A wide band gap organic-inorganic hybrid perovskite battery module driven under indoor light for degrading organic pollutants

Abstract

The present application relates to the technical field of solar cells, in particular to a wide-bandgap organic-inorganic hybrid perovskite battery module for driving degradation of organic pollutants under indoor light. The structure of the wide-bandgap organic-inorganic hybrid perovskite battery module is n-i-p type or p-i-n type, which is formed by laser scribing P1-P2-P3 of single cells in series. The wide-bandgap organic-inorganic hybrid perovskite battery module comprises a wide-bandgap perovskite thin film light absorption layer, which is prepared by spin-coating a PbI2 precursor solution on the surface of an n-type electron transport layer or a p-type electron transport layer and then annealing 1, and spin-coating a perovskite precursor solution and annealing 2. The perovskite solar cell module has good visible light utilization rate, and even under the condition of indoor weak light illumination with a color temperature of 3000K and an illumination of 1000lux, it still has high photoelectric conversion efficiency. The photovoltaic-driven catalytic degradation of organic pollutants system has excellent organic pollutant degradation effect.

Description

Technical Field

[0001] This invention relates to the field of solar cell technology, and in particular to a wide-bandgap organic-inorganic hybrid perovskite solar cell module that degrades organic pollutants under indoor light. Background Technology

[0002] Drinking water safety is a critical global issue. Organic pollutants enter the ecosystem through the discharge of domestic, industrial, and medical wastewater. These pollutants are toxic and reduce dissolved oxygen levels in water bodies, causing severe water pollution. Photocatalysts, often in powder form, are introduced into water bodies. Under light irradiation, they generate photogenerated electron-hole pairs. These electrons and holes react with oxygen and water to produce a large number of superoxide radicals. Superoxide radicals are strong oxidants and can oxidize and degrade organic pollutants in water.

[0003] However, traditional photocatalysts suffer from problems such as rapid recombination of photogenerated electrons and holes, making it difficult to recover the powder after it enters water bodies. By applying an external voltage, the high-efficiency separation of photogenerated electron-hole pairs can be achieved, significantly improving the catalytic degradation efficiency of organic pollutants. In traditional photoelectrocatalytic systems, the power supply is mostly an external DC power source, which imposes high requirements on power system transmission and environmental conditions in practical applications, hindering industrial production and practical applications, and limiting the further development and promotion of photoelectrocatalytic technology. Summary of the Invention

[0004] In view of this, the present invention provides a wide-bandgap organic-inorganic hybrid perovskite battery module for indoor light-driven degradation of organic pollutants.

[0005] To achieve the above objectives, the present invention provides the following solution:

[0006] One of the technical solutions of this invention is a wide-bandgap organic-inorganic hybrid perovskite battery module for indoor light-driven degradation of organic pollutants. The module has a nip-type or pin-type structure and is composed of single cells connected in series by laser scribing lines P1-P2-P3.

[0007] When the structure of the wide-bandgap organic-inorganic hybrid perovskite solar cell module is nip type, it includes, from bottom to top, a conductive substrate, an n-type electron transport layer, a wide-bandgap perovskite thin film light absorption layer, a p-type hole transport layer, and a metal back electrode.

[0008] When the structure of the wide-bandgap organic-inorganic hybrid perovskite solar cell module is pin-type, it includes, from bottom to top, a conductive substrate, a p-type hole transport layer, a wide-bandgap perovskite thin film light absorption layer, an n-type electron transport layer, and a metal back electrode.

[0009] When the structure of the wide-bandgap organic-inorganic hybrid perovskite solar cell module is nip-type or pin-type, the preparation method of the wide-bandgap perovskite thin film light-absorbing layer includes the following steps:

[0010] After spin-coating a PbI2 precursor solution onto the surface of an n-type electron transport layer or a p-type hole transport layer and annealing for 1, a perovskite precursor solution is spin-coated and annealed for 2 to obtain a wide-bandgap perovskite thin film light-absorbing layer.

[0011] In a preferred embodiment of the present invention, the PbI2 precursor solution is prepared by dissolving PbI2 and PbBr2 in a DMF / DMSO mixed organic solvent; the concentration of PbI2 in the PbI2 precursor solution is 1.4 mol / L; the mass ratio of PbI2 to PbBr2 is 7:3; the volume ratio of DMF:DMSO is 9:3; and the annealing conditions are set as follows: annealing at 50-80°C for 1 minute.

