Nano-fluid photoelectric energy conversion film with vacancy regulation and control function and preparation method and application of nano-fluid photoelectric energy conversion film

Abstract

The invention belongs to the technical field of nanofluid photoelectric energy conversion, and discloses a vacancy-regulated nanofluid photoelectric energy conversion film and a preparation method and application thereof. The film is formed by stacking vacancy-adjustable semiconductor nanosheets, the semiconductor nanosheets are prepared by a hydrothermal synthesis method, the vacancy can be regulated and controlled to be 0.15-0.75 by controlling the dosage of reactants, the band gap width and the surface electrification can be effectively controlled at the same time, and the obtained photoelectric energy conversion film shows good photoresponse characteristics and relatively high ion selectivity, and can be applied to the field of photoelectric energy conversion. And efficient photoelectric energy conversion can be realized. The membrane can directly convert light energy into driving force for ion transport in a balanced electrolyte solution system and convert the light energy into electric energy in an ion form, has the advantages of high efficiency and universality, and can be further applied to light-enhanced salinity gradient energy conversion; in the aspect of concentration gradient transport resistance, ion diffusion under the concentration gradient can be resisted through light-induced ion directional transport, and concentration gradient transport resistance is achieved.

Description

Technical Field

[0001] The present invention relates to the technical field of nanofluid photoelectric energy conversion, and in particular to a vacancy-controlled nanofluid photoelectric energy conversion film and a preparation method and application thereof. Background Art

[0002] The energy shortage problem is becoming more and more serious, and there is an urgent need to develop clean and efficient renewable energy. Solar energy has the advantages of abundant reserves, easy access, and sustainability. Its efficient development and utilization is conducive to alleviating the problem of energy shortage. A large number of photoelectric conversion devices are designed to develop this clean and renewable energy. In recent years, the light-driven ion transport nanofluid system developed based on the photoelectric energy conversion of ion transport by imitating bacteriorhodopsin can effectively convert light energy into electrical energy.

[0003] As the core component of the nanofluid photoelectric energy conversion system, the photoresponse and ion selective permeability of nanochannel membrane materials are crucial. However, it is difficult to simply and simultaneously achieve the regulation of their ion selective permeability and photoresponsiveness with existing membrane materials. For example, the surface charge is improved by introducing surface functional groups or changing the material phase structure, and the band structure is regulated by surface modification or heterojunction construction. These methods are relatively complex to operate and may introduce other groups into the channel to hinder ion transport, and there is a lack of effective strategies to simultaneously regulate their surface charge and photoresponsiveness to achieve efficient photoelectric energy conversion.

[0004] Therefore, there is an urgent need to develop a nanofluidic channel membrane that can simultaneously and simply regulate ion selective permeability and photoresponsiveness to achieve efficient photoelectric energy conversion. Summary of the invention

[0005] The purpose of the present invention is to provide a vacancy-regulated nanofluid photoelectric energy conversion film and its preparation method and application, so as to solve the problem that the photoelectric energy conversion film prepared by the prior art cannot simultaneously regulate the surface charge and light response to achieve efficient photoelectric energy conversion.

[0006] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0007] The present invention provides a vacancy-regulated nanofluid photoelectric energy conversion film, wherein the vacancy-regulated nanofluid photoelectric energy conversion film comprises a semiconductor nanosheet layer with adjustable vacancy;

[0008] The vacancy-tunable semiconductor nanosheet layer is composed of vacant WO 3-x Nanosheet composition.

[0009] Preferably, in the above-mentioned vacancy-regulated nanofluid photoelectric energy conversion film, the vacancy WO 3-x In the nanosheet, x is 0.15 to 0.75.

[0010] Preferably, in the above-mentioned vacancy-regulated nanofluid photoelectric energy conversion film, the thickness of the vacancy-adjustable semiconductor nanosheet layer is 3 to 3.5 μm.

[0011] The present invention also provides a method for preparing a vacancy-controlled nanofluid photoelectric energy conversion film, comprising the following steps:

[0012] Sodium tungstate dihydrate, citric acid and water are mixed, and then D(+)-glucose and hydrochloric acid are added in sequence to obtain a precursor solution; the precursor solution is subjected to hydrothermal synthesis in a reactor to obtain vacant WO 3-x Nanosheets; vacant WO 3-x The nanosheets are dispersed in water to form a dispersion, and the dispersion is vacuum filtered using a polycarbonate membrane as a filter membrane to obtain a vacancy-controlled nanofluid photoelectric energy conversion membrane.

