CN108149227B - TiO 22-WO3/rGO composite photoelectric energy storage material and preparation method and application thereof - Google Patents

TiO 22-WO3/rGO composite photoelectric energy storage material and preparation method and application thereof Download PDF

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CN108149227B
CN108149227B CN201711337754.6A CN201711337754A CN108149227B CN 108149227 B CN108149227 B CN 108149227B CN 201711337754 A CN201711337754 A CN 201711337754A CN 108149227 B CN108149227 B CN 108149227B
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CN108149227A (en
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陈卓元
姜旭宏
孙萌萌
荆江平
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Institute of Oceanology of CAS
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    • C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
    • C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
    • C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
    • C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
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Abstract

The invention belongs to the field of photoelectrochemical cathodic protection, and particularly relates to TiO2‑WO3a/rGO composite photoelectric energy storage material, a preparation method and application thereof. The composite photoelectric energy storage material is WO3rGO nanorod composites and TiO2Powder of WO3rGO nanorod composites and TiO2The amount (by mass) of the powder added was 1: 1. TiO prepared by the invention2‑WO3The self-corrosion potential of the 304 stainless steel can be reduced after the/rGO composite photoelectric energy storage photo-anode is coupled with the 304 stainless steel, and the photo-induced potential and the photo-generated current density show slow return rates in a dark state after photo-chopping, which shows that the composite photoelectric energy storage photo-anode has a good continuous cathode protection function. The method has simple experimental operation steps and solves the problem of continuous cathodic protection under cloudy and dark conditions.

Description

TiO 22-WO3/rGO composite photoelectric energy storage material and preparation method and application thereof
Technical Field
The invention belongs to the field of photoelectrochemical cathodic protection, and particularly relates to TiO2-WO3a/rGO composite photoelectric energy storage material, a preparation method and application thereof.
Background
Metal corrosion represents a serious economic loss and is accompanied by environmental pollution. In the face of increasing energy consumption and serious environmental problems, there is a need to develop an anti-corrosion technology that is environmentally friendly and utilizes clean energy. Over the last 20 years, it has been found that the photovoltaic effect of semiconductors can provide photogenerated electrons to coupled metal substrates, providing cathodic protection. Illumination can stimulate the production of photo-generated electrons, if in sufficient quantitiesThe photoproduction electrons are transferred and accumulated on the coupled metal, and the effective photoelectrochemical cathodic protection can be achieved by only utilizing solar energy. TiO 22It has been widely studied in the field of photoelectrochemistry because of its good electron transport properties, excellent chemical stability and appropriate energy band position.
Since the emergence of graphene in 2004, its unique quasi-two-dimensional (2D) structure and extraordinary electronic and physicochemical properties have become potential candidates for building highly active photocatalyst composites. The graphene can assist in capturing photo-generated electrons, improve the transmission efficiency of the photo-generated electrons, and can also be used as an electron library for capturing/transmitting the photo-generated electrons generated from a semiconductor. However, in the field of photoelectrochemical cathode protection, little mention is made of the role of transporting, capturing and assisting in the storage of photoelectrons.
WO3Is an electronic library material. WO3The nanoparticles can be applied to coating materials to store photo-generated electrons due to the energy storage capacity of the nanoparticles, and provide continuous cathodic protection for metals. This will help to solve the problem of continuous cathodic protection in cloudy and dark conditions.
Disclosure of Invention
Aiming at the problem of delayed cathodic protection, the invention aims to provide TiO2-WO3a/rGO composite photoelectric energy storage material, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
TiO 22-WO3the/rGO composite photoelectric energy storage material is WO3rGO nanorod composites and TiO2Powder of WO3rGO nanorod composites and TiO2The amount (by mass) of the powder added was 1: 1.
Said WO3the/rGO nanorod compound is synthesized by combining a solvothermal method and an in-situ growth method, and specifically, the required solution a and solution b are mixed in a high-pressure reaction kettle according to the mass ratio of 0.1-0.3:100 for synthesis, wherein the solution a is 0.5mg/mL GO dispersion liquid, and the solution b is 1mM WCl6The ethanol of (3) to obtain a mixed solution.
TiO 22-WO3Preparation method of/rGO composite photoelectric energy storage material, wherein the energy storage material is WO3rGO nanorod composites and TiO2Powder of WO3rGO nanorod composites and TiO2The filling amount (mass) of the powder is 1: 1; said WO3the/rGO nanorod compound is prepared by enabling WO to grow in situ by a solvothermal method3Complexes formed on the GO sheet.
