CN114134506A - Porous composite photoelectric energy storage material for photoinduced continuous cathodic protection and preparation and application thereof - Google Patents
Porous composite photoelectric energy storage material for photoinduced continuous cathodic protection and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of photoelectrochemical cathodic protection, and particularly relates to a porous composite photoelectric energy storage material (TiO) for photoinduced continuous cathodic protection2/SnIn4S8) And preparation and application thereof. The composite photoelectric energy storage material is TiO2SnIn grown in situ in gaps and upper parts of nano shrubs4S8The porous composite photoelectric energy storage material is obtained by the three-dimensional nanoflower. The invention provides a valuable reference for optimally designing a high-efficiency energy storage photoelectric material system and promoting long-acting continuous photoelectric cathode protection on metal in a marine environment.
Description
Technical Field
The invention belongs to the field of photoelectrochemical cathodic protection, and particularly relates to a porous composite photoelectric energy storage material (TiO) for photoinduced continuous cathodic protection2/SnIn4S8) And preparation and application thereof.
Background
The photocathode protection (PCP) technology is a promising marine metal corrosion prevention technology. The technology utilizes light energy in the sea to generate photo-generated electrons through a photoelectric conversion semiconductor material, and provides the photo-generated electrons for metal to carry out cathodic protection. However, a significant challenge currently faced by photocathode protection technology is that the cathodic protection properties of the photoelectrochemical response cannot be exploited in the absence of light.
Aiming at the problem, on one hand, the charge storage capacity is hopeful to be improved by optimizing the structure of the porous membrane layer, so that the cathode protection effect can be generated in a dark state after illumination. To TiO 22Research on photoanodes shows that the three-dimensional titanium dioxide nanowire mesh film, the flower-shaped titanium dioxide film and the mesoporous titanium dioxide film all show an electronic storage effect, which is mainly due to the unique porous micro-nano structure with large specific surface area. Thus, by manipulating TiO2The shape of the electrode is beneficial to improving the charge storage capacity. And TiO frequently used for preparing photoelectric anode2Nanotubes do not exhibit electron storage effects [1 ]]。
On the other hand, the compound of the semiconductor with the charged storage component is expected to further improve the charge storage property of the semiconductor photoelectric conversion film material and maintain the continuous protection performance in a dark state. The multi-transition metal compound can reversibly react with Na through oxidation-reduction reaction of variable valence metal ions+、Li+、H+And the crystal lattice is inserted to realize the storage and release of electrons. Conventional charge storage semiconductor transition metal oxide WO3、SnO2Although the material has excellent electron storage performance, the material has a large forbidden band width, a narrow light absorption range and low photoelectric conversion efficiency, and reduces the protection performance of a photocathode while storing energy. Multicomponent transition metal sulfide ZnIn2S4、AgInS2Although the narrow forbidden band width and the relatively negative conduction band potential have good photoelectrochemical and photocathode protection performances, the dark state after illumination cannot provide the delayed photocathode protection performance [2, 3)]。
Therefore, aiming at the current serious challenge of the photocathode protection technology, which is the defects that the cathode protection performance of photoelectrochemical response cannot be continuously exerted and the efficiency is low under the condition of no illumination, the structurally optimized nano-composite semiconductor photoanode material for continuously protecting the dark state after illumination is provided, and the marine metal continuous photocathode protection is realized by utilizing the material.
[1]H.Li,W.Song,X.Cui,Y.Li,B.Hou,L.Cheng,P.Zhang,Preparation of SnIn4S8/TiO2 Nanotube Photoanode and Its Photocathodic Protection for Q235 Carbon Steel Under Visible Light,Nanoscale Res Lett,16(2021)10.
[2]X.Jiang,M.Sun,Z.Chen,J.Jing,G.Lu,C.Feng,Boosted photoinduced cathodic protection performance of ZnIn2S4/TiO2 nanoflowerbush with efficient photoelectric conversion in NaCl solution,Journal of Alloys and Compounds,876(2021).
[3]G.Lu,M.Sun,Z.Chen,X.Jiang,J.Jing,Efficient TiO2/AgInS2/ZnS Nanoarchitecture Photoelectrode for the Photoelectrochemical Cathodic Protection of Copper in NaCl Solution,Journal of The Electrochemical Society,167(2020).
Disclosure of Invention
The invention aims to provide a porous composite photoelectric energy storage material (TiO) for photo-induced continuous cathodic protection2/SnIn4S8) And preparation and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a porous composite photoelectric energy-storing material for photo-induced continuous cathode protection is TiO2SnIn grown in situ in gaps and upper parts of nano shrubs4S8The porous composite photoelectric energy storage material is obtained by the three-dimensional nanoflower.
