Self-driven perovskite photoelectrode electro-catalysis device and manufacturing method and application thereof

Abstract

The invention belongs to the technical field of photoelectrocatalysis, and provides a self-driven perovskite photoelectrode electro-catalysis device and a manufacturing method and application thereof.The device comprises a perovskite photoanode end, a fusible metal layer and an electro-catalysis end; the perovskite photoanode end comprises a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer and a metal electrode; the electro-catalysis end comprises foamy copper and a catalyst layer on the surface of one side of the foamy copper; and the fusible metal layer is arranged between the metal electrode and the foamy copper and is used for connecting the perovskite photoanode end and the electro-catalysis end. The perovskite material is used as the photo-anode to directly transfer holes to the catalyst layer, so that efficient value-added reaction of biomass organic matters such as furfural can be realized, and hydrogen evolution reaction can be carried out at the same time. Different from a traditional photocatalysis device, the device does not depend on the intervention of an external circuit, the system design can be simplified, the dependence of a traditional electro-catalysis system on a power supply is avoided, and the energy efficiency is effectively improved.

Description

Technical Field

[0001] The present invention belongs to the technical field of photoelectrocatalysis, and relates to a self-driven perovskite photoanode electrocatalytic device, a manufacturing method thereof and uses thereof. Background Art

[0002] With the rapid development of sustainable energy and environmental protection technologies, photocatalysis technology has become a research hotspot because it can utilize solar energy for organic matter decomposition and environmental treatment. The photocatalytic reaction involves using a photoanode material to convert light energy into chemical energy to drive redox reactions. In recent years, perovskite photoanode materials have become important research objects in the field of photocatalysis due to their excellent optoelectronic properties. Perovskite materials not only have advantages such as a broad light absorption range, high carrier mobility, and long carrier lifetime, but also can achieve self-driven electrocatalytic reactions through reasonable design.

[0003] Perovskite photoanode electrocatalytic devices are currently mostly applied in fields such as photoelectrochemical water splitting (hydrogen production or oxygen production), photocatalytic degradation of organic pollutants, etc. Taking water splitting as an example, common configurations include a perovskite material as the photoanode, a conductive material (such as a conductive oxide, a metal thin film, etc.) as the electrode, and an electrolyte solution for promoting ion conduction. In these systems, the photoanode material generates electron-hole pairs under light illumination. The holes promote the oxidation reaction at the anode, and the electrons enter the cathode through an external circuit to participate in the hydrogen production or oxygen production reaction. Although certain progress has been made in these studies, the existing technologies still have some obvious drawbacks, especially in terms of reaction diversity, reaction efficiency, and system complexity. Most traditional perovskite photoanode devices rely on an external circuit to provide current support, which increases the complexity and energy consumption of the device and also reduces the energy conversion efficiency; at the same time, the selectivity and efficiency of the catalytic reaction are limited, and only a single reaction can be achieved, lacking the integration of multiple reaction processes.

[0004] In addition to water splitting, the oxidation reaction of biomass-derived organic matter also has important research value. Among them, furfural is an important biomass-derived chemical, usually obtained by pyrolyzing lignocellulose. The oxidation reaction of furfural (converting furfural to furoic acid) is of great significance for improving the added value of biomass and developing green chemistry. Traditional furfural oxidation processes usually rely on an external power source or an external catalyst, with low efficiency and sustainability. Therefore, studying the use of a self-driven photoanode electrocatalytic device that can directly utilize solar energy to drive the reaction and improve energy utilization efficiency has important practical significance. Summary of the Invention

[0005] In view of the problems existing in the prior art, the purpose of the present invention is to provide a self-driven perovskite photoanode electrocatalytic device, its manufacturing method and uses. The device includes a perovskite photoanode end, a fusible metal layer, and an electrocatalytic end; the perovskite photoanode end includes a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode; the electrocatalytic end includes copper foam and a catalyst layer on one surface of the copper foam; the fusible metal layer is disposed between the metal electrode and the copper foam for connecting the perovskite photoanode end and the electrocatalytic end. Using the perovskite material as the photoanode to directly transfer holes to the catalyst layer can not only achieve efficient value-added reactions of biomass organic substances such as furfural, but also simultaneously generate hydrogen. Different from traditional photocatalytic devices, this device does not rely on the intervention of an external circuit, which can simplify the system design, avoid the dependence on a power source in traditional electrocatalytic systems, and effectively improve energy efficiency.

[0006] To achieve this purpose, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a self-driven perovskite photoanode electrocatalytic device, including: a perovskite photoanode end, a fusible metal layer, and an electrocatalytic end; the perovskite photoanode end includes a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode; the electrocatalytic end includes copper foam and a catalyst layer on one surface of the copper foam; the fusible metal layer is disposed between the metal electrode and the copper foam for connecting the perovskite photoanode end and the electrocatalytic end.

