CN110760881B - Organic photocathode taking copper nanosheet as supporting framework and preparation method thereof - Google Patents

Organic photocathode taking copper nanosheet as supporting framework and preparation method thereof Download PDF

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CN110760881B
CN110760881B CN201911202026.3A CN201911202026A CN110760881B CN 110760881 B CN110760881 B CN 110760881B CN 201911202026 A CN201911202026 A CN 201911202026A CN 110760881 B CN110760881 B CN 110760881B
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程雅慧
孙兴军
刘晖
张瑞
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Nankai University
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Abstract

An organic photocathode taking a copper nanosheet as a supporting framework and a preparation method thereof are disclosed, wherein the preparation method of the organic photocathode comprises the following steps: 1) preparing a copper nanosheet by adopting an electrodeposition method, adding soluble copper (II) salt, sodium hypophosphite, sodium citrate, boric acid and polyethylene glycol into deionized water, stirring to obtain a uniform copper salt solution, dropwise adding an alkaline aqueous solution into the copper salt solution, regulating the pH of the solution to be 7.5-9.5, and stirring for 5-10 min to obtain a solution I; pouring the solution I obtained in the step 1.1 into an electrolytic bath, carrying out electro-deposition on FTO plated with a copper seed layer for 25-35 min to obtain a sample, washing the sample, and carrying out vacuum drying to obtain a copper nanosheet with the FTO as a substrate; 2) and loading the hole transport layer and the organic absorption layer on a metal framework of a copper nanosheet with the FTO as a substrate by adopting a spin coating method to obtain the organic photocathode.

Description

Organic photocathode taking copper nanosheet as supporting framework and preparation method thereof
Technical Field
The invention belongs to a preparation technology of an organic photocathode taking copper nanosheets as a supporting framework, and relates to a preparation method of nanosheets growing on a substrate and a method for preparing the photocathode by spin-coating an organic absorption layer on the nanosheets, which are simple and controllable in shape and can be used for the fields of catalysis and clean energy production.
Background
In recent years, with the increasing severity of environmental pollution and the increasing exhaustion of fossil energy, environmental and energy problems have become two major problems that plague the world. Energy is the power for maintaining human development, so that the development of sustainable energy is urgently needed. The solar energy is inexhaustible, so that the solar energy enters the sight of scientific research personnel. Based on the principle that semiconductors can absorb sunlight to generate electron-hole pairs, photocatalytic technology has been found, and the degradation of organic matters and the generation of the cleanest energy, such as hydrogen, can be realized by photocatalysis. At present, metal oxides are increasingly applied to the field of photocatalysis, and the metal oxides are easy to synthesize and widely applied, so that much attention is paid to the metal oxides. However, the synthesis and application of the metal simple substance are not highly concerned, and the metal simple substance is not easy to grow on a substrate due to harsh synthesis conditions, and is not applied to the aspect of photoelectrocatalysis. Copper is the most efficient element for reducing carbon dioxide in photoelectrocatalysis, and the single metal catalyst copper has unique capability for converting carbon dioxide or carbon monoxide into C with obvious selectivity2+The product and the influence of the copper nano morphology on the aspects of Catalysis and the like are different, and an independent triangular two-dimensional copper nanosheet capable of selectively exposing a {111} surface is manufactured in Nature Catalysis 2019, 2 and 423 by a liquid phase reduction method. The two-dimensional triangular copper nanoplates produced in this method are powdered, but they are effective at sequestering CO2Is converted into acetate.
In addition, the organic semiconductor has the advantages of various types, controllable shape, high light absorption coefficient, full liquid phase processing and the like, and has good application in the field of photocatalysis. P3HT and PCBM have high photoelectric conversion efficiency, and have become more studied materials in organic semiconductor materials. The exciton dissociation energy of P3HT is approximately between 0.1eV and 0.4eV, so dissociation of excitons in P3HT is difficult (Chemical Reviews 2017, 117, 796), and therefore P3HT is typically used in admixture with PCBM. P3HT prepared by adding PCBM, wherein the PCBM heterojunction structure has more contact interfaces at which photogenerated excitons in the organic matter can be effectively separated. However, even though PCBM is added, under the same test conditions, the photocurrent of the organic absorption layer is two to three orders of magnitude smaller than that of the inorganic material, so in order to increase the photocurrent of the organic semiconductor, it is proposed to combine the copper metal nanosheet with the substrate with the organic semiconductor, to promote the generation of electron-hole pairs of the organic absorption layer by utilizing the advantage of large specific surface area of the copper metal nanosheet, and to produce hydrogen by decomposing water by utilizing the electron-hole pairs.