The method specifically comprises the following steps:
1) preparation of GO stable dispersion: adding GO into ethanol to form a stable dispersion liquid;
2)WCl6preparation of the solution: under the magnetic stirring, WCl with the mass ratio of 8:1-10:1 is added under the magnetic stirring6And ZnCl2Dissolving in mixed solution of ethanol and polyethylene glycol; wherein the volume of the ethanol in the mixed solution is 30-50mL, and the volume of the polyethylene glycol is 15-25 mL.
3)WO3Preparation of/rGO nanorod composite: mixing the solutions obtained in the steps 1) and 2), forming a uniform solution under magnetic stirring, and then heating at the temperature of 170 ℃ and 190 ℃ for 22-26 hours to obtain a blue precipitate WO3a/rGO nanorod complex;
4)TiO2-WO3the/rGO composite photoelectric energy storage material: subjecting the WO prepared in step 3)3rGO nanorod composites and TiO2And (P25) weighing the powder in equal proportion.
TiO 22-WO3The application of the/rGO composite photoelectric energy storage material is characterized in that: the composite photoelectric energy storage material is used as an anti-corrosion protective film for inhibiting metal corrosion.
The composite photoelectric energy storage material is applied to continuous protection in a dark state as an anti-corrosion protective film for inhibiting metal corrosion.
TiO 22-WO3rGO composite photoelectric energy-storage electrode, TiO2-WO3WO in/rGO composite photoelectric energy storage material3rGO nanorod composites and TiO2(P25) powder was ground uniformly and then the area of the powder was equal to the area (10X 10 mm)2) Is applied to a conductive substrate (FT)O conductive glass) surface.
Further, the TiO is added2(P25) and WO3Mixing and grinding rGO in a mortar by deionized water for 10 minutes to form slurry respectively, and mixing the obtained slurry with equal proportional area (10 multiplied by 10 mm)2) Coating the mixture on the surface of a conductive substrate (FTO conductive glass), naturally drying the mixture, and keeping the temperature of 80 ℃ for 2 hours to prepare TiO2-WO3the/rGO composite photoelectric energy storage electrode. Wherein, the FTO conductive glass is SnO with F-doped conductive film component2The FTO glass was cut into 30X 10mm pieces2Size, first ultrasonically cleaned in analytically pure acetone for 5 minutes, and then rinsed with deionized water. The FTO glass is then blown dry. The long conductive edge of the FTO glass was covered with an insulating tape to expose two 5X 10mm test areas2。
TiO 22-WO3The application of the/rGO composite photoelectric energy storage electrode is used as an anti-corrosion protective film for inhibiting metal corrosion.
The composite photoelectric energy storage electrode is applied to continuous protection in a dark state as an anti-corrosion protective film for inhibiting metal corrosion.
Further, when 304 stainless steel is coupled to the photo-anode, 304SS-TiO2-WO3the/rGO system is irradiated by 304SS-TiO under the white light2The photo-induced mixed potential drop of the system is approximately equivalent, but 304SS-TiO is used after white light is cut off2-WO3The potential of the 304SS electrode in the/rGO system returns to its original value at a slower rate, showing some electron storage properties.
For the TiO prepared for the continuous photoelectrochemical cathodic protection2-WO3Coating the composite photoelectric energy storage material on the surface of a substrate to form a photo-anode, testing the photo-anode for a photoelectrochemical cathodic protection effect, specifically representing by using the change of a photo-induced open-circuit potential and a photo-induced current density, and measuring by recording the change information of the photo-induced current density and the open-circuit potential along with time under the condition of opening/closing light. The specific measuring device is divided into two reaction cells, namely an etching cell and a photoelectrochemical cell, as shown in fig. 2. Photoelectrochemical cellAnd the electrolyte in the corrosion tank is 3.5% NaCl solution, and the two tanks are connected through a salt bridge. The photoelectrode is placed in a photoelectrochemical cell, and 304 stainless steel is placed in a corrosion cell. A xenon lamp is used as a light source (no filter is added) to provide simulated sunlight. At the center of the front face of the photovoltaic cell there is a quartz window of about 30mm in diameter through which the incident light passes to impinge on the surface of the photoelectrode.