[0008] Different from the traditional technology that requires an external power source to provide current, the self-driven perovskite photoanode electrocatalytic device of the present invention utilizes the photoelectric effect of the perovskite photoanode end to drive the electrocatalytic reaction through light irradiation to achieve complete self-driving. This not only simplifies the device design, reduces energy consumption, but also improves the system integration and operability. And the self-driven perovskite photoanode electrocatalytic device has multiple reaction capabilities. Compared with traditional perovskite photoanode devices that usually only focus on a single reaction such as hydrogen production, the present invention can realize the oxidation reaction of biomass organic substances such as furfural while generating a small amount of hydrogen, thereby improving the economy and versatility of the reaction.

[0009] The following are preferred technical solutions of the present invention, but not limitations to the technical solutions provided by the present invention. Through the following technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.

[0010] It should be noted that in the present invention, in addition to setting the perovskite photoanode end, the photoelectric effect is used to generate electron-hole pairs to drive the reaction at the electrocatalytic end. In this case, the band gap, photoelectric properties, stability, and catalytic performance of these materials should be sufficient to support the value-added reaction (such as oxidation reaction) of biomass organic compounds such as furfural. The electrocatalytic end uses copper-based material copper foam, which can significantly reduce the potential required for the oxidation reaction. In this way, combined with the power supply of the perovskite photoanode end, self-driving can be achieved.

[0011] As a preferred technical solution of the present invention, the metal element in the fusible metal layer includes at least one of In, Sn, or Bi.

[0012] Preferably, the melting point of the fusible metal layer is 50-150 °C, such as 50 °C, 60 °C, 70 °C, 80 °C, 90 °C, 100 °C, 110 °C, 120 °C, 130 °C, 140 °C, or 150 °C, etc. Exemplarily, an alloy of In, Sn, and Bi has a melting point of 58 °C.

[0013] Preferably, the thickness of the fusible metal layer is 50-300 μm, such as 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 130 μm, 150 μm, 180 μm, 200 μm, 220 μm, 240 μm, 260 μm, 280 μm, or 300 μm, etc., and preferably 80-120 μm.

[0014] In the present invention, if the thickness of the soluble metal layer is too thin, it may cause an increase in resistance, and it needs to have a certain thickness to ensure the connection stability and mechanical strength, so that the fusible metal layer will not break or fall off due to external forces or other factors during the use of the device.

[0015] As a preferred technical solution of the present invention, an external lead is provided on the surface of the transparent electrode away from the electron transport layer, and the external lead is used to connect to the cathode.

[0016] Preferably, the external lead includes a metal copper wire cured by conductive silver paste.

[0017] In the present invention, the positive hole of the perovskite photoanode end is transferred to the electrocatalytic end, and the electrons at the negative electrode need to be conducted out, otherwise they are easily accumulated and recombined, reducing the photocurrent. Therefore, it is necessary to directly connect to the counter electrode (cathode) such as a platinum sheet on one side of the transparent electrode by using an external lead, which is equivalent to the perovskite photoanode providing electrons to the cathode; specifically, the connection method of the external lead is often realized by fixing the copper wire with conductive silver paste.

[0018] Preferably, the outer surface of the perovskite anode end further includes an epoxy resin sealing and protecting layer.

[0019] It is understandable that in the present invention, an epoxy resin sealing protective layer is used to cover the perovskite anode end to play a protective role and prevent the perovskite anode end from being eroded by water and oxygen, which affects stability and lifespan. However, the electrocatalytic end (including copper foam) should be exposed to facilitate reaction mass transfer.

[0020] Preferably, the copper-based catalyst includes at least one of copper oxide, copper metal, or copper sulfide.

[0021] Preferably, the copper oxide includes cuprous oxide nanowires.

[0022] In the present invention, copper-based catalysts are preferably used as they require a lower oxidation voltage, which helps to achieve the self-driven effect. Therefore, the substrate is preferably copper foam, and the catalyst is preferably cuprous oxide nanowires, which can produce a small amount of hydrogen while oxidizing furfural to form furoic acid. Other catalysts that can integrate the value-added reaction of biomass-like organic compounds and the hydrogen evolution reaction can also be applicable, but it should be ensured that they can work synergistically with the perovskite photoanode end.

[0023] As a preferred technical solution of the present invention, the transparent electrode includes ITO glass.

[0024] Preferably, the electron transport layer includes tin dioxide.

[0025] Preferably, the perovskite component of the perovskite layer is ABX3, where A includes at least one of FA + , MA + or Cs + , B includes Sn 2+ and / or Pb 2+ , X includes at least one of I - , Br - or Cl - .

[0026] Preferably, the hole transport layer includes spiro-OMeTAD.

[0027] Preferably, the metal electrode includes gold.

[0028] Preferably, the thickness of the metal electrode is 80 - 120 nm, such as 80 nm, 85 nm, 90 nm, 95 nm, 100 nm, 105 nm, 110 nm, 115 nm, or 120 nm, etc.

[0029] Preferably, a coating or surface modification layer is provided on the surface of the metal electrode away from the electron transport layer to enhance the selectivity and stability of the reaction.