[0013] Preferably, in the above-mentioned method for preparing a vacancy-regulated nanofluid photoelectric energy conversion film, the molar ratio of sodium tungstate dihydrate, citric acid, and D(+)-glucose is 1-5:1-8:0-6.

[0014] Preferably, in the above-mentioned method for preparing a vacancy-regulated nanofluid photoelectric energy conversion film, the temperature of the hydrothermal synthesis is 100 to 140° C.; and the time of the hydrothermal synthesis is 12 to 15 hours.

[0015] Preferably, in the above-mentioned method for preparing a vacancy-regulated nanofluid photoelectric energy conversion film, the hydrothermal synthesis further includes sequentially cooling, washing, and drying.

[0016] The present invention also provides a vacancy-regulated nanofluid photoelectric energy conversion film or a vacancy-regulated nanofluid photoelectric energy conversion film preparation method and its application in photoelectric energy conversion of a balanced electrolyte solution system.

[0017] The present invention also provides a vacancy-regulated nanofluid photoelectric energy conversion film or a vacancy-regulated nanofluid photoelectric energy conversion film preparation method and its application in anti-concentration gradient transport.

[0018] The present invention also provides a vacancy-regulated nanofluid photoelectric energy conversion film or a vacancy-regulated nanofluid photoelectric energy conversion film prepared by a method for preparing the vacancy-regulated nanofluid photoelectric energy conversion film and its application in light-synergistic salt difference energy conversion.

[0019] It can be seen from the above technical solution that compared with the prior art, the present invention has the following beneficial effects:

[0020] (1) The vacancy-regulated nanofluid photoelectric energy conversion membrane of the present invention is formed by stacking semiconductor nanosheets with adjustable vacancies. The semiconductor nanosheets are prepared by a hydrothermal synthesis method, which is simple to operate and universal. By controlling the amount of reactants, the vacancy can be regulated by 0.15 to 0.75, and the band gap width and surface charge can be effectively controlled at the same time. The constructed photoelectric energy conversion membrane exhibits good light response characteristics and high ion selectivity, further realizing efficient photoelectric energy conversion.

[0021] (2) The present invention can realize the preparation of a photoelectric energy conversion membrane with excellent light response and high ion selective permeability through a simple hydrothermal synthesis and vacuum filtration method. The method is simple to operate, has mild reaction conditions, and has high repeatability.

[0022] (3) The vacancy-controlled nanofluid photoelectric energy conversion membrane of the present invention can directly convert light energy into the driving force of ion transport in a balanced electrolyte solution system, and convert light energy into electrical energy in the form of ions, which has the advantages of high efficiency and universality, and has extremely high cycle and long-term stability. -4 M KCl balanced electrolyte solution system can generate 0.9μA / cm 2 The photocurrent is more than three times that of the film with less vacancies. Moreover, in terms of resistance to concentration gradient transport, the light-induced ion directional transport can counteract the ion diffusion under the concentration gradient and achieve resistance to concentration gradient transport. Relevant experimental results show that the photoelectric energy conversion film can resist five times the concentration gradient. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required to be used in the description of the embodiments or the prior art are briefly introduced below.

[0024] Figure 1 This is a schematic diagram of the preparation method of the vacancy-controlled nanofluid photoelectric energy conversion film of the present invention;

[0025] Figure 2 WO prepared in Example 1 2.66 AFM characterization of nanosheets;

[0026] Figure 3 WO prepared in Example 1 2.66 Physical picture of the membrane;

[0027] Figure 4 WO prepared in Example 1 2.66 Surface SEM characterization of the membrane;

[0028] Figure 5 WO prepared in Example 12.66 SEM characterization of the cross section of the membrane;

[0029] Figure 6 WO in Example 6 2.66 Schematic diagram of the application of membrane in photoelectric energy conversion in balanced electrolyte solution system;

[0030] Figure 7 is WO in Example 27 2.66 Schematic diagram of the application of membranes in transport against concentration gradients. DETAILED DESCRIPTION

[0031] The present invention provides a vacancy-regulated nanofluid photoelectric energy conversion film, wherein the vacancy-regulated nanofluid photoelectric energy conversion film comprises a semiconductor nanosheet layer with adjustable vacancy.

[0032] In the present invention, the vacancy adjustable semiconductor nanosheet layer is preferably composed of vacancy WO 3-x The WO of the present invention is composed of nanosheets. 3-x The vacancy content of the nanosheets is easily regulated, and the light absorption range is in the visible light region.