[0012] In a preferred embodiment of the present invention, the perovskite precursor solution is prepared by dissolving CH(NH2)2I, CH3NH3Br and CH3NH3Cl in an organic solvent (isopropanol); the mass-to-volume ratio of CH(NH2)2I, CH3NH3Br, CH3NH3Cl to the organic solvent is 77mg:9.4mg:6.8mg:1ml; the annealing conditions for the second annealing are set as follows: annealing at 120-180℃ for 10-20 minutes.

[0013] When the structure of the wide-bandgap organic-inorganic hybrid perovskite solar cell module is nip or pin type, the conductive substrate includes, but is not limited to, indium tin oxide (ITO) or fluorine-doped indium tin oxide (FTO).

[0014] In a preferred embodiment of the present invention, the thickness of the wide-bandgap perovskite thin film light-absorbing layer is 400 nm.

[0015] In a preferred embodiment of the present invention, when the structure of the wide-bandgap organic-inorganic hybrid perovskite battery module is nip-type, the n-type electron transport layer is an n-type semiconductor material layer with a thickness of 15 nm, and the n-type semiconductor material is at least one of titanium oxide (TiO2), tin oxide (SnO2), zinc oxide (ZnO), vanadium oxide (V2O5), and zinc tin oxide (Zn2SnO4); the p-type hole transport layer is a Spiro-OMeTAD hole transport layer with a thickness of 100 nm, and the metal back electrode is an Ag back electrode with a thickness of 100 nm;

[0016] In a preferred embodiment of the present invention, when the structure of the wide-bandgap organic-inorganic hybrid perovskite battery module is pin-type, the p-type hole transport layer is a 15nm thick p-type semiconductor material layer, the p-type semiconductor material is poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), and the n-type electron transport layer is a 22nm thick C 60 Electron transport layer; the metal back electrode is a 100nm thick Ag back electrode;

[0017] The second technical solution of this invention is a photovoltaic-driven catalytic degradation system for organic pollutants, comprising a light source, a power supply, a photoanode material, and a counter electrode; wherein, the light source can be sunlight or an LED lamp with a color temperature of 3000K and an illuminance of 1000 lux; the power supply is the aforementioned wide-bandgap organic-inorganic hybrid perovskite battery module; the photoanode material is a WSe2@WS2 composite photoanode material; and the counter electrode is a Pt electrode.

[0018] The wide-bandgap organic-inorganic hybrid perovskite solar cell module of this invention serves as a power source. Its operation is based on the photovoltaic effect of semiconductors. Under illumination, valence band electrons in the emitter, barrier, and base regions of the perovskite material absorb the energy of incident photons and transition to the conduction band, thereby generating electron-hole pairs. When the perovskite layer is illuminated, internal excitons separate to generate electron-hole pairs. Electrons are led out through the electron transport layer, and holes are led out through the hole transport layer. When a photoanode material and a counter electrode are connected to the device, a complete circuit can be formed.

[0019] In this invention, the photoanode material is connected to the power source via a wire.

[0020] In a preferred embodiment of the present invention, the preparation method of the WSe2@WS2 composite photoanode material includes the following steps:

[0021] A sulfur source is coated onto the surface of a tungsten wire mesh and then calcined to obtain WS2 / W material;

[0022] After cleaning and drying, the WS2 / W material was placed in a boat, and its surface was coated with a selenium source. The mixture was then calcined for 2 days to obtain the WSe2@WS2 composite photoanode material.

[0023] In a preferred embodiment of the present invention, the sulfur source is sulfur powder, and the mass-to-area ratio of the sulfur source to the tungsten wire mesh is 10 mg / cm². 2 The selenium source is selenium powder; the mass-to-area ratio of the selenium source to the tungsten wire mesh is 5 mg / cm². 2The conditions for calcination 1 are set as follows: under an inert atmosphere, the temperature is increased to 800-900℃ at a heating rate of 10℃ / min, and then held for calcination for 2-4 hours; the conditions for calcination 2 are set as follows: under an inert atmosphere, the temperature is increased to 700-750℃ at a heating rate of 10℃ / min, and then held for calcination for 2-4 hours.

[0024] The third technical solution of this invention is the application of the aforementioned wide-bandgap organic-inorganic hybrid perovskite solar cell module, or the aforementioned photovoltaic-driven catalytic degradation system for organic pollutants, in the photoelectrocatalytic degradation of organic pollutants. The organic pollutant is Rhodamine B.

[0025] The photovoltaic-driven catalytic degradation system for organic pollutants of this invention has the advantages of being green and environmentally friendly, recyclable, not generating toxic byproducts, and capable of self-purification. It also has low energy consumption, mild reaction conditions, wide applicability, and can reduce secondary pollution.