[0030] Preferably, the active area of the perovskite photoanode end is 0.2 - 0.35 cm 2 , such as 0.2 cm2 、 0.23 cm 2 、 0.25 cm 2 、 0.28 cm 2 、 0.3 cm 2 、 0.32 cm 2 or 0.35 cm 2 etc.

[0031] In a second aspect, the present invention provides a method for manufacturing the self-driven perovskite photoanode electrocatalytic device described in the first aspect. The manufacturing method includes the following steps:

[0032] Prepare a perovskite photoanode end, an electrocatalytic end, and a fusible metal layer respectively; assemble the perovskite photoanode end, the electrocatalytic end, and the fusible metal layer so that the fusible metal layer is disposed between the metal electrode in the perovskite photoanode end and the copper foam in the electrocatalytic end to connect the perovskite photoanode end and the electrocatalytic end.

[0033] As a preferred technical solution of the present invention, when the perovskite photoanode end is a photoanode, the method for preparing the perovskite photoanode end includes: providing a transparent electrode, and sequentially preparing an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode thereon to obtain the perovskite photoanode end.

[0034] Preferably, the transparent electrode is pre-cleaned; the cleaning process includes sequentially performing ultrasonic treatment with a detergent, acetone, deionized water, and IPA for 15 - 20 min, such as 15 min, 16 min, 17 min, 18 min, 19 min, or 20 min, etc., and then drying with a nitrogen stream;

[0035] Preferably, after the transparent electrode is cleaned, before preparing the electron transport layer, ultraviolet ozone treatment is performed for 5 - 20 min, such as 5 min, 8 min, 10 min, 12 min, 14 min, 16 min, 18 min, or 20 min, etc.

[0036] Preferably, when the electron transport layer includes tin dioxide, the method for preparing the electron transport layer includes: taking a tin oxide solution with a mass concentration of 10% - 20%, such as 10%, 12%, 14%, 16%, 18% or 20%, and spin-coating it at 2000 - 4000 rpm, such as 2000 rpm, 2300 rpm, 2500 rpm, 2800 rpm, 3000 rpm, 3200 rpm, 3500 rpm, 3800 rpm or 4000 rpm, for 20 - 40 s, such as 20 s, 23 s, 25 s, 28 s, 30 s, 32 s, 35 s, 38 s or 40 s, and then annealing it at 130 - 170 °C, such as 130 °C, 140 °C, 150 °C, 160 °C or 170 °C, for 20 - 40 min, such as 20 min, 23 min, 25 min, 28 min, 30 min, 33 min, 35 min, 38 min or 40 min.

[0037] Preferably, the method for preparing the perovskite layer includes: preparing a perovskite precursor solution, accelerating it at an acceleration of 100 - 300 rpm / s, such as 100 rpm / s, 130 rpm / s, 150 rpm / s, 180 rpm / s, 200 rpm / s, 230 rpm / s, 250 rpm / s, 280 rpm / s or 300 rpm / s, raising the speed to 800 - 1200 rpm, such as 800 rpm, 850 rpm, 900 rpm, 950 rpm, 1000 rpm, 1050 rpm, 1100 rpm, 1150 rpm or 1200 rpm, and spin-coating it for 8 - 12 s, such as 8 s, 9 s, 10 s, 11 s or 12 s, and then accelerating it at an acceleration of 800 - 1200 rpm / s, such as 800 / s, 900 / s, 1000 / s, 1100 / s or 1200 / s, raising the speed to 4800 - 5200 rpm, such as 4800 rpm, 4900 rpm, 5000 rpm, 5100 rpm or 5200 rpm, spin-coating it for 28 - 32 s, such as 28 s, 29 s, 30 s, 31 s or 32 s, dropping an anti-solvent at the 35th second after starting the spin-coating, the anti-solvent including chlorobenzene; the dosage of the anti-solvent is 80 - 120 μL, such as 80 μL, 90 μL, 100 μL, 110 μL or 120 μL, and then annealing it at 120 - 180 °C, such as 120 °C, 130 °C, 140 °C, 150 °C, 160 °C, 170 °C or 180 °C, for 5 - 15 min, such as 5 min, 6 min, 7 min, 8 min, 9 min, 10 mim, 11 mim, 12 mim, 13 mim, 14 mim or 15 mim.

[0038] Preferably, when the hole transport layer comprises spiro-OMeTA, the method for preparing the hole transport layer comprises formulating a solution of spiro-OMeTA and a solvent at a concentration of 70-80 mg / mL, such as 70 mg / mL, 72 mg / mL, 74 mg / mL, 76 mg / mL, 78 mg / mL or 80 mg / mL, etc. The solvent comprises chlorobenzene, and an additive is added simultaneously. The additive comprises 15-25 μL of tert-butylpyridine, such as 15 μL, 16 μL, 17 μL, 18 μL, 19 μL, 20 μL, 21 μL, 22 μL, 23 μL, 24 μL or 25 μL, etc., and 10-20 μL, such as 10 μL, 12 μL, 14 μL, 16 μL, 18 μL or 20 μL, etc. of an acetonitrile solution of lithium bis(trifluoromethanesulfonyl)imide at a concentration of 500-550 mg / mL, such as 500 mg / mL, 510 mg / mL, 520 mg / mL, 530 mg / mL, 540 mg / mL or 550 mg / mL, etc. Spin coating is carried out at 3000-5000 rpm, such as 3000 rpm, 3300 rpm, 3500 rpm, 3800 rpm, 4000 rpm, 4500 rpm or 5000 rpm, etc. for 20-40 s, such as 20 s, 23 s, 25 s, 28 s, 30 s, 33 s, 35 s, 38 s or 40 s, etc.