Disclosure of Invention
In order to solve the defect that the photocurrent of the organic semiconductor is relatively small, the invention provides a structure for increasing the photocurrent of the organic semiconductor by utilizing the large specific surface area of a copper metal nanosheet. The structure improves the light receiving area of the organic absorption layer by adjusting the contact area of the metal nanosheets, the hole transport layer and the organic absorption layer, and increases photocurrent.
The invention provides an organic photocathode taking copper nanosheets as a supporting framework, which is characterized in that the preparation method of the organic photocathode comprises the following steps:
1) preparation of copper nanosheet by electrodeposition
1.1) adding soluble copper (II) salt, sodium hypophosphite, sodium citrate, boric acid and polyethylene glycol into deionized water, stirring to obtain a uniform copper salt solution, dropwise adding an alkaline aqueous solution into the copper salt solution, regulating the pH value of the solution to be 7.5-9.5, and stirring for 5-10 min to obtain a solution I, wherein the concentrations of the soluble copper (II) salt (calculated by copper (II), the sodium hypophosphite, the sodium citrate and the boric acid in the solution I are respectively 24-30 mmol/L, 240-300 mmol/L, 40-50 m mol/L and 32-50 mmol/L;
1.2) pouring the solution I obtained in the step 1.1) into an electrolytic tank, performing electrodeposition for 25-35 min at a voltage of-0.9V to-1.0V (vs. SCE) relative to a saturated calomel electrode by using FTO (TCO conductive glass) plated with a copper seed layer as a working electrode, a platinum rod as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrodeThen obtaining a sample, washing and vacuum drying the sample to obtain a copper nanosheet with FTO as a substrate, wherein the ratio of the volume of the solution I to the surface area of the FTO is 40-50 ml/cm2；
2) Loading the hole transport layer and the organic absorption layer on a metal framework of a copper nanosheet with the FTO as a substrate by adopting a spin coating method to obtain an organic photocathode;
2.1) putting the copper nanosheet with the FTO obtained in the step 1.2) as the substrate on a spin coater, dripping a CuI acetonitrile solution into the copper nanosheet, standing the copper nanosheet for 30 to 60 seconds, starting spin coating at the rotating speed of 2500 to 3000 r/min for 30 to 60 seconds, then putting the copper nanosheet into a vacuum drying oven for drying to obtain a photocathode I, wherein the concentration of the CuI acetonitrile solution is 5 to 15g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of the FTO is 5 to 25 mu L/cm2；
2.2) place the photocathode I on the spin coater again, drop P3HT (poly 3-hexylthiophene): PCBM ([6, 6 ]]-phenyl-C61-methyl butyrate), standing for 30-60 s, starting the first spin coating: the rotating speed is 600-800 r/min, the rotating time is 5-10 s, and then the spin coating is carried out for the second time: the rotating speed is 1500-2000 rpm, the rotating time is 50-100 s, after the spin coating is finished, the organic photocathode taking the copper nanosheet as a supporting framework is obtained by heating the organic photocathode for 15-30 min at 120-140 ℃ in the atmosphere of nitrogen protection, and the weight ratio of P3HT: the PCBM mixed solution is a P3HT PCBM o-dichlorobenzene solution, the total concentration of P3HT and PCBM is 25-35 mg/mL, the concentration ratio of P3HT to PCBM is 1: 0.8-1.2, the ratio of P3HT: the ratio of the dropping amount of the PCBM mixture to the surface area of the FTO is 75 to 100 μ L/cm2。
The organic photocathode with the copper nanosheets as the supporting framework is characterized in that polyethylene glycol 6000 is adopted, and the concentration of the polyethylene glycol 6000 in the solution II is 30-50 ppm.
The organic photocathode taking the copper nanosheet as the supporting framework is characterized in that the electrodeposition time in the step 1.2) is 30 min.
The organic photocathode with the copper nanosheets as the supporting framework is characterized in that in the preparation method, the concentration of the CuI acetonitrile solution in the step 2.1) is preferably 8-12 g/L, and the addition amount of the CuI acetonitrile solution and the surface area of FTO (fluorine-doped tin oxide) areThe ratio of the amount of the water to the amount of the water is 8 to 12 μ L/cm2(ii) a The concentration of the CuI acetonitrile solution is more preferably 10g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of FTO is more preferably 10 mu L/cm2。
The organic photocathode with copper nanosheets as supporting frameworks is characterized in that in the preparation method, in step 2.2), the P3HT: in the mixed liquid of PCBM, the total concentration of P3HT and PCBM is 28-32 mg/mL, the concentration ratio of P3HT to PCBM is 1: 0.95-1.05, more preferably the total concentration of P3HT and PCBM is 30mg/mL, and the concentration ratio of P3HT to PCBM is 1: 1.