[0026] The photoanode material of this invention, upon photoexcitation, generates photogenerated electron-hole pairs within the material. Since the conduction band (CB) energy of WSe2 is higher than that of WS2, when WSe2 is selectively excited with appropriately energetic light, electrons in WSe2 will transfer from the conduction band of WSe2 to the conduction band of WS2. This process is achieved through interlayer electronic state hybridization, providing a rapid channel for electron transfer and enabling efficient separation of photogenerated carrier-hole pairs. A large number of reactive oxygen species are generated on the photoanode surface. These reactive oxygen species possess strong oxidizing properties and can effectively oxidize and decompose organic pollutants in water.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] 1. The wide-bandgap perovskite solar cell module designed in this invention has excellent visible light utilization, maintaining high photoelectric conversion efficiency even under low-light indoor lighting conditions with a color temperature of 3000K and an illuminance of 1000 lux. Compared to traditional DC power supplies, it offers environmental flexibility, eliminating the need for circuit installation and power maintenance, thus reducing the manufacturing cost for industrial mass production.

[0029] 2. The photovoltaic-driven catalytic degradation system for organic pollutants of the present invention has excellent degradation effect on organic pollutants and can quickly and effectively degrade organic pollutants represented by Rhodamine B.

[0030] 3. The photoanode material used in the photovoltaic-driven catalytic degradation system for organic pollutants of the present invention can be recycled directly after use by rinsing with deionized water and drying. In the present invention, three repeated recycling experiments were conducted, and the catalytic performance of the system for degrading organic pollutants did not change significantly. This overcomes the disadvantage that traditional photocatalytic nanomaterials cannot be recycled and is more environmentally friendly than ordinary photocatalytic nanomaterials. Attached Figure Description

[0031] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0032] Figure 1 This is a schematic diagram of the photoelectrocatalytic system driven by a wide-bandgap perovskite solar cell module under indoor light, as shown in Embodiment 1 of the present invention.

[0033] Figure 2 The images show SEM planar and cross-sectional views (a, b) of the wide-bandgap perovskite thin film obtained in Example 1 of the present invention, SEM surface morphology images (c, d) of the prepared photoanode material, and scanned images (e, f) of the WSe2 photoanode material used in Comparative Example 1 and Comparative Example 2.

[0034] Figure 3 The JV curve of the wide-bandgap perovskite solar cell module obtained in Example 1 of the present invention under LED lighting conditions of 3000K and 1000lux.

[0035] Figure 4 This is a comparison image of the XRD pattern of the WSe2@WS2 photoanode material obtained in Example 1 of this invention with that of a standard card;

[0036] Figure 5 The above are time-concentration relationship graphs for the degradation of the target pollutant Rhodamine B in aqueous solution in Examples 1-4 and Comparative Examples 1-2 of the present invention.

[0037] Figure 6 The photovoltaic-driven catalytic degradation system for organic pollutants obtained in Example 1 of this invention is applied to the degradation of Rhodamine B, and the ultraviolet-visible absorption spectrum changes over time.

[0038] Figure 7 The graph shows the degradation efficiency of the photovoltaic-driven catalytic degradation system for organic pollutants obtained in Example 1 of this invention after photoelectrocatalytic treatment, recovery of the photoanode material, rinsing with deionized water and re-drying, and repeated catalytic experiments. Detailed Implementation

[0039] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0040] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0041] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar to or equivalent to those described herein may be used in the implementation or testing of this invention.

[0042] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0043] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0044] Unless otherwise specified, "room temperature" in this invention refers to 20–30°C.

[0045] The photovoltaic-driven catalytic degradation system for organic pollutants of this invention can make multiple uses of indoor visible lighting, has good photoelectric conversion capability, and is low in manufacturing cost. It can be applied under both strong outdoor light and weak indoor light conditions. It exhibits excellent pollutant degradation performance, achieving effective and rapid degradation of Rhodamine B within 120 minutes, and also demonstrates good recovery performance.

[0046] Unless otherwise specified, the technical solutions described in this invention are all conventional solutions in the field, and the reagents or raw materials used are all purchased from commercial channels or are publicly available unless otherwise specified.

[0047] The tungsten wire mesh used in this embodiment of the invention is a 1000-mesh single-material tungsten wire mesh with an effective area of ​​1cm*2cm and a wire diameter of 0.05mm. 2 .

[0048] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0049] Example 1

[0050] Fabrication of a nip-type wide-bandgap perovskite solar cell module:

[0051] Step 1: Using a PV-HL030 laser scribing tool and P1 laser etching technology, multiple parallel sub-cells are connected in series. This connection method helps to improve the module's output voltage, while ensuring that the module's photocurrent is consistent with that of each sub-cell. The conductive layer of the transparent conductive substrate is etched using P1 etching. After P1 processing, the conductive layer on the large-area substrate is divided into a series of parallel, independent sub-cell conductive substrates.

