CN113161153A - Preparation method of visible light multi-band resonant photo-anode - Google Patents
Preparation method of visible light multi-band resonant photo-anode Download PDFInfo
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- 238000004140 cleaning Methods 0.000 claims description 20
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- 239000006185 dispersion Substances 0.000 claims description 14
- 238000004070 electrodeposition Methods 0.000 claims description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000137 annealing Methods 0.000 claims description 12
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- 229910052719 titanium Inorganic materials 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/542—Dye sensitized solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a preparation method of an Ag tree/TiO 2 nanometer bowl array photo-anode capable of realizing multi-frequency absorption of visible light bands, which comprises the following steps: a) removing impurities on the surface of the ITO conductive glass; b) preparing TiO2 sol; c) preparing a TiO2 inverse opal single-layer bowl array; d) evaporating Ag nano-crystals by an electron beam evaporation process; e) an Ag tree/TiO 2 inverse opal single layer bowl array was prepared. The preparation method can quickly prepare the photoelectric conversion material capable of realizing multi-frequency and broadband absorption, and has good stability; the preparation process is simple to operate, reliable in repeatability and environment-friendly. In addition, the Ag tree/TiO 2 nanometer bowl array photoanode material prepared by the method can be tightly combined with the substrate ITO and directly applied to photoelectric reaction.
Description
Technical Field
The invention belongs to the technical field of photoelectric materials, and particularly relates to a preparation method of a visible light multiband resonant photo-anode.
Background
With the development of human society, the demand of people for energy is continuously increasing. The development of clean energy to replace the existing non-renewable fossil energy can relieve the dual pressure of environment and resources. The solar energy is inexhaustible, and the conversion from the solar energy to the chemical energy can be realized through the photocatalyst. In 1972, Fujishima reported the use of TiO in the journal of Nature for the first time2The catalyst can be used for realizing the photoelectrocatalysis of water decomposition. TiO22Is stable and environment-friendly, is an ideal catalytic material, and is still used as a star catalytic material in the active and catalytic fields at present. But TiO22The intrinsic band gap of the catalyst is wide (about 3.2 eV), only ultraviolet light can excite the electron-hole separation of the catalyst to be applied to catalytic reaction, and the visible light energy is low and is not enough to realize the catalytic reaction, so that the solar energy cannot be fully utilized. Researchers have tried to TiO by2Doping, surface modification and member heterojunction are performed to improve the light absorption range, but multi-frequency and broadband absorption of sunlight is still difficult to realize.
The nano array material has high specific surface area and multiple active sites, can realize multiple reflection scattering of incident light, and increases optical paths. Design and preparation of TiO2The inverse opal array structure can realize a slow light effect, and is expected to improve the light absorption capacity and catalytic activity of the inverse opal array structure. Due to the specific fractal structure of the branch array sample, the electromagnetic response of the branch structures of different levels to external incident light can be realized, so that the absorption of the incident light of different frequency bands can be realized. And the preparation of the noble metal-based nanoscale dendritic structure by adjusting the size of the branches is expected to realize multi-frequency absorption of visible light wave bands. If TiO2 is added2The inverse opal array structure and the noble metal nanometer branch array are tightly combined to be used as a photo-anode, so that the multi-frequency and broadband light absorption of the composite material is hopeful to be realized, and the photoelectric conversion efficiency of the composite material is improved.