Furthermore, Sn, In and S sources are firstly soaked into the surface with TiO In an ion state by a solvothermal method2Growing nano flower-shaped SnIn on the porous base layer of the nano bush in situ4S8Obtaining SnIn4S8With TiO2A composite photoelectric energy storage material with a tight interface combination; wherein SnIn in the composite material is adjusted by controlling hydrothermal time4S8Thickness and surface topography of (A), typical hydrothermal time of approximately 12-18h, and TiO2/SnIn4S8The thickness of the composite porous structure is approximately 20 μm or so.
A process for preparing the porous composite photoelectric energy-accumulating material used for photo-induced continuous cathode protection features that TiO is grown on it2SnIn in-situ grown on surface of porous base layer of nano shrub4S8Obtaining a porous composite photoelectric energy storage material by using the three-dimensional nanoflower; wherein the growth has TiO2The base layer of the nanometer shrub is obtained by in-situ growth on the surface of the FTO conductive substrate through a solvothermal method.
The method specifically comprises the following steps:
1) preparation of the porous base layer: placing the pretreated FTO substrate in an inner container of a high-pressure reaction kettle, placing the conductive surface of the FTO substrate at an angle of 45 degrees with the kettle wall, adding the solution a into the high-pressure reaction kettle to immerse the FTO substrate, heating the FTO substrate at the temperature of 170 ℃ and 190 ℃ for 8 to 10 hours, and directly growing TiO with a porous nano bush structure on the FTO conductive substrate2A material; then, after the reaction kettle is cooled, the FTO conductive substrate is taken and calcined to obtain white TiO2A nanoporous base layer; wherein the solution a is prepared by weighing 0.001-0.003mol of K2TiO(C2O4)2Adding 5-15ml of water (potassium titanium oxalate, PTO), heating and stirring until the solution is dissolved, wherein the volume of diethylene glycol DEG is 1-3 times of the volume of the added water;
2)SnIn4S8preparation of hydrothermal solution: SnCl4·5H2O and InCl3Dissolving in absolute ethyl alcohol, and stirring at room temperature; when the solution becomes transparent, weighing a proper amount of thiourea as a sulfur source to be introduced, wherein SnCl4·5H2O：InCl3: the stoichiometric ratio of thiourea is 1:4:8-10, and the mixture is stirred until a transparent solution b is obtained;
3)TiO2/SnIn4S8preparing a composite material: TiO obtained in the step 1)2Putting the base layer into a high-pressure reaction kettle with the conductive surface facing downwards, pouring the uniform transparent solution b obtained in the step 2) into the reaction kettle, and heating at the temperature of 160-200 ℃ for 9-18 hours to obtain the orange porous composite photoelectric energy storage material on the surface of the base layer.
In the step 1), the base layer is taken out and washed by deionized water, dried in an oven, and then placed in a tubular furnace to be calcined for 0.5 to 1.5 hours at the temperature rising rate of 10 to 15 ℃/min to 400-500 ℃.
The application of the composite photoelectric energy storage material in continuously protecting metal in a dark state as an anti-corrosion protective film for inhibiting metal corrosion.
The composite photoelectric energy storage electrode is applied to the continuous protection in a dark state as a photoelectric cathode protection anti-corrosion photo-anode for inhibiting metal corrosion.
Further, TiO2/SnIn4S8Coupling a photoanode and a pure copper electrode, and putting the photoanode and the pure copper electrode into a NaCl solution in a dark state after illumination, wherein the TiO is2/SnIn4S8The photo-cathodic protection current density of the photo-anode slowly decreases and the photo-potential drop returns to the original potential at a slower rate for-15 h. The time-lapse cathodic protection performance is also improved. And this TiO2/SnIn4S8The photo-anode pair 316L SS has better photo-electric continuous cathodic protection performance after 15 h.
The electrode takes FTO conductive glass as a substrate, the composite photoelectric energy storage material grows in situ on the surface of the substrate to serve as a semiconductor photoelectric conversion and electronic storage layer, and then insulating glue is coated on the joint of the FTO conductive surface scraped from the surface of the prepared material to prepare the composite photoelectric energy storage electrode.
The application of the electrode is to the application of the composite photoelectric energy storage electrode as a photocathode protection anti-corrosion photo-anode for inhibiting metal corrosion.