[0052] Step 2: Soak the ITO conductive glass substrate in detergent, deionized water, isopropanol and anhydrous ethanol in sequence, then dry it in a 60°C oven. Finally, place the cleaned conductive glass substrate in an ultraviolet-ozone generator for 50 minutes to improve the surface wettability of the conductive glass substrate and reduce defects.

[0053] Step 3: Prepare the electron transport layer using spin coating. Prepare the electron transport layer stock solution by mixing a 15% (w / w) tin dioxide pentahydrate solution with deionized water at a volume ratio of 1:4. Place the transparent conductive substrate, treated with ozone for 15 minutes, onto the spin coater, adding 110 μl drop by drop. Adjust the spin coater speed to 3800 rpm to ensure the formation of a dense SnO2 layer of suitable thickness. After spin coating, anneal at 150°C for 40 minutes to obtain an electron transport layer with a thickness of 15 nm.

[0054] Step 4: Based on Step 3, a two-step spin-coating method is used to prepare the perovskite layer. The entire operation is carried out under a nitrogen atmosphere. PbI2 powder and PbBr2 powder are weighed and mixed at a mass ratio of 7:3, then dissolved in 2 ml of a DMF / DMSO mixed organic solvent (DMF:DMSO volume ratio = 9:3) to prepare a 1.4 mol / L PbI2 precursor solution. 77 mg of CH(NH2)2I (FAI), 9.4 mg of CH3NH3Br (MABr), and 6.8 mg of CH3NH3Cl (MACl) are weighed and dissolved in 1 ml of isopropanol solution to prepare the perovskite precursor solution.

[0055] Step 5: Place the substrate on a spin coater, add 70 μl of PbI2 precursor solution, and spin at 1500 rpm for 20 seconds. After spin coating, place it on a 70°C hot plate for annealing for 1 minute.

[0056] Step 6: Place the sample obtained in Step 5 on a spin coater, add 100 μl of perovskite precursor solution, and spin at 2000 rpm for 20 seconds. After spin coating, place it on a 150°C heating plate for annealing for 20 minutes to prepare a wide-bandgap perovskite thin film light-absorbing layer with a thickness of 400 nm.

[0057] Step 7: Weigh 71 mg Spiro-OMeTAD, 27 μl Li-TFSI, 35.6 μl TBP solution, 28.5 μl FK209, and 1 ml chlorobenzene into a 3 ml glass bottle to prepare the Spiro-OMeTAD hole transport layer solution. Use a pipette to measure 50 μl of the Spiro-OMeTAD solution and dynamically spin-coat the solution onto a perovskite film to prepare a hole transport layer with a thickness of approximately 100 nm.

[0058] Step 8: Using a PV-HL030 laser scribing tool and P2 laser etching technology, the transport layer and perovskite active layer of the device prepared in step 7 are etched down to the transparent substrate conductive layer to form a series channel between adjacent sub-cells.

[0059] Step 9: Using thermal evaporation deposition, a 100 nm thick Ag layer is deposited at a rate of 0.5 Å / s as the back electrode.

[0060] Step 10: Using a PV-HL030 laser scribing tool and P3 laser etching technology, the functional layers (transport layer, active layer, and electrode layer) of the wide-bandgap perovskite solar cell prepared in Step 9 are etched to separate the sub-cells, resulting in a complete tandem perovskite solar cell module with an area of ​​5×5cm. 2 .

[0061] Preparation of WSe2@WS2 composite photoanode material:

[0062] Step 11: Cut a tungsten wire mesh with an area of ​​1cm × 2cm, soak it in 30ml of anhydrous ethanol for 20 minutes to remove any oxide layer that may exist on the surface of the tungsten wire mesh, and then dry it with nitrogen gas for later use.

[0063] Step 12: Place 40 mg of sulfur powder and the cleaned and dried tungsten wire mesh together in the reaction boat. Place the reaction boat in the center of the tube furnace and purge the quartz tube of the tube furnace with a high flow rate of argon for 5 minutes. Raise the temperature to 850°C at a heating rate of 10°C / min and hold for 2 hours to obtain WS2 / W material.

[0064] The WS2 / W material was removed, cleaned, and vacuum dried. 20 mg of selenium powder was added to coat the sample surface. The sample was then placed in a tube furnace and heated to 750 °C at a rate of 10 °C / min, and held at that temperature for 2 hours.

[0065] Step 13: After calcination, control the cooling rate to be no more than 10℃ / min, cool to room temperature, take out the sample and wash it with deionized water, and vacuum dry it at 60℃ for 6 hours to obtain WSe2@WS2 composite photoanode material.