[0033] In the present invention, the vacancy WO 3-x In the nanosheet, x is preferably 0.15 to 0.75, more preferably 0.25 to 0.55, and still more preferably 0.34.

[0034] In the present invention, the thickness of the semiconductor nanosheet layer with adjustable vacancy is preferably 3 to 3.5 μm, more preferably 3.1 to 3.4 μm, and even more preferably 3.3 μm.

[0035] In the present invention, the vacancy-regulated nanofluid photoelectric energy conversion film preferably further comprises a base film; the vacancy-adjustable semiconductor nanosheet layer is located on the base film. In other words, the vacancy-regulated nanofluid photoelectric energy conversion film comprises, from bottom to top, a base film and a vacancy-adjustable semiconductor nanosheet layer.

[0036] In the present invention, the base film is preferably a polycarbonate film; the thickness of the base film is preferably 30 μm.

[0037] The present invention also provides a method for preparing a vacancy-controlled nanofluid photoelectric energy conversion film, such as Figure 1 As shown, the following steps are included:

[0038] Sodium tungstate dihydrate, citric acid and water are mixed, and then D(+)-glucose and hydrochloric acid are added in sequence to obtain a precursor solution; the precursor solution is subjected to hydrothermal synthesis in a reactor to obtain vacant WO 3-x Nanosheets; vacant WO 3-xThe nanosheets are dispersed in water to form a dispersion, and the dispersion is vacuum filtered using a polycarbonate membrane as a filter membrane to obtain a vacancy-controlled nanofluid photoelectric energy conversion membrane.

[0039] In the present invention, the molar ratio of sodium tungstate dihydrate, citric acid, and D(+)-glucose is preferably 1-5:1-8:0-6, more preferably 1-3:1.2-4:3-5, and more preferably 1:1.5:5. The present invention can adjust the WO by controlling the amount of reactants. 3-x Vacancy content of nanosheets.

[0040] In the present invention, the usage ratio of sodium tungstate dihydrate, water and hydrochloric acid is preferably 1-5 mmol:30 mL:1-5 mL, more preferably 1-3 mmol:30 mL:2-4 mL, and more preferably 1 mmol:30 mL:3 mL.

[0041] In the present invention, the concentration of the hydrochloric acid is preferably 6M.

[0042] In the present invention, the step of adding D(+)-glucose further includes stirring; the stirring time is preferably 10 minutes.

[0043] In the present invention, the step of adding hydrochloric acid further includes stirring; the stirring time is preferably 30 minutes.

[0044] In the present invention, the temperature of the hydrothermal synthesis is preferably 100-140°C, more preferably 110-130°C, and more preferably 120°C; the time of the hydrothermal synthesis is preferably 12-15h, more preferably 13-15h, and more preferably 14h.

[0045] In the present invention, the hydrothermal synthesis further includes cooling, washing and drying in sequence.

[0046] In the present invention, the washing is preferably performed using water and anhydrous ethanol in sequence until the pH of the supernatant is neutral.

[0047] In the present invention, the drying temperature is preferably 60° C.; the drying time is preferably 24 hours.

[0048] In the present invention, the pore size of the polycarbonate membrane is preferably 0.1 μm.

[0049] In the present invention, the vacant WO in the dispersion 3-x The content of the nanosheets is preferably 10 mg.

[0050] In the present invention, the pressure of the vacuum filtration is preferably 1 bar.

[0051] In the present invention, the vacuum filtration further includes natural drying.

[0052] The present invention also provides a vacancy-regulated nanofluid photoelectric energy conversion film or a vacancy-regulated nanofluid photoelectric energy conversion film preparation method and its application in photoelectric energy conversion of a balanced electrolyte solution system.

[0053] The present invention also provides a vacancy-controlled nanofluid photoelectric energy conversion film or a vacancy-controlled nanofluid photoelectric energy conversion film preparation method, and its application in anti-concentration gradient transport. The vacancy-controlled nanofluid photoelectric energy conversion film can resist ion transport under the action of salt difference energy through light-driven ion transport, thereby realizing anti-concentration gradient transport.

[0054] The present invention also provides a vacancy-regulated nanofluid photoelectric energy conversion film or a vacancy-regulated nanofluid photoelectric energy conversion film prepared by a method for preparing the vacancy-regulated nanofluid photoelectric energy conversion film, and its application in light-synergistic salt difference energy conversion. The vacancy-regulated nanofluid photoelectric energy conversion film can coordinate light-driven ion transport with ion transport under the action of salt difference energy to achieve light-synergistic salt difference energy conversion, and simultaneously convert light energy and salt difference energy into electrical energy.