Disclosure of Invention
In order to solve the technical problem, the invention provides a preparation method of a visible light multiband resonant photo-anode, and the method is used for preparing the visible light multiband resonant photo-anodeThe photo-anode comprises Ag tree and/or TiO2The preparation method of the nanometer bowl comprises the following steps:
step 1, cleaning the surfaces of substrate glass and ITO conductive glass, firstly cleaning the surfaces with cleaning powder, then ultrasonically cleaning the substrate glass and the ITO conductive glass with acetone, ethanol and deionized water, and reserving the cleaned ITO conductive glass in the ethanol for later use;
step 3 preparation of TiO2Sol: preparing TiO2 sol by using a water bath heating method by using water, acetic acid and isopropanol as solvents and isopropyl titanate as a titanium source;
step 4, taking a preset amount of 500 nm PS microsphere dispersion liquid, slowly coating the PS microsphere dispersion liquid on the surface of the substrate glass, and slowly allowing the PS microsphere dispersion liquid to flow down along the surface of the substrate glass to reach TiO2Self-assembling the sol and the air interface to form a single-layer close-packed PS microsphere, wherein the TiO2 sol is adsorbed at the bottom of the PS microsphere;
step 5, taking out the ITO conductive glass stored in the ethanol, and cleaning and drying the ITO conductive glass by using deionized water; one side of the ITO conductive glass is slowly inclined into the TiO2In the sol, the PS microspheres are slowly fished up close to the lower part of the single-layer densely arranged PS microspheres, and the PS microspheres and the TiO2 sol adsorbed at the bottom are transferred to the ITO conductive glass;
step 6, removing the PS microspheres from the ITO conductive glass treated in the step 5 through air annealing to obtain anatase TiO2An inverse opal single layer bowl array;
step 7, using electron beam evaporation process to remove the impurities in the TiO2Performing electron beam evaporation on the surface of the nano bowl array to obtain an Ag nanocrystalline layer modified TiO2An inverse opal single layer bowl array;
step 8, modifying the TiO with the Ag nano-crystal prepared in the step 72The inverse opal single-layer bowl array is used as a cathode, the Ag sheet is used as an anode, low-temperature electrodeposition is adopted, the deposition voltage and the deposition time are controlled, and the Ag tree/TiO tree is prepared2Inverse opal single layer bowl arrays.
Further, the length and the width of the ITO conductive glass in the step 1 are respectively 3cm and 1 cm, and the resistance of the ITO conductive glass is 7 ohms; the length and width of the substrate glass are both 2 cm.
Further, TiO2The solvent of the sol is a mixture of water, acetic acid and isopropanol, wherein the acetic acid accounts for 20-25% of the mass of the solvent, and the isopropanol accounts for 0.5-0.7% of the mass of the water; TiO22Isopropyl titanate in the sol is used as a titanium source and accounts for 10-12% of the mass of the solvent.
Further, the water bath heating method in the step 3 has the water bath temperature of 75-85 ℃ and the water bath time of 10 hours.
Further, in the step 6, the annealing temperature is 450-470 ℃, and the annealing time is 2-3 hours.
Further, the step 7 of preparing the Ag nanocrystalline layer by electron beam evaporation, wherein the thickness of the Ag nanocrystalline layer is 2 nm, and the vacuum degree during evaporation is 2 x 10-6～4*10-6 Pa。
Further, the electrolyte solvent of the electrodeposition process in the step 8 is water, silver nitrate is used as a silver source, the silver nitrate accounts for 0.02-0.03% of the solvent by mass, PEG20000 provides a steric hindrance effect, and the PEG20000 accounts for 20-25% of the solvent by mass.
Further, the electrodeposition of the step 8 is carried out in an ice bath environment; the distance between the anode and the cathode is 0.5-0.6 cm; the electro-deposition voltage is-0.7V to-0.8V, and the time is 90-120 s.
Further, the substrate glass of the step 1 is subjected to ultrasonic treatment for 15 min by using acetone and ethanol respectively, and then is subjected to H treatment2O2The volume ratio of the water to the water is 7: 3 for 30 min, and is washed clean with deionized water and dried before use.
Further, the photoanode has absorption enhancement at 300 nm-400 nm of ultraviolet light, and has light absorption enhancement at multiple frequency bands of 492 nm, 565 nm, 605 nm, 673 nm and 729 nm.
By the process of the invention, TiO is reacted2After the nanometer bowl is combined with the Ag tree branch, the higher photocurrent density is obtained under illumination, and the built-in electricity is generated in the Fermi level balancing process at the contact interface of the nanometer bowl and the Ag tree branch due to different work functionsAnd the field promotes photo-generated electrons to flow to the Ag nano particles from the TiO2, so that the recombination of photo-generated carriers in the semiconductor can be effectively inhibited, meanwhile, the Ag dendritic array generates plasmon resonance under the irradiation of visible light, and the resonance energy further stimulates the generation of Ag nanocrystalline thermal electrons, so that the composite material shows more excellent photoelectric response. The sample is stable in the test process and can be used as a photo-anode for a photoelectrocatalysis reaction.
