper oxide foam, and keeping the temperature at 50-60 ℃ for 2-4 hours;
the concentration of the sodium chloroaurate solution is 0.1-0.8 mM;
(4) naturally cooling, taking out the foam copper, washing with deionized water and ethanol, and drying; and obtaining the gold-doped copper-based self-supporting electrode.
The pretreated foamy copper is diluted H 2 SO 4 After soaking, ultrasonic washing is carried out in acetone, deionized water and absolute ethyl alcohol in turn.
The foam copper is placed in a tube furnace at the temperature of 280 ℃ and 350 ℃ and is kept for 0.5-1.5 hours, and the heating rate is 8-10 ℃/min.
The electrode is applied to electrocatalytic water decomposition oxygen analysis reaction.
Further, specification requirements of the copper foam, area: 1 x 2 cm 2 (ii) a Thickness: 1 mm; and, at 1M H 2 SO 4 Soaking for 5 min, and sequentially performing ultrasonic treatment in acetone, deionized water and anhydrous ethanol for 30 min.
Further, placing the foamy copper in the center of the tube furnace, setting the temperature to 300 ℃ and keeping the temperature for 1 hour, heating the foamy copper at the rate of 10 ℃/min, and taking out the foamy copper with oxidized surface after the temperature of the tube furnace is reduced to 25 ℃.
Further, the temperature was slowly raised under heating, and the temperature was maintained at 60 ℃ for 2 hours.
Further, a 10 mL glass bottle is naturally cooled to 30 ℃ in an oven, and the front and back surfaces of the copper foam are respectively washed three times by deionized water and ethanol after being clamped out by a pair of tweezers, so that impurities and the catalyst with weak adhesive force are removed.
Further, the rinsed copper foam was placed in a vacuum drying oven for drying for 12 hours.
Furthermore, the ultrasonic frequency of the used ultrasonic equipment is 50-53 KHz.
The invention also provides application of the electrocatalyst prepared by the preparation method of the self-supporting copper-based electrocatalyst, and the self-supporting copper-based electrocatalyst is directly used as a working electrode to be placed in electrolyte to perform electrocatalytic water decomposition Oxygen Evolution Reaction (OER) in a standard three-electrode system (Hg/HgO is used as a reference electrode, and a platinum wire is used as a counter electrode and the working electrode).
Further, the above electrolyte uses 1M Na 2 CO 3 And (3) solution.
The invention adopts an electrochemical displacement method, the foamy copper with oxidized surface layer is placed in a sodium chloroaurate solution, and the gold-doped copper-based self-supporting electrode is synthesized under the heating condition for water decomposition reaction.
Compared with the prior art, the invention has the following advantages:
1. according to the gold-doped copper-based self-supporting electrode prepared by the method, the catalyst layer uniformly grows in situ on the foam copper substrate, and a binder required by the electrode does not need to be dripped.
2. The electrochemical displacement method utilizes different standard reduction potentials of elements to carry out reaction, and when the reaction is carried out among the elements with larger standard reduction potential difference, the reaction condition is relatively mild. Compared with chemical vapor deposition and other methods which have complex operation and need expensive equipment, the electrochemical displacement method has the advantages of low cost, simple and convenient operation, controllable preparation process and the like; the method has great advantages in future material development.
3. The electrochemical performance is an important index for evaluating the quality of the electrocatalyst. At 1M Na 2 CO 3 In the system, Au-CuO x CuF at 10 mA-cm -2 Has smaller overpotential under the current density, is obviously superior to other reference terms, and has small tafel slope, which shows that the current density has fast OER kinetic process, Au-CuO x the/CuF has a large active surface area, accelerates the charge transfer process, and shows excellent OER activity. Au-CuO x CuF at 10 mA cm -2 The current density is stable for more than 25 h, and the electrochemical performance is not obviously reduced before and after the stability test, which shows that the electrochemical stability is good.
In summary, the preparation method of the electrode material is simple and easy to operate, does not need subsequent high-temperature treatment, and is easy for large-scale production. The prepared electrode material has obvious advantages in the aspects of electrocatalytic oxygen evolution reaction and energy conversion, and the electrode has smaller overpotential in the OER process and has excellent electrochemical stability.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings required to be used in the embodiments will be briefly described below.
FIG. 1 shows Au-CuO as a copper-based self-supporting electrode doped with gold prepared by electrochemical displacement method x X-ray diffraction spectrum of/CuF.