[0066] Under weak light conditions with an LED lamp at a color temperature of 3000K and an illuminance of 1000 lux as the light source, the prepared wide-bandgap perovskite solar cell module was used as the photoelectrocatalytic power source, and the prepared WSe2@WS2 composite photoanode material and Pt electrode were used as the counter electrode to carry out photoelectrocatalytic degradation of the organic pollutant Rhodamine B at a concentration of 10 mg / L (using PBS buffer solution as the simulated environment).

[0067] Example 2

[0068] Fabrication of pin-type wide-bandgap perovskite solar cell modules:

[0069] Step 1: Same as Step 1 in Example 1.

[0070] Step 2 is the same as step 2 in Example 1.

[0071] Step 3: Dissolve 631 mg of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) in 2 ml of chlorobenzene, drop the PTAA solution onto a glass substrate, rotate it at 2000 rpm for 20 s, and then anneal the sample at 120 °C for 10 minutes to prepare a PTAA layer of about 20 nm as a p-type transport layer.

[0072] Steps 4 to 6 are the same as steps 4 to 6 in Example 1.

[0073] Step 7, perform C coating using a high-vacuum evaporation coating machine. 60 In the preparation of the thin film layer, the vacuum level of the evaporation space is reduced to below 10 Pa using a mechanical pump, and a high vacuum environment is achieved using a secondary molecular pump, resulting in a vacuum level of 5 × 10⁻⁶ Pa in the evaporation space. -3 When Pa is below, 22 nm C is deposited at a rate of 0.5 Å / s. 60 Thin film, as an n-type transport layer.

[0074] Step 8: Using thermal evaporation deposition, a BCP layer with a thickness of 7 nm is deposited at a rate of 0.2 Å / s as a buffer layer.

[0075] Step 9: Using thermal evaporation deposition, a 100 nm thick Ag layer is deposited at a rate of 0.5 Å / s as the back electrode.

[0076] Under weak light conditions with an LED lamp at a color temperature of 3000K and an illuminance of 1000 lux as the light source, the prepared pin-type wide-bandgap perovskite solar cell module was used as the photoelectrocatalytic power source, the WSe2@WS2 composite photoanode material (prepared in the same way as in Example 1) was used as the photoanode material, and the Pt electrode was used as the counter electrode to degrade the organic pollutant Rhodamine B.

[0077] Example 3

[0078] Fabrication of conventional bandgap perovskite solar cell modules using nip-type technology:

[0079] Step 1: Same as Step 1 in Example 1.

[0080] Step 2 is the same as step 2 in Example 1.

[0081] Step 3 is the same as step 3 in Example 1.

[0082] Step 4: Based on Step 3, a two-step spin-coating method is used to prepare the perovskite layer. The entire operation is carried out under a nitrogen atmosphere. PbI2 powder is weighed and dissolved in a DMF / DMSO mixed organic solvent (DMF:DMSO volume ratio = 9:3) to prepare a 1.4 mol / L PbI2 precursor solution. 77 mg of CH(NH2)2I (FAI) and 6.8 mg of CH3NH3Cl (MACl) are weighed and dissolved in 1 ml of isopropanol solution to prepare the perovskite precursor solution.

[0083] Step 5: Place the substrate on a spin coater, add 70 μl of PbI2 precursor solution, and spin at 1500 rpm for 20 seconds. After spin coating, place it on a 70°C hot plate for annealing for 1 minute.

[0084] Step 6: Place the sample obtained in Step 5 on a spin coater, add 100 μl of perovskite precursor solution, and spin at 2000 rpm for 20 seconds. After spin coating, place it on a 150°C heating plate for annealing for 20 minutes to prepare a conventional bandgap perovskite thin film light-absorbing layer with a thickness of 400 nm.

[0085] Step 7 is the same as step 7 in Example 1.

[0086] Step 8 is the same as step 8 in Example 1.

[0087] Step 9 is the same as step 9 in Example 1.

[0088] Step 10 is the same as step 10 in Example 1.

[0089] Under weak light conditions with an LED lamp of 3000K color temperature and 1000 lux as the light source, the prepared conventional bandgap perovskite solar cell module was used as the photoelectrocatalytic power source, the WSe2@WS2 composite photoanode material (prepared in the same way as in Example 1) was used as the photoanode material, and the Pt electrode was used as the counter electrode to photoelectrocatalytically degrade the organic pollutant Rhodamine B.

[0090] Example 4

[0091] Fabrication of pin-type conventional bandgap perovskite solar cell modules:

[0092] Step 1: Same as Step 1 in Example 3.