Drawings
Fig. 1 (a) and (b) are SEM photograph and XRD chart, respectively, of example 1.
FIGS. 2 (a) - (d) are SEM photographs of example 2 and comparative examples 1-3, respectively.
Figure 3 is the uv-vis absorption of example 1 and example 2.
Fig. 4 is a graph of the current versus voltage response for examples 1 and 2 under full spectrum illumination.
FIG. 5 shows the response of the current of example 1 and example 2 with time under the bright and dark conditions at a fixed applied voltage of 0.8V.
Detailed Description
The invention aims to solve the technical problem of providing the Ag tree/TiO tree branch with simple, convenient and easy operation and low cost aiming at the defects of the existing material2A preparation method of a nanometer bowl photo-anode. The technical scheme adopted by the invention is to prepare TiO on the surface of ITO glass by utilizing a template-assisted sol transfer method2And preparing the nano silver branch array by using a nano bowl and then adopting an electrodeposition method.
The invention provides a preparation method of a visible light multiband resonant photo-anode, wherein the photo-anode comprises Ag tree branches/TiO2The preparation method of the nanometer bowl comprises the following steps:
step 1, cleaning the surfaces of substrate glass and ITO glass, firstly cleaning the surfaces with cleaning powder, then ultrasonically cleaning the substrate glass and the ITO conductive glass with acetone, ethanol and deionized water, and reserving the cleaned ITO glass in the ethanol for later use;
step 3 preparation of TiO2Sol: preparing TiO by using water bath heating method by using water, acetic acid and isopropanol as solvents and isopropyl titanate as titanium source2Sol;
step 4, taking a predetermined amount of 500 nm PS ball dispersion liquid, slowly coating the PS ball dispersion liquid on the surface of the substrate glass, and slowly allowing the PS ball dispersion liquid to flow down along the surface of the substrate glass to reach TiO2Self-assembling after the interface of sol and air to form a single-layer close-packed PS ball, wherein TiO is2The sol is adsorbed at the bottom of the microsphere;
step 5, taking out the ITO glass stored in the ethanol, and cleaning and drying the ITO glass by using deionized water; one side of the ITO glass is slowly inclined into the TiO2In the sol, the microspheres are slowly fished up close to the lower part of the PS single-layer spheres, and the PS microspheres and the TiO adsorbed at the bottom are2Transferring the sol to ITO glass;
step 6, removing the PS microspheres from the ITO glass treated in the step 5 through air annealing to obtain anatase TiO2An inverse opal single layer bowl array;
step 7, using electron beam evaporation process to remove the impurities in the TiO2Performing electron beam evaporation on the surface of the nano bowl array to obtain an Ag nanocrystalline layer modified TiO2An inverse opal single layer bowl array;
step 8, modifying the TiO with the Ag nano-crystal prepared in the step 72The inverse opal single-layer bowl array is used as a cathode, the Ag sheet is used as an anode, low-temperature electrodeposition is adopted, the deposition voltage and the deposition time are controlled, and the Ag tree/TiO tree is prepared2Inverse opal single layer bowl arrays.
Further, the length and the width of the ITO conductive glass in the step 1 are respectively 3cm and 1 cm, and the resistance of the ITO conductive glass is 7 ohms; the length and width of the substrate glass are both 2 cm.
Further, TiO2The solvent of the sol is a mixture of water, acetic acid and isopropanol, wherein the acetic acid accounts for 20-25% of the mass of the solvent, and the TiO is2Isopropyl titanate in the sol is used as a titanium source and accounts for 10-12% of the mass of the solvent; the balance of water, and the isopropanol accounts for 0.5-0.7% of the mass of the water.
Further, the water bath heating method in the step 3 has the water bath temperature of 75-85 ℃ and the water bath time of 10 hours.
Further, in the step 6, the annealing temperature is 450-470 ℃, and the annealing time is 2-3 hours.