The basic principle of the invention is as follows: under illumination, TiO2Electrons in the valence band are excited to the conduction band to form photogenerated electrons. While WO3Electrons in the valence band are also excited into the conduction band to form photogenerated electrons. Since WO3Fermi level ratio of (TiO)2While the Fermi level of the metal 304SS is also more positive than that of TiO2And (4) correcting. So that the transmission of these photogenerated electron moieties to the coupled metal 304SS electrode provides photoelectrochemical cathodic protection thereto, and the transmission of excess photogenerated electrons to the WO3Is stored therein. When WO is3When hybridized with rGO, WO3The binding interface of the/rGO hybrid compound will be WO3Easier electron transport is created at the interface of the nanorods and rGO sheets. And WO3The nanorods are shortened after the rGO is introduced, and the refined nanostructure can effectively promote the electrolyte to diffuse into the interior, increase the charge contact area and improve the charging reaction. Therefore, under illumination, a large amount of photo-generated electrons are transmitted and stored in WO3In the/rGO hybrid complex. In the dark state, WO3The photogenerated electrons stored in/rGO are released again to provide continuous cathodic protection for 304 SS. WO3The refinement of the nano-rod provides more contact area and more storage space for the stored electrons, and ensures that more photogenerated electrons are stored in WO3In the nano-rod, the performance of continuously releasing electrons for a long time in a dark state is finally improved. Thus, coating TiO2-WO3The photoelectrode of the base material of the/rGO composite photoelectric energy storage material can generate continuous photoelectrochemical cathodic protection effect on metal
The invention has the advantages that:
the invention relates to a photoelectric material and WO3Energy storage type material is anchored with excellent electronic conductor graphene, and electricity is well integrated through multiphase heterojunction structure of the energy storage type materialThe transmission performance of the photon further transmits and stores photogenerated electrons through the 2D graphene structure3In the structure, the problem of continuous cathodic protection under cloudy and dark conditions is further assisted to be solved; specifically, the method comprises the following steps:
1. the invention synthesizes WO by solvothermal method and in-situ growth method3Reduced graphene oxide (WO)3The method is simple and easy, and only GO needs to be stably dispersed with WCl6The mixed solution of the ethanol is put into a reaction kettle for alcohol heat treatment and then dried. Obtained WO3rGO complexes with pure WO3Compared with the formation of shorter tungsten oxide nano-rods, the method is beneficial to improving the electrochemical cycling stability of the material.
2. TiO of the invention2-WO3rGO complexes with pure TiO2Compared with the prior art, the device can continuously release stored photo-generated electrons for a long time in a dark state, and provides continuous cathodic protection for metal, so that the problem of continuous cathodic protection in cloudy days and dark conditions is solved.
3. When the composite light anode prepared by the invention is coupled with a 304 stainless steel electrode, the photoinduced potential of the 304 stainless steel electrode in a corrosion tank is reduced to 570mV under the irradiation of white light, the stable potential can reach-450 mV and is far lower than the self-corrosion potential, and good cathode polarization occurs. The photoelectrochemistry cathode protection effect is good.
Drawings
FIG. 1 is a diagram of TiO provided in an embodiment of the present invention2-WO3rGO and TiO2(right) optical photograph of powder coated FTO conductive glass electrode.
Fig. 2 is a diagram of a photoelectrochemical cathodic protection testing device for a photoelectric material according to an embodiment of the present invention, where a left diagram is a schematic connection diagram of a device for measuring a photo-generated current density, and a right diagram is a schematic connection diagram of a device for measuring a photo-generated open circuit potential.
FIG. 3 shows a pure WO according to an embodiment of the present invention3(a) And WO3SEM images of/rGO (b, c, d) complexes.
FIG. 4 shows a 304SS electrode and pure TiO provided by an embodiment of the present invention2Electrode and TiO2-WO3And (3) a change curve of the photo-induced potential along with time after the/rGO composite photo-anode is coupled. Wherein the abscissa is time and the ordinate is electrode potential (vs. Ag/AgCl).
FIG. 5 shows a 304SS electrode prepared by the present invention in 3.5% NaCl solution with pure TiO2Electrode and TiO2-WO3The change curve of the photoproduction current density along with time under the intermittent white light irradiation after the rGO composite photo anode is coupled.
FIG. 6 shows a 304SS electrode prepared by the present invention in 3.5% NaCl solution with pure TiO2Powder electrode and TiO2-WO3And (3) a change curve of the photo-induced potential along with time after the/rGO composite photo-anode is coupled. Wherein the abscissa is time and the ordinate is electrode potential (vs. Ag/AgCl).
FIG. 7 shows a 304SS electrode prepared by the present invention in 3.5% NaCl solution with pure TiO2Powder electrode and TiO2-WO3The change curve of the photoproduction current density along with time under the intermittent white light irradiation after the rGO composite photo anode is coupled.
FIG. 8 shows the combination of a 304SS electrode and pure TiO in 3.5% NaCl solution according to an embodiment of the present invention2Powder electrode and TiO2-WO3And (3) a change curve of the photo-induced potential along with time after the/rGO composite photo-anode is coupled. Wherein the abscissa is time and the ordinate is electrode potential (vs. Ag/AgCl).