For the TiO prepared for the continuous photoelectrochemical cathodic protection2/SnIn4S8The composite photoelectric energy storage material is prepared into a photo-anode, and the photo-anode is subjected to a test of a photoelectrochemical cathodic protection effect, specifically adopting the change of a photo-induced open-circuit potential and a photo-induced current densityThe measurement is carried out by recording the change information of the photo-generated current density and the open circuit potential along with the time under the condition of opening/closing light. And the charge quantity of photo-generated electrons provided by the photoelectrode to the pure copper electrode under illumination and the electric quantity of the photoelectrode continuously discharging to the copper electrode under a dark state after the illumination is cut off are obtained by integrating the photo-induced current density curve, so that the TiO is researched2/SnIn4S8The storage and slow-release photo-generated electronic performance of the photoelectrode. The specific measuring device is divided into two reaction cells, namely an etching cell and a photoelectrochemical cell, as shown in fig. 3A and 3B. The electrolyte in the photoelectrochemistry pool and the corrosion pool is 3.5% NaCl solution, and the two pools are connected through a salt bridge. The photoelectrode is placed in a photoelectrochemical cell and pure copper or 316L SS is placed in an etching cell. The light source used in this study was a 300-W xenon lamp (PLS-SXE300, Beijing Pofely Lighting, Inc., China). By adding an AM1.5 filter to the light source, simulated sunlight is obtained. The illumination intensity is 100mW/cm2Intermittently simulating these tests under solar irradiation. 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:
due to SnIn4S8And TiO2The energy band potential of the titanium dioxide can form gradient matching, and the energy band potential of the titanium dioxide can be matched with the energy band potential of the titanium dioxide in a TiO manner2Overgrowth of composite SnIn4S8A large amount of internal heterojunction electrostatic field will then be established. SnIn4S8(conduction band potential of (-0.30V vs. SHE) vs. TiO2Is more negative (-0.18V vs. she), so that photogenerated electrons generated under the excitation of simulated solar illumination are emitted from SnIn4S8Transfer of CB to TiO2To reduce energy. With photogenerated holes from the TiO2VB of (2) to SnIn4S8And thus greatly facilitates the separation of photo-generated electrons and holes. In the case of an n-type semiconductor, as the photo-generated electrons accumulate on CB under light irradiation, the quasi-fermi level of the photo-generated electrons is shifted negatively, accompanied by a negative OCP shift of the system. Thus, for TiO2/SnIn4S8The large number of photo-generated electrons pushes the quasi-Fermi level of the photo-generated electronsTo a more negative potential than the other sample photo-anodes. When TiO is present2/SnIn4S8When coupled to a metal, the photo-generated electrons are transferred to the metal electrode to which they are coupled, providing PEC cathodic protection. Under the irradiation of simulated sunlight, the light is absorbed by TiO2/SnIn4S8Generating photo-generated electrons, SnIn4S8Three-dimensional nanoflower and TiO2Due to the combination of the porous nano branch structure, the electric double layer capacitance is greatly increased, and the electronic storage performance is enhanced. Under the irradiation of light, the electric double layer capacitor with large porous electrochemical active surface area is charged, and in a dark state, electrons are released and transported to the protected metal. On the other hand, SnIn4S8In (iii)3+Having multiple valence states, In part under light3+Converting the photo-generated electrons into In+Na accompanied by NaCl+Inserting SnIn4S8Form Na inxSnIn4S8. After the illumination is stopped, photo-generated electrons are released. Both of these properties of storing photo-generated electrons contribute to the continuous cathodic protection of metals in the dark. Thus, in situ grown TiO2/SnIn4S8The photoelectric anode of the composite photoelectric energy storage material can generate continuous photoelectrochemical cathodic protection effect on metal.
The invention has the advantages that:
the invention regulates and controls TiO2Micro-nano structure of material and integration of photo-generated electron storage material SnIn4S8The method helps to solve the problem of continuous cathodic protection under cloudy and dark conditions. On the one hand, due to TiO2Special porous multi-branched microscopic nano structure of base layer and SnIn4S8The growth morphology of nano petals enables TiO to be2/SnIn4S8Has high storage and slow release performance to photo-generated electrons. Due to TiO2/SnIn4S8Electric double layer capacitance and electrochemical active surface area ratio SnIn4S8And thus greater storage capacity for photo-generated electrons. On the other hand, due to SnIn4S8Middle valence-changing component In3+Under the simulated sunlightCan be converted into In by photo-generated electrons+Storing part of photo-generated electrons, and releasing the photo-generated electrons after light is cut off, so that TiO2/SnIn4S8The photoanode also has electron storage properties in the nature of pseudocapacitance. Thus, TiO2/SnIn4S8Has stronger photoelectric continuous cathodic protection performance to metal. Specifically, the method comprises the following steps:
1. the TiO prepared by the solvothermal method of the invention2/SnIn4S8SnIn in photo-anode4S8Fully combined with in-situ growth on TiO2On the base layer, the photo-generated electrons can be rapidly transferred in the composite light anode, and the photoelectric conversion and the photoelectric cathode protection performance are enhanced.
