CN112885607A - Composite photo-anode structure of compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and preparation method thereof - Google Patents
Composite photo-anode structure of compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and preparation method thereof Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 44
- 239000002073 nanorod Substances 0.000 title claims abstract description 42
- 239000002096 quantum dot Substances 0.000 title claims abstract description 34
- 229940056932 lead sulfide Drugs 0.000 title claims abstract description 27
- 229910052981 lead sulfide Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 title claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 76
- 239000011521 glass Substances 0.000 claims abstract description 19
- 229910052979 sodium sulfide Inorganic materials 0.000 claims abstract description 12
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 8
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 238000004528 spin coating Methods 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 229940079101 sodium sulfide Drugs 0.000 claims description 11
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 4
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000004729 solvothermal method Methods 0.000 claims description 4
- 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 4
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 229940046892 lead acetate Drugs 0.000 claims description 3
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 claims description 3
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 claims description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical class CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003599 detergent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- YADLXYVOUBVKQR-UHFFFAOYSA-N ethane-1,1-dithiol ethane-1,2-dithiol Chemical compound C(C)(S)S.C(CS)S YADLXYVOUBVKQR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004519 grease Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 1
- 239000010408 film Substances 0.000 description 12
- 239000000126 substance Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 1
- PMXRKXVFZJUCLO-UHFFFAOYSA-N 3-ethyl-3h-dithiole Chemical compound CCC1SSC=C1 PMXRKXVFZJUCLO-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000000584 ultraviolet--visible--near infrared spectrum Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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Abstract
A composite photo-anode structure of a compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and a preparation method thereof relate to a composite photo-anode structure and a preparation method thereof, and are characterized in that the composite photo-anode structure of the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method thereof are composed of fluorine-doped SnO2 conductive glass, a titanium dioxide nanorod array and a precursor solution; the precursor solution consists of a lead salt solution, namely an A solution, a sodium sulfide solution, namely a B solution, and an ethanedithiol solution, namely a C solution.
Description
Technical Field
The invention relates to a composite photo-anode structure and a preparation method thereof, in particular to a composite photo-anode structure of a compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and a preparation method thereof.
Background
In recent years, with the increasing energy crisis and the increasing environmental pollution, the development and utilization of clean energy, especially solar energy, are receiving attention from various countries. China definitely puts forward that the capacity of a solar power generation device reaches 1.6 hundred million kilowatts and the annual power generation amount reaches 1700 hundred million kilowatt hours by the end of 2020. In recent years, research on quantum dot sensitized solar cells has progressed rapidly, and the maximum photoelectric conversion efficiency has reached 16.6%. The lead sulfide quantum dot has a larger exciton Bohr radius (18nm), a higher light absorption coefficient and a proper forbidden bandwidth, so that the lead sulfide quantum dot sensitized solar cell is a potential solar cell.
At present, the methods for preparing quantum dots are a physical method and a chemical method, wherein the chemical method is most widely applied, and the chemical method can be subdivided into a thermal injection synthesis method and an in-situ growth method. The hot injection method needs to be carried out at the high temperature of 150-. The in-situ growth method includes a continuous ion layer adsorption and reaction (SILAR) method and a chemical bath method, and the photoanode needs to be soaked in a solution for a certain time or is soaked for multiple times continuously, and the two methods are long in time consumption and difficult to control the particle size of the quantum dot.
Disclosure of Invention
Therefore, the invention provides a composite photo-anode structure of a compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and a preparation method thereof, which are used for solving the problems of long time consumption and difficulty in controlling the particle size of quantum dots in the prior art.
The invention provides a composite photo-anode structure of a compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and a preparation method thereof, which consists of fluorine-doped SnO2 conductive glass, a titanium dioxide nanorod array and a precursor solution; the precursor solution consists of a lead salt solution, namely an A solution, a sodium sulfide solution, namely a B solution, and an ethylene dithiol solution, namely a C solution.