[0055] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0056] Example 1

[0057] This embodiment provides a vacancy-controlled nanofluid photoelectric energy conversion film, and the preparation method thereof comprises the following steps:

[0058] (1) 1 mmol sodium tungstate dihydrate and 1.5 mmol citric acid were added to 30 mL deionized water and stirred until completely dissolved to form a transparent solution. Then 5 mmol D(+)-glucose was added and stirred vigorously for 10 min to ensure complete dissolution. Then 3 mL 6 M hydrochloric acid was added and stirred for another 30 min to obtain a precursor solution. The precursor solution was transferred to a 50 mL polytetrafluoroethylene-lined autoclave, sealed, and subjected to hydrothermal reaction at 120° C. for 14 h. After cooling to room temperature, the product was centrifuged and separated. The product was washed with deionized water and anhydrous ethanol in turn until the pH of the supernatant was neutral. Then, the product was dried in a vacuum oven at 60° C. for 24 h to obtain WO 2.66 Nanosheets;

[0059] (2) Will WO 2.66The nanosheets and water formed a 1 mg / mL dispersion. A polycarbonate membrane with a pore size of 0.1 μm and a thickness of 30 μm was fixed as a filter membrane on the sand core of the filtration device. 10 mL of the dispersion was vacuum filtered at a pressure of 1 bar to form WO on the polycarbonate membrane. 2.66 The nanosheets were then dried naturally at room temperature to obtain a vacancy-controlled nanofluid photoelectric energy conversion film, denoted as WO 2.66 membrane.

[0060] Will WO 2.66 The nanosheets were characterized by AFM. Figure 2 As shown. Figure 2 It can be seen that WO 2.66 The thickness of the nanosheet is about 7.5 nm.

[0061] WO 2.66 The actual picture of the membrane is as follows Figure 3 As shown. Figure 3 It can be seen that WO 2.66 The film has good flexibility.

[0062] Will WO 2.66 The surface and cross section of the membrane were characterized by SEM. Figures 4-5 As shown. Figure 4 It can be seen that WO 2.66 Two-dimensional WO is evenly distributed on the membrane surface 2.66 Nanosheets. Figure 5 It can be seen that WO 2.66 WO in the membrane 2.66 The thickness of the nanosheet layer is 3.3 μm.

[0063] Embodiments 2 to 5

[0064] The difference between Examples 2 to 5 and Example 1 is that the amount of D(+)-glucose in step (1) is adjusted to 0, 3, 4, and 6 mmol (corresponding to Examples 2 to 5, respectively), and other conditions remain unchanged, to obtain WO 2.85 Membrane, WO 2.75 Membrane, WO 2.70 Membrane, WO 2.25 membrane.

[0065] Example 6

[0066] This embodiment provides the WO of embodiment 1 2.66 The application of membrane in photoelectric energy conversion of balanced electrolyte solution system, the schematic diagram of the device used is shown in Figure 6 As shown, there is a transparent electrolyte tank on each side of the device, which can be used to place electrolyte and connect electrodes. 2.66The membrane is tightly fixed between the two electrolyte tanks. 5 mL of the same electrolyte solution (10 -4 M KCl solution), insert Ag / AgCl electrodes and connect external circuits, and protect the electrodes with light shields. The right side of the device is grounded, and in the absence of external voltage, a wavelength of 470nm and an intensity of 138mW / cm is applied to the left side of the device. 2 , when the visible light lasts for 30s, 0.9μA / cm 2 of the photocurrent.

[0067] Example 7

[0068] The difference between this embodiment and embodiment 6 is that no visible light is applied, and other conditions remain unchanged, and the photocurrent cannot be measured. 2.66 The photoelectric conversion of the film is caused by light.

[0069] Example 8

[0070] The difference between this embodiment and embodiment 6 is that the WO of embodiment 1 is replaced by 2.66 The membrane was replaced with a polycarbonate membrane with a pore size of 0.1 μm, and other conditions remained unchanged. As a result, no photocurrent could be measured. This indicates that the photoelectric conversion characteristics are derived from the vacant WO prepared by the present invention. 3-x Nanosheets.