2. TiO of the invention2/SnIn4S8Composites with pure TiO2And pure SnIn4S8Compared 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. The alcohol thermal synthesis time of the TiO prepared by the invention is 15h2/SnIn4S8The photo-anode has the optimal photo-cathodic protection current density and photo-induced mixed potential drop of 40.8 muA-cm for copper within 15h-2And 176 mV. In the dark state after illumination, TiO2/SnIn4S8The photo-induced cathodic protection current density of the photo-anode slowly decreases within 15 h. And TiO2/SnIn4S8The photo-anode pair 316 LSS has better photo-sustaining cathodic protection performance for-15 h, and the photo-potential drop returns to the original potential at a slower rate.
Drawings
Fig. 1 is a flowchart of a process for preparing an optoelectronic material according to an embodiment of the present invention.
FIG. 2 is a schematic view of a porous TiO according to an embodiment of the present invention2Electron microscopy of the brush base layer.
Fig. 3 is a diagram of a photoelectrochemical cathodic protection testing device for a photoelectric material according to an embodiment of the present invention, in which fig. 3A is a schematic connection diagram of a device for measuring a photo-generated current density, and fig. 3B is a schematic connection diagram of a device for measuring a photo-induced open circuit potential.
FIG. 4 shows TiO prepared at different hydrothermal times according to examples of the present invention2/SnIn4S8The current density (a) and the potential (b) of the coupling system of the photoanode and the pure copper electrode change along with time under the condition of intermittent on-off light.
FIG. 5 is a diagram of a TiO prepared according to the present invention2、SnIn4S8And TiO2/SnIn4S8Photoelectrode schematic.
FIG. 6 shows TiO provided in an embodiment of the present invention2/SnIn4S8-15h Complex (a) and pure SnIn4S8(b) SEM image of (d).
FIG. 7 shows TiO provided in an embodiment of the present invention2、SnIn4S8And TiO2/SnIn4S8-15h photoelectrode and pure copper electrode, current density (a) and potential (b) curves over time under intermittent on-off light conditions.
FIG. 8 shows TiO provided in an embodiment of the present invention2/SnIn4S815h of a coupling system of a photoanode and different metal electrodes, and a current density (a) and a potential (b) change curve with time under the condition of intermittent on-off light.
FIG. 9 shows TiO prepared by hydrothermal reaction for 15h according to example of the present invention2/SnIn4S8And (4) estimating the electric quantity released by the pure copper electrode and the electric quantity released by the 316L SS electrode in a dark state after the light anode is illuminated for 50 s.
Detailed Description
The invention will be further described, by way of example, without in any way being restricted to the following figures.
The invention constructs loose and porous 3D TiO by simple two-step solvothermal method in-situ interface compounding2/SnIn4S8The green and environment-friendly photoelectric film system enhances the continuous photoelectric cathode protection of the metal pure copper in the NaCl solution without the cavity removal auxiliary agent under the simulated marine environment, under the illumination and in the dark stateAnd (4) performance. TiO 22/SnIn4S8Middle and thin SnIn4S8In-situ growth of nano-petal interface on nano-branched TiO2And (4) a base layer structure. The 3D porous structure brings large electrochemical surface area and electric double layer capacitance, and In of valence-variable indium ions3+And In+The valence change is increased from two aspects, and the characteristics of storing and slowly releasing photo-generated electrons in a dark state are improved. The dual characteristics promote continuous photocathode protection of metal in the dark of the photoanode; while preparing the resulting TiO under preferred conditions2/SnIn4S8The material has the photoinduced cathodic protection performance of AM1.5 simulated solar illumination on pure copper and 316L SS and the dark state time-delay cathodic protection capability in NaCl solution.
Example 1
TiO for continuous photoelectrochemical cathodic protection2/SnIn4S8Preparing a composite photoelectric energy storage photoanode (the preparation process is shown in figure 1):
1)TiO2preparation of the porous base layer: placing the pretreated substrate in an inner container of a high-pressure reaction kettle, placing the conductive surface of the pretreated substrate at an angle of 45 degrees with the kettle wall, adding the solution a into the high-pressure reaction kettle, immersing the substrate in the solution a, heating the solution at 180 ℃ for 9 hours, and directly growing TiO with a porous nano bush structure on the substrate2A material; and cooling the reaction kettle, taking out the FTO conductive glass, washing the FTO conductive glass by using deionized water, and drying the FTO conductive glass in a 60 ℃ oven. Finally, the prepared TiO is mixed2Calcining the nano material in a tubular furnace at 450 ℃ for 1h at the heating rate of 10 ℃/min to obtain TiO2A porous substrate (see fig. 2).
The solution a is 0.002mol K weighed2TiO(C2O4)2(potassium titanium oxalate, PTO) 10mL of water was added followed by 20mL of diethylene glycol DEG and stirring was continued for twenty minutes.
FIG. 2 shows that the TiO obtained by the present invention2The porous base layer is of a three-dimensional nano dendritic structure and grows on the surface of the FTO substrate irregularly and vertically, and the porous sparse base layer structure is beneficial to storage and release of photo-generated electrons.