FIG. 2 shows Au-CuO as a Cu-based self-supporting electrode doped with Au and prepared by electrochemical displacement method x Scanning electron microscope image of/CuF.
FIG. 3 shows Au-CuO as a Cu-based self-supporting electrode doped with Au and prepared by electrochemical displacement method x Transmission electron micrograph of/CuF.
FIG. 4 shows Au-CuO as a Cu-based self-supporting electrode doped with Au and prepared by electrochemical displacement method x EDS energy spectrum of/CuF.
FIG. 5 (a) shows Au-CuO as a gold-doped copper-based self-supporting electrode prepared by electrochemical displacement x LSV curves for CuF and its control; (b) Au-CuO (gold-doped copper-based self-supporting electrode) prepared by electrochemical displacement method x The Tafel slope of CuF and its control; (c) Au-CuO (gold-doped copper-based self-supporting electrode) prepared by electrochemical displacement method x Active surface area of/CuF and its control; (d) Au-CuO (gold-doped copper-based self-supporting electrode) prepared by electrochemical displacement method x I-t test of/CuF.
FIG. 6 shows a copper oxide electrode CuO obtained by high-temperature calcination x In situ Raman testing of/CuF.
FIG. 7 shows Au-CuO as a Cu-based self-supporting electrode doped with Au and prepared by electrochemical displacement method x In situ Raman testing of/CuF.
Detailed Description
In order that the invention may be more readily understood, the following examples are preferred and are to be considered in connection with the accompanying drawings. The starting materials are available from open commercial sources unless otherwise specified.
EXAMPLE 1 preparation of gold-doped copper-based electrode
Foam copper (CuF) (area: 1X 2 cm) 2 (ii) a Thickness: 1 mm) at 1M H 2 SO 4 Soaking for 5 min, and sequentially performing ultrasonic treatment in acetone, deionized water and anhydrous ethanol for 30 min;
placing the foamy copper in the center of a tube furnace, setting the temperature to 300 ℃ and keeping the temperature for 1 hour, wherein the heating rate is 10 ℃/min, and taking out the foamy copper with oxidized surface after the temperature of the tube furnace is reduced to 25 ℃;
80 μ L of aqueous sodium chloroaurate solution (NaAuCl) 4 ) Adding into a mixed solution of 4 mL water and 4 mL ethanol, and performing ultrasonic treatment for 30 s; obtaining 0.495 mM/L sodium chloroaurate solution
Transferring the sodium chloroaurate solution into a 10 mL glass bottle, vertically placing the copper oxide foam into the glass bottle, and keeping the temperature at 60 ℃ for 2 hours;
the obtained sample was kept at 60 ℃ under vacuum for 12 hours.
The Au atom proportion on the electrode surface was determined to be 5% by inductively coupled plasma emission spectrometer (ICP).
Example 2 application of gold-doped copper-based self-supporting electrode in alkaline electrocatalytic water splitting
(1) Preparation of working electrode
The prepared dried Au-CuO x /CuF cut into 1 × 2 cm 2 Directly to the working electrode;
(3) electrocatalytic oxygen evolution reaction
All electrochemical tests were performed at room temperature in a conventional three-electrode system using a platinum wire electrode as the counter electrode, the prepared catalyst and the control sample as the working electrode, and a Hg/HgO electrode as the reference electrode. 1M Na 2 CO 3 Used as electrolyte for all electrochemical tests. Before the electrochemical OER test, the electrodes were activated by CV for 10 cycles at a sweep rate of 50 mV. multidot.s -1 。
EXAMPLE 3 Performance of gold-doped copper-based self-supporting electrode
（1）Au-CuO x Characterization before CuF catalytic reaction
From the XRD pattern of fig. 1, it can be seen that the two strong peaks at 43.4 and 50.4 can be assigned to the (111) and (200) crystallographic planes respectively originating from copper in the copper foam substrate. After electrochemical displacement reaction with Cu 2 The peak at 36.4 position corresponding to the crystal face of O phase (111) became strong, and Cu 2 The new peak corresponding to the crystal plane of O phase (200) appeared at 42.3. The peak at 38.9 corresponding to the (111) crystal plane of the CuO phase was unchanged. No XRD diffraction peak of gold species was detected due to trace doping. Fig. 2 shows, in a Scanning Electron Microscope (SEM), a dense cubic layer formed on a foamed copper substrate. The Transmission Electron Microscope (TEM) of FIG. 3 shows a regular-morphology cube with an average size of 250 nm. EDX (energy dispersive x-ray) analysis of fig. 4 shows a uniform distribution of copper and oxygen elements within the cube, with the doped gold species mainly present in the center of the cube.
