CN114134506B - Porous composite photoelectric energy storage material for photoinduced continuous cathode protection and preparation and application thereof - Google Patents

Porous composite photoelectric energy storage material for photoinduced continuous cathode protection and preparation and application thereof Download PDF

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CN114134506B
CN114134506B CN202111374208.6A CN202111374208A CN114134506B CN 114134506 B CN114134506 B CN 114134506B CN 202111374208 A CN202111374208 A CN 202111374208A CN 114134506 B CN114134506 B CN 114134506B
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snin
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孙萌萌
鹿桂英
姜旭宏
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Institute of Oceanology of CAS
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Abstract

The invention belongs to the field of photoelectrochemical cathode protection, in particular to a porous composite photoelectric energy storage material (TiO 2 /SnIn 4 S 8 ) And preparation and application thereof. The composite photoelectric energy storage material is TiO 2 Nanometer bush gap and in-situ growth of SnIn on upper part 4 S 8 The three-dimensional nanoflower is used for obtaining the porous composite photoelectric energy storage material. The invention provides valuable reference for optimally designing a high-efficiency energy-storage photoelectric material system and promoting long-acting continuous photoelectric cathode protection of metal in marine environment.

Description

Porous composite photoelectric energy storage material for photoinduced continuous cathode protection and preparation and application thereof
Technical Field
The invention belongs to the field of photoelectrochemical cathode protection, in particular to a porous composite photoelectric energy storage material (TiO 2 /SnIn 4 S 8 ) And preparation and application thereof.
Background
Photo-cathodic protection (PCP) technology is a promising technology for corrosion protection of marine metals. The technology utilizes the light energy in the ocean to generate photo-generated electrons through photoelectric conversion of semiconductor materials, and provides the photo-generated electrons for metal for cathodic protection. However, a significant challenge currently faced by photocathode protection techniques is that the cathodic protection performance of the photoelectrochemical response cannot be exerted in the absence of light.
On the one hand, the porous membrane layer structure is optimized, so that the charge storage capacity is hopefully improved, and the cathode protection effect can be generated in the dark state after illumination. For TiO 2 The study of the photo anode shows that the three-dimensional titanium dioxide nanowire reticular film, the flower-shaped titanium dioxide film and the mesoporous titanium dioxide film all show the electron storage effect, which is mainly attributed toDue to their unique porous, large specific surface area micro-nano structure. Thus, by regulating and controlling TiO 2 Is beneficial to improving the charge storage capacity. And preparing TiO (titanium dioxide) which is frequently used for photoelectric anode 2 Nanotubes do not exhibit electron storage effects [1 ]]。
On the other hand, the composition with the semiconductor of the charged storage component is expected to further improve the charge storage characteristic of the semiconductor photoelectric conversion film material and maintain the continuous protection performance in the dark state. The multi-element transition metal compound can be prepared by oxidation-reduction reaction of variable valence metal ions and reversibly reacting Na + 、Li + 、H + Inserting into the lattice to realize the storage and release of electrons. Conventional charge storage semiconductor transition metal oxide WO 3 、SnO 2 Although the photoelectric cathode has excellent electron storage performance, the photoelectric cathode has the advantages of large forbidden bandwidth, narrow light absorption range, low photoelectric conversion efficiency and reduced protection performance of the photoelectric cathode while storing energy. Multielement transition metal sulfide ZnIn 2 S 4 、AgInS 2 Although having a narrow forbidden band width, a relatively negative conduction band potential has good photoelectrochemical and photocathode protection properties, the dark state after illumination cannot provide delayed photocathode protection properties [2,3 ]]。
Therefore, aiming at 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 photoelectrochemical protection technology provides the nano composite semiconductor photoanode material with optimized structure for continuously protecting the dark state after illumination, and the material is used for realizing the continuous photoelectrochemical protection of ocean metal.
[1]H.Li,W.Song,X.Cui,Y.Li,B.Hou,L.Cheng,P.Zhang,Preparation of SnIn 4 S 8 /TiO 2 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 ZnIn 2 S 4 /TiO 2 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 TiO 2 /AgInS 2 /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) 2 /SnIn 4 S 8 ) And preparation and application thereof.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
porous composite photoelectric energy storage material for photoinduced continuous cathode protection, wherein the composite photoelectric energy storage material is prepared from TiO 2 Nanometer bush gap and in-situ growth of SnIn on upper part 4 S 8 The three-dimensional nanoflower is used for obtaining the porous composite photoelectric energy storage material.
Further, the Sn, in and S sources are impregnated with TiO on the surface In an ionic state by solvothermal method 2 On the porous base layer of the nanometer shrub, then in-situ growing into nanometer flower-shaped SnIn on the base layer 4 S 8 Obtained SnIn 4 S 8 With TiO 2 A composite photoelectric energy storage material tightly combined with an interface; wherein, snIn in the composite material is regulated by controlling the hydrothermal time 4 S 8 The thickness and surface morphology of (C) are generally about 12-18h, and TiO 2 /SnIn 4 S 8 The thickness of the composite porous structure is approximately 20 μm.