2)SnIn4S8Preparation of hydrothermal solution: 0.35g SnCl4·5H2O (1mmol) and 0.88g InCl3(4mmol) was dissolved in 30mL of absolute ethanol and stirred at room temperature. When the solution became transparent, 0.76g of thiourea (10mmol) was weighed as a sulfur source and introduced, and the mixture was stirred for about 30 minutes again to become a transparent solution b;
3)TiO2/SnIn4S8preparing a composite light anode: TiO obtained in the step 1)2Putting the basal layer into a high-pressure reaction kettle with the conductive surface facing downwards, pouring the uniform transparent solution b obtained in the step 2) into the reaction kettle, and heating the solution at 180 ℃ for 9, 12, 15 and 18 hours respectively to obtain an orange compound TiO2/SnIn4S8Composite photoelectric energy storage material and prepared into energy storage photoelectrode which is respectively marked as TiO2/SnIn4S8-9h，TiO2/SnIn4S8-12h，TiO2/SnIn4S8-15h，TiO2/SnIn4S8-18h；
Further, growing the TiO on the substrate2/SnIn4S8Scraping a conductive surface from the long conductive edge of the FTO glass of the composite photoelectric energy storage material, and coating insulating glue at the joint of the composite photoelectric energy storage material and the conductive surface to ensure that the exposed test area is 10 multiplied by 10mm2To produce TiO2/SnIn4S8And (3) compounding photoelectric energy storage electrodes. Wherein, the FTO conductive glass is SnO with F-doped conductive film component2Cutting the FTO glass into pieces of 20X 10mm2Size, first ultrasonically cleaned in analytically pure acetone for 5 minutes, and then rinsed with deionized water.
For TiO obtained by the above preparation2/SnIn4S8And (3) testing the photoelectrochemical cathode protection performance of the system thin film photoelectrode: in the experimental setup, schematically shown in fig. 3, the electrochemical workstation of CHI 660E of shanghai chenhua instruments was used to monitor the intensity of the photo-induced current between the coupling of the photo-electrode and the pure copper electrode under white light irradiation (fig. 4a) and the change of the photo-induced mixed potential of the coupling system (fig. 4 b). The electrolyte in the photoelectrochemical cell and the corrosion cell is 3.5 percent NaCl solution.
FIGS. 4a, b show the TiO produced by hydrothermal reaction at different times2/SnIn4S8After the photoanode is coupled with a pure copper electrode, the PEC cathodic protection performance of the pure copper in a NaCl solution under the condition of intermittent AM1.5 simulated sunlight on-off light, namely the change curves of the photo-induced cathodic protection current density (a) and the photo-induced potential drop (b). It can be seen that TiO increases with the alcohol heating time from 9h to 15h2/SnIn4S8The photocathode protection and the electron storage capacity of the photoanode are gradually improved. Wherein, the alcohol thermal synthesis time is 15h to prepare TiO2/SnIn4S8The photo-anode has the optimal photo-cathodic protection current density and photo-induced mixed potential drop of 40.8 muA-cm for copper within 15h-2And 176 mV. In the dark state after illumination, TiO2/SnIn4S8The photo-cathodic protection current density of the photo-anode slowly decreases and the photo-potential drop returns to the original potential at a slower rate for-15 h. The time-lapse cathodic protection performance is also improved. This is due to the growth to TiO as the hot time of the alcohol increases2SnIn on4S8And more photo-generated electrons can be stored, and the stored photo-generated electrons are continuously released to the pure copper electrode after illumination. However, with further extension of the alcoholic heating time from 15h to 18h, TiO was produced2/SnIn4S8Photoanode photocathode protection and delayed cathodo protection performance begin to degrade. This is due to excessive SnIn4S8Deposited on TiO2The porous structure is accumulated, the transmission of photo-generated electrons between the porous structure and the substrate is blocked due to the excessively thick film layer, and the photo-generated electrons and holes are difficult to effectively collect. Thus, for TiO2/SnIn4S8The optimal alcohol thermal synthesis time of the photo-anode is 15h, and TiO can be fully exerted2/SnIn4S8The photocathode of the photoanode protects and stores the electronic ability.
Example 2
1)TiO2Preparation of the porous base layer: placing the pretreated substrate in an inner container of a high-pressure reaction kettle, placing the conductive surface of the pretreated substrate downwards and forming an angle of 45 degrees with the kettle wall, adding the solution a into the high-pressure reaction kettle, immersing the substrate, and then placing the substrate in the high-pressure reaction kettleHeating at 180 ℃ for 9 hours to directly grow TiO with porous nanometer bush structure on the substrate2Material (see fig. 2); and cooling the reaction kettle, taking out the FTO conductive glass, washing the FTO conductive glass by using deionized water, and drying the FTO conductive glass in a 60 ℃ oven. Finally, the prepared TiO is mixed2Calcining the nano material in a tubular furnace at 450 ℃ for 1h at the heating rate of 10 ℃/min to obtain TiO2The nanoporous base layer (see fig. 2).