FIG. 9 shows a 304SS electrode prepared by the present invention in 3.5% NaCl solution with pure TiO2Powder electrode and TiO2-WO3The change curve of the photoproduction current density along with time under the intermittent white light irradiation after the rGO composite photo anode is coupled.
Detailed Description
The invention will be further described, by way of example, without in any way being restricted to the following figures.
The method firstly combines a solvothermal method and an in-situ growth method to synthesize WO3a/rGO nanorod complex; then the obtained WO3rGO nano rod compound and TiO2Uniformly grinding the powder, and coating the powder on FTO conductive glass in equal area to prepare the glassAnd an electrode. TiO to be prepared2-WO3The self-corrosion potential of the 304 stainless steel can be reduced after the/rGO composite photoelectric energy storage photo-anode is coupled with the 304 stainless steel, and the photo-induced potential and the photo-generated current density show slow return rates in a dark state after photo-chopping, which shows that the composite photoelectric energy storage photo-anode has a good continuous cathode protection function. The method has simple experimental operation steps and solves the problem of continuous cathodic protection under cloudy and dark conditions.
Example 1
TiO for continuous photoelectrochemical cathodic protection2-WO3Preparing a/rGO composite photoelectric energy storage photo-anode:
1) firstly, a certain amount of GO is added into ethanol and dispersed for 2 hours by ultrasonic vibration to form a stable GO dispersion liquid with the concentration of 0.5 mg/mL.
2)WO3The preparation of the/rGO nanorod composite is based on a simple solvothermal method and an in-situ growth method: adding the stable GO dispersion obtained in step 1) to a homogeneous solution (according to WO)30.1 wt% of the mass), stirred uniformly to form a uniform solution, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, heated under water at 180 ℃ for 24 hours, centrifuged to collect a blue precipitate, and washed with ethanol several times. The product was ground in an agate mortar for further characterization.
Wherein, the homogeneous solution is: under magnetic stirring, WCl6(0.4g) and ZnCl2(0.0492 g) was dissolved in a mixture of ethanol (40mL) and polyethylene glycol (20 mL).
At the same time, pure WO3The nano-rod consists of WCl only6The ethanol mixed solution is put into a reaction kettle for alcohol heat treatment without adding GO so as to compare pure WO3And WO3Morphological differences of/rGO complexes (see fig. 3).
3)TiO2-WO3The preparation of the/rGO system film photo-anode is as follows: adding TiO into the mixture2(P25) and WO3Respectively uniformly coating the powder slurry of the/rGO sample on FTO conductive glass in an equal area (see the left part of the figure 1);
the method comprises the following steps: the component of the FTO conductive glass (which is commercially available) conductive film is F-doped SnO2Cutting it into rulerInch of 30X 10mm2The electrode sheet of (1) was ultrasonically cleaned in analytically pure acetone for 5 minutes and then rinsed with deionized water. The FTO glass is then blown dry. The long conductive edge of the FTO glass was covered with an insulating tape to expose two 10X 10mm test areas2. Thereafter, 10mg of TiO2(P25) and WO3the/rGO powders were mixed separately with 0.1mL deionized water in a mortar (simultaneously, with TiO)2(P25) and WO3As a control, among others, TiO2(P25) and WO3Mixing rGO powder in equal weight proportion, TiO2(P25) and WO3Powder and the like) in equal weight proportions, and the mixture was ground for 10 minutes to form a slurry. The slurry is respectively and uniformly coated on the exposed effective surface area of the FTO glass, and the temperature is kept for 2h at 80 ℃ after natural air drying so as to improve the adhesive force of the film. The uncovered part is sealed by insulating silica gel to only leave 5 x 10mm2As shown on the left of fig. 1.
Pure TiO2(P25) electrode fabrication process and TiO2-WO3the/rGO system thin film composite photoelectrode is similar to the manufacture, and the difference lies in TiO2-WO3The coating area of the/rGO composite photo-electrode is two blocks of 10 multiplied by 10mm2Pure and pure TiO2(P25) coating area of 10X 10mm2As shown on the right of fig. 1.
For TiO obtained by the above preparation2-WO3Testing the photoelectrochemical cathode protection performance of a/rGO system thin film photoelectrode: on the apparatus shown in the schematic diagram of the experimental apparatus 2, the intensity of the photo-induced current between the coupling of the photoelectrode and the 304SS electrode under the irradiation of white light (fig. 5) and the change of the photo-induced mixed potential of the coupling system (fig. 4) were monitored by using the electrochemical workstation of CHI660D of shanghai chenhua instruments. The electrolyte in the photoelectrochemical cell and the corrosion cell is 3.5 percent NaCl solution.