Further, the composite photo-anode structure of the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method are carried out according to the following steps:
cutting and cleaning fluorine-doped SnO2 conductive glass, cutting the conductive glass into 1.5cm by 2.0cm, and soaking in saturated isopropanol solution of NaOH, potassium dichromate and concentrated sulfuric acid aqueous solution for 6 hours respectively to remove grease and pollutants on the surface of the glass; then, continuously cleaning the conductive glass for 30 minutes by using a water solution of a commercially available detergent in an ultrasonic oscillator, and finally respectively ultrasonically cleaning the conductive glass for 30 minutes each time by using deionized water and absolute ethyl alcohol for 1 time; after the above process is finished, drying the fabric by using a blower, and storing the fabric in a clean box;
secondly, preparing a titanium dioxide nanorod array by a solvothermal method; growing a titanium dioxide nanorod array on the FTO coated with the titanium dioxide dense layer by a solvothermal method by taking tetraisopropyl titanate or tetrabutyl titanate as a titanium source and concentrated hydrochloric acid aqueous solution as a solvent, wherein the volume ratio of concentrated hydrochloric acid to deionized water in the solvent is 1:1-1:2, the preparation temperature is 150-; after natural cooling, washing the conductive glass with the titanium dioxide nanorod array by using a large amount of deionized water and ethanol;
and thirdly, preparing a lead salt solution which is easily soluble in water, namely the solution A, a sodium sulfide solution which is the solution B, and an ethyl dithiol solution which is the solution C. Solution A: 0.0828g of Pb (NO3)2 was dissolved in 2.5mL of deionized water, stirred completely, and 47.5mL of methanol was added thereto to obtain 50mL of a Pb (NO3)2 solution with a concentration of 0.005 mol/L. Solution B: the volume ratio of the anhydrous methanol to the deionized water in the sodium sulfide solution is 95: 5; sodium sulfide nonahydrate is dissolved in deionized water to prepare 0.1mol/L sodium sulfide aqueous solution. Then, a certain amount of the solution and deionized water are respectively removed and added into methanol to obtain 0.002mol/L sodium sulfide solution. Solution C: adding 1, 2-ethanedithiol (ethanedithiol) into absolute ethyl alcohol to obtain an ethanedithiol solution with the volume fraction of 1%;
fourthly, spin-coating the precursor solution; firstly, FTO conductive glass on which a titanium dioxide nanorod array grows is placed in the center of a rotary table of a spin coater, and a vacuum pump is started to pump a vacuum button for firm suction. Dropping the solution A on the surface of the titanium dioxide nanorod array, quickly starting a spin coating button, spin-coating for 20-30 s at 1500 r.min < -1 >, then dropping the solution B on the surface of the titanium dioxide nanorod array which just adsorbs the solution A, spin-coating for 20-30 s at 1500r/min, then dropping the solution 100 mu L C, and spin-coating for 20-30 s at 1500 r.min < -1 >. The above three steps of spin coating are repeated for 20, 30 and 40 times as a cycle.
Further, the lead salt solution, i.e., the a solution, may be lead nitrate or lead acetate.
Compared with the prior art, the invention provides the composite photo-anode structure of the high-quality and compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method thereof, the structure has high light absorption efficiency, is beneficial to the injection and transmission of electrons and holes, and the preparation method has simple equipment and low energy consumption and is suitable for large-scale production; meanwhile, the lead sulfide quantum dot sensitized titanium dioxide nanorod array photoanode prepared by the method has the advantages of uniform quantum dot particle size, high quantum dot film coverage rate, large adsorption space and the like, and the titanium dioxide nanorods have larger adsorption space, can be co-sensitized by other semiconductor quantum dots, and can further improve the photoelectric performance of a photovoltaic device.