The solution a is 0.002mol K weighed2TiO(C2O4)2(potassium titanium oxalate, PTO) 10mL of water was added, followed by 20mL of diethylene glycol DEG and stirring was continued for twenty minutes.
2)SnIn4S8Preparation of hydrothermal solution: 0.35g SnCl4·5H2O (1mmol) and 0.88g InCl3(4mmol) was dissolved in 30mL of absolute ethanol and stirred at room temperature. When the solution became transparent, 0.76g of thiourea (10mmol) was weighed as a sulfur source and introduced, and the mixture was stirred for about 30 minutes again to become a transparent solution b;
3)TiO2/SnIn4S8preparing a composite light anode: TiO obtained in the step 1)2Putting the basal layer into a high-pressure reaction kettle with the conductive surface facing downwards, pouring the uniform transparent solution b obtained in the step 2) into the reaction kettle, heating the solution at 180 ℃ for 15 hours, and growing an orange compound TiO on the surface of the substrate2/SnIn4S8The obtained orange compound is TiO2/SnIn4S8A composite photo-anode (see fig. 5 and 6);
4)SnIn4S8preparing a composite light anode: putting the clean FTO conductive surface downwards into a high-pressure reaction kettle, pouring the uniform transparent solution b obtained in the step 2) into the reaction kettle, heating at 180 ℃ for 15 hours, and growing orange single SnIn on the surface of the substrate4S8And preparing the obtained SnIn4S8A pure photo anode (see fig. 5 and 6);
TiO can be seen from FIG. 62/SnIn4S8-15h composite photo-anode (FIG. 6a) and pure SnIn4S8Top SEM image, cross-sectional SEM image of photo-anode (FIG. 6b) and correspondingThe EDS elements map the image. As can be seen from FIG. 6a, in TiO2Upper composite growth of SnIn4S8After that, in TiO2The surface forms a layer of flower-shaped three-dimensional interconnected porous structure. TiO 22/SnIn4S8The thickness of the heterojunction film can reach 20 μm. Can be divided into basic TiO2SnIn compositely grown in porous gaps on nano fine branches4S8Nanospheres and an upper layer interconnected micro-nano petal hole structure, and Sn, In and S elements are uniformly distributed on the cross section. And pure SnIn from FIG. 6b4S8As can be seen from the SEM image of the photo-anode, pure SnIn4S8When directly grown on an FTO substrate, the film bottom layer is slightly compact and SnIn4S8The thickness of the film was 6.7 μm, and the surface layer was a three-dimensional network structure. A comparative analysis of the results in FIGS. 6a and b shows that TiO2The existence of the nanometer bush base layer enables SnIn to grow compositely on the nanometer bush base layer4S8The composite layer is more loose and more uniformly distributed, and finally a porous and loose thick film layer is formed, which is formed by superfine highly branched porous TiO2The nano bush base layer promotes SnIn4S8Is caused by the uniform dispersion growth of the silicon carbide. The porous and loose thick film layer is beneficial to the storage and slow release of photo-generated electrons. Prepared TiO2/SnIn4S8SnIn in photo-anode4S8Fully combined with in-situ growth on TiO2On the base layer, the photo-generated electrons can be rapidly transferred in the composite light anode, and the photoelectric conversion and the photoelectric cathode protection performance are enhanced. Finally, the thick film layer is beneficial to playing the role of slowly releasing photo-generated electrons in a dark state after photoelectric energy storage and illumination stop under illumination, and further continuously providing the stored photo-generated electrons for metal for cathodic protection.
Preparation of TiO Using the above examples2/SnIn4S8Preparation of TiO from composite photoelectric energy storage material2/SnIn4S8And (3) compounding the photoelectric energy storage electrode:
growing the crystal with TiO2/SnIn4S8Scraping a conductive surface from the long conductive edge of the FTO glass made of the composite photoelectric energy storage material, and intersecting the scraped conductive surface with the composite photoelectric energy storage materialCoating insulating glue on the joint to expose TiO2/SnIn4S8The test area of the composite photoelectric energy storage material is 10 multiplied by 10mm2To produce TiO2/SnIn4S8A composite photovoltaic energy storage electrode (see fig. 5). Wherein, the FTO conductive glass is SnO with F-doped conductive film component2Cutting the FTO glass into pieces of 20X 10mm2Size, first ultrasonically cleaned in analytically pure acetone for 5 minutes, and then rinsed with deionized water.