[0039] Preferably, the method for preparing the metal electrode comprises evaporation deposition under a vacuum condition of ≤ 1×10 -3 Pa, such as 9×10 -4 Pa, 7×10 -4 Pa, 5×10 -4 Pa, 3×10 -4 Pa or 1×10 -4 Pa, etc.

[0040] As a preferred technical solution of the present invention, when the catalyst of the catalyst layer comprises cuprous oxide nanowires, the method for preparing the electrocatalytic end comprises:

[0041] Anodic oxidation is carried out on copper foam to form cupric hydroxide nanowires grown on the copper foam, and then heat treatment is carried out in an inert atmosphere. The cupric hydroxide nanowires are converted into cuprous oxide nanowires to form a catalyst layer, and an electrocatalytic end is obtained.

[0042] The present invention prepares cupric hydroxide nanowires by anodic oxidation on the surface of copper foam and obtains cuprous oxide nanowires through high-temperature treatment. As an alternative, cuprous oxide nanowires or other metal-based catalysts (such as copper-based alloys, platinum-based catalysts, etc.) can be prepared by methods such as sol-gel method, chemical vapor deposition (CVD), hydrothermal synthesis method, etc.

[0043] Preferably, the copper foam is pre-cleaned, and the cleaning process includes sequentially performing ultrasonic treatment in ethanol, 1M HCl, and pure water for 5 - 15 min, such as 5 min, 6 min, 7 min, 8 min, 9 min, 10 min, 11 min, 12 min, 13 min, 14 min, or 15 min, etc.

[0044] Preferably, the counter electrode of the anodization method includes a platinum sheet, the electrolyte includes 1M NaOH and / or 1M KOH, the time is 5 - 30 min, such as 5 min, 8 min, 10 min, 12 min, 13 min, 15 min, 18 min, 20 min, 23 min, 25 min, 28 min, or 30 min, etc., and the constant current density is 20 - 100 mA·cm -2 , such as 20 mA·cm -2、 30 mA·cm -2 , 40 mA·cm -2 , 50 mA·cm -2 , 60 mA·cm -2 , 70 mA·cm -2 , 80 mA·cm -2 , 90 mA·cm -2 or 100 mA·cm -2 etc.

[0045] Preferably, the heating rate of the heat treatment is 2 - 8 °C / min, such as 2 °C / min, 3 °C / min, 4 °C / min, 5 °C / min, 6 °C / min, 7 °C / min, or 8 °C / min, etc., the temperature is 300 - 500 °C, such as 300 °C, 330 °C, 350 °C, 380 °C, 400 °C, 430 °C, 450 °C, 480 °C, or 500 °C, etc., and the time is 1 - 3 h, such as 1 h, 1.2 h, 1.5 h, 1.8 h, 2 h, 2.3 h, 2.5 h, 2.8 h, or 3 h, etc.

[0046] As a preferred technical solution of the present invention, the method for preparing the fusible metal layer includes laying the fusible metal on a hot plate above its melting point, melting and flattening it to form a thin film, and cutting it after cooling to room temperature.

[0047] Preferably, the method for connecting the perovskite photoanode end and the electrocatalytic end includes, after the assembly is obtained by the assembly, performing heat treatment on the assembly to melt the fusible metal layer, and then cooling it to achieve connection.

[0048] Preferably, the temperature of the heat treatment is 20 - 30°C higher than the melting point of the fusible metal layer, such as 20°C, 22°C, 24°C, 26°C, 28°C or 30°C, etc. Exemplarily, if an alloy of In, Sn and Bi with a melting point of 58°C is used, the temperature of the heat treatment can be 70°C.

[0049] In the present invention, one end of the metal electrode at the perovskite photoanode end and one end of the copper foam at the electrocatalytic end need to be combined in order to transfer holes (positive charges) to the copper foam for anodic oxidation reaction. Preferably, the present invention uses a low-temperature fusible metal to form a fusible metal layer for bonding the two, so heat treatment is required. If heat treatment is not used, directly bonding with a tape that conducts electricity through both sides is also a feasible solution, but the conductivity of the resulting device is not ideal.

[0050] Preferably, the manufacturing method further includes using conductive silver paste to cure copper wires on the side of the transparent electrode away from the electron transport layer to form an external lead for leading out electrons.

[0051] Preferably, the preparation method further includes using epoxy resin to seal and dry the perovskite photoanode end to form an epoxy resin sealing protection layer.