Drawings
FIG. 1 is a schematic diagram of a composite photo-anode structure of a compact lead sulfide quantum dot thin film sensitized titanium dioxide nanorod array and a preparation process thereof according to the present invention;
FIG. 2 is a schematic structural view of a composite photo-anode structure of a dense lead sulfide quantum dot thin film sensitized titanium dioxide nanorod array and a preparation method thereof;
FIG. 3 is an SEM photograph of a cross section of a photo-anode obtained by the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array when the composite photo-anode structure of the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method thereof have different spin coating cycle times;
FIG. 4 shows XRD diffraction patterns (a) of a common scan and (b) of a photo-anode obtained by the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array when the composite photo-anode structure of the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method thereof are subjected to different spin coating cycle times.
FIG. 5 shows the UV-VIS-NIR absorption spectra of photoanodes obtained by sensitizing titanium dioxide nanorod arrays with dense lead sulfide quantum dot films at different spin coating cycle times.
Fig. 6 shows (a) a photocurrent-photovoltage characteristic curve of a compact lead sulfide quantum dot thin film sensitized titanium dioxide nanorod array photoanode applied to a solar cell in different spin coating cycles, and (b) an incident monochromatic photon-electron conversion efficiency (IPCE) spectrum of the compact lead sulfide quantum dot thin film sensitized solar cell when the spin coating cycle is 30 times.
Detailed Description
In order that the objects and advantages of the invention will be more clearly understood, the invention will now be further described with reference to the following examples; it should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Preferred embodiments of the present invention are described below with reference to the accompanying drawings. It should be understood by those skilled in the art that these embodiments are only for explaining the technical principle of the present invention, and do not limit the scope of the present invention.
It should be noted that in the description of the present invention, the terms of direction or positional relationship indicated by the terms "upper", "lower", "left", "right", "inner", "outer", etc. are based on the direction or positional relationship shown in the drawings, which are only for convenience of description, and do not indicate or imply that the device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Furthermore, it should be noted that, in the description of the present invention, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
The first embodiment is as follows: solution A: accurately weighed 0.0828g of lead nitrate was added into 2.5mL of deionized water, stirred by a glass rod until completely dissolved, and then 47.5mL of anhydrous methanol was pipetted and added to obtain a lead nitrate solution with a total volume of 50mL and a concentration of 0.005 mol/L. Accurately weighing 0.0600g of sodium sulfide nonahydrate in the solution B, adding 2.5mL of deionized water, stirring and dissolving, transferring by using a pipette, and adding 47.5mL of anhydrous methanol to obtain a sodium sulfide solution with the total volume of 50mL and the concentration of 0.005 mol/L. Solution C: 0.5mL of ethanedithiol is transferred and added with 49.5mL of absolute ethyl alcohol, and the mixture is shaken and fully mixed to obtain the ethanedithiol ethyl alcohol solution with the volume fraction of 1 percent.
And placing the FTO conductive glass on which the titanium dioxide nanorod array grows in the center of a turntable of a spin coater, and starting a vacuum pump to pump a vacuum button for firmly sucking. Dropping 100 mu L A solution on the surface of the titanium dioxide nanorod array, quickly starting a spin coating button, spin coating for 20s at 1500 r.min < -1 >, then dropping 100 mu L of B solution on the surface of the titanium dioxide nanorod array which just adsorbs the A solution, spin coating for 20s at 1500r/min, then dropping 100 mu L of C solution, and spin coating for 20s at 1500 r.min < -1 >. The above three steps of spin coating are repeated as a cycle for 20, 30, 40 times, respectively.
The second embodiment is as follows: the present embodiment differs from the first embodiment in that: the solution A is lead acetate. The rest is the same as the first embodiment.