Further, the step 7 of preparing the Ag nanocrystalline layer by electron beam evaporation, wherein the thickness of the Ag nanocrystalline layer is 2 nm, and the vacuum degree during evaporation is 2 x 10-6～4*10-6 Pa。
Further, the electrolyte solvent of the electrodeposition process in the step 8 is water, silver nitrate is used as a silver source, the silver nitrate accounts for 0.02-0.03% of the solvent by mass, PEG20000 provides a steric hindrance effect, and the PEG20000 accounts for 20-25% of the solvent by mass.
Further, the electrodeposition of the step 8 is carried out in an ice bath environment; the distance between the anode and the cathode is 0.5-0.6 cm; the electro-deposition voltage is-0.7V to-0.8V, and the time is 90-120 s.
Further, the substrate glass of step 1. Ultrasonic treating with acetone and ethanol for 15 min, respectively, and treating with H2O2The volume ratio of the water to the water is 7: 3 for 30 min, and is washed with deionized water and dried before use.
Furthermore, the photoanode has absorption enhancement at 300 nm-400 nm of ultraviolet light, and has light absorption enhancement at multiple frequency bands of 492 nm, 565 nm, 605 nm, 673 nm and 729 nm.
The following detailed description of embodiments of the invention refers to the accompanying drawings.
The ITO conductive glass used in the embodiment of the invention has the resistance of 7 ohms and the size of 1 x 3cm2。
Example 1TiO2Inverse opal single layer bowl array
(a) Cleaning a substrate and ITO conductive glass: the substrate is 2 x 2cm2The glass of (2). Cleaning with decontamination powder before use, ultrasonic treating with acetone and ethanol for 15 min, and treating with H2O2And H2The volume ratio of O is 7: 3 for 30 min to improve surface hydrophilicity, and washing with deionized water and drying. Cleaning the ITO conductive glass by using cleaning powder, then ultrasonically cleaning the ITO conductive glass in acetone-ethanol, and keeping the ITO conductive glass in the ethanol for later use;
(b) polystyrene (PS) sphere dispersion: dispersing 500 nm PS microspheres in water: ethanol is 2: 1, the dispersed microspheres are subjected to ultrasonic treatment for 20 min before use to ensure uniform dispersion in the solvent;
（c）TiO2sol preparation: adding 62.5 ml of deionized water and 20 ml of acetic acid into a round-bottom flask; subsequently, 0.5 ml of isopropanol and 9.5 ml of tetraisopropyl titanate were dropped in, and vigorously stirred in a water bath for 1 hour to obtain a pale yellow sol; then stirring for 10 h at 80 ℃ to obtain white TiO2Sol;
(d) self-assembly of single-layer PS spheres: mu.l of 500 nm PS sphere dispersion was applied slowly to the surface of the glass substrate. The PS ball dispersion liquid slowly flows down along the surface of the substrate, and self-assembly is carried out after the PS ball dispersion liquid reaches the interface of the sol and the air, so that a single-layer close-packed 500 nm PS ball is formed.
(e) PS microsphere transfer: the ITO glass is firstly cleaned by deionized water to remove ethanol on the surface, and then dried by an ear washing ball. One side of the ITO glass slowly inclines into the sol and is close to the lower part of the PS single-layer ball, the microspheres are slowly fished up, and the PS microspheres and the TiO adsorbed at the bottom can be obtained in the process2The sol was transferred to ITO glass.
(f) Annealing to obtain TiO2Nano bowl array: air atmosphere 450oC annealing for 2h, and the heating rate is 5oC/min to finally obtain TiO2Inverse opal single layer bowl arrays.
FIGS. 1 (a) and (b) are SEM photograph and XRD pattern, respectively, of example 1. FIG. 1 (a) demonstrates TiO2The inverse opal single-layer bowl array structure has a period of about 500 nm; FIG. 1 (b) is a graph showing that the crystal form of example 1 is anatase type TiO after annealing treatment2。
Example 2Ag dendron/TiO2Inverse opal single layer bowl array
(a) Ag nanocrystals were deposited on the surface of the film obtained in example 1, and the degree of vacuum of the deposition was adjusted to 4 x 10 by the electron beam evaporation method-6Pa, and deposition was performed while setting the Ag film thickness to 2 nm.