[0052] In a third aspect, the present invention provides a use of the self-driven perovskite photoanode electrocatalytic device described in the first aspect, and the use includes oxygen value-added reaction and hydrogen production of biomass organic substances; the biomass organic substances include at least one of furfural, ethanol or acetone; the value-added reaction includes an oxidation reaction.

[0053] It should be noted that when applying the self-driven perovskite photoanode electrocatalytic device for photoelectrochemical reaction, the reaction conditions (such as temperature, light intensity, etc.) and reaction processes (such as adding electrolysis, acidification and other pretreatments) should be reasonably adjusted according to the actual reaction target object.

[0054] It should be noted that due to space limitations and to avoid redundancy, the present invention does not exhaustively list all the point values within the above numerical range, but is not limited to the listed values either. Other unlisted values within the above numerical range are equally applicable.

[0055] Compared with the prior art solutions, the present invention has at least the following beneficial effects:

[0056] Different from the traditional technology that requires an external power supply to provide current, the self-driven perovskite photoanode electrocatalytic device of the present invention utilizes the photoelectric effect at the perovskite photoanode end to drive the electrocatalytic reaction through light irradiation, achieving complete self-driving. This not only simplifies the device design, reduces energy consumption, but also improves the system integration and operability. Moreover, the self-driven perovskite photoanode electrocatalytic device has multiple reaction capabilities. Compared with traditional perovskite photoanode devices that usually focus on a single reaction (hydrogen production or oxygen production), the present invention can achieve the oxidation reaction of biomass organic substances such as furfural while generating a small amount of hydrogen, thereby improving the economy and versatility of the reaction. Brief Description of the Drawings

[0057] Figure 1 It is a schematic structural diagram of the self-driven perovskite photoanode electrocatalytic device in Example 1 and a schematic flow diagram of its manufacturing method.

[0058] Figure 1 In which: 10 - fusible metal layer, 20 - electrocatalytic end, 21 - copper foam, 22 - catalyst layer, 30 - perovskite photoanode end, 31 - transparent electrode, 32 - electron transport layer, 33 - perovskite layer, 34 - hole transport layer, 35 - metal electrode.

[0059] Figure 2 It is a scanning electron microscope image of the cuprous oxide nanowires obtained in Example 1.

[0060] Figure 3 It is a scanning electron microscope image of the perovskite layer obtained in Example 1;

[0061] Figure 4 It is a J-V curve diagram of the perovskite photoanode end obtained in Example 1.

[0062] Figure 5 It is a linear sweep voltammogram of the self-driven perovskite photoanode electrocatalytic device obtained in Example 1 for furfural oxidation application.

[0063] Figure 6 It is a bar chart of the content of furfural and furoic acid in the sample for quantitative analysis by injecting the electrolyte into a high-performance liquid chromatograph after 30 minutes of light irradiation reaction for the self-driven perovskite photoanode electrocatalytic device obtained in Example 1 for furfural oxidation application.

[0064] Figure 7 It is a linear sweep voltammogram of the electrocatalytic device obtained in Comparative Example 1 for furfural oxidation application. Detailed Embodiments

[0065] The technical solutions of the present invention will be further described below through specific embodiments.

[0066] Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations to the present invention.

[0067] Example 1

[0068] This embodiment provides a self-driven perovskite photoanode electrocatalytic device, as Figure 1 shown, including: a perovskite photoanode end 30, a fusible metal layer 10, and an electrocatalytic end 20; the perovskite photoanode end 30 includes a transparent electrode 31, an electron transport layer 32, a perovskite layer 33, a hole transport layer 34, and a metal electrode 35; the electrocatalytic end 20 includes copper foam 21 and a catalyst layer 22 on one side surface of the copper foam 21; the fusible metal layer 10 is disposed between the metal electrode 35 and the copper foam 21 for connecting the perovskite photoanode end 30 and the electrocatalytic end 20; a conductive metal layer is further disposed on the side surface of the transparent electrode 31 away from the electron transport layer 32, and the metal elements of the conductive metal layer include silver;

[0069] The metal elements in the fusible metal layer 10 include In, Sn, and Bi, which is an SnBi alloy with a melting point of 58 °C; the thickness of the fusible metal layer 10 is 100 μm; the catalyst in the catalyst layer 22 is cuprous oxide nanowires; the perovskite photoanode end 30 is a photoanode that provides holes to the electrocatalytic end 20; the transparent electrode 31 is ITO glass; the electron transport layer 32 is tin dioxide; the perovskite component of the perovskite layer 33 is ABX3, where A is FA + , MA + , and Cs + , B is Pb 2+ , X is I - , Br - , and Cl - ; the hole transport layer 34 is spiro-OMeTAD; the metal electrode 35 is gold with a thickness of 100 nm; the active area of the perovskite photoanode end 30 is 0.28 cm 2 .