From FIG. 3 it can be seen that pure WO is obtained3(a) Nanorods and WO3SEM image of/rGO (b, c and d) nanorod complexes. It can be seen that a single WO3The nanorods are about 33-47 nm and 190nm in diameter and length, respectively, whereas WO3The diameter and length of the/rGO nanorod composite are about-4.8 nm and 70nm, respectively. The reason is that in WO3/rGO nanorod compositeIn (WO)3The nano-rods are grown on the GO sheet, and the GO sheet layer not only provides nucleation points, but also limits WO3Growth of nanorods resulting in WO3in/rGO complex with pure WO3WO shorter than formed3And (4) nanorods.
From FIG. 4, it can be seen that the 304SS electrode is formed with pure TiO2Electrode and TiO2-WO3And (3) a change curve of the photoinduced potential along with time after the rGO composite photo-electrode is coupled. . After stabilization in the dark, the 304SS electrode was coupled to pure TiO2Thin film electrode (labeled 304 SS-TiO)2) Has a potential of-0.09V and a 304SS electrode coupled to the TiO2-WO3Electrode of/rGO system (304 SS-TiO)2-WO3The potential of/rGO 0.1) is-0.09V. The mixing potential of the coupling electrode is instantaneously shifted negatively at the start of white light irradiation and gradually decreased as the light irradiation time increases. And instantaneously shifts up and gradually returns to its original potential value when the white light is turned off. Photoactivatable 304SS-TiO compounds2The variation of the mixed potential is about 530mV for GO, as in WO3304SS-TiO in an amount of 0.1 wt% in/rGO complex2-WO3the/rGO system is 550 mV. In the third on-off light cycle, with 304SS-TiO2Comparison of the coupling System, 304SS-TiO2-WO3The potential of the 304SS electrode in the/rGO 0.1 system returns to its original value at a very slow rate after chopping the white light. And after being cut off for 100s by illumination, 304SS-TiO2-WO3The mixed potential of/rGO 0.1 is-0.37V, and the ratio is 304SS-TiO2More negative (-0.32V), indicating WO3the/rGO 0.1 composite shows very good electronic storage performance.
The photo-induced changes in the coupling current intensity of the 304SS electrode and the prepared photoelectrode under intermittent white light illumination can be seen in fig. 5. The coupling current density between the 304SS electrode and the photo electrode increases sharply when white light is on, and the photo-induced current density under white light illumination is positive, indicating that electrons flow from the photo electrode to the 304SS electrode via the electrochemical workstation, providing cathodic protection for the 304 SS. 304SS-TiO2And 304SS-TiO2-WO3The photoinduced changes in coupling current density in the/rGO 0.1 system were about 40 and 25. mu.A-cm, respectively-2. When light is emittedAfter being cut off, with TiO2In contrast, TiO2-WO3the/rGO 0.1 shows the electron sustained release performance and the slow current intensity return rate.
Example 2
TiO for continuous photoelectrochemical cathodic protection2-WO3Preparing a/rGO composite photoelectric energy storage photo-anode:
1) firstly, a certain amount of GO is added into ethanol and dispersed for 2 hours by ultrasonic vibration to form a stable GO dispersion liquid with the concentration of 0.5 mg/mL.
2)WO3The preparation of the/rGO nanorod composite is based on a simple solvothermal method and an in-situ growth method: adding the stable GO dispersion obtained in step 1) to a homogeneous solution (according to WO)30.2 wt% of the mass), stirred uniformly to form a uniform solution, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, heated under water at 180 ℃ for 24 hours, centrifuged to collect a blue precipitate, and washed with ethanol several times. The product was ground in an agate mortar for further characterization.
Wherein, the homogeneous solution is: under magnetic stirring, WCl6(0.4g) and ZnCl2(0.0492 g) was dissolved in a mixture of ethanol (40mL) and polyethylene glycol (20 mL).
3)TiO2-WO3the/rGO system film photo-anode is manufactured as follows: adding TiO into the mixture2(P25) and WO3the/rGO sample powder slurry is respectively and uniformly coated on the FTO conductive glass in an equal area.
The method comprises the following steps: the component of the FTO conductive glass (which is commercially available) conductive film is F-doped SnO2Cutting into pieces of 30X 10mm in size2The electrode sheet of (1) was ultrasonically cleaned in analytically pure acetone for 5 minutes and then rinsed with deionized water. The FTO glass is then blown dry. The long conductive edge of the FTO glass was covered with an insulating tape to expose two 10X 10mm test areas2. Thereafter, 10mg of TiO2(P25) and WO3the/rGO powders were mixed separately with 0.1mL deionized water in a mortar (simultaneously, with TiO)2(P25) and WO3As a control, among others, TiO2(P25) and WO3rGO powder in equal weight proportionMixed, TiO2(P25) and WO3Powder and the like) in equal weight proportions, and the mixture was ground for 10 minutes to form a slurry. The slurry is respectively and uniformly coated on the exposed effective surface area of the FTO glass, and the temperature is kept for 2h at 80 ℃ after natural air drying so as to improve the adhesive force of the film. The uncovered part is sealed by insulating silica gel to only leave 5 x 10mm2As shown on the left of fig. 1.