[0093] Step 2 is the same as step 2 in Example 3.

[0094] Step 3: Dissolve 631 mg of poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA) in 2 ml of chlorobenzene, drop the PTAA solution onto a glass substrate, rotate it at 2000 rpm for 20 s, and then anneal the sample at 120 °C for 10 minutes to prepare a PTAA layer of about 20 nm as a p-type transport layer.

[0095] Steps 4 to 6 are the same as steps 4 to 6 in Example 3.

[0096] Step 7, perform C coating using a high-vacuum evaporation coating machine. 60 In the preparation of the thin film layer, the vacuum level of the evaporation space is reduced to below 10 Pa using a mechanical pump, and a high vacuum environment is achieved using a secondary molecular pump, resulting in a vacuum level of 5 × 10⁻⁶ Pa in the evaporation space. -3 When Pa is below, 22 nm C is deposited at a rate of 0.5 Å / s. 60 Thin film, as an n-type transport layer.

[0097] Step 8: Using thermal evaporation deposition, a BCP layer with a thickness of 7 nm is deposited at a rate of 0.2 Å / s as a buffer layer.

[0098] Step 9: Using thermal evaporation deposition, a 100 nm thick Ag layer is deposited at a rate of 0.5 Å / s as the back electrode.

[0099] Under weak light conditions with an LED lamp at a color temperature of 3000K and an illuminance of 1000 lux as the light source, the prepared pin-type conventional bandgap perovskite solar cell module was used as the photoelectrocatalytic power source, the WSe2@WS2 composite photoanode material (prepared in the same way as in Example 1) was used as the photoanode material, and the Pt electrode was used as the counter electrode to degrade the organic pollutant Rhodamine B.

[0100] Comparative Example 1

[0101] The only difference from Example 1 is that the preparation of the WSe2@WS2 composite photoanode material is omitted, and WS2 / W is used as the WS2 photoanode material.

[0102] The preparation method of WS2 / W as a photoanode material includes the following steps:

[0103] A 1cm × 2cm tungsten wire mesh was cut and soaked in 30ml of anhydrous ethanol for 20 minutes to remove any possible oxide layer on the surface. It was then dried with nitrogen. 40mg of sulfur powder was placed together with the cleaned and dried tungsten wire mesh in a reaction boat. The reaction boat was placed in the center of a tube furnace, and the quartz tube of the furnace was purged with a high flow rate of argon for 5 minutes. The temperature was increased to 850℃ at a rate of 10℃ / min and held for 2 hours to obtain the WS2 / W material.

[0104] Comparative Example 2

[0105] The only difference from Example 2 is that the preparation of the WSe2@WS2 composite photoanode material is omitted, and WSe2 / W is used as the WSe2 photoanode material.

[0106] The preparation method of WSe2 photoanode material is as follows:

[0107] A 1cm × 2cm tungsten wire mesh was cut and soaked in 30ml of anhydrous ethanol for 20 minutes to remove any possible oxide layer on the surface. It was then dried with nitrogen. 20mg of selenium powder was placed together with the cleaned and dried tungsten wire mesh in a reaction boat. The reaction boat was placed in the center of a tube furnace, and the quartz tube of the furnace was purged with a high flow rate of argon for 5 minutes. The temperature was increased to 750℃ at a rate of 10℃ / min and held for 2 hours to obtain the WSe2 / W material.

[0108] Figure 1 This is a schematic diagram of the system for driving the catalytic degradation of organic pollutants using a wide-bandgap perovskite solar cell, as obtained in Example 1 of the present invention.

[0109] Figure 2 The images show SEM planar and cross-sectional views (a, b) of the wide-bandgap perovskite thin film obtained in Example 1 of this invention, SEM surface morphology images (c, d) of the prepared photoanode material, and scanned images (e, f) of the WS2 and WSe2 photoanode materials used in Comparative Examples 1 and 2. Figure 2 As can be observed in a and b, the perovskite film obtained in Example 1 is dense and has uniform crystal growth, which is beneficial for electron transport and enhances its photoelectric conversion efficiency. Figure 2 In images c and d, it can be observed that the WSe2@WS2 photoanode material exhibits a densely stacked layered structure, which facilitates rapid electron conduction. Figure 2 In the middle e and f, linear growth is observed, and the growth is relatively sparse.

[0110] Figure 3The JV curve of the wide-bandgap perovskite solar cell module obtained in Example 1 of the present invention was measured under weak light conditions with an LED lamp as the light source at a color temperature of 3000K and an illuminance of 1000 lux. Its photoelectric conversion efficiency can reach 31.9%, the fill factor is 76%, and the open-circuit voltage can reach 6.7V, which shows good photoelectric conversion efficiency.

