CN114892211B - Visual electrocatalytic material and preparation method and application thereof - Google Patents
Visual electrocatalytic material and preparation method and application thereof Download PDFInfo
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/133—Renewable energy sources, e.g. sunlight
Abstract
A visual electrocatalytic material and a preparation method and application thereof belong to the technical field of electrolyzed water catalyst materials. The single-atom Pt modified WO growing on the silver nanowire is prepared by a simple and convenient electrodeposition method and a plasma enhanced chemical vapor deposition method x Is a nanocomposite of (a). The hydrogen evolution performance of the electrolyzed water is visually tested by combining an electrochemical workstation and an ultraviolet-visible spectrophotometer, and the hydrogen evolution performance of the electrolyzed water is visually characterized by the color change of the material.
Description
Technical Field
The present invention relates to a single atom Pt modified WO grown in situ on silver nanowires (Ag NWs) x Nanocomposite Pt-WO x A preparation method of Ag NWs, which belongs to the technical field of electrolyzed water catalyst materials.
Background
The hydrogen energy is taken as a clean and renewable energy source, has the advantages of high energy density, convenient storage and transportation and zero carbon dioxide emission, and is regarded as an ideal energy carrier and an alternative energy source of the most potential traditional fossil energy sources. Electrolytic water hydrogen production is an effective technique for converting electrical energy into chemical energy to produce high purity hydrogen, and is considered to be a very promising and cleanest method for obtaining hydrogen energy. However, the electrochemical process of electrolyzing water is complex and variable, and is a redox reaction process involving multiple electron transfer between the positive and negative electrodes. Existing methods for evaluating the performance of electrolyzed water to produce hydrogen are such as electrochemical test analysis techniques (data recording and results analysis of chemical reaction processes using electrochemical workstations) and product fractionationAnalytical techniques (gas chromatograph for reaction product H) 2 Capture analysis) and the like are susceptible to external factors such as test conditions, test environments, instrument equipment precision and the like, so that the test result is inaccurate, and the evaluation of the catalytic performance and the actual production and application are affected. In addition, none of the above methods intuitively exhibit the chemical reaction process occurring on the electrode surface. Currently, visual smart device apparatuses such as electrochromic batteries (which reflect energy storage levels during battery charging and discharging through visual color changes), electrochromic capacitors (which display charge storage states of capacitors through visual color changes), and other devices such as electrochromic current early warning apparatuses have begun to be applied to modern man-machine interaction smart devices. Therefore, developing a visual electrocatalytic material is important to realize more efficient performance evaluation and application in the water electrolysis reaction process. WO (WO) 3 As the earliest cathode electrochromic material, the material has the characteristics of large capacity, good cycle stability, high coloring efficiency, quick response time and the like, and has excellent optical performance, but the application of the material in the field of electrocatalysis is limited due to the problems of low conductivity and intrinsic catalytic activity. Although some existing methods such as structure densification, ion doping and material compounding are used for modification, most existing preparation methods are complex, and problems such as poor stability and poor optical performance of the material are caused by problems such as increased voltage polarization or excessively high compounding proportion of the prepared material. Thus, a visual WO with both excellent electrochromic and electrolyzed water catalytic properties was sought 3 The preparation of the base catalyst is challenging and of great importance.
Disclosure of Invention
The primary object of the present invention is to provide a single atom Pt modified WO grown in situ on silver nanowires, which solves the problems of the prior art x Is Pt-WO x Process for the preparation of Ag NWs.