A process for preparing the porous composite photoelectric energy-storage material used for photoinduced continuous cathode protection includes such steps as growing TiO 2 In-situ growth of SnIn on surface of porous base layer of nano shrub 4 S 8 Obtaining a porous composite photoelectric energy storage material by the three-dimensional nanoflower; wherein the TiO is grown 2 The base layer of the nanometer bush is obtained by in-situ growth on the surface of the FTO conductive substrate by a solvothermal method.
The method comprises the following steps:
1) Preparation of a porous base layer: placing a pretreated FTO substrate in a liner of a high-pressure reaction kettle, placing a conductive surface downwards at an angle of 45 degrees with the kettle wall, adding the solution a into the high-pressure reaction kettle to submerge the FTO substrate, heating at 170-190 ℃ for 8-10 hours, and directly growing TiO with a porous nano bush structure on the FTO conductive substrate 2 A material; then, after the reaction kettle is cooled, the FTO conductive substrate is calcined to obtain white TiO 2 A nanoporous substrate; wherein the solution a is prepared by weighing 0.001-0.003mol K 2 TiO(C 2 O 4 ) 2 Adding 5-15ml of water into (potassium titanium oxalate, PTO), heating and stirring until the mixture is dissolved, wherein the volume of diethylene glycol DEG is 1-3 times of the volume of the added water;
2)SnIn 4 S 8 preparation of a hydrothermal solution: snCl is added 4 ·5H 2 O and InCl 3 Dissolving in absolute ethyl alcohol, and stirring at room temperature; when the solution becomes transparent, a proper amount of thiourea is weighed and introduced as a sulfur source, wherein SnCl 4 ·5H 2 O：InCl 3 : the stoichiometric ratio of thiourea is 1:4:8-10, and the mixture is stirred again until a transparent solution b is obtained;
3)TiO 2 /SnIn 4 S 8 preparation of the composite material: tiO obtained in the step 1) is prepared 2 Placing the conductive surface of the base layer downwards into a high-pressure reaction kettle, pouring the uniform transparent solution b obtained in the step 2) into the reaction kettle, and heating at 160-200 ℃ for 9-18 hours to obtain the orange porous composite photoelectric energy storage material on the surface of the base layer.
And (2) calcining in the step (1) to take out the base layer, cleaning the base layer by deionized water, drying the base layer by an oven, and then placing the base layer in a tube furnace to calcine the base layer for 0.5 to 1.5 hours at a heating rate of 10 to 15 ℃/min to 400 to 500 ℃.
The application of the composite photoelectric energy storage material in the continuous protection of metal in a dark state as an anti-corrosion protection film for inhibiting metal corrosion.
The composite photoelectric energy storage electrode is applied to protecting an anti-corrosion photo-anode as a photoelectric cathode for inhibiting metal corrosion and continuously protecting the photo-anode in a dark state.
Further, tiO 2 /SnIn 4 S 8 Coupling the photo anode with a pure copper electrode, and then placing the photo anode and the pure copper electrode in NaCl solution, and in a dark state after illumination, tiO 2 /SnIn 4 S 8 The photocathode protection current density of the photoanode drops slowly and the photocell drops back to the original potential at a slower rate. The delayed cathodic protection performance is also improved. And this TiO 2 /SnIn 4 S 8 The 15h photo-anode has better photoelectric continuous cathode protection performance on 316L SS.
TiO (titanium dioxide) 2 /SnIn 4 S 8 The composite photoelectric energy storage electrode comprises a photoelectric conversion layer, an electronic storage layer and a conductive layer, wherein the composite photoelectric energy storage material is used as a semiconductor photoelectric conversion and electronic storage layer.
The electrode takes FTO conductive glass as a substrate, the composite photoelectric energy storage material is grown in situ on the surface of the substrate to serve as a semiconductor photoelectric conversion and electron storage layer, and then an insulating adhesive is coated on the junction of the FTO conductive surface scraped out of the surface of the prepared material to prepare the composite photoelectric energy storage electrode.
The application of the electrode is that the composite photoelectric energy storage electrode is used as a photoelectric cathode protection anti-corrosion photo-anode for inhibiting metal corrosion.