[0070] As Figure 1 shown, the manufacturing method of the self-driven perovskite photoanode electrocatalytic device includes:

[0071] (1) Preparation of the perovskite photoanode 30: Using the rigid ITO glass substrate as the transparent electrode 31, it was successively ultrasonically treated with detergent, acetone, deionized water, and IPA for 18 min, and then dried with a nitrogen stream. Subsequently, the pre-cleaned ITO glass substrate was placed under ultraviolet ozone treatment for 13 min. The tin oxide solution with a mass concentration of 15% (aqueous dispersion, diluted by mixing with deionized water in a volume ratio of 1:3) was deposited on the ITO glass substrate by spin coating at 3000 rpm for 30 s, and then placed on a hot plate at 150 °C for annealing for 30 min to form the electron transport layer 32; in a nitrogen atmosphere, the perovskite precursor solution was prepared by dissolving a mixture of PbI2 (742.2 mg), FAI (224.4 mg), MABr (16.2 mg), MACl (20.3 mg), and CsI (19.8 mg) in 1 mL of anhydrous DMF / DMSO mixed solvent (volume ratio 4:1). 50 μL of the perovskite precursor solution was evenly covered on the surface of the electron transport layer 32, and spin coating was carried out to form a film by a segmented spin coating process. The steps included 10 s at 1000 rpm (acceleration of 200 rpm / s), 30 s at 5000 rpm (acceleration of 1000 rpm / s), and at the 35th second of spin coating, 100 μL of chlorobenzene was quickly dropped as an antisolvent treatment. Then, the film was placed on a hot plate at 150 °C for annealing for 10 min to obtain the perovskite layer 33. Then, by spin coating at 4000 rpm for 30 s, the hole transport layer 34 spiro-OMeTAD was deposited on the perovskite layer 33 (the specific preparation process was to dissolve 76 mg of spiro-OMeTAD in 1 mL of solvent chlorobenzene, and add 20.5 μL of tert-butylpyridine and 15 μL of 520 mg / mL lithium bis(trifluoromethanesulfonyl)imide acetonitrile solution as additives) to form the hole transport layer 34. Finally, under a vacuum condition of 1×10 -4 Pa, 100 nm thick gold was evaporated and deposited on the hole transport layer 34 as the top electrode, that is, the metal electrode 35.

[0072] (2) Preparation of the electrocatalytic end 20: The copper foam 21 was cut into a rectangle with dimensions of 3 cm × 1 cm, and then successively ultrasonically treated in ethanol (ultrasonic treatment for 10 min), 1 M HCl (ultrasonic treatment for 10 min), and pure water (ultrasonic treatment for 10 min) to remove surface impurities. First, Cu(OH)2 nanowires were prepared by anodic oxidation method, that is, using a platinum sheet as the counter electrode, the cleaned copper foam 21 was anodized in 1 M NaOH for 20 min, and at 60 mA·cm -2Anodization was carried out at a constant current density. Then, the Cu(OH)₂ nanowires grown on the copper foam 21 were placed in a high-temperature tube furnace for treatment. The specific process was annealing at 400 °C for 2 h at a heating rate of 5 °C / min under an argon atmosphere to obtain Cu₂O nanowires, forming the catalyst layer 22.

[0073] (3) Assembly: The prepared perovskite photoanode end 30 was combined with the electrocatalytic end 20 using a solid fusible metal (InSnBi alloy, melting point 58 °C). Specifically, a solid fusible metal block was thinly spread on a hot plate at 70 °C to melt and flatten it, then cooled to room temperature and cut into a size similar to that of the metal electrode 35 of the perovskite photoanode end 30 to obtain the fusible metal layer 10. The fusible metal layer 10 was placed on the metal electrode 35, and then the exposed side of the copper foam 21 in the electrocatalytic end 20 without the catalyst layer 22 was placed on the soluble metal sheet and assembled into a composite structure to achieve the connection between the perovskite photoanode end 30 and the electrocatalytic end 20. To form an electrical contact between the catalyst layer 22 of the cuprous oxide nanowires and the transparent electrode 31, conductive silver paste was coated on the surface of the transparent electrode 31 far from the electron transport layer 32 and a copper wire was led out to direct the electrons in the perovskite photovoltaic cell to the clip of the counter electrode platinum sheet to avoid excessive accumulation of electrons. Finally, the perovskite photoanode end 30 was sealed with epoxy resin and dried overnight.

[0074] Comparative Example 1

[0075] This example provides a self-driven perovskite photoanode electrocatalytic device. The device does not contain the fusible metal layer 10 and the perovskite photoanode end, and only uses the electrocatalytic end 20. Except for the above, other conditions are exactly the same as those in Example 1.

[0076] Characterization and Testing

[0077] Figure 2 Figure 16 shows the scanning electron microscope image of the cuprous oxide nanowires obtained in Example 1. It can be seen that rod-shaped cuprous oxide structures are formed on the surface.

[0078] Figure 3 Figure 20 shows the scanning electron microscope image of the perovskite layer 33 obtained in Example 1. It can be seen that the perovskite crystal structure is plump, dense, and has good crystallinity.

[0079] Figure 4 Figure 24 shows the J-V curve of the perovskite photoanode end 30 obtained in Example 1. It was tested under the simulated sunlight intensity of 1 sun by a xenon lamp, and it can be seen that its optoelectronic performance is good.