The invention also provides a preparation method of the organic photocathode taking the copper nanosheet as the supporting framework, which is characterized by comprising the following steps of:
1) preparation of copper nanosheet by electrodeposition
1.1) adding soluble copper (II) salt, sodium hypophosphite, sodium citrate, boric acid and polyethylene glycol into deionized water, stirring to obtain a uniform copper salt solution, dropwise adding an alkaline aqueous solution into the copper salt solution, regulating the pH value of the solution to be 7.5-9.5, and stirring for 5-10 min to obtain a solution I, wherein the concentrations of the soluble copper (II) salt (calculated by copper (II), the sodium hypophosphite, the sodium citrate and the boric acid in the solution I are respectively 24-30 mmol/L, 240-300 mmol/L, 40-50 m mol/L and 32-50 mmol/L;
1.2) pouring the solution I obtained in the step 1.1) into an electrolytic tank, performing electrodeposition for 25-35 min under the voltage of-0.9V to-1.0V (vs. SCE) by using FTO (TCO conductive glass) plated with a copper seed layer as a working electrode, a platinum rod as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode to obtain a sample, washing and vacuum drying the sample to obtain a copper nanosheet with FTO as a substrate, wherein the ratio of the volume of the solution I to the surface area of the FTO is 40-50 ml/cm2；
2) Loading the hole transport layer and the organic absorption layer on a metal framework of a copper nanosheet with the FTO as a substrate by adopting a spin coating method to obtain an organic photocathode;
2.1) putting the copper nanosheet with the FTO obtained in the step 1.2) as the substrate on a spin coater, dripping a CuI acetonitrile solution, standing for 30-60 s, and then starting spin coating at the rotating speed of 2500-3000 r/min, the rotation time is 30-60 s, then the photocathode I is put into a vacuum drying oven for drying, the concentration of the CuI acetonitrile solution is 5-15 g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of FTO is 5-25 mu L/cm2；
2.2) place the photocathode I on the spin coater again, drop P3HT (poly 3-hexylthiophene): PCBM ([6, 6 ]]-phenyl-C61-methyl butyrate), standing for 30-60 s, starting the first spin coating: the rotating speed is 600-800 r/min, the rotating time is 5-10 s, and then the spin coating is carried out for the second time: the rotating speed is 1500-2000 rpm, the rotating time is 50-100 s, after the spin coating is finished, the organic photocathode taking the copper nanosheet as a supporting framework is obtained by placing the organic photocathode in a nitrogen atmosphere and heating the organic photocathode at 120-140 ℃ for 15-30 min, and the P3HT: the PCBM mixed solution is a P3HT PCBM o-dichlorobenzene solution, the total concentration of P3HT and PCBM is 25-35 mg/mL, the concentration ratio of P3HT to PCBM is 1: 0.8-1.2, the ratio of P3HT: the ratio of the dropping amount of the PCBM mixture to the surface area of the FTO is 75 to 100 μ L/cm2。
The preparation method is characterized in that the polyethylene glycol is polyethylene glycol 6000, and the concentration of the polyethylene glycol 6000 in the solution II is 30-50 ppm.
The preparation method is characterized in that the electrodeposition time in the step 1.2) is 30 min.
In the preparation method, the concentration of the CuI acetonitrile solution in the step 2.1) is preferably 8-12 g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of the FTO is 8-12 mu L/cm2(ii) a The concentration of the CuI acetonitrile solution is more preferably 10g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of FTO is more preferably 10 mu L/cm2。
In the preparation method, step 2.2) of the P3HT: in the mixed liquid of PCBM, the total concentration of P3HT and PCBM is 28-32 mg/mL, the concentration ratio of P3HT to PCBM is 1: 0.95-1.05, more preferably the total concentration of P3HT and PCBM is 30mg/mL, and the concentration ratio of P3HT to PCBM is 1: 1.