(b) Taking the example 1 treated in the step (a) as a cathode and an Ag sheet anode, wherein the distance between the two electrodes is 0.55 cm; the specific formula of the electrolyte is that 1 mg AgNO3Dissolving in 5 ml water to obtain solution A, dissolving 1.2 g PEG20000 in 5 ml water to obtain solution B, dripping the solution A into the solution B, and cold preserving in dark place for 12 hr;
(c) filling the electrolyte between the cathode and the anode at 2oIn the environment C, a voltage of-0.8V is applied to the cathode for 120 s.
Comparative example 1 Ag Branch/TiO2Inverse opal single layer bowl array
(a) Taking the cathode of the embodiment 1 and an Ag sheet anode, wherein the distance between the two electrodes is 0.55 cm; the specific formula of the electrolyte is that 1 mg AgNO is added3Dissolving in 5 ml water to obtain solution A, dissolving 1.2 g PEG20000 in 5 ml water to obtain solution B, dripping the solution A into the solution B, and cold preserving in dark place for 12 hr;
(b) filling the electrolyte between the cathode and the anode at 2oIn the environment C, a voltage of-0.8V is applied to the cathode for 120 s.
Comparative example 2Ag Branch/TiO2Inverse opal single layer bowl array
(a) Ag nanocrystals were deposited on the surface of the film obtained in example 1, and the degree of vacuum of the deposition was adjusted to 4 x 10 by the electron beam evaporation method-6Pa, setting the thickness of the Ag film to be 2 nm and carrying out evaporation;
(b) taking the example 1 treated in the step (a) as a cathode and an Ag sheet anode, wherein the distance between the two electrodes is 0.55 cm; the specific formula of the electrolyte is that 1 mg AgNO is added3Dissolving in 5 ml water to obtain solution A, dissolving 1.2 g PEG20000 in 5 ml water to obtain solution B, dripping the solution A into the solution B, and cold preserving in dark place for 12 hr;
(c) filling the electrolyte between the cathode and the anode at 2oIn the environment C, a voltage of-0.8V is applied to the cathode for 200 s.
Comparative example 3Ag Branch/TiO2Inverse opal single layer bowl array
(a) Ag nanocrystals were deposited on the surface of the film obtained in example 1, and the degree of vacuum of the deposition was adjusted to 4 x 10 by the electron beam evaporation method-6Pa, setting the thickness of the Ag film to be 2 nm and carrying out evaporation;
(b) example 1 treated in step (a) was used as a cathode, an Ag plate anode, andthe distance between the electrodes is 0.55 cm; the specific formula of the electrolyte is that 1 mg AgNO is added3Dissolving in 5 ml water to obtain solution A, dissolving 1.2 g PEG20000 in 5 ml water to obtain solution B, dripping the solution A into the solution B, and cold preserving in dark place for 12 hr;
(c) filling the electrolyte between the cathode and the anode at 2oIn the environment C, a voltage of-0.8V is applied to the cathode for 60 s.
FIGS. 2 (a) - (d) are SEM photographs of example 2 and comparative examples 1-3, respectively. As can be seen from FIG. 2 (a), in example 2, the dendrites are uniformly distributed and TiO is uniformly distributed2The surface of the nanometer bowl; in comparative example 1, as shown in FIG. 2 (b), Ag dendrites were distributed only in a small area, mainly due to TiO not having an Ag film deposited thereon2The bowl surface has poor conductivity, so that the uniform deposition is difficult to realize in the process of preparing the Ag tree branches by electrodeposition; in comparative example 2, the voltage application time for preparing Ag dendrites was long, and as shown in FIG. 2 (c), the Ag dendrite samples grew in a large area with overlapping portions of the area covered with TiO2A nanometer bowl; while the voltage application time for preparing Ag dendrites in comparative example 3 was too short, as shown in fig. 2 (d), the Ag dendrite sample was not completely molded and the deposition time was still required to be prolonged. Therefore, on the basis of enhancing the conductivity of the substrate, the preparation time is reasonably controlled, and a complete and uniform Ag dendritic sample can be obtained.