[0080] Figure 5The linear sweep voltammogram of the self-driven perovskite photoanode electrocatalytic device obtained in Example 1 in a 1 M KOH solution containing 100 mM furfural shows that a current density can be generated without an external voltage, which is used for electrocatalytic biomass valorization.

[0081] Figure 6 The bar chart shows the quantitative analysis of the furfural and furoic acid contents in the sample by injecting the electrolyte into a high-performance liquid chromatograph after 30 minutes of light irradiation (intensity of 1 sun) for the furfural oxidation application of the self-driven perovskite photoanode electrocatalytic device obtained in Example 1. It can be seen that the proportion of furoic acid content reaches 99.5%, indicating that the oxidation reaction is sufficient. Combining with the reaction equation shown in the figure, it can be known that a small amount of hydrogen is generated during the oxidation of furfural to furoic acid. This shows that the self-driven perovskite photoanode electrocatalytic device of the present invention can realize the reaction of furfural oxidation to furoic acid without the introduction of an external voltage.

[0082] Figure 7 The linear sweep voltammogram of the electrocatalytic device without a perovskite photoanode in Comparative Example 1 shows that the current density is significantly lower than that of the device integrated with the perovskite photoanode at different voltages. The current density corresponding to the electrocatalytic device with the perovskite photoanode obtained in Example 1 is 0.709 mA / cm at a voltage of 0.1 V. 2 The current density corresponding to the electrocatalytic device obtained in Comparative Example 1 is only 0.048 mA / cm at a voltage of 0.1 V. 2 The results of Comparative Example 1 show that it is almost difficult to detect the current density except at low voltages, indicating the superiority of the self-driven perovskite photoanode electrocatalytic device of the present invention.

[0083] In summary, different from the traditional technology that requires an external power supply to provide current, the self-driven perovskite photoanode electrocatalytic device of the present invention utilizes the photoelectric effect at the perovskite photoanode end to drive the electrocatalytic reaction through light irradiation, achieving complete self-driving. This not only simplifies the device design, reduces energy consumption, but also improves the system integration and operability. And the self-driven perovskite photoanode electrocatalytic device has multiple reaction capabilities. Compared with the traditional perovskite photoanode device that usually focuses on a single reaction (hydrogen production or oxygen production), the present invention can realize the oxidation reaction of biomass organic substances such as furfural while generating a small amount of hydrogen, thus improving the economy and versatility of the reaction.

[0084] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept scope of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0085] In addition, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any appropriate manner without conflict. To avoid unnecessary repetition, the present invention will not separately describe various possible combination methods.

[0086] Furthermore, any combination can be made among the various different embodiments of the present invention, as long as it does not violate the idea of the present invention, and it should also be regarded as the content disclosed by the present invention.

Claims

1. A self-driven perovskite photoanode electrocatalytic device, characterized in that, Including: A perovskite photoanode, a fusible metal layer, and an electrocatalytic end; the perovskite photoanode includes a transparent electrode, an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode; the electrocatalytic end includes copper foam and a catalyst layer on one side surface of the copper foam; the fusible metal layer is disposed between the metal electrode and the copper foam for connecting the perovskite photoanode and the electrocatalytic end.

2. The self-driven perovskite photoanode electrocatalytic device according to claim 1, wherein The metal element in the fusible metal layer includes at least one of In, Sn, or Bi; Preferably, the melting point of the fusible metal layer is 50 - 150 °C; Preferably, the thickness of the fusible metal layer is 50 - 300 μm.

3. The self-driven perovskite photoanode electrocatalytic device according to claim 1, characterized in that An external lead is disposed on the side surface of the transparent electrode away from the electron transport layer, and the external lead is used to connect to the cathode; Preferably, the external lead includes a metal copper wire cured with conductive silver paste; Preferably, the outer surface of the perovskite photoanode further includes an epoxy resin sealing and protecting layer.

4. The self-driven perovskite photoanode electrocatalytic device according to claim 1, wherein The catalyst in the catalyst layer includes a copper-based catalyst and / or a platinum-based catalyst; Preferably, the copper-based catalyst includes at least one of copper oxide, copper metal, or copper sulfide; Preferably, the copper oxide includes cuprous oxide nanowires.

5. The self-driven perovskite photoanode electrocatalytic device according to claim 1, characterized in that, The transparent electrode includes ITO glass; Preferably, the electron transport layer includes tin dioxide; Preferably, the perovskite component of the perovskite layer is ABX3, where A includes FA + , MA + or Cs + and at least one of them, B includes Sn 2+ and / or Pb 2+ , X includes I - , Br - or Cl - and at least one of them; Preferably, the hole transport layer includes spiro-OMeTAD; Preferably, the metal electrode includes gold; Preferably, the thickness of the metal electrode is 80 - 120 nm; Preferably, the active area of the perovskite photoanode is 0.2 to 0.35 cm 2 .