The invention provides an organic photocathode taking copper nano-sheets as a supporting framework and a preparation method thereof, which utilize the specific surface area characteristic of a metal framework of the copper nano-sheets with FTO as a substrate to load a hole transport layer and an organic absorption layer on the metal framework, and under the same test condition, the photocurrent of the photocathode is increased by two or three orders of magnitude compared with the photocurrent of the photocathode without a copper nano-sheet supporting structure, thereby effectively solving the defect of small photocurrent of an organic semiconductor, being capable of being connected with an inorganic semiconductor material in series, realizing a spontaneous photoelectrochemical cell and promoting the hydrogen production by decomposing water. In the scheme screening, the electrodeposition time has a significant influence on the performance of the finally obtained organic photocathode when the copper nanosheet with the FTO as the substrate is prepared by the electrodeposition method, the obtained copper nanosheet with the FTO as the substrate can show better performance after being further prepared into the organic photocathode only within the preferable electrodeposition time in the technical scheme of the invention, and the hydrogen production efficiency is higher when the copper nanosheet is used for producing hydrogen by using illumination to decompose water.
Drawings
Fig. 1 is an SEM image of copper nanoplates obtained in step 1) of the embodiment;
FIG. 2 is an XRD pattern of the copper nanosheet obtained in step 1) of the embodiment;
FIG. 3 is a SEM image of the cross section of the organic photocathode obtained in example 4.
Detailed Description
The model of the spin coater: KW-4A type desk type spin coater
A preparation method of an organic photocathode taking copper nanosheets as a supporting framework comprises the following steps:
1) preparing a copper nanosheet by adopting an electrodeposition method;
1.1) adding 3mmol of CuSO4·5H2O、30mmol NaH2PO2·H2O、5mmol Na3C6H5O7·2H2O、40mmol H3BO3Adding 5mg of polyethylene glycol 6000 into 100mL of deionized water, stirring for 30min to obtain a uniform copper salt solution, dropwise adding 1mol/L NaOH solution into the copper salt solution, regulating the pH of the solution to 8.5, and stirring for 5-10 min to obtain about 110mL of solution I;
1.2) pouring the solution I obtained in the step 1.1) into an electrolytic tank, carrying out electrodeposition under the voltage of-0.9V (vs SCE) by using FTO (1cm multiplied by 2cm) plated with a copper seed layer as a working electrode, a platinum rod as a counter electrode and a saturated calomel electrode as a reference electrode, depositing tmin to obtain a sample, washing the sample, and drying the sample at 65 ℃ in vacuum for 3 hours to obtain the copper nanosheet with the FTO as a substrate. A Scanning Electron Microscope (SEM) image of the copper nanoplates is shown in fig. 1, and an X-ray diffraction (XRD) image is shown in fig. 2.
2) And loading the hole transport layer and the organic absorption layer on the metal framework by adopting a spin coating method to obtain the photocathode.
2.1) putting the copper nanosheet with the FTO obtained in the step 1.2) as the substrate on a spin coater, dripping 20 mu L of CuI acetonitrile solution of 10g/L, standing for 30s, starting spin coating, wherein the rotation speed is 2500 rpm, the rotation time is 50s, and then putting the copper nanosheet into a vacuum drying oven to be dried for 20min at 130 ℃ to obtain a photocathode I.
2.2) the photocathode I is again placed on the spin coater, spin-coated in two steps, and 15mg/mL P3HT: PCBM mixed solution 180 mu L, standing for 60s, spin-coating for the first time: the rotating speed is 800 revolutions per minute, the rotating time is 10s, and the second spin coating: the rotating speed is 2000 rpm, the rotating time is 60s, and then the organic photocathode with the copper nanosheet as the supporting framework is obtained by placing the organic photocathode in the nitrogen atmosphere and heating the organic photocathode at 130 ℃ for 20 min.
Samples of examples 1 to 6 were obtained by changing the electrodeposition time t in step 1.2), and samples without electrodeposition (t ═ 0) were used as comparative examples, and the organic photocathode samples of comparative examples and examples 1 to 6 were tested in electrochemical workstations, respectively, by a three-electrode method, with the organic photocathode being a working electrode, a platinum rod being a counter electrode, an Ag/AgCl (3.5M KCl) electrode being a reference electrode, and an electrolyte being 0.5M Na2SO4(pH 6.8) solution. The relevant parameters and test results of the examples and comparative examples are shown in the following table:
Figure GDA0002930631740000051
the data show that when the electrodeposition time is 25-35 min (examples 3-5) through the optimized process, the photocurrent density reaches the maximum relative to the Reversible Hydrogen Electrode (RHE) at 0V, the difference between the photocurrent and the dark current is in positive correlation with the electron-hole pairs generated by the semiconductor under illumination, the larger the difference is, the more electron-hole pairs are generated, and the faster the hydrogen generation rate is when the organic photocathode is used for decomposing water into hydrogen through illumination, wherein example 4(t is 30min) is the optimal example, and the Scanning Electron Microscope (SEM) image of the organic photocathode obtained in example 4 is shown in fig. 3.