Figure 3 is the uv-vis absorption of example 1 and example 2. As can be seen, example 1 is a wide band gap semiconductor, and thus has absorption enhancement at 300 nm to 400 nm of ultraviolet light, i.e., ultraviolet light can be absorbed for exciting electron-hole separation, and the absorption enhancement at 400 nm is mainly due to the slow light effect of the inverse opal array structure. In example 2, the absorption at 300 nm except ultraviolet light is enhanced, and the absorption at multiple frequency sections of 383 nm, 492 nm, 565 nm, 605 nm, 673 nm and 729 nm is enhanced, wherein the absorption is derived from the hierarchical structure of Ag tree branches, and the solid absorption curve proves that TiO is formed by TiO2The composite material combined with the Ag nano tree branches can indeed realize multi-frequency absorption.
Example 3 photoelectrochemical testing
Photoelectrochemical testing was performed using the CHI660 electrochemical workstation. The light source is provided by a xenon lamp and is used in the experimental processThe intensity of the used full spectrum light and visible light is 100 mW.cm-2. The electrode adopts a standard three-electrode, namely a Pt electrode is taken as a counter electrode, an Ag/AgCl electrode is taken as a reference electrode, and the working electrodes of the embodiment 1 and the embodiment 2 are respectively taken as working electrodes; electrolyte is 0.5 mol. L-1Na2SO4And (3) solution. In the photocurrent test, the voltage range of the current-voltage test is selected to be 0.5-1.2V relative to an Ag/AgCl reference electrode, the sweep rate is 10 mV/s, and the illumination/dark time is 10 s. Current test applied constant voltage was 0.8V versus Ag/AgCl reference electrode for 250 s.
Fig. 4 is a graph of the current versus voltage response for examples 1 and 2 under full spectrum illumination. Compared with example 1, when the silver-doped copper alloy is combined with Ag branches, the photocurrent is improved by about 2 times under the same voltage condition. For example 2, the photocurrent increased significantly with increasing voltage, indicating the resistive properties of the sample. The photo-anode has better photoelectric conversion efficiency than that of the embodiment 1.
FIG. 5 shows the response of the current of example 1 and example 2 with time under the bright and dark conditions at a fixed applied voltage of 0.8V. Wherein fig. 5(a) is the current versus voltage response of examples 1 and 2 under visible light conditions. As can be seen from the figure, compared to example 1, in example 2, the photocurrent is increased by about 10 times under the irradiation of visible light, and mainly results from the photoelectric response realized by the multi-frequency and broadband absorption of visible light by the Ag nano dendritic array. Fig. 5(b) is a graph of the current versus voltage response for examples 1 and 2 under full spectrum illumination conditions. Adding TiO into the mixture2After the nanometer bowl is combined with the Ag tree branch, the higher photocurrent density is obtained under illumination, and the built-in electric field is generated in the Fermi level balancing process at the contact interface of the nanometer bowl and the Ag tree branch due to different work functions, so that photogenerated electrons are promoted to be formed by TiO2When the Ag nano-particles flow to the Ag nano-particles, the recombination of photogenerated carriers in a semiconductor can be effectively inhibited, meanwhile, the Ag branch array generates plasmon resonance under the irradiation of visible light, and the resonance energy further stimulates the generation of thermal electrons of the Ag nano-crystals, so that the composite material shows more excellent photoelectric response. The sample is stable in the test process and can be used as a photo-anode for a photoelectrocatalysis reaction.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the embodiments of the present invention and not for limiting, and although the embodiments of the present invention are described in detail with reference to the above preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the embodiments of the present invention without departing from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a visible light multiband resonant photo-anode is characterized in that the photo-anode comprises Ag branches and/or TiO2The preparation method of the nanometer bowl comprises the following steps:
step 1, cleaning the surfaces of substrate glass and ITO conductive glass, firstly cleaning the surfaces with cleaning powder, then ultrasonically cleaning the substrate glass and the ITO conductive glass with acetone, ethanol and deionized water, and reserving the cleaned ITO conductive glass in the ethanol for later use;