So far, the technical solutions of the present invention have been described in connection with the preferred embodiments shown in the drawings, but it is easily understood by those skilled in the art that the scope of the present invention is obviously not limited to these specific embodiments. Equivalent changes or substitutions of related technical features can be made by those skilled in the art without departing from the principle of the invention, and the technical scheme after the changes or substitutions can fall into the protection scope of the invention.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention; various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A composite photo-anode structure of a compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and a preparation method thereof are characterized in that the composite photo-anode structure of the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method thereof are composed of fluorine-doped SnO2 conductive glass, a titanium dioxide nanorod array and a precursor solution; the precursor solution consists of a lead salt solution, namely an A solution, a sodium sulfide solution, namely a B solution, and an ethanedithiol solution, namely a C solution.
2. The composite photo-anode structure of the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method thereof as claimed in claim 1, wherein the composite photo-anode structure of the compact lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method thereof are carried out according to the following steps:
cutting and cleaning fluorine-doped SnO2 conductive glass, cutting the conductive glass into 1.5cm by 2.0cm, and soaking in saturated isopropanol solution of NaOH, potassium dichromate and concentrated sulfuric acid aqueous solution for 6 hours respectively to remove grease and pollutants on the surface of the glass; continuously cleaning the conductive glass for 30 minutes by using a water solution of a commercially available detergent in an ultrasonic oscillator, and finally ultrasonically cleaning the conductive glass for 30 minutes each time by using deionized water and absolute ethyl alcohol respectively for 1 time; after the above process is finished, drying the fabric by using a blower, and storing the fabric in a clean box;
secondly, preparing a titanium dioxide nanorod array by a solvothermal method; growing a titanium dioxide nanorod array on the FTO coated with the titanium dioxide dense layer by a solvothermal method by taking tetraisopropyl titanate or tetrabutyl titanate as a titanium source and concentrated hydrochloric acid aqueous solution as a solvent, wherein the volume ratio of concentrated hydrochloric acid to deionized water in the solvent is 1:1-1:2, the preparation temperature is 150-; after natural cooling, washing the conductive glass with the titanium dioxide nanorod array by using a large amount of deionized water and ethanol;
and thirdly, preparing a lead salt solution which is easily soluble in water, namely the solution A, a sodium sulfide solution which is the solution B, and an ethanedithiol solution which is the solution C. Solution A: 0.0828g of Pb (NO3)2 was dissolved in 2.5mL of deionized water, stirred completely, and 47.5mL of methanol was added thereto to obtain 50mL of a Pb (NO3)2 solution with a concentration of 0.005 mol/L. Solution B: the volume ratio of the anhydrous methanol to the deionized water in the sodium sulfide solution is 95: 5; sodium sulfide nonahydrate is dissolved in deionized water to prepare 0.1mol/L sodium sulfide aqueous solution. Then, a certain amount of the solution and deionized water are respectively removed and added into methanol to obtain 0.002mol/L sodium sulfide solution. Solution C: adding 1, 2-ethanedithiol (ethanedithiol) into absolute ethyl alcohol to obtain an ethanedithiol solution with the volume fraction of 1%;
fourthly, spin-coating the precursor solution; firstly, FTO conductive glass on which a titanium dioxide nanorod array grows is placed in the center of a rotary table of a spin coater, and a vacuum pump is started to pump a vacuum button for firm suction. Dropping the solution A on the surface of the titanium dioxide nanorod array, quickly starting a spin coating button, spin-coating for 20-30 s at 1500 r.min < -1 >, then dropping the solution B on the surface of the titanium dioxide nanorod array which just adsorbs the solution A, spin-coating for 20-30 s at 1500r/min, then dropping the solution 100 mu L C, and spin-coating for 20-30 s at 1500 r.min < -1 >. The three steps of spin coating are repeated for 20, 30 and 40 times as a cycle.
3. The composite photoanode structure of the dense lead sulfide quantum dot film sensitized titanium dioxide nanorod array and the preparation method of the composite photoanode structure of the dense lead sulfide quantum dot film sensitized titanium dioxide nanorod array according to claim 2, wherein the lead salt solution, namely the solution A, can be lead nitrate or lead acetate.
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