For TiO obtained by the above preparation2/SnIn4S8And (3) testing the photoelectrochemical cathode protection performance of the system thin film photoelectrode: in the experimental setup, schematically shown in fig. 3, the electrochemical workstation of CHI 660E of shanghai chenhua instruments was used to monitor the intensity of the photo-induced current between the coupling of the photo-electrode and the pure copper electrode under white light irradiation (fig. 7a) and the change of the photo-induced mixed potential of the coupling system (fig. 7 b). The electrolyte in the photoelectrochemical cell and the corrosion cell is 3.5 percent NaCl solution.
FIGS. 7a, b show a single TiO2、SnIn4S815h and TiO2/SnIn4S8And the composite photo-anode material has the photocathode protection performance on pure copper under AM1.5 simulated sunlight within 15 h. As shown in FIG. 7a, SnIn in 3.5 wt% NaCl solution under AM1.5 simulated solar irradiation due to light induced electron burst generation4S815h and TiO2/SnIn4S8The composite photo-anode for 15h shows larger instantaneous photocathode protection current density for pure copper. TiO after the current density of the photo-induced cathode protection reaches the stable state2/SnIn4S8Photo-cathodically protected current density of-15 h-Cu (about 40.8. mu.A-cm)-2) Is obviously higher than TiO2About (1.2. mu.A. cm) of-Cu-2) And SnIn4S815h-Cu (about 22.0. mu.A. cm)-2) In (1). As shown in FIG. 7b, the OCP of the pure copper electrode in 3.5 wt% NaCl solution was-0.18V, while the prepared SnIn4S815h or TiO2/SnIn4S8After the photoelectrode is coupled for 15h, the mixed potential of the coupling system is respectively shifted to-0.218V and-0.366V under the irradiation of simulated sunlight (figure 7 b). And with TiO2The photoelectrode is coupled with a pure copper electrode without obvious potential drop change. This is because TiO2/SnIn4S815h-Cu, due to the heterojunction effect, the separation and collection of photogenerated electrons and holes are obviously enhanced, and TiO is improved2The photocathode protection performance of the photoanode.
For TiO obtained by the above preparation2/SnIn4S8The photoelectrochemical cathode protection performance of the thin film photoelectrode of the system is tested for 15 h: on the apparatus shown in the schematic diagram of the experimental apparatus 3, the electrochemical workstation of CHI 660E of shanghai chenhua instruments company was used to monitor the variation of the photo-induced current intensity between the coupling of the photoelectrode and the pure copper or 316L SS electrode under the irradiation of white light (fig. 8a) and the photo-induced mixed potential of the coupling system (fig. 8 b). The electrolyte in the photoelectrochemical cell and the corrosion cell is 3.5 percent NaCl solution. And the charge quantity of photo-generated electrons provided by the photo-electrode to the pure copper electrode under illumination and the electric quantity of the photo-electrode continuously discharging to the copper electrode under a dark state after chopping illumination are obtained by integrating the photo-induced current density curve, so that the TiO is researched2/SnIn4S8The storage and slow-release photo-generated electronic performance of the photoelectrode.
FIG. 8a shows TiO in comparison with FIG. 8b2/SnIn4S8And (4) the cathodic protection performance of the photo-anode for 15h on pure copper and 316L stainless steel. TiO 22/SnIn4S8The photo-cathodic protection current density after the photo-anode is coupled with pure copper is 15h higher than that of the photo-cathodic protection current density of 316L stainless steel. TiO 22/SnIn4S8The mixed potential return rate of the photo-anode and 316L stainless steel coupling system after illumination for 15h is slower than that of TiO2/SnIn4S8Coupling system with pure copper for 15 h. The self-corrosion rate of the pure copper surface is higher than that of 316L stainless steel, the reaction rate between copper surface electrons and a solution is higher, and a large amount of photo-generated electrons are transferred to the copper surface and then enter the reaction with the solution. Although the photo-induced cathodic protection current density is larger than that of the coupling system of 316L SS, photo-generated electrons are not sufficiently accumulated on the copper surface, so that the return rate of the photo-induced cathodic protection potential after the light irradiation is stopped is faster than that of the coupling system of 316L SS. Synthetic light generationThe TiO can be used for cathode protection current density and light induced potential drop2/SnIn4S8The photo-anode pair 316L SS has better photo-electric continuous cathodic protection performance after 15 h.
FIG. 9 shows TiO2/SnIn4S8-current density profile after sufficient relaxation of electrons after a sufficient amount of AM1.5 simulating solar illumination (50 s). The total charge of the photo-generated electrons transferred to the copper under illumination and the electric quantity of the photo-generated electrons continuously released to the pure copper after light cutting can be estimated by integrating the i-t curve. Wherein, TiO2/SnIn4S8The photo-cathode protection capacity of the-15 h-Cu photo-anode is optimal, the total charge quantity of photo-generated electrons transferred onto copper under illumination is 4791 mu C, and the capacity of continuously releasing photo-generated electrons to pure copper after light cutting is 1390 mu C. Correspondingly, FIG. 9 also shows TiO2/SnIn4S8Current density curve after sufficient slow release of electrons after sufficient amount of AM1.5 simulated solar illumination (50s) of-15 h-316L SS. TiO 22/SnIn4S8The photo-anode was coupled to 316L SS for 15h, and the total charge of photo-generated electrons transferred to 316L SS under light irradiation was 909 μ C, and the charge of photo-generated electrons released continuously to 316L SS after light-cut was 297 μ C.