step 2, dispersing polystyrene PS microspheres: ultrasonically dispersing PS microspheres with the diameter of 500 nm in a mixed solvent of water and ethanol, wherein the mixed solvent comprises water and ethanol, and the mass ratio of the water to the ethanol is 2: 1;
step 3 preparation of TiO2Sol: preparing TiO2 sol by using a water bath heating method by using water, acetic acid and isopropanol as solvents and isopropyl titanate as a titanium source;
step 4, taking a preset amount of 500 nm PS microsphere dispersion liquid, slowly coating the PS microsphere dispersion liquid on the surface of the substrate glass, and slowly allowing the PS microsphere dispersion liquid to flow down along the surface of the substrate glass to reach TiO2Self-assembling after the interface of the sol and the air to form a single-layer close-packed PS microsphere, wherein TiO is2The sol is absorbed at the bottom of the PS microspheres;
step 5, taking out the ITO conductive glass stored in the ethanol, and cleaning and drying the ITO conductive glass by using deionized water; one side of the ITO conductive glass is slowly inclined into the TiO2In the sol, the PS microspheres are slowly fished up near the lower part of the single-layer densely arranged PS microspheres, and the PS microspheres and TiO adsorbed at the bottom are2Transferring the sol to ITO conductive glass;
step 6, removing the PS microspheres from the ITO conductive glass treated in the step 5 through air annealing,obtaining anatase type TiO2An inverse opal single layer bowl array;
step 7, using electron beam evaporation process to remove the impurities in the TiO2Performing electron beam evaporation on the surface of the nano bowl array to obtain an Ag nanocrystalline layer modified TiO2An inverse opal single layer bowl array;
step 8, modifying the TiO with the Ag nano-crystal prepared in the step 72The inverse opal single-layer bowl array is used as a cathode, the Ag sheet is used as an anode, low-temperature electrodeposition is adopted, the deposition voltage and the deposition time are controlled, and the Ag tree/TiO tree is prepared2Inverse opal single layer bowl arrays.
2. The method for preparing the photoanode as claimed in claim 1, wherein the length and width of the ITO conductive glass in step 1 are 3cm and 1 cm respectively, and the resistance of the ITO conductive glass is 7 ohms; the length and width of the substrate glass are both 2 cm.
3. The method of preparing a photoanode of claim 1, wherein: TiO22The solvent of the sol is a mixture of water, acetic acid and isopropanol, wherein the acetic acid accounts for 20-25% of the mass of the solvent, and the isopropanol accounts for 0.5-0.7% of the mass of the water; isopropyl titanate in the TiO2 sol is used as a titanium source and accounts for 10-12% of the mass of the solvent.
4. The method for preparing the photoanode, according to claim 1, wherein the water bath heating method in step 3 has a water bath temperature of 75 to 85 ℃ and a water bath time of 10 hours.
5. The method for preparing the photoanode according to claim 1, wherein the annealing temperature in step 6 is 450-470 ℃ and the annealing time is 2-3 hours.
6. The method for preparing a photoanode of claim 1, wherein the step 7 of electron beam evaporation is to prepare the Ag nanocrystalline layer with a film thickness of 2 nm and a vacuum degree of 2 x 10 during evaporation-6～4*10-6 Pa。
7. The method of preparing a photoanode of claim 1, wherein: the electrolyte solvent of the electrodeposition process in the step 8 is water, silver nitrate is used as a silver source, the silver nitrate accounts for 0.02-0.03% of the mass of the solvent, PEG20000 provides a steric hindrance effect, and the PEG20000 accounts for 20-25% of the mass of the solvent.
8. The method for preparing a photoanode according to claim 1, wherein the electrodeposition of step 8 is performed in an ice bath environment; the distance between the anode and the cathode is 0.5-0.6 cm; the electro-deposition voltage is-0.7V to-0.8V, and the time is 90-120 s.
9. The method for preparing the photoanode as claimed in claim 1, wherein the substrate glass of step 1 is treated with ultrasound for 15 min using acetone and ethanol, and then treated with H2O2The volume ratio of the water to the water is 7: 3 for 30 min, and is washed clean with deionized water and dried before use.
10. The method of claim 1, wherein the photoanode has an absorption enhancement at 300 nm to 400 nm of ultraviolet light and an absorption enhancement at multiple frequency bands of 492 nm, 565 nm, 605 nm, 673 nm, and 729 nm.
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