The above description has fully demonstrated the method for preparing an organic photocathode using copper nanosheets as the supporting framework, and it should be emphasized that it is obvious to those skilled in the art that modifications and touch-up can be made without departing from the scope of the claims of the present invention, and such modifications and touch-up also fall into the scope of the present invention.

Claims (10)

1. An organic photocathode taking copper nanosheets as a supporting framework is characterized in that the preparation method of the organic photocathode comprises the following steps:
1) preparation of copper nanosheet by electrodeposition
1.1) adding soluble copper (II) salt, sodium hypophosphite, sodium citrate, boric acid and polyethylene glycol into deionized water, stirring to obtain a uniform copper salt solution, dropwise adding an alkaline aqueous solution into the copper salt solution, regulating the pH value of the solution to be 7.5-9.5, and stirring for 5-10 min to obtain a solution I, wherein the concentrations of the soluble copper (II) salt, the sodium hypophosphite, the sodium citrate and the boric acid in the solution counted by copper (II) are respectively 24-30 mmol/L, 240-300 mmol/L, 40-50 mmol/L and 32-50 mmol/L;
1.2) pouring the solution I obtained in the step 1.1 into an electrolytic tank, performing electrodeposition for 25-35 min at a voltage of-0.9V to-1.0V relative to a saturated calomel electrode by using an FTO plated with a copper seed layer as a working electrode, a platinum rod as a counter electrode and the saturated calomel electrode as a reference electrode to obtain a sample, washing and vacuum drying the sample to obtain a copper nanosheet with the FTO as a substrate, wherein the ratio of the volume of the solution I to the surface area of the FTO is 40-50 ml/cm2；
2) Loading the hole transport layer and the organic absorption layer on a metal framework of a copper nanosheet with the FTO as a substrate by adopting a spin coating method to obtain an organic photocathode;
2.1) putting the copper nanosheet with the FTO obtained in the step 1.2) as the substrate on a spin coater, dripping a CuI acetonitrile solution into the copper nanosheet, standing the copper nanosheet for 30 to 60 seconds, starting spin coating at the rotating speed of 2500 to 3000 r/min for 30 to 60 seconds, then putting the copper nanosheet into a vacuum drying oven for drying to obtain a photocathode I, wherein the concentration of the CuI acetonitrile solution is 5 to 15g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of the FTO is 5 to 25 mu L/cm2；
2.2) place the photocathode I on the spin coater again, drop P3HT: PCBM mixed liquor is kept still for 30-60 s, and first spin coating is started: the rotating speed is 600-800 r/min, the rotating time is 5-10 s, and then the spin coating is carried out for the second time: the rotating speed is 1500-2000 rpm, the rotating time is 50-100 s, after the spin coating is finished, the organic photocathode taking the copper nanosheet as a supporting framework is obtained by heating the organic photocathode for 15-30 min at 120-140 ℃ in the atmosphere of nitrogen protection, and the weight ratio of P3HT: the PCBM mixed solution is a P3HT PCBM o-dichlorobenzene solution, the total concentration of P3HT and PCBM is 25-35 mg/mL, the concentration ratio of P3HT to PCBM is 1: 0.8-1.2, the ratio of P3HT: the ratio of the dropping amount of the PCBM mixture to the surface area of the FTO is 75 to 100 μ L/cm2(ii) a The P3HT is poly 3-hexylthiophene, and PCBM is [6, 6 ]]-phenyl-C61-butyric acid methyl ester.
2. The organic photocathode taking copper nanosheets as a supporting framework according to claim 1, wherein the polyethylene glycol is polyethylene glycol 6000, and the concentration of the polyethylene glycol 6000 in the solution I is 30-50 ppm.
3. The organic photocathode using copper nanosheets as a supporting framework according to claim 1 or 2, wherein in the preparation method, the concentration of the CuI acetonitrile solution in the step 2.1) is preferably 8-12 g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of the FTO is 8-12 μ L/cm2。
4. The organic photocathode taking copper nanosheets as a supporting framework according to claim 3, wherein in the preparation method, the CuI acetonitrile solution in the step 2.1)The concentration of the solution is 10g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of the FTO is 10 mu L/cm2。
5. The organic photocathode taking copper nanosheets as a supporting framework according to claim 1 or 2, wherein in the preparation method, step 2.2) of the P3HT: the total concentration of P3HT and PCBM in the PCBM mixed solution is 28-32 mg/mL, and the ratio of the concentration of P3HT and PCBM is 1: 0.95-1.05.