Pure TiO2(P25) electrode fabrication process and TiO2-WO3the/rGO system thin film composite photoelectrode is similar to the manufacture, and the difference lies in TiO2-WO3The coating area of the/rGO composite photo-electrode is two blocks of 10 multiplied by 10mm2Pure and pure TiO2(P25) coating area of 10X 10mm2As shown on the right of fig. 1.
For TiO obtained by the above preparation2-WO3Testing the photoelectrochemical cathode protection performance of a/rGO system thin film photoelectrode: on the apparatus shown in the schematic diagram of the experimental apparatus 2, the intensity of the photo-induced current between the coupling of the photoelectrode and the 304SS electrode under the irradiation of white light (fig. 7) and the change of the photo-induced mixed potential of the coupling system (fig. 6) were monitored by using the electrochemical workstation of CHI660D of shanghai chenhua instruments. The electrolyte in the photoelectrochemical cell and the corrosion cell is 3.5 percent NaCl solution.
FIG. 6 shows that the 304SS electrode is in contact with pure TiO2Electrode and TiO2-WO3And (3) a change curve of the photoinduced potential along with time after the rGO composite photo-electrode is coupled. After stabilization in the dark, the 304SS electrode was coupled to pure TiO2Thin film electrode (labeled 304 SS-TiO)2) Has a potential of-0.09V and a 304SS electrode coupled to the TiO2-WO3Electrode of/rGO system (304 SS-TiO)2-WO3potential/rGO 0.2) was 0.11V. The mixing potential of the coupling electrode is instantaneously shifted negatively at the start of white light irradiation and gradually decreased as the light irradiation time increases. And instantaneously shifts up and gradually returns to its original potential value when the white light is turned off. Photoactivatable 304SS-TiO compounds2The variation of the mixed potential is about 530mV for GO, as in WO3304SS-TiO in an amount of 0.2 wt% in/rGO complex2-WO3the/rGO system is 570 mV. In the third on/off light cycle, and 304SS-TiO2Comparison of the coupling System, 304SS-TiO2-WO3The potential of the 304SS electrode in the/rGO 0.2 system returns to its original value at a very slow rate after chopping the white light. And after being cut off for 100s by illumination, 304SS-TiO2-WO3The mixed potential of/rGO 0.2 shows the most negative value (-0.42V) compared with 304SS-TiO2More negative (-0.32V), indicating WO3the/rGO 0.2 complex exhibits very good electron storage properties.
The photo-induced changes in the coupling current intensity of the 304SS electrode and the prepared photoelectrode under intermittent white light illumination can be seen from fig. 7. The coupling current density between the 304SS electrode and the photo electrode increases sharply when white light is on, and the photo-induced current density under white light illumination is positive, indicating that electrons flow from the photo electrode to the 304SS electrode via the electrochemical workstation, providing cathodic protection for the 304 SS. 304SS-TiO2And 304SS-TiO2-WO3The photoinduced changes in coupling current density in the/rGO 0.2 system were about 40 and 32. mu.A-cm, respectively-2. When the light is cut off, the light reacts with TiO2In contrast, TiO2-WO3the/rGO 0.2 shows the electron sustained release performance and the slow current intensity return rate.
Example 3
TiO for continuous photoelectrochemical cathodic protection2-WO3Preparing a/rGO composite photoelectric energy storage photo-anode:
1) firstly, a certain amount of GO is added into ethanol and dispersed for 2 hours by ultrasonic vibration to form a stable GO dispersion liquid with the concentration of 0.5 mg/mL.
2)WO3The preparation of the/rGO nanorod composite is based on a simple solvothermal method and an in-situ growth method: adding the stable GO dispersion obtained in step 1) to a homogeneous solution (according to WO)30.3 wt% of the mass), stirred uniformly to form a uniform solution, then transferred to a stainless steel reaction kettle with a polytetrafluoroethylene lining, heated under water at 180 ℃ for 24 hours, centrifuged to collect a blue precipitate, and washed with ethanol several times. The product was ground in an agate mortar for further characterization.
Wherein, the homogeneous solution is: under magnetic stirring, WCl6(0.4g) and ZnCl2(0.0492 g) was dissolved in a mixture of ethanol (40mL) and polyethylene glycol (20 mL).