[0111] Figure 4 The XRD pattern of the WSe2@WS2 composite photoanode material obtained in Example 1 of this invention is compared with that of the standard card. The characteristic peaks at 40.3°, 58.4° and 73.3° in the XRD pattern of this material correspond to the standard card of elemental tungsten (PDF#00-001-1203), monoclinic WS2 (PDF#00-071-4832) and hexagonal WSe2 (PDF#04-004-4470), which proves the successful synthesis of WSe2@WS2.

[0112] The degradation test was conducted using the perovskite solar cell modules obtained in Examples 1, 2, 3, and 4 of this invention as the power source, and simultaneously using WSe2@WS2 as described in the examples and WSe2 as described in Comparative Examples 1 and 2 as the photoanode material, with a Pt electrode as a dual-electrode system. The light source was an indoor LED lamp with a color temperature of 3000K and an illuminance of 1000 lux. Before the degradation test, 100 ml of Rhodamine B solution (concentration of 10 mg / L) and a magnetic stir bar were added to a transparent beaker as the reaction vessel. The electrodes (photoanode exposed area of ​​2 cm²) were assembled in the device. 2 The solution was stirred with a magnetic rotor for 20 minutes in a dark, current-free environment, after which illumination was introduced and timed to begin PEC catalysis. Initially, after 20 minutes in the dark, and every 10 minutes after the start of PEC catalysis, 1000 μl of the solution and 2000 μl of deionized water were pipetted into a quartz cuvette and thoroughly mixed. The absorption spectrum of the cuvette solution in the 500-600 nm wavelength range was measured using a Shimadzu UV-Vis spectrophotometer (model UV-1800), and the concentration of Rhodamine B in the sample was determined by the absorbance at 554 nm.

[0113] Depend on Figure 5 The comparison shows that the nip and pin type wide-bandgap perovskite solar cell modules obtained in Example 1 and Example 2, with WSe2@WS2 as the photoanode material and Pt electrode as the counter electrode, effectively degraded Rhodamine B within 120 minutes; the degradation rate of Rhodamine B reached 100% at 120 minutes.

[0114] In Examples 3 and 4, the conventional bandgap perovskite solar cell modules used have good photoelectric conversion efficiency under strong light conditions due to their narrow bandgap. However, under weak light conditions indoors, they are difficult to effectively utilize light energy, resulting in reduced degradation capacity and low degradation efficiency.

[0115] Comparing Examples 1 and 2 with Comparative Examples 1 and 2 reveals that, under low-light conditions, all used wide-bandgap perovskite solar cell modules as the power source. However, the photoanode materials selected in Examples 1 and 2 differed from those in Comparative Examples 1 and 2. Examples 1 and 2 used WSe2@WS2 as the photoanode material, while Comparative Examples 1 and 2 used WSe2. Under the same illumination environment and power source selection, Examples 1 and 2 exhibited significantly greater degradation capabilities for Rhodamine B than Comparative Examples 1 and 2. This is because the photogenerated electron-hole pairs generated by WSe2 in Comparative Examples 1 and 2 recombine rapidly, failing to produce a large number of reactive oxygen species, ultimately leading to a significant decrease in the degradation capability for organic pollutants.

[0116] Figure 6 The graph shows the changes in the UV-Vis absorption spectra of the organic pollutant Rhodamine B aqueous solution before and after the photoelectrocatalytic treatment reaction in Example 1 of this invention. As can be seen from the graph, the UV-Vis absorption peak gradually decreases with increasing degradation time, proving that the Rhodamine B solution has been effectively degraded. A slight blue shift is observed in the absorption peak, which corresponds to the absorption wavelength of its intermediate degradation products. Rhodamine B can ultimately be further mineralized into CO2 and water.

[0117] Figure 7 The graph shows the degradation efficiency of the photoanode material after photoelectrocatalytic treatment in Example 1 of this invention, followed by rinsing with deionized water and re-drying. The graph shows that the photoelectrocatalytic system still has good photoelectrocatalytic effect after being reused three times, proving that the system has good repeatability and recyclability, is environmentally friendly, and meets the requirements of green development.