The process is based mainly on WO with excellent optical properties 3 The transition metal type catalyst is prepared and grown in the silver nano by a simple and convenient electro-deposition method and a plasma enhanced chemical vapor deposition methodMonoatomic Pt modified WO on nanowires x Comprises the following steps:
(1) Preparation of Ag-containing NWs slides:
first silver nanowires are prepared, preferably: an ethylene glycol solution containing 1.0 g of polyvinylpyrrolidone, 1.0 g of silver nitrate and 10.0 mg of ferric chloride which are uniformly dispersed is placed in an oil bath at the normal pressure of 110 ℃ for reaction for 12 hours, naturally cooled to room temperature, and then respectively washed by acetone and ethanol and dispersed in ethanol;
uniformly spraying the silver nanowires dispersed by ethanol on a glass slide by adopting an ink-jet printing technology to obtain a glass slide containing Ag NWs;
(2) Containing WO x Preparation of @ Ag NWs slides:
immersing the obtained glass slide containing Ag NWs in electrolyte, using graphite sheet as counter electrode and calomel electrode as reference electrode, applying continuous-0.4V-0.8V working voltage for 10-30 seconds by electrochemical workstation, washing the working electrode with ethanol, drying, transferring to a plasma enhanced chemical vapor deposition reaction device, purifying the reaction cavity environment with pure hydrogen for 3 times, and introducing 95% H into the system with the assistance of plasma of 80W-120W 2 And 5% N 2 After 30 minutes of reaction, the product WO is obtained x Ag NWs; the electrolyte is a mixed solution of tungsten powder, hydrogen peroxide, absolute ethyl alcohol and acetic acid, and each 12.0 g of tungsten powder corresponds to 88 ml of hydrogen peroxide, 88 ml of absolute ethyl alcohol and 24 ml of acetic acid;
(3)Pt-WO x preparation of @ Ag NWs:
WO obtained by the above x Immersing glass slide of @ Ag NWs as working electrode in electrolyte, immersing platinum sheet as counter electrode, calomel electrode as reference electrode, cyclic voltammetry with electrochemical working station, applying working voltage from-0.3 to-0.7V, scanning at 40.0-60.0mV/s for 100-1000 circles, washing the working electrode with ethanol, and drying to obtain Pt-WO x Ag NWs; the electrolyte is sulfuric acid solution containing chloroplatinic acid; the concentration of sulfuric acid in the electrolyte is 0.4-0.6 mol/LThe concentration of chloroplatinic acid is 30.0-80 micromoles per liter.
Another object of the present invention is to provide a monoatomic Pt modified WO grown in situ on silver nanowires x Nanocomposite Pt-WO x @ag NWs. The resulting materials were assembled into a three-electrode system and the electrolyzed water hydrogen evolution performance of the catalyst was tested using electrochemical workstation CHI 660E.
Another object of the present invention is to provide a monoatomic Pt modified WO grown in situ on silver nanowires x Nanocomposite Pt-WO x @ag NWs. The resulting materials were assembled into a three-electrode system and the electrochromic properties of the catalysts were tested using an ultraviolet-visible spectrophotometer TU-1880.
Another object of the present invention is to provide a monoatomic Pt modified WO grown in situ on silver nanowires x Nanocomposite Pt-WO x @ag NWs. Modeling the obtained material structure, and revealing single-atom Pt and WO by using VASP through density functional theory x For Pt-WO x Influence of @ Ag NWs.
Another object of the present invention is to provide a monoatomic Pt modified WO grown in situ on silver nanowires x Nanocomposite Pt-WO x @ag NWs. The resulting materials are assembled into a three-electrode system and the catalyst is tested for electrolyzed water hydrogen evolution performance visualization using an electrochemical workstation such as CHI660E and an ultraviolet-visible spectrophotometer such as TU-1880 in combination with in situ photoelectric performance testing.
The invention has the beneficial effects that:
(1) The invention constructs a three-dimensional conductive net by adopting silver nanowires as conductive substrates, and provides rich active sites and channels for charge transfer and substance transportation.
(2) The invention adopts WO 3 As a support for electrochromic materials and monoatomic platinum, and in WO 3 Oxygen vacancy defects are structured on the surface, and the coloring efficiency and the optical modulation performance of the sample are effectively improved.
(3) The invention is described in WO x Surface anchoring monoatoms as efficient hydrogen evolution catalystsThe site effectively reduces the utilization of noble metal, reduces the cost, promotes the hydrogen evolution performance of the electrolyzed water, and simultaneously improves the stability of electrochromic performance.
(4) The invention realizes visual hydrogen evolution through in-situ photo-electrochemical performance test, and provides theoretical basis for future application of multifunctional intelligent visual materials and devices.
Description of the drawings:
FIG. 1 shows Pt-WO prepared in example 1 x @Ag NWs、WO x @Ag NWs、WO 3 XRD patterns for Ag NWs and Ag NWs.
FIG. 2 shows Pt-WO prepared in example 1 x @Ag NWs、WO x @Ag NWs、WO 3 XPS graphs of Ag NWs and Ag NWs.
FIG. 3 shows Pt-WO prepared in example 1 x SEM images of @ Ag NWs.
FIG. 4 shows Pt-WO prepared in example 1 x High resolution TEM images of @ Ag NWs.
FIG. 5 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Linear scan polarization plot for @ Ag NWs.
FIG. 6 shows Pt-WOx@Ag NWs, WO prepared in example 1 x Ag NWs and WO 3 Tafel slope plot of @ Ag NWs.
FIG. 7 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Impedance plot of @ Ag NWs
FIG. 8 shows Pt-WO prepared in example 1 x Ag NWs and WO 3 H of @ Ag NWs 2 Free energy of O adsorption (DeltaG) H2O ) And H adsorption free energy (. DELTA.G) H* ) A drawing.