3)TiO2-WO3the/rGO system film photo-anode is manufactured as follows: adding TiO into the mixture2(P25) and WO3the/rGO sample powder slurry is respectively and uniformly coated on the FTO conductive glass in an equal area.
The method comprises the following steps: the component of the FTO conductive glass (which is commercially available) conductive film is F-doped SnO2Cutting into pieces of 30X 10mm in size2The electrode sheet of (1) was ultrasonically cleaned in analytically pure acetone for 5 minutes and then rinsed with deionized water. The FTO glass is then blown dry. The long conductive edge of the FTO glass was covered with an insulating tape to expose two 10X 10mm test areas2. Thereafter, 10mg of TiO2(P25) and WO3the/rGO powders were mixed separately with 0.1mL deionized water in a mortar (simultaneously, with TiO)2(P25) and WO3As a control, among others, TiO2(P25) and WO3Mixing rGO powder in equal weight proportion, TiO2(P25) and WO3Powder and the like) in equal weight proportions, and the mixture was ground for 10 minutes to form a slurry. The slurry is respectively and uniformly coated on the exposed effective surface area of the FTO glass, and the temperature is kept for 2h at 80 ℃ after natural air drying so as to improve the adhesive force of the film. The uncovered part is sealed by insulating silica gel to only leave 5 x 10mm2As shown on the left of fig. 1.
Pure TiO2(P25) electrode fabrication process and TiO2-WO3the/rGO system thin film composite photoelectrode is similar to the manufacture, and the difference lies in TiO2-WO3The coating area of the/rGO composite photo-electrode is two blocks of 10 multiplied by 10mm2Pure and pure TiO2(P25) coating area of 10X 10mm2As shown on the right of fig. 1.
For TiO obtained by the above preparation2-WO3Testing the photoelectrochemical cathode protection performance of a/rGO system thin film photoelectrode: in the experimental setup, schematically shown in FIG. 2, the intensity of the photo-induced current between the coupling of the photoelectrode and the 304SS electrode under white light irradiation (FIG. 9) and the photo-induced mixed potential of the coupling system (FIG. 9) were monitored by using CHI660D electrochemical workstation of Shanghai Chenghua instruments8) And (4) changing. The electrolyte in the photoelectrochemical cell and the corrosion cell is 3.5 percent NaCl solution.
FIG. 8 shows the 304SS electrode and pure TiO2Electrode and TiO2-WO3And (3) a change curve of the photoinduced potential along with time after the rGO composite photo-electrode is coupled. After stabilization in the dark, the 304SS electrode was coupled to pure TiO2Thin film electrode (labeled 304 SS-TiO)2) Has a potential of-0.09V and a 304SS electrode coupled to the TiO2-WO3Electrode of/rGO system (304 SS-TiO)2-WO3The potential of/rGO 0.3) is-0.05V. The mixing potential of the coupling electrode is instantaneously shifted negatively at the start of white light irradiation and gradually decreased as the light irradiation time increases. And instantaneously shifts up and gradually returns to its original potential value when the white light is turned off. Photoactivatable 304SS-TiO compounds2The variation of the mixed potential is about 530mV for GO, as in WO3304SS-TiO in an amount of 0.3 wt% in/rGO complex2-WO3the/rGO system is 450 mV. In the third on-off light cycle, with 304SS-TiO2Comparison of the coupling System, 304SS-TiO2-WO3The potential of the 304SS electrode in the/rGO 0.3 system returns to its original value at a very slow rate after chopping the white light. And after being cut off for 100s by illumination, 304SS-TiO2-WO3The mixed potential of/rGO 0.3 shows the most negative value (-0.37V) compared with 304SS-TiO2More negative (-0.32V), indicating WO3the/rGO 0.3 complex exhibits very good electron storage properties.
The photo-induced changes in the coupling current intensity of the 304SS electrode and the prepared photoelectrode under intermittent white light illumination can be seen in fig. 9. The coupling current density between the 304SS electrode and the photo electrode increases sharply when white light is on, and the photo-induced current density under white light illumination is positive, indicating that electrons flow from the photo electrode to the 304SS electrode via the electrochemical workstation, providing cathodic protection for the 304 SS. 304SS-TiO2And 304SS-TiO2-WO3The photoinduced variation of the coupling current density in the/rGO 0.3 system was about 40 and 35. mu.A-cm, respectively-2. When the light is cut off, the light reacts with TiO2In contrast, TiO2-WO3the/rGO 0.3 shows the electron sustained release performance and the slow current intensity return speedAnd (4) rate.