[0118] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A photovoltaic-driven catalytic degradation system for organic pollutants, characterized in that, It includes a light source, a power supply, a photoanode material, and a counter electrode; wherein, the light source is an AM 1.5G solar simulator or an indoor low-light LED light; the power supply is a wide-bandgap organic-inorganic hybrid perovskite battery module; the photoanode material is a WSe2@WS2 composite photoanode material; and the counter electrode is a Pt electrode. The structure of the wide-bandgap organic-inorganic hybrid perovskite battery module is nip-type or pin-type, and is formed by connecting single cells in series by laser scribing P1-P2-P3. When the structure of the wide-bandgap organic-inorganic hybrid perovskite solar cell module is nip type, it includes, from bottom to top, a conductive substrate, an n-type electron transport layer, a wide-bandgap perovskite thin film light absorption layer, a p-type hole transport layer, and a metal back electrode. When the structure of the wide-bandgap organic-inorganic hybrid perovskite solar cell module is pin-type, it includes, from bottom to top, a conductive substrate, a p-type hole transport layer, a wide-bandgap perovskite thin film light absorption layer, an n-type electron transport layer, and a metal back electrode. When the structure of the wide-bandgap organic-inorganic hybrid perovskite solar cell module is nip-type or pin-type, the preparation method of the wide-bandgap perovskite thin film light-absorbing layer includes the following steps: After spin-coating a PbI2 precursor solution onto the surface of an n-type electron transport layer or a p-type hole transport layer and annealing for 1, a perovskite precursor solution is then spin-coated and annealed for 2 to obtain a wide-bandgap perovskite thin film light-absorbing layer. The preparation method of WSe2@WS2 composite photoanode material includes the following steps: A sulfur source was coated onto the surface of a tungsten wire mesh and calcined to obtain WS2 / W material; After cleaning and drying the WS2 / W material with nitrogen, it was placed in a boat, and its surface was coated with a selenium source. The mixture was then calcined for 2 days to obtain the WSe2@WS2 composite photoanode material. The sulfur source is sulfur powder, and the mass-to-area ratio of the sulfur source to the tungsten wire mesh is 10 mg / cm². 2 The selenium source is selenium powder; the mass-to-area ratio of the selenium source to the tungsten wire mesh is 5 mg / cm². 2 The conditions for calcination 1 are set as follows: under an inert atmosphere, the temperature is increased to 800-900℃ at a heating rate of 10℃ / min and held for 2-4 hours; the conditions for calcination 2 are set as follows: under an inert atmosphere, the temperature is increased to 700-750℃ at a heating rate of 10℃ / min and held for 2-4 hours.

2. The photovoltaic-driven catalytic degradation system for organic pollutants according to claim 1, characterized in that, The PbI2 precursor solution was prepared by dissolving PbI2 and PbBr2 in a DMF / DMSO mixed organic solvent; the concentration of PbI2 in the PbI2 precursor solution was 1.4 mol / L; the mass ratio of PbI2 to PbBr2 was 7:3; the volume ratio of DMF:DMSO was 9:3; the annealing conditions were set as follows: annealing at 50-80℃ for 1 minute.

3. The photovoltaic-driven catalytic degradation system for organic pollutants according to claim 1, characterized in that, The perovskite precursor solution was prepared by dissolving CH(NH2)2I, CH3NH3Br and CH3NH3Cl in an organic solvent; the mass-to-volume ratio of CH(NH2)2I, CH3NH3Br, CH3NH3Cl to the organic solvent was 77 mg:9.4 mg:6.8 mg:1 ml; the annealing conditions for the second annealing were set as follows: annealing at 120–180 °C for 10–20 minutes.

4. The photovoltaic-driven catalytic degradation system for organic pollutants according to claim 1, characterized in that, The thickness of the wide-bandgap perovskite thin film light-absorbing layer is 400 nm.

5. The photovoltaic-driven catalytic degradation system for organic pollutants according to claim 1, characterized in that, When the structure of the wide-bandgap organic-inorganic hybrid perovskite battery module is nip-type, the n-type electron transport layer is an n-type semiconductor material layer with a thickness of 15nm, and the n-type semiconductor material is at least one of titanium oxide (TiO2), tin oxide (SnO2), zinc oxide (ZnO), vanadium oxide (V2O5), and zinc tin oxide (Zn2SnO4); the p-type hole transport layer is a Spiro-OMeTAD hole transport layer with a thickness of 100nm, and the metal back electrode is an Ag back electrode with a thickness of 100nm.

6. The photovoltaic-driven catalytic degradation system for organic pollutants according to claim 1, characterized in that, When the structure of the wide-bandgap organic-inorganic hybrid perovskite solar cell module is pin-type, the p-type hole transport layer is a 15nm thick p-type semiconductor material layer, and the p-type semiconductor material is poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine], and the n-type electron transport layer is a 22nm thick C 60 Electron transport layer; the metal back electrode is an Ag back electrode with a thickness of 100 nm.

7. The application of the photovoltaic-driven catalytic degradation system for organic pollutants as described in any one of claims 1 to 6 in the photoelectrocatalytic degradation of organic pollutants.

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