TiO for continuous photoelectrochemical cathodic protection prepared as described above 2 /SnIn 4 S 8 The composite photoelectric energy storage material is prepared into a photo anode, the photo anode is tested for photoelectrochemical cathodic protection effect, the photo anode is specifically characterized by adopting the change of photo-induced open-circuit potential and photo-generated current density, and the photo-generated current density and the change information of the open-circuit potential with time under the condition of opening/closing light are recorded for measurement. And the photo-induced current density curve is integrated to obtain the charge quantity of photo-generated electrons provided by the photoelectric electrode to the pure copper electrode under illumination and the charge quantity of continuous discharge of the photoelectric electrode to the copper electrode in dark state after the illumination is cut off, so that TiO is researched 2 /SnIn 4 S 8 The storage of the photoelectrode slowly releases the photo-generated electron performance. The specific measuring device is divided into two reaction cells, namely, a corrosion cell and a photoelectrochemical cell, as shown in fig. 3A and 3B.The electrolyte in the photoelectrochemical cell and the corrosion cell is 3.5% NaCl solution, and the two cells 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-SXE 300, beijing Porphy lighting Co., ltd., china). By adding an AM1.5 filter to the light source, simulated sunlight is obtained. At an illumination intensity of 100mW/cm 2 Are intermittently simulated in the presence of sunlight. At the front center of the photocell there is a quartz window of about 30mm in diameter through which incident light impinges on the photoelectrode surface.
The basic principle of the invention is as follows:
due to SnIn 4 S 8 And TiO 2 Can form gradient collocation on the energy band potential of the TiO 2 Upper growth of composite SnIn 4 S 8 A large internal heterojunction electrostatic field will be established afterwards. SnIn 4 S 8 Conduction band potential of (-0.30V vs. SHE) versus TiO 2 More negative (-0.18V vs. SHE) so that the photo-generated electrons generated under simulated solar illumination excitation are extracted from SnIn 4 S 8 CB to TiO transfer to 2 To reduce energy. At the same time photo-generated holes from TiO 2 VB on transfer to SnIn 4 S 8 Thereby greatly facilitating the separation of photogenerated electrons and holes. In the case of an n-type semiconductor, when irradiated with light, the quasi-fermi level of the photogenerated electrons moves negatively with the accumulation of photogenerated electrons on the CB, and the OCP of the system moves negatively. Thus, for TiO 2 /SnIn 4 S 8 The large number of photo-generated electrons will push the quasi-fermi level of the photo-generated electrons to a more negative potential than the other sample photo-anode. When TiO 2 /SnIn 4 S 8 When 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 simulated sunlight irradiation, along with TiO 2 /SnIn 4 S 8 Generate photo-generated electrons on SnIn 4 S 8 Three-dimensional nanoflower and TiO 2 The combination of the porous nano branch structure greatly increases the electric double layer capacitance and enhances the electron storage performance. Porous double layer electrotransport with large electrochemically active surface area under illuminationCharge is accommodated and electrons are released to be transported to the protected metal in the dark state. On the other hand, snIn 4 S 8 In (a) 3+ Has multiple valence states, and part of In under illumination 3+ Converting the accepting photo-generated electrons into In + Na accompanied by NaCl + Insertion of SnIn 4 S 8 Form Na in (a) x SnIn 4 S 8 . And releasing photo-generated electrons after the illumination is stopped. Both of these photo-generated electron storage properties contribute to continuous cathodic protection of the metal in the dark. Thus, in situ grown TiO 2 /SnIn 4 S 8 The photoelectrode of the composite photoelectrode energy storage material can generate continuous photoelectrochemical cathodic protection effect on metal.
The invention has the advantages that:
the invention adjusts and controls TiO 2 Micro-nano structure of material and integrated photo-generated electron storage material SnIn 4 S 8 The method helps to solve the problem of continuous cathodic protection in cloudy days and dark conditions. On the one hand due to TiO 2 Special porous multi-branched micro-nano structure of base layer and SnIn 4 S 8 The growth morphology of the nanometer petals enables TiO 2 /SnIn 4 S 8 Has higher storage and slow release performance for the photo-generated electrons. Due to TiO 2 /SnIn 4 S 8 Electric double layer capacitor of (c) and electrochemical active surface area ratio (SnIn) 4 S 8 And thus the storage capacity for photo-generated electrons. On the other hand, due to SnIn 4 S 8 Medium valence variable component In 3+ The photo-generated electrons received under the simulated sunlight are converted into In + A part of photo-generated electrons are stored and released after light is cut off, so that TiO 2 /SnIn 4 S 8 The photoanode also has electron storage properties in pseudocapacitive nature. Thus, tiO 2 /SnIn 4 S 8 Has stronger photoelectric continuous cathode protection performance to metal. Specifically:
1. TiO prepared by solvothermal method 2 /SnIn 4 S 8 SnIn in photoanode 4 S 8 Fully combine with in-situ growth in TiO 2 On the base layer, the method is also beneficial to the rapid transfer of photo-generated electrons in the composite photo-anode, and enhances the photoelectric conversion and the photoelectric cathode protection performance.
2. TiO of the invention 2 /SnIn 4 S 8 Composite and pure TiO 2 Pure SnIn 4 S 8 Compared with the method, the method can continuously release the stored photo-generated electrons for a long time in a dark state, and provide continuous cathodic protection for metal, so as to help solve the problem of continuous cathodic protection in overcast days and dark conditions.