Claims (8)

1. TiO 22-WO3the/rGO composite photoelectric energy storage material is characterized in that: the composite photoelectric energy storage material is WO3rGO nanorod composites and TiO2Powder of WO3rGO nanorod composites and TiO2The adding amount of the powder is 1:1 by mass;
said WO3the/rGO nanorod compound is synthesized by combining a solvothermal method and an in-situ growth method, and specifically, the required solution a and solution b are mixed and placed in a high-pressure reaction kettle according to the mass ratio of 0.1-0.3:100 for synthesis, wherein the solution a is 0.5mg/mL GO dispersion liquid, and the solution b is 1mM WCl6The ethanol of (3) to obtain a mixed solution.
2. The TiO of claim 12-WO3The preparation method of the/rGO composite photoelectric energy storage material is characterized by comprising the following steps: the energy storage material is WO3rGO nanorod composites and TiO2Powder of WO3rGO nanorod composites and TiO2The adding amount of the powder is 1:1 by mass; said WO3the/rGO nanorod compound is prepared by enabling WO to grow in situ by a solvothermal method3Complexes formed on the GO sheet.
3. TiO according to claim 22-WO3The preparation method of the/rGO composite photoelectric energy storage material is characterized by comprising the following steps:
1) preparation of GO stable dispersion: adding GO into ethanol to form a stable dispersion liquid;
2)WCl6preparation of the solution: under the magnetic stirring, WCl with the mass ratio of 8:1-10:1 is added6And ZnCl2Dissolving in mixed solution of ethanol and polyethylene glycol;
3)WO3preparation of/rGO nanorod composite: mixing the solutions obtained in the steps 1) and 2), forming a uniform solution under magnetic stirring, and then heating at the temperature of 170 ℃ and 190 ℃ for 22-26 hours to obtain a blue precipitate WO3a/rGO nanorod complex;
4)TiO2-WO3the/rGO composite photoelectric energy storage material: subjecting the WO prepared in step 3)3rGO nanorod composites and TiO2And weighing the powder in equal proportion.
4. The TiO of claim 12-WO3The application of the/rGO composite photoelectric energy storage material is characterized in that: the composite photoelectric energy storage material is used as an anti-corrosion protective film for inhibiting metal corrosion.
5. TiO according to claim 42-WO3The application of the/rGO composite photoelectric energy storage material is characterized in that: the composite photoelectric energy storage material is applied to continuous protection in a dark state as an anti-corrosion protective film for inhibiting metal corrosion.
6. TiO 22-WO3the/rGO composite photoelectric energy storage electrode is characterized in that: TiO 22-WO3WO in/rGO composite photoelectric energy storage material3rGO nanorod composites and TiO2And respectively grinding the powder uniformly, and coating the powder on the surface of the conductive base material in an equal proportional area.
7. The TiO of claim 62-WO3The application of the/rGO composite photoelectric energy storage electrode is characterized in that: the composite photoelectric energy storage electrode is used as an anti-corrosion protective film for inhibiting metal corrosion.
8. TiO according to claim 72-WO3The application of the/rGO composite photoelectric energy storage electrode is characterized in that: the composite photoelectric energy storage electrode is applied to continuous protection in a dark state as an anti-corrosion protective film for inhibiting metal corrosion.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102142317A (en) * 2011-01-14 2011-08-03 天津师范大学 Solar battery with graphite interface layer and manufacturing method thereof
CN106555188A (en) * 2016-11-24 2017-04-05 中国科学院海洋研究所 For the preparation method of the Ag/ Graphenes/titania nanotube composite film photo-anode of photoproduction cathodic protection

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130056068A1 (en) * 2011-09-06 2013-03-07 Korea Institute Of Science And Technology Preparation method of flexible electrodes and flexible dye-sensitized solar cells using the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102142317A (en) * 2011-01-14 2011-08-03 天津师范大学 Solar battery with graphite interface layer and manufacturing method thereof
CN106555188A (en) * 2016-11-24 2017-04-05 中国科学院海洋研究所 For the preparation method of the Ag/ Graphenes/titania nanotube composite film photo-anode of photoproduction cathodic protection

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
High Performance Solid-state Asymmetric Supercapacitor using Green Synthesized Graphene-WO3 Nanowires Nanocomposite;Arpan Kumar Nayak;《Sustainable Chemistry & Engineering》;20170925;"EXPERIMENTAL SECTION" *
TiO2-WO3/rGO体系提高的延时光电化学阴极保护性能的研究;孙萌萌;《2016年全国腐蚀电化学及测试方法学术交流会》;20160713;第38页第1-2段 *
孙萌萌.TiO2-WO3/rGO体系提高的延时光电化学阴极保护性能的研究.《2016年全国腐蚀电化学及测试方法学术交流会》.2016,第38-39页. *

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