[0071] Examples 9 to 12

[0072] The difference between Examples 9 to 12 and Example 6 is that the visible light intensity is adjusted to 36, 59, 78, and 115 mW / cm 2 (corresponding to Examples 9 to 12, respectively), other conditions remain unchanged, the measured photocurrents are 0.3, 0.4, 0.6, 0.8 μA / cm 2 . This shows that the photoelectric conversion characteristics gradually increase with the increase of light intensity.

[0073] Embodiment 13

[0074] In this embodiment, the illumination conditions of embodiment 6 are repeated 50 times, and other conditions remain unchanged, and the measured photocurrent value remains substantially unchanged, indicating that the photoelectric conversion has extremely high cycle stability.

[0075] Embodiment 14

[0076] The difference between this embodiment and embodiment 6 is that the duration of visible light illumination is adjusted to 1000s, and other conditions remain unchanged, and the measured photocurrent value remains unchanged, which indicates that the photoelectric conversion has extremely high long-term stability.

[0077] Embodiments 15 to 18

[0078] The difference between Examples 15 to 18 and Example 6 is that the WO 2.66 The membranes were replaced with WO 2.85 Membrane, WO of Example 3 2.75 Membrane, WO of Example 4 2.70 Membrane, WO of Example 5 2.25 The other conditions were unchanged, and the measured photocurrents were 0.2, 0.3, 0.5, and 0.5 μA / cm 2 This indicates that the photoelectric conversion characteristics gradually increase with the increase of vacancy content, but too high vacancies will cause it to decrease.

[0079] Examples 19 to 22

[0080] The difference between Examples 19 to 22 and Example 6 is that the KCl solution is replaced by NaCl, LiCl, CaCl2, and MgCl2 solutions (corresponding to Examples 19 to 22, respectively), and other conditions remain unchanged. The measured photocurrents are 0.5, 0.5, 0.4, and 0.4 μA / cm, respectively. 2 . This shows that the photoelectric conversion characteristics are universal to various electrolyte solutions.

[0081] Embodiments 23 to 26

[0082] The difference between Examples 23 to 26 and Example 6 is that the concentration of the KCl solution is adjusted to 10 -6 M, 10 -5 M, 10 -3 M, 10 -2 M (corresponding to Examples 23 to 26, respectively), other conditions remain unchanged, the measured photocurrents are 0.3, 0.5, 1.5, 3.7 μA / cm 2 This indicates that the photoelectric conversion characteristics gradually increase with the increase of electrolyte solution concentration.

[0083] Embodiment 27

[0084] This embodiment provides the WO of embodiment 1 2.66 The application of membrane in transport against concentration gradient, the schematic diagram of the device used is as follows Figure 7 As shown, the WO of Example 1 2.66 The membrane was placed between two solution pools and fixed tightly. The left and right solution pools were filled with 10 -5 M and 4×10 -5 M KCl electrolyte solution, and insert Ag / AgCl electrodes to connect to the external circuit. The diffusion current at this time is 0.2μA / cm 2 A wave with a wavelength of 470 nm and an intensity of 138 mW / cm was applied to the left side of the electrolytic cell. 2When the visible light lasts for 30 seconds, the photocurrent is measured to be 0.02μA / cm 2 The direction of the ion current is reversed, indicating that anti-concentration gradient transport can be achieved under light.

[0085] Embodiments 28 to 31

[0086] The difference between Examples 28 to 31 and Example 27 is that the visible light intensity is adjusted to 36, 59, 78, and 115 mW / cm 2 (corresponding to Examples 28 to 31, respectively), other conditions remain unchanged, the measured ion currents are -0.15, -0.1, -0.06, 0 μA / cm 2 . This indicates that anti-concentration gradient transport can be achieved under a certain light intensity.

[0087] Embodiment 32

[0088] In this example, the illumination conditions of Example 27 were repeated 4 times while other conditions remained unchanged. The same anti-concentration gradient transport phenomenon was observed, indicating that the anti-concentration gradient transport stability is high.

[0089] Embodiments 33 to 35

[0090] The difference between Examples 33 to 35 and Example 27 is that the solution pool on the right side (the concentration of the KCl solution is 4×10 -5 The concentration of KCl solution was 2×10 -5 M, 3×10 -5 M, 5×10 -5 M (corresponding to Examples 33 to 35, respectively), other conditions remain unchanged, the measured ion currents are 0.2, 0.12, 0 μA / cm 2 . This shows that anti-concentration gradient transport can be achieved under various concentration gradients.