3. TiO prepared under the condition that the alcohol thermal synthesis time is 15h 2 /SnIn 4 S 8 15h photo-anode with optimal photo-cathodic protection current density and photo-mixing potential drop for copper of 40.8 μA cm respectively -2 And 176mV. TiO in dark state after illumination 2 /SnIn 4 S 8 The photocathode protection current density of the photoanode drops slowly for 15 h. And TiO 2 /SnIn 4 S 8 The 15h photo-anode pair 316L SS has better photo-continuous cathodic protection performance, the photo-induced potential drop returns to the original potential at a slower rate.
Drawings
Fig. 1 is a flowchart of preparation of an optoelectronic material according to an embodiment of the present invention.
FIG. 2 shows porous TiO according to an embodiment of the present invention 2 Electron microscopy of nanobush substrates.
Fig. 3 is a diagram of a photoelectrochemical cathodic protection testing device for a photoelectric material according to an embodiment of the present invention, where fig. 3A is a schematic diagram of a device for measuring a photo-generated current density, and fig. 3B is a schematic diagram of a device for measuring a photo-induced open circuit potential.
FIG. 4 shows TiO of different hydrothermal time periods according to an embodiment of the present invention 2 /SnIn 4 S 8 The coupling system of the photo anode and the pure copper electrode has a change curve of current density (a) and potential (b) with time under the intermittent light opening and closing condition.
FIG. 5 shows a finished TiO according to an embodiment of the present invention 2 、SnIn 4 S 8 And TiO 2 /SnIn 4 S 8 Photoelectrode schematic.
FIG. 6 shows a TiO according to an embodiment of the present invention 2 /SnIn 4 S 8 -15h Complex (a) and pure SnIn 4 S 8 (b) SEM images of (a).
FIG. 7 shows a TiO according to an embodiment of the present invention 2 、SnIn 4 S 8 And TiO 2 /SnIn 4 S 8 -15h of a coupling system of the photoelectrode and the pure copper electrode, and a change curve of current density (a) and potential (b) with time under the intermittent light opening and closing condition.
FIG. 8 shows a TiO according to an embodiment of the present invention 2 /SnIn 4 S 8 -15h of a coupling system of a photo-anode and different metal electrodes, and a current density (a) and a potential (b) change curve with time under the intermittent light opening and closing condition.
FIG. 9 shows TiO prepared by hydrothermal treatment for 15h according to an embodiment of the present invention 2 /SnIn 4 S 8 And (5) 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 photo anode is illuminated for 50 s.
Detailed Description
The invention is further described below by way of example with reference to the accompanying drawings, without limiting the invention in any way.
The invention constructs loose and porous 3D TiO through simple two-step solvothermal method in-situ interface composite construction 2 /SnIn 4 S 8 The nanometer heterojunction structure is characterized in that the green and environment-friendly photoelectric film system enhances the continuous photoelectric cathode protection performance of the metal pure copper in NaCl solution without hole removal auxiliary agent under simulated ocean environment, illumination and dark state. TiO (titanium dioxide) 2 /SnIn 4 S 8 In thinner SnIn 4 S 8 The nanometer petal interface grows in situ on nanometer branched TiO 2 On the base structure. The 3D porous structure brings about large electrochemical surface area, double electric layer capacitance and In of valence-variable indium ions 3+ With In + The inter-valence increases the characteristics of storing and slowly releasing photo-generated electrons in a dark state from two aspects. The dual characteristics promote the continuous photocathode protection of metal in the dark of the photoanode; at the same time under the preferred conditions to prepare the obtained TiO 2 /SnIn 4 S 8 The material has the photo-induced cathode protection performance of AM1.5 simulation sun light to pure copper and 316L SS in NaCl solution, and also has the dark state time delay cathode protection capability.
Example 1
TiO for continuous photoelectrochemical cathodic protection 2 /SnIn 4 S 8 Preparation of a composite photoelectric energy storage photo-anode (the preparation process is shown in figure 1):
1)TiO 2 preparation of a porous base layer: placing a pretreated substrate in a liner of a high-pressure reaction kettle, placing a conductive surface downwards at an angle of 45 degrees with the kettle wall, adding a solution a into the high-pressure reaction kettle to immerse the substrate, heating at 180 ℃ for 9 hours, and directly growing TiO with a porous nano shrub structure on the substrate 2 A material; and then, after the reaction kettle is cooled, taking out the FTO conductive glass, cleaning the FTO conductive glass by deionized water, and drying the FTO conductive glass in a 60 ℃ oven. Finally, the prepared TiO 2 Calcining the nano material in a tube furnace at 450 ℃ for 1h at a heating rate of 10 ℃/min to obtain TiO 2 Porous substrates (see fig. 2).
The solution a is prepared by weighing 0.002mol K 2 TiO(C 2 O 4 ) 2 (Potassium titanium oxalate, PTO) 10mL of water was added, and 20mL of diethylene glycol DEG was added and stirring was continued for twenty minutes.
As can be seen from FIG. 2, the TiO of the present invention 2 The porous base layer is 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 favorable for storage and release of photo-generated electrons.