FIG. 9 shows Pt-WO prepared in example 1 x State density (PDOS) plot of Ag NWs versus isolated Pt atoms.
FIG. 10 shows Pt-WO prepared in example 1 x @ag NWs local electric field profile.
FIG. 11 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Optical transmittance plot for @ Ag NWs.
FIG. 12 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Optical response time plot for @ Ag NWs.
FIG. 13 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Optical coloring efficiency plot of @ Ag NWs.
FIG. 14 shows Pt-WO prepared in example 1 x Real-time transmittance changes for @ Ag NWs and color and H as a function of applied potential sweep 2 A variation graph.
FIG. 15 shows Pt-WO prepared in example 1 x Transmittance of @ Ag NWs, H 2 Real-time change graph of turnover frequency and energy consumption.
The specific embodiment is as follows:
the present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
Example 1:
(1) A uniformly dispersed ethylene glycol solution containing 1.0 g of polyvinylpyrrolidone, 1.0 g of silver nitrate and 10.0 mg of ferric chloride is placed in an oil bath at the normal pressure of 110 ℃ for reaction for 12 hours, naturally cooled to room temperature, and then washed with acetone and ethanol respectively, and dispersed in ethanol. And uniformly spraying the silver nanowires dispersed by ethanol on a glass slide by adopting an ink-jet printing technology to obtain the glass slide containing Ag NWs. Immersing the obtained glass slide containing Ag NWs with the size of 1 square centimeter in an electrolyte containing 12.0 g tungsten powder, 88 ml hydrogen peroxide, 88 ml absolute ethyl alcohol and 24 ml acetic acid, taking a graphite sheet as a working electrode, taking a calomel electrode as a reference electrode, applying continuous-0.6V working voltage for 20 seconds by using a cinnabar CHI660E electrochemical workstation, washing the working electrode with ethanol, drying, transferring to a plasma enhanced chemical vapor deposition reaction device, pumping the system into 1Pa basic pressure, and purifying with pure hydrogen for 3 times. Then with the aid of plasma (100W) 95% H was introduced into the system 2 And 5% N 2 After 30min of reaction, the product WO is obtained x @ag NWs. WO obtained by the above x Slide immersion size 1cm area at @ Ag NWs containing 0.5 moles per liter of dilute sulfuric acid and 50.0 micromoles per literIn the electrolyte of chloroplatinic acid with raised concentration, platinum sheet is used as counter electrode, calomel electrode is used as reference electrode, cyclic voltammetry of electrochemical workstation CHI660E is adopted, working voltage from-0.3V to-0.7V is applied, scanning speed is 50.0 mV per second, scanning cycle number is 200 circles, after completion, the working electrode is washed with ethanol and dried to obtain Pt-WO x @Ag NWs。
(2) The specific composition and structure of the material was characterized by XRD testing. FIG. 1 is a Pt-WO prepared in example 1 x @Ag NWs、WO x @Ag NWs、WO 3 XRD patterns for Ag NWs and Ag NWs. As can be confirmed by comparing pdf cards, four main peaks of 38.1 °, 44.3 °, 77.5 °, and 64.4 ° in the map correspond to (111), (200), (220), and (311) planes of Ag (JCPLDS No. 87-0597), respectively, and no observation with WO was made 3 Signals associated with the Pt phase, possibly due to WO in the prepared samples 3 And the lower Pt content, the weaker signal compared to the Ag NWs signal. The elemental composition of the material was characterized by XPS testing. FIG. 2 shows Pt-WO prepared in example 1 x @Ag NWs、WO x @Ag NWs、WO 3 XPS graphs of Ag NWs and Ag NWs. From the figures it can be seen that WO 3 W4f x ray photoelectron Spectrometry (XPS) of the @ Ag NWs sample has a pair of peaks at 35.5eV and 37.7eV corresponding to W 6+ 4f7/2 and 4f5/2 in the oxidized state, indicating that electrodeposition gives a fully oxidized WO 3 . And WO x Ag NWs and Pt-WO x XPS spectrum of @ Ag NWs sample showed three peaks and shifted to a ratio of WO 3 Lower binding energy of @ Ag NWs, corresponding to two different W oxidation states, indicates W 6+ And W is 5+ At the same time, it was confirmed that the plasma enhanced chemical vapor deposition method was in WO x The oxygen vacancies were successfully constructed. The morphology of the material was characterized by SEM testing.