（2）Au-CuO x /CuF electrochemical test
At 1M Na 2 CO 3 For Au-CuO in electrolyte (pH = 11.4) x CuF electrode and CuO x the/CuF electrodes were subjected to LSV, ECSA, Tafel slope and stability tests, the results of which are shown in FIG. 5. FIG. 5Wherein (a) is Au-CuO x CuF electrode and CuO x the/CuF reverse scanning LSV diagram shows that Au-CuO x 10 mA-cm of CuF electrode -2 Over potential of 380 mV compared to CuO x The over potential of/CuF is 480 mV, which is obviously improved. As can be seen from FIG. 5 (b), Au-CuO x Tafel slope of/CuF is 73 mv/dec; this indicates Au-CuO x CuO with 130 mv/dec of ratio CuF to Tafel slope x the/CuF has a faster kinetic process. The electrochemical active surface area (ECSA) was tested as a function of the relationship between the charging current and the cyclic voltammetry sweep rate. The results of the ECSA test are shown in FIG. 5 (c), CuO x The specific surface area of electrochemical activity of the/CuF electrode is 9.3 mF/cm 2 Is less than CuO x Electrochemical active specific surface area of CuF electrode is 11.4 mF/cm 2 . Indicating Au-CuO x The enhancement of the catalytic activity of/CuF is not due to ECSA effect but due to the real catalytic ability of the doped Au. FIG. 5 (d) shows Au-CuO x The electrode of/CuF is at 10 mA-cm -2 Shows long-term stability of up to 25 hours at constant current.
（3）Au-CuO x Electrochemical Raman test analysis of/CuF electrode
Enhanced CuO for further interpretation of Au doping x The mechanism of the performance of the catalyst OER is that an in-situ electrochemical Raman spectrum experiment is carried out at different potentials. For comparison, the same experiment was also applied to CuO without Au doping x 。
With CuO x (0.65V → 0.5V) compared to the reverse scan condition (0.75V → 0.45V), the intermediate disappeared at 0.45V. This indicates that Au-CuO is doped due to gold x Has a specific ratio of CuO x Lower OER onset potential, indicating Au-CuO x Has better performance than CuO x Excellent electrocatalytic activity.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. A gold-doped copper-based self-supporting electrode for alkaline electrolysis of water, characterized in that: the electrode grows Au-CuO on a foam copper substrate through electrochemical displacement reaction x Nanocubes, the size of which is 0.1um-1um, Au in Au-CuO x The center of the nanocube; wherein, the atom proportion of Au is 3-8%.
2. The method for preparing the gold-doped copper-based self-supporting electrode for alkaline electrolyzed water according to claim 1, which is characterized by comprising the following steps of:
(1) pretreating the foam copper, and drying for later use;
(2) placing the foamy copper in a tube furnace, oxidizing at the temperature of 280-350 ℃, cooling after oxidizing, and taking out;
(3) adding the sodium chloroaurate aqueous solution into the ethanol and the aqueous solution which are mixed in the same volume, and performing ultrasonic treatment to obtain a sodium chloroaurate solution; placing the sodium chloroaurate solution in a reaction container, vertically placing the copper oxide foam, and keeping the temperature at 50-60 ℃ for 2-4 hours;
the concentration of the sodium chloroaurate solution is 0.1-0.8 mM;
(4) naturally cooling, taking out the foam copper, washing with deionized water and ethanol, and drying; and obtaining the gold-doped copper-based self-supporting electrode.
3. The method for preparing gold-doped copper-based self-supporting electrode for alkaline electrolysis of water according to claim 2, wherein: the pretreated foamy copper is diluted H 2 SO 4 After soaking, ultrasonic washing is carried out in acetone, deionized water and absolute ethyl alcohol in turn.
4. The method for preparing gold-doped copper-based self-supporting electrode for alkaline electrolysis of water according to claim 2, wherein: the foam copper is placed in a tube furnace at the temperature of 280 ℃ and 350 ℃ and is kept for 0.5-1.5 hours, and the heating rate is 8-10 ℃/min.
5. Use of a gold-doped copper-based self-supporting electrode for alkaline electrolysis of water according to claim 1, characterized in that: the electrode is applied to electrocatalytic water decomposition oxygen analysis reaction.
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