2)SnIn 4 S 8 Preparation of a hydrothermal solution: 0.35g SnCl 4 ·5H 2 O (1 mmol) and 0.88g InCl 3 (4 mmol) was dissolved in 30mL absolute ethanol and stirred at room temperature. When the solution became transparent, 0.76g of thiourea (10 mmol) was weighed as a sulfur source and introduced, and the mixture was stirred for about 30 minutes again to become transparent solution b;
3)TiO 2 /SnIn 4 S 8 preparation of a composite photo-anode: tiO obtained in the step 1) is prepared 2 Placing the conductive surface of the base layer downward into a high-pressure reaction kettle, and then pouring the uniform transparent solution b obtained in the step 2)Heating in a reaction kettle at 180deg.C for 9, 12, 15, 18 hr to obtain orange compound as TiO 2 /SnIn 4 S 8 The composite photoelectric energy storage material is prepared into energy storage photoelectrodes which are respectively marked as TiO 2 /SnIn 4 S 8 -9h，TiO 2 /SnIn 4 S 8 -12h，TiO 2 /SnIn 4 S 8 -15h，TiO 2 /SnIn 4 S 8 -18h；
Further, the catalyst is grown with TiO 2 /SnIn 4 S 8 Scraping a conductive surface from a 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 enable the exposed test area to be 10 multiplied by 10mm 2 To obtain TiO 2 /SnIn 4 S 8 Composite photoelectric energy storage electrode. Wherein the FTO conductive glass is F doped SnO as a conductive film component 2 The FTO glass was cut into pieces of 20X 10mm 2 The dimensions were first sonicated in analytically pure acetone for 5 minutes and rinsed with deionized water.
For the TiO prepared by the above 2 /SnIn 4 S 8 The photoelectrochemical cathode protection performance of the system film photoelectrode is tested: the change of the photoinduced current intensity between the photoelectrode and the pure copper electrode coupled under the irradiation of white light (figure 4 a) and the photoinduced mixed potential of the coupling system (figure 4 b) was monitored on the device shown in the schematic diagram 3 of the experimental device by using the CHI 660E electrochemical workstation of Shanghai Chen Hua instruments. The electrolyte in the photoelectrochemical cell and the corrosion cell are 3.5% NaCl solution.
FIGS. 4a, b show TiO produced hydrothermally at different times 2 /SnIn 4 S 8 The photocathode is coupled with a pure copper electrode, and then PEC cathodic protection performance of pure copper, namely a change curve of photo-induced cathodic protection current density (a) and photo-induced potential drop (b), is carried out in NaCl solution under the condition of simulating sunlight opening and closing by using intermittent AM 1.5. It can be seen that as the alcohol heat time is extended from 9h to 15h, tiO 2 /SnIn 4 S 8 The photocathode protection and electron storage capacity of the photoanode are gradually improved. Wherein, the TiO is prepared under the condition that the alcohol thermal synthesis time is 15h 2 /SnIn 4 S 8 15h photo-anode with optimal photo-cathodic protection current density and photo-mixing potential drop for copper of 40.8 μA cm respectively -2 And 176mV. TiO in dark state after illumination 2 /SnIn 4 S 8 The photocathode protection current density of the photoanode drops slowly and the photocell drops back to the original potential at a slower rate. The delayed cathodic protection performance is also improved. This is due to the growth to TiO with the increase of the alcohol heating time 2 SnIn on 4 S 8 The number of photo-generated electrons is increased, so that the photo-generated electrons can be stored more, and the stored photo-generated electrons are continuously released to the pure copper electrode after illumination. However, the time of alcohol heating is further prolonged from 15h to 18h, and the prepared TiO 2 /SnIn 4 S 8 Photo-anode photocathode protection and delayed cathode protection performance begin to decline. This is due to excessive SnIn 4 S 8 Deposited on TiO 2 The porous structure is accumulated, and the transmission of photo-generated electrons between the porous structure and the substrate is blocked due to the excessively thick film layer, so that the photo-generated electrons and holes are difficult to collect effectively. Thus, for TiO 2 /SnIn 4 S 8 Photo-anode, optimal alcohol thermal synthesis time is 15h, and TiO can be fully developed 2 /SnIn 4 S 8 Photocathode protection and electron storage capability of the photoanode.
Example 2
1)TiO 2 Preparation of a porous base layer: placing a pretreated substrate in a liner of a high-pressure reaction kettle, placing a conductive surface downwards at an angle of 45 degrees with the kettle wall, adding a solution a into the high-pressure reaction kettle to immerse the substrate, heating at 180 ℃ for 9 hours, and directly growing TiO with a porous nano shrub structure on the substrate 2 Material (see fig. 2); and then, after the reaction kettle is cooled, taking out the FTO conductive glass, cleaning the FTO conductive glass by deionized water, and drying the FTO conductive glass in a 60 ℃ oven. Finally, the prepared TiO 2 Calcining the nano material in a tube furnace at 450 ℃ for 1h at a heating rate of 10 ℃/min to obtain TiO 2 A nanoporous base layer (see fig. 2).