In summary, the invention is realized by constructing porous TiO2Nano-based and composite porous interconnected SnIn4S8The nano flower successfully prepares the photo-anode with the energy storage effect, and can provide continuous photo-cathode protection performance for the dark state of pure copper after light is cut off.
Claims (8)
1. A porous composite photoelectric energy storage material for photo-induced continuous cathodic protection is characterized in that: the composite photoelectric energy storage material is TiO2SnIn grown in situ in gaps and upper parts of nano shrubs4S8The porous composite photoelectric energy storage material is obtained by the three-dimensional nanoflower.
2. The porous composite photoelectric energy storage material for photo-induced continuous cathodic protection according to claim 1, characterized in that: by solvothermal method, Sn, In and S sources are firstly usedWith TiO impregnated into the surface in ionic state2Growing nano flower-shaped SnIn on the porous base layer of the nano bush in situ4S8Obtaining SnIn4S8With TiO2And the composite photoelectric energy storage material is tightly combined with the interface.
3. A method for preparing the porous composite photoelectric energy storage material for photo-induced continuous cathodic protection according to claim 1, which is characterized in that: in the growth of TiO2SnIn in-situ grown on surface of porous base layer of nano shrub4S8Obtaining a porous composite photoelectric energy storage material by using the three-dimensional nanoflower; wherein the growth has TiO2The base layer of the nanometer shrub is obtained by in-situ growth on the surface of the FTO conductive substrate through a solvothermal method.
4. The method for preparing the porous composite photoelectric energy storage material for photo-induced continuous cathodic protection according to claim 3, characterized in that:
1) preparation of the porous base layer: placing the pretreated FTO substrate in an inner container of a high-pressure reaction kettle, placing the conductive surface of the FTO substrate at an angle of 45 degrees with the kettle wall, adding the solution a into the high-pressure reaction kettle to immerse the FTO substrate, heating the FTO substrate at the temperature of 170 ℃ and 190 ℃ for 8 to 10 hours, and directly growing TiO with a porous nano bush structure on the FTO conductive substrate2A material; then, after the reaction kettle is cooled, the FTO conductive substrate is taken and calcined to obtain white TiO2A nanoporous base layer; wherein the solution a is prepared by weighing 0.001-0.003mol of K2TiO(C2O4)2Adding 5-15ml of water (potassium titanium oxalate, PTO), heating and stirring until the solution is dissolved, wherein the volume of diethylene glycol DEG is 1-3 times of the volume of the added water;
2)SnIn4S8preparation of hydrothermal solution: SnCl4·5H2O and InCl3Dissolving in absolute ethyl alcohol, and stirring at room temperature; when the solution becomes transparent, weighing a proper amount of thiourea as a sulfur source to be introduced, wherein SnCl4·5H2O：InCl3: the stoichiometric ratio of thiourea is 1:4:8-10, and the mixture is stirred until transparentSolution b;
3)TiO2/SnIn4S8preparing a composite material: TiO obtained in the step 1)2Putting the base layer into a high-pressure reaction kettle with the conductive surface facing downwards, pouring the uniform transparent solution b obtained in the step 2) into the reaction kettle, and heating at the temperature of 160-200 ℃ for 9-18 hours to obtain the orange porous composite photoelectric energy storage material on the surface of the base layer.
5. The method for preparing the porous composite photoelectric energy storage material for photo-induced continuous cathodic protection according to claim 4, characterized in that: in the step 1), the base layer is taken out and washed by deionized water, dried in an oven, and then placed in a tubular furnace to be calcined for 0.5 to 1.5 hours at the temperature rising rate of 10 to 15 ℃/min to 400-500 ℃.
6. The application of the composite photoelectric energy storage material of claim 1, wherein: the composite photoelectric energy storage material is applied to continuously protecting metals in a dark state as an anti-corrosion protective film for inhibiting metal corrosion.
7. TiO 22/SnIn4S8Compound photoelectricity energy storage electrode, electrode include photoelectric conversion layer, electron storage layer, conducting layer, its characterized in that: the composite photoelectric energy storage material of claim 1 is used as a semiconductor photoelectric conversion and electron storage layer.
8. Use of an electrode according to claim 7, wherein: the composite photoelectric energy storage electrode is applied to a photocathode protection anti-corrosion photo-anode for inhibiting metal corrosion.
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