[0091] Embodiment 36

[0092] This embodiment provides the WO of embodiment 1 2.66 The application of the membrane in light-synergistic salt difference energy conversion is to convert the WO 2.66 The membrane was placed between two solution pools and fixed tightly. The left and right solution pools were filled with 10 -2 M and 10 -3 M KCl electrolyte solution, and insert Ag / AgCl electrodes to connect the external circuit. The diffusion current at this time is 95μA / cm 2 A wave with a wavelength of 470 nm and an intensity of 138 mW / cm was applied to the left side of the electrolytic cell. 2 When the visible light lasts for 30 seconds, the photocurrent is measured to be 111 μA / cm 2, realizing photosynthetic salt difference energy conversion.

[0093] Embodiments 37 to 40

[0094] The difference between Examples 37 to 40 and Example 36 is that the KCl solution is replaced by NaCl, LiCl, MgCl2, and CaCl2 solutions (corresponding to Examples 37 to 40, respectively), and other conditions remain unchanged. The diffusion currents are 105, 62, 78, and 94 μA / cm, respectively. 2 After visible light irradiation, the photocurrents increased to 122, 82, 88, and 109 μA / cm, respectively. 2 , indicating that the photosynthetic salt difference energy conversion characteristics are universal to a variety of electrolyte solutions.

[0095] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principle of the present invention. These improvements and modifications should also be regarded as the scope of protection of the present invention.

Claims

1. A vacancy-controlled nanofluid photoelectric energy conversion film, characterized in that: The vacancy-regulated nanofluid photoelectric energy conversion film comprises a semiconductor nanosheet layer with adjustable vacancy; The vacancy-tunable semiconductor nanosheet layer is composed of vacant WO 3-x Nanosheet composition.

2. The vacancy-controlled nanofluid photoelectric energy conversion film according to claim 1, characterized in that: The vacancy WO 3-x In the nanosheet, x is 0.15 to 0.

75.

3. The vacancy-controlled nanofluid photoelectric energy conversion film according to claim 2, characterized in that: The thickness of the semiconductor nanosheet layer with adjustable vacancy is 3-3.5 μm.

4. The method for preparing a vacancy-controlled nanofluid photoelectric energy conversion film according to any one of claims 1 to 3, characterized in that: The following steps are involved: Sodium tungstate dihydrate, citric acid and water are mixed, and then D(+)-glucose and hydrochloric acid are added in sequence to obtain a precursor solution; the precursor solution is subjected to hydrothermal synthesis in a reactor to obtain vacant WO 3-x Nanosheets; vacant WO 3-x The nanosheets are dispersed in water to form a dispersion, and the dispersion is vacuum filtered using a polycarbonate membrane as a filter membrane to obtain a vacancy-controlled nanofluid photoelectric energy conversion membrane.

5. The method for preparing a vacancy-controlled nanofluid photoelectric energy conversion film according to claim 4, characterized in that: The molar ratio of the sodium tungstate dihydrate, citric acid and D(+)-glucose is 1-5:1-8:0-6.

6. The method for preparing a vacancy-controlled nanofluid photoelectric energy conversion film according to claim 4 or 5, characterized in that: The temperature of the hydrothermal synthesis is 100-140° C.; the time of the hydrothermal synthesis is 12-15 hours.

7. The method for preparing a vacancy-controlled nanofluid photoelectric energy conversion film according to claim 6, characterized in that: The hydrothermal synthesis further includes sequentially cooling, washing and drying.

8. Application of a vacancy-regulated nanofluid photoelectric energy conversion membrane prepared by the preparation method of a vacancy-regulated nanofluid photoelectric energy conversion membrane as described in any one of claims 1 to 3 or a vacancy-regulated nanofluid photoelectric energy conversion membrane as described in any one of claims 4 to 7 in photoelectric energy conversion in a balanced electrolyte solution system.

9. Application of a vacancy-regulated nanofluid photoelectric energy conversion membrane prepared by the preparation method of a vacancy-regulated nanofluid photoelectric energy conversion membrane as described in any one of claims 1 to 3 or a vacancy-regulated nanofluid photoelectric energy conversion membrane as described in any one of claims 4 to 7 in anti-concentration gradient transport.

10. Application of a vacancy-regulated nanofluid photoelectric energy conversion film prepared by the preparation method of a vacancy-regulated nanofluid photoelectric energy conversion film as described in any one of claims 1 to 3 or a vacancy-regulated nanofluid photoelectric energy conversion film as described in any one of claims 4 to 7 in light-synergistic salt difference energy conversion.

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