The solution a is prepared by weighing 0.002mol K 2 TiO(C 2 O 4 ) 2 (Potassium titanium oxalate, PTO) addition10mL of water and 20mL of diethylene glycol DEG were added and stirring continued for twenty minutes.
2)SnIn 4 S 8 Preparation of a hydrothermal solution: 0.35g SnCl 4 ·5H 2 O (1 mmol) and 0.88g InCl 3 (4 mmol) was dissolved in 30mL absolute ethanol and stirred at room temperature. When the solution became transparent, 0.76g of thiourea (10 mmol) was weighed as a sulfur source and introduced, and the mixture was stirred for about 30 minutes again to become transparent solution b;
3)TiO 2 /SnIn 4 S 8 preparation of a composite photo-anode: tiO obtained in the step 1) is prepared 2 Placing the conductive surface of the base layer downward 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-yellow composite TiO on the surface of the substrate 2 /SnIn 4 S 8 The orange compound is TiO 2 /SnIn 4 S 8 Composite photo-anode (see fig. 5 and 6);
4)SnIn 4 S 8 preparation of a composite photo-anode: placing clean FTO conductive surface downward 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 substrate 4 S 8 And preparing SnIn 4 S 8 Pure photo-anode (see fig. 5 and 6);
from FIG. 6, it can be seen that TiO 2 /SnIn 4 S 8 -15h composite photoanode (FIG. 6 a) with pure SnIn 4 S 8 Top-view SEM image, cross-sectional SEM image of photoanode (fig. 6 b) and corresponding EDS element-mapped image. As can be seen from fig. 6a, in TiO 2 Upper composite growth of SnIn 4 S 8 After that, in TiO 2 The surface forms a layer of flower-like three-dimensional interconnected porous structure. TiO (titanium dioxide) 2 /SnIn 4 S 8 The thickness of the heterojunction film can reach 20 mu m. Can be divided into base layer TiO 2 SnIn compositely grown in porous gaps on nanometer branches 4 S 8 Nanospheres and upper layer interconnection micro-nano petal hole structures, and Sn, in and S elements are uniformly distributed on the cross section. While from FIG. 6b pure SnIn 4 S 8 Guang YangThe SEM of the pole shows that the SnIn is pure 4 S 8 When directly growing on the FTO substrate, the bottom layer of the film is slightly compact and SnIn 4 S 8 The thickness of the film is 6.7 mu m, and the surface layer is of a net-shaped three-dimensional structure. Comparison of the results of FIGS. 6a, b shows that TiO 2 The existence of the nanometer bush base layer enables the SnIn to grow on the nanometer bush base layer in a composite way 4 S 8 The composite layer is more loose and more uniformly distributed, and finally a porous loose thick film layer is formed, which is formed by superfine highly branched porous TiO 2 Nanometer bush base layer promotes SnIn 4 S 8 Is brought about by the uniformly dispersed growth of (a). The porous loose thick film layer is beneficial to the storage and slow release of photo-generated electrons. Prepared TiO 2 /SnIn 4 S 8 SnIn in photoanode 4 S 8 Fully combine with in-situ growth in TiO 2 On the base layer, the method is also beneficial to the rapid transfer of photo-generated electrons in the composite photo-anode, and enhances the photoelectric conversion and the photoelectric cathode protection performance. Finally, the thick film layer is helpful to play roles of photoelectric energy storage under illumination and slow release of photo-generated electrons under dark state after the illumination is stopped, so as to continuously provide the stored photo-generated electrons for metal and perform cathodic protection.
Preparation of TiO using the above examples 2 /SnIn 4 S 8 TiO (TiO) preparation method of composite photoelectric energy storage material 2 /SnIn 4 S 8 Composite photoelectric energy storage electrode:
growing the TiO 2 /SnIn 4 S 8 Scraping a conductive surface from a 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 scraped conductive surface to expose TiO 2 /SnIn 4 S 8 The test area of the composite photoelectric energy storage material is 10 multiplied by 10mm 2 To obtain TiO 2 /SnIn 4 S 8 A composite photovoltaic energy storage electrode (as in fig. 5). Wherein the FTO conductive glass is F doped SnO as a conductive film component 2 The FTO glass was cut into pieces of 20X 10mm 2 The dimensions were first sonicated in analytically pure acetone for 5 minutes and rinsed with deionized water.
For the TiO prepared by the above 2 /SnIn 4 S 8 The photoelectrochemical cathode protection performance of the system film photoelectrode is tested: the change of the photoinduced current intensity between the photoelectrode and the pure copper electrode coupled under the irradiation of white light (figure 7 a) and the photoinduced mixed potential of the coupling system (figure 7 b) was monitored on the device shown in the schematic diagram 3 of the experimental device by using the CHI 660E electrochemical workstation of Shanghai Chen Hua instruments. The electrolyte in the photoelectrochemical cell and the corrosion cell are 3.5% NaCl solution.