6. A manufacturing method of the self-driven perovskite photoanode electrocatalytic device according to any one of claims 1-5, characterized in that, The manufacturing method includes the following steps: Prepare the perovskite photoanode, the electrocatalytic end, and the fusible metal layer respectively; assemble the perovskite photoanode, the electrocatalytic end, and the fusible metal layer such that the fusible metal layer is disposed between the metal electrode in the perovskite photoanode and the copper foam in the electrocatalytic end to connect the perovskite photoanode and the electrocatalytic end.

7. The manufacturing method of the self-driven perovskite photoanode electrocatalytic device according to claim 6, characterized in that, When the perovskite photoanode is a photoanode, the method for preparing the perovskite photoanode includes: providing a transparent electrode, and sequentially preparing an electron transport layer, a perovskite layer, a hole transport layer, and a metal electrode thereon to obtain the perovskite photoanode; Preferably, the transparent electrode is pre-cleaned; the cleaning process includes sequentially ultrasonic treating with detergent, acetone, deionized water, and IPA for 15 - 20 min, and then drying with a nitrogen gas stream; Preferably, after the transparent electrode is cleaned, before preparing the electron transport layer, it is subjected to ultraviolet ozone treatment for 5 - 20 min; Preferably, when the electron transport layer includes tin dioxide, the method for preparing the electron transport layer includes spin-coating a 10% - 20% mass concentration tin oxide solution at 2000 - 4000 rpm for 20 - 40 s, and then annealing at 130 - 170 °C for 20 - 40 min; Preferably, the method for preparing the perovskite layer includes formulating a perovskite precursor solution, accelerating the speed to 800 - 1200 rpm at an acceleration of 100 - 300 rpm / s and spin-coating for 8 - 12 s, then accelerating the speed to 4800 - 5200 rpm at an acceleration of 800 - 1200 rpm / s and spin-coating for 28 - 32 s. At the 35th second after the start of spin-coating, an anti-solvent is added dropwise. The anti-solvent includes chlorobenzene; the dosage of the anti-solvent is 80 - 120 μL, and then annealing is performed at 120 - 180 °C for 5 - 15 min; Preferably, when the hole transport layer includes spiro-OMeTA, the method for preparing the hole transport layer includes formulating a solution of spiro-OMeTA and a solvent with a concentration of 70 - 80 mg / mL. The solvent includes chlorobenzene, and an additive is added simultaneously. The additive includes 15 - 25 μL of tert-butylpyridine and 10 - 20 μL of an acetonitrile solution of lithium bis(trifluoromethanesulfonyl)imide with a concentration of 500 - 550 mg / mL, and spin-coating at 3000 - 5000 rpm for 20 - 40 s; Preferably, the method for preparing the metal electrode includes performing evaporation deposition under a vacuum condition of ≤ 1×10 -3 Pa.

8. The manufacturing method of the self-driven perovskite photoanode electrocatalytic device according to claim 6, wherein When the catalyst of the catalyst layer includes cuprous oxide nanowires, the method for preparing the electrocatalytic end includes: Performing anodic oxidation on copper foam to form cupric hydroxide nanowires grown on the copper foam, and then performing heat treatment in an inert atmosphere. The cupric hydroxide nanowires generate cuprous oxide nanowires to form a catalyst layer, obtaining an electrocatalytic end; Preferably, the copper foam is pre-cleaned, and the cleaning process includes sequentially performing ultrasonic treatment in ethanol, 1 M HCl, and pure water for 5 - 15 min; Preferably, the counter electrode of the anodic oxidation method comprises a platinum sheet, the electrolyte comprises 1M NaOH and / or 1M KOH, the time is 5 to 30 min, and the constant current density is 20 to 100 mA·cm -2 ; Preferably, the heating rate of the heat treatment is 2 - 8 °C / min, the temperature is 300 - 500 °C, and the time is 1 - 3 h.

9. The manufacturing method of the self-driven perovskite photoanode electrocatalytic device according to claim 6, characterized in that, The method for preparing the fusible metal layer includes laying the fusible metal on a hot plate above its melting point, melting and flattening it to form a thin film, and cutting it after cooling to room temperature; Preferably, the method for connecting the perovskite photoanode end and the electrocatalytic end includes, after obtaining the assembly by the above assembly, performing heat treatment on the assembly to melt the fusible metal layer, and then cooling to achieve connection; Preferably, the temperature of the heat treatment is 20 - 30 °C higher than the melting point of the fusible metal layer; Preferably, the manufacturing method further includes using conductive silver paste to cure a copper wire on the side of the transparent electrode away from the electron transport layer to form an external lead for leading out electrons; Preferably, the preparation method further includes using epoxy resin to seal and dry the perovskite photoanode end to form an epoxy resin sealing protection layer.

10. Use of the self-driven perovskite photoanode electrocatalytic device according to any one of claims 1-5, characterized in that, The uses include value-added reaction of biomass-based organic matter with simultaneous hydrogen evolution; the biomass-based organic matter includes at least one of furfural, ethanol, or acetone; the value-added reaction includes an oxidation reaction.

Images