(3) FIG. 3 shows Pt-WO prepared in example 1 x SEM images of @ Ag NWs. Uniformly depositing WO on the surface of Ag NWs x Layer, WO x The layer maintains the three-dimensional structure of the Ag NWs network, but forms a rough particle form on the surface, provides more active sites, and is favorable for the infiltration of electrolyte and the release of hydrogen. Junction to materials by TEM testThe construct was further characterized. FIG. 4 shows Pt-WO prepared in example 1 x High resolution TEM images of @ Ag NWs. In WO x The evenly dispersed bright spots are correspondingly recombined into atomic Pt. Regular atomic arrangements with lattice distances of 0.267 and 0.263nm (measured by fast fourier transformation) correspond to WO, respectively 3 The (021) and (201) plane spacing of monoclinic crystal face (JCPDS No. 75-2072).
Example 2:
(1) And (3) researching the electrocatalytic hydrogen evolution performance of the prepared material. The hydrogen evolution activity of the material was characterized by the LSV test. FIG. 5 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Linear scan polarization plot for @ Ag NWs. Pt-WO x @Ag NWs、WO x Ag NWs and WO 3 Current densities of @ Ag NWs at-400 mV overpotential were 30.32, 14.14 and 2.53mA cm, respectively -2 It was confirmed that enhancement of HER activity was anchored by Pt atoms and WO 3 The upper oxygen vacancies are built up. FIG. 6 shows Pt-WO prepared in example 1 x Tafel slope plot of @ Ag NWs. Pt-WO x The Tafel slope of @ Ag NWs was 86.3 mV.dec -1 Far below WO x @Ag NWs(157.4mV·dec -1 ) And WO 3 @Ag NWs(267.3mV·dec -1 ) The rapid HER kinetics caused by platinum atom modification and oxygen vacancies are revealed.
(2) The charge transport properties of the materials were characterized by EIS testing. FIG. 7 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Impedance plot of @ Ag NWs. Pt-WO x Charge transfer resistance (Rct) of @ Ag NWs (4.8 ohms) was lower than WO x Ag NWs (25.0 ohm) and WO 3 @Ag NWs (44.2 ohm) mainly due to the platinum atoms and WO x The strong metal-carrier interactions between them regulate the electronic structure.
(3) And carrying out theoretical verification on the material performance through the structural simulation calculation of the VASP on the material. FIG. 8 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 H of @ Ag NWs 2 Free energy of O adsorption (DeltaG) H2O ) And H adsorption free energy (. DELTA.G) H* ) A drawing. ΔG H2O Is empty of oxygenBit (-0.17 eV) vs H 2 The adsorption capacity of O is much higher than that of Pt vacancy (-0.05 eV), which explains the water molecules in Pt-WO x Preferential adsorption on the oxygen vacancies of the @ Ag NWs. In addition, a milder ΔG was achieved in Pt-WOx@Ag NWs (0.38 eV) H* Closer to 0eV, indicating that HER has a higher active site. FIG. 9 is a Pt-WO prepared in example 1 x State density diagram of @ Ag NWs with isolated Pt atoms. In contrast to the discrete orbitals of isolated Pt atoms, pt-WO x Continuous distribution of orbitals of Pt atoms in the @ Ag NWs, indicating Pt atoms with WO x The hybridization of the orbit is stronger. Pt-WO x The d-band center of @ Ag NWs shifted more to the Fermi level of 0.54eV than the isolated Pt atom, indicating reduced H adsorption, thus promoting Pt-WO x H-spill at Ag NWs, eventually promoting H 2 Is generated. FIG. 10 shows Pt-WO prepared in example 1 x @ag NWs local electric field profile. Pt atom and WO x The strong metal-carrier interactions between the carriers result in a redistribution of charge density around the Pt atoms, which exhibits a poor electron region and a rich electron distribution characteristic. In particular, the electron rich region is located on top of the Pt atoms and on the side of the O atoms near the Pt, forming a localized tip enhanced electric field around the Pt region.