FIGS. 7a, b show a single TiO 2 、SnIn 4 S 8 -15h and TiO 2 /SnIn 4 S 8 -15h of photoelectric cathode protection performance of the composite photo-anode material on pure copper under AM1.5 simulated sunlight. As shown in FIG. 7a, snIn due to abrupt generation of photo-induced electrons in 3.5wt% NaCl solution under AM1.5 simulated solar irradiation 4 S 8 -15h and TiO 2 /SnIn 4 S 8 The 15h composite photo-anode shows a larger instantaneous photo-cathodic protection current density for pure copper. After the current density of the photocathode protection reaches the stability, tiO 2 /SnIn 4 S 8 Photocathode protection current density of 15h-Cu (about 40.8. Mu.A.cm) -2 ) Is obviously higher than TiO 2 Cu is about (1.2. Mu.A.cm) -2 ) With SnIn 4 S 8 15h-Cu (about 22.0. Mu.A.cm) -2 ) A kind of electronic device. As shown in FIG. 7b, the OCP of the pure copper electrode in 3.5wt% NaCl solution was-0.18V, which was equal to that of SnIn 4 S 8 -15h or TiO 2 /SnIn 4 S 8 After 15h photoelectrode coupling, the mixed potential of the coupling system was negatively shifted to-0.218 and-0.366V under simulated solar irradiation, respectively (fig. 7 b). And with TiO 2 The pure copper electrode coupled with the photoelectrode has no obvious potential drop change. This is because of TiO 2 /SnIn 4 S 8 15h-Cu, the heterojunction effect obviously enhances the separation and collection of photo-generated electrons and holes, and enhances TiO 2 Photocathode protection performance of photoanode.
For the TiO prepared by the above 2 /SnIn 4 S 8 -testing photoelectrochemical cathode protection performance of a 15h system film photoelectrode: CHI 660E electricity of Shanghai Chen Hua instruments Co was used on the device shown in the schematic diagram 3 of the experimental deviceA chemical workstation, monitoring the photo-induced current intensity between the photoelectrode and the pure copper or 316L SS electrode coupled under white light irradiation (fig. 8 a), and the photo-induced mixed potential of the coupling system (fig. 8 b). The electrolyte in the photoelectrochemical cell and the corrosion cell are 3.5% NaCl solution. And the photo-induced current density curve is integrated to obtain the charge quantity of photo-generated electrons provided by the photoelectric electrode to the pure copper electrode under illumination and the charge quantity of continuous discharge to the copper electrode by the photoelectric electrode in dark state after cutting off the illumination, thus researching TiO 2 /SnIn 4 S 8 The storage of the photoelectrode slowly releases the photo-generated electron performance.
FIG. 8a shows TiO in comparison with FIG. 8b 2 /SnIn 4 S 8 Cathodic protection performance of 15h photoanode against pure copper and 316L stainless steel. TiO (titanium dioxide) 2 /SnIn 4 S 8 The photo-cathodic protection current density after coupling the photo-anode with pure copper for 15 hours is greater than that for 316L stainless steel. TiO (titanium dioxide) 2 /SnIn 4 S 8 The mixed potential return rate of the coupling system of the 15h photo anode and the 316L stainless steel after illumination is slower than that of TiO 2 /SnIn 4 S 8 -15h of coupling system with pure copper. This is because the self-corrosion rate of pure copper surfaces is greater than that of 316L stainless steel, the reaction rate between copper surface electrons and solution is faster, and a large amount of photo-generated electrons are transferred to copper surfaces and enter the reaction with solution in a large amount. Although the photocathode protection current density is greater than the 316L SS coupling system, the photo-generated electrons do not accumulate sufficiently on the copper surface, so the photocathode protection potential returns faster after stopping the illumination than the 316L SS coupling system. From the result of combining the photocathode protection current density and the photoinduced potential drop, the TiO 2 /SnIn 4 S 8 The 15h photo-anode has better photoelectric continuous cathode protection performance on 316L SS.
FIG. 9 shows TiO 2 /SnIn 4 S 8 -current density profile after sufficient slow-release of electrons after sufficient AM1.5 to simulate solar illumination (50 s). The total charge amount of the photo-generated electrons transferred to the copper under illumination can be estimated by integrating the i-t curve, and the charge amount of the photo-generated electrons continuously released to the pure copper after light cutting. Wherein T isiO 2 /SnIn 4 S 8 The photocathode protection electric quantity of the 15h-Cu photoanode is optimal, the total electric quantity of photo-generated electrons transferred to copper under illumination is 4791 mu C, and the electric quantity of photo-generated electrons continuously released to pure copper after light cutting is 1390 mu C. Correspondingly, FIG. 9 also shows TiO 2 /SnIn 4 S 8 -15h-316L SS current density profile after sufficient amount AM1.5 simulates solar illumination (50 s) and sufficient electron release. TiO (titanium dioxide) 2 /SnIn 4 S 8 The 15h photo-anode was coupled to 316L SS, the total charge of photo-generated electrons transferred to 316L SS under illumination was 909. Mu.C, and the charge of photo-generated electrons continuously released to 316L SS after light cutting was 297. Mu.C.