6. The organic photocathode taking copper nanosheets as a supporting framework according to claim 5, wherein in the preparation method, the total concentration of P3HT and PCBM in step 2.2) is 30mg/mL, and the ratio of the concentration of P3HT to the concentration of PCBM is 1: 1.
7. A preparation method of an organic photocathode taking copper nanosheets as a supporting framework is characterized by comprising the following steps:
1) preparation of copper nanosheet by electrodeposition
1.1) adding soluble copper (II) salt, sodium hypophosphite, sodium citrate, boric acid and polyethylene glycol into deionized water, stirring to obtain a uniform copper salt solution, dropwise adding an alkaline aqueous solution into the copper salt solution, regulating the pH value of the solution to be 7.5-9.5, and stirring for 5-10 min to obtain a solution I, wherein the concentrations of the soluble copper (II) salt, the sodium hypophosphite, the sodium citrate and the boric acid in the solution counted by copper (II) are respectively 24-30 mmol/L, 240-300 mmol/L, 40-50 mmol/L and 32-50 mmol/L;
1.2) pouring the solution I obtained in the step 1.1 into an electrolytic tank, performing electrodeposition for 25-35 min at a voltage of-0.9V to-1.0V relative to a saturated calomel electrode by using an FTO plated with a copper seed layer as a working electrode, a platinum rod as a counter electrode and the saturated calomel electrode as a reference electrode to obtain a sample, washing and vacuum drying the sample to obtain a copper nanosheet with the FTO as a substrate, wherein the ratio of the volume of the solution I to the surface area of the FTO is 40-50 ml/cm2；
2) Loading the hole transport layer and the organic absorption layer on a metal framework of a copper nanosheet with the FTO as a substrate by adopting a spin coating method to obtain an organic photocathode;
2.1) putting the copper nanosheet with the FTO obtained in the step 1.2) as the substrate on a spin coater, dripping a CuI acetonitrile solution into the copper nanosheet, standing the copper nanosheet for 30 to 60 seconds, starting spin coating at the rotating speed of 2500 to 3000 r/min for 30 to 60 seconds, then putting the copper nanosheet into a vacuum drying oven for drying to obtain a photocathode I, wherein the concentration of the CuI acetonitrile solution is 5 to 15g/L, and the ratio of the addition amount of the CuI acetonitrile solution to the surface area of the FTO is 5 to 25 mu L/cm2；
2.2) place the photocathode I on the spin coater again, drop P3HT: PCBM mixed liquor is kept still for 30-60 s, and first spin coating is started: the rotating speed is 600-800 r/min, the rotating time is 5-10 s, and then the spin coating is carried out for the second time: the rotating speed is 1500-2000 rpm, the rotating time is 50-100 s, after the spin coating is finished, the organic photocathode taking the copper nanosheet as a supporting framework is obtained by placing the organic photocathode in a nitrogen atmosphere and heating the organic photocathode at 120-140 ℃ for 15-30 min, and the P3HT: the PCBM mixed solution is a P3HT PCBM o-dichlorobenzene solution, the total concentration of P3HT and PCBM is 25-35 mg/mL, the concentration ratio of P3HT to PCBM is 1: 0.8-1.2, the ratio of P3HT: the ratio of the dropping amount of the PCBM mixture to the surface area of the FTO is 75 to 100 μ L/cm2The P3HT is poly 3-hexylthiophene, and PCBM is [6, 6 ]]-phenyl-C61-butyric acid methyl ester.
8. The method according to claim 7, wherein the polyethylene glycol is polyethylene glycol 6000, and the concentration of the polyethylene glycol 6000 in the solution II is 30 to 50 ppm.
9. The method according to claim 7 or 8, wherein the concentration of the CuI acetonitrile solution in the step 2.1) is preferably 8 to 12g/L, and the ratio of the amount of the CuI acetonitrile solution added to the surface area of the FTO is 8 to 12 μ L/cm2。
10. The process according to claim 7 or 8, wherein in step 2.2) the ratio of P3HT: the total concentration of P3HT and PCBM in the PCBM mixed solution is 28-32 mg/mL, and the ratio of the concentration of P3HT and PCBM is 1: 0.95-1.05.
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