Example 3:
(1) The optical properties of the materials were characterized by spectroscopic testing. FIG. 11 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Optical transmittance plot for @ Ag NWs. The prepared material showed excellent optical modulation properties in visible wavelengths and light modulation ranges (difference in transmittance in colored state and bleached state) at 630nm were 36.0%, 37.3% and 30.7%, respectively. WO (WO) x The light modulation enhancement of the @ Ag NWs may be due to WO 3 O vacancy position pair H of @ Ag NWs surface 2 O has better adsorption affinity. For Pt-WO x Low Pt content (only 3.6% wt%) for WO @ Ag NWs x The electrochromic properties of (2) are not greatly affected. Furthermore, WO x Pt sites with appropriate H binding energy on them can promote H effectively * Conversion and H of (2) 2 This results in a final release of H during electrochromic + Is inserted and withdrawn symmetrically. Drawings12 is Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Optical response time plot for @ Ag NWs. When the transmittance modulation was changed by 90%, both dyeing and bleaching times were 4s. The three-dimensional silver nanowire conductive net has a large active surface and good conductivity, and is a main reason for a rapid electrochemical process. FIG. 13 shows Pt-WO prepared in example 1 x @Ag NWs、WO x Ag NWs and WO 3 Optical coloring efficiency plot of @ Ag NWs. WO (WO) x The coloring efficiency of @ Ag NWs was 236.1cm 2 ·C -1 And the coloring efficiency was 129.5cm 2 ·C -1 Is WO 3 Double the @ Ag NWs. The improvement in electrochromic efficiency is due to the hydrogen ion to H at the oxygen vacancies 2 The preferential adsorption affinity of O reduces the potential barrier of hydrogen ions to transfer to the surface and promotes electrochromic reaction kinetics. Pt-WO x The coloring efficiency of @ Ag NWs was 195.7cm 2 ·C -1 Higher than WO 3 @Ag NWs, but lower than WO x @ag NWs. This can be explained by the fact that platinum atoms are present in combination with WO x Strong metal-carrier interaction, effectively promoting adsorbed H * Conversion at active surface and H 2 Is released to replace adsorbed H + Insertion of WO x An internal process.
(2) The visual hydrogen evolution property of the material is characterized by in-situ photo-electric testing. FIG. 14 shows Pt-WO prepared in example 1 x Real-time transmittance changes for @ Ag NWs and color and H as a function of applied potential sweep 2 Evolution behavior diagram. Pt-WO x @Ag NWs，WO x Ag NWs and WO 3 Digital photographs of @ Ag NWs from bleached to colored state show H 2 The number of bubbles gradually increased, eventually from a deep colored Pt-WO x The @ Ag NWs surface releases sharply. FIG. 15 shows Pt-WO prepared in example 1 x Transmittance of @ Ag NWs, H 2 Real-time change graph of turnover frequency and energy consumption. At 630nm wavelength, the transmittance is synchronously changed from 80.3% to 48.7%, H 2 The turnover frequency is from 0 to 2.26s -1 Synchronous change, the energy consumption in 1 hour is changed from 0 to 0.74 W.h synchronously, and the HER performance change is intuitively displayed through the color.
Claims (1)
1. The preparation method of the visual electrocatalytic material is characterized by comprising the following steps of: monoatomic Pt-modified WO grown in situ on silver nanowires x Is Pt-WO x Ag NWs; the method comprises the following steps:
(1) Preparation of Ag-containing NWs slides:
uniformly spraying the silver nanowires dispersed by ethanol on a glass slide by adopting an ink-jet printing technology to obtain a glass slide containing Ag NWs;
(2) Containing WO x Preparation of @ Ag NWs slides:
immersing the obtained glass slide containing Ag NWs in electrolyte, using graphite sheet as counter electrode and calomel electrode as reference electrode, applying continuous-0.4V-0.8V working voltage for 10-30 seconds by electrochemical workstation, washing the working electrode with ethanol, drying, transferring to a plasma enhanced chemical vapor deposition reaction device, purifying the reaction cavity environment with pure hydrogen for 3 times, and introducing 95% H into the system with the assistance of plasma of 80W-120W 2 And 5% N 2 After 30 minutes of reaction, the product WO is obtained x Ag NWs; the electrolyte is a mixed solution of tungsten powder, hydrogen peroxide, absolute ethyl alcohol and acetic acid, and each 12.0 g of tungsten powder corresponds to 88 ml of hydrogen peroxide, 88 ml of absolute ethyl alcohol and 24 ml of acetic acid;
(3)Pt-WO x preparation of @ Ag NWs:
WO obtained by the above x Immersing glass slide of @ Ag NWs as working electrode in electrolyte, immersing platinum sheet as counter electrode, calomel electrode as reference electrode, cyclic voltammetry with electrochemical working station, applying working voltage from-0.3 to-0.7V, scanning at 40.0-60.0mV/s for 100-1000 circles, washing the working electrode with ethanol, and drying to obtain Pt-WO x Ag NWs; the electrolyte is sulfuric acid solution containing chloroplatinic acid; the concentration of sulfuric acid in the electrolyte is 0.4-0.6 mole per liter, and the concentration of chloroplatinic acid is 30.0-80 micromole per liter.
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