As described above, the present invention is achieved by constructing porous TiO 2 Nanometer base layer and composite porous interconnected SnIn 4 S 8 The nano flower successfully prepares the photo anode with energy storage effect, and can provide continuous photocathode protection performance for the dark state of pure copper after light is closed.

Claims (7)

1. A porous composite photoelectric energy storage material for photoinduced continuous cathode protection, which is characterized in that: the composite photoelectric energy storage material is TiO 2 Nanometer bush gap and in-situ growth of SnIn on upper part 4 S 8 Obtaining a porous composite photoelectric energy storage material by the three-dimensional nanoflower; the Sn, in and S sources are soaked In ion state to the surface of the material with TiO by a solvothermal method 2 On the porous base layer of the nanometer shrub, then in-situ growing into nanometer flower-shaped SnIn on the base layer 4 S 8 Obtained SnIn 4 S 8 With TiO 2 A composite photoelectric energy storage material with tight interface combination.
2. A method for preparing a porous composite photoelectric energy storage material for photoinduced continuous cathode protection as claimed in claim 1, which is characterized in that: on the growth of TiO 2 In-situ growth of SnIn on surface of porous base layer of nano shrub 4 S 8 Obtaining a porous composite photoelectric energy storage material by the three-dimensional nanoflower; wherein the TiO is grown 2 The base layer of the nanometer bush is conductive on the FTO by solvothermal methodAnd (5) growing the surface of the substrate in situ.
3. The method for preparing the porous composite photoelectric energy storage material for photoinduced continuous cathode protection according to claim 2, wherein the method comprises the following steps:
1) Preparation of a porous base layer: placing a pretreated FTO substrate in a liner of a high-pressure reaction kettle, placing a conductive surface downwards at an angle of 45 degrees with the kettle wall, adding the solution a into the high-pressure reaction kettle to submerge the FTO substrate, heating at 170-190 ℃ for 8-10 hours, and directly growing TiO with a porous nano bush structure on the FTO conductive substrate 2 A material; then, after the reaction kettle is cooled, the FTO conductive substrate is calcined to obtain white TiO 2 A nanoporous substrate; wherein the solution a is prepared by weighing 0.001-0.003mol K 2 TiO(C 2 O 4 ) 2 Adding 5-15 parts of ml parts of water into (potassium titanium oxalate, PTO) and heating and stirring until the diethylene glycol DEG is dissolved, wherein the volume of diethylene glycol DEG is 1-3 times of the volume of the added water;
2）SnIn 4 S 8 preparation of a hydrothermal solution: snCl is added 4 ·5H 2 O and InCl 3 Dissolving in absolute ethyl alcohol, and stirring at room temperature; when the solution becomes transparent, a proper amount of thiourea is weighed and introduced as a sulfur source, wherein SnCl 4 ·5H 2 O：InCl 3 : the stoichiometric ratio of thiourea is 1:4:8-10, and the mixture is stirred again until a transparent solution b is obtained;
3）TiO 2 /SnIn 4 S 8 preparation of the composite material: tiO obtained in the step 1) is prepared 2 Placing the conductive surface of the base layer downwards into a high-pressure reaction kettle, pouring the uniform transparent solution b obtained in the step 2) into the reaction kettle, and heating at 160-200 ℃ for 9-18 hours to obtain the orange porous composite photoelectric energy storage material on the surface of the base layer.
4. A method for preparing a porous composite photoelectric energy storage material for photoinduced continuous cathode protection as claimed in claim 3, wherein: and (2) calcining in the step (1) to take out the base layer, cleaning the base layer by deionized water, drying the base layer by an oven, and then placing the base layer in a tube furnace to calcine the base layer at 0.5-1.5. 1.5h at the temperature rising rate of 10-15 ℃/min to 400-500 ℃.
5. Use of a porous composite photovoltaic energy storage material for photoprotective according to claim 1, characterized in that: the composite photoelectric energy storage material is applied to the continuous protection of metal in a dark state as an anti-corrosion protection film for inhibiting metal corrosion.
6. TiO (titanium dioxide) 2 /SnIn 4 S 8 The composite photoelectric energy storage electrode comprises a photoelectric conversion layer, an electron storage layer and a conductive layer, and is characterized in that: the composite photoelectric energy storage material of claim 1 as a semiconductor photoelectric conversion and electron storage layer.
7. Use of an electrode according to claim 6, characterized in that: the composite photoelectric energy storage electrode is applied to a photoelectric cathode protection anti-corrosion photo-anode for inhibiting metal corrosion.
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