Semiconductor photoanode modified by aniline molecules, preparation method thereof and application of the semiconductor photoanode in photoelectrocatalytic oxidation of glycerol

Abstract

The application discloses aniline molecular modified semiconductor photoanode and a preparation method and photoelectrocatalytic glycerol oxidation application thereof; the photoanode takes WO3, TiO2 or BiVO4 and the like grown on a conductive glass (FTO) substrate as a base material, and then grafts an aniline monomer molecule at a molecular level on the surface of the base material; the modification method can not only optimize the electronic structure of the base photoanode material to obtain higher photo-generated electron-hole pair migration efficiency and survival time, but also form steric hindrance to affect the adsorption state of glycerol molecules on the surface of the photoanode material, so that the selectivity is improved; the improved photoanode material of the application shows excellent catalytic activity and stability in the application of photoelectrocatalytic glycerol oxidation into glycerol aldehyde, glyceric acid, dihydroxyacetone and other high-value-added three-carbon products.

Description

Technical Field

[0001] This invention relates to the fields of semiconductor photoanode materials and photoelectrocatalytic glycerol oxidation, specifically to a semiconductor photoanode material modified at the molecular level of aniline monomers and its preparation method, as well as its application in the photoelectrocatalytic selective oxidation reaction of glycerol. Background Technology

[0002] Glycerol, a major byproduct of biodiesel production (US$0.24 / kg), has surplus production capacity and abundant hydroxyl functional groups, making it a valuable platform compound for catalytic conversion into high-value-added fine chemicals. Glycerol can be converted into a series of aldehydes and ketones through catalytic oxidation reactions. These products have wide applications in the pharmaceutical, fragrance, and food additive industries and possess significant economic value.

[0003] Currently, there are two main production processes for glyceraldehyde and glyceric acid: (1) Using glycerol as raw material, glyceraldehyde and glyceric acid are obtained by oxidation with a strong oxidant. However, the reaction process is complicated and the products are complex, which will produce many glycerol derivatives, making it difficult to separate and extract the products in the later stage. (2) Microbial fermentation process, which has mild reaction conditions, high raw material utilization rate, and is green and environmentally friendly, but has limited production efficiency and long production cycle, and cannot fully utilize the production capacity of the production equipment; and during use, the cells in the fermentation broth often adhere to the membrane, which greatly shortens the service life of the membrane and limits its practical application. The emerging photoelectrocatalysis technology uses clean and renewable solar energy to excite semiconductor materials to generate charge-hole carriers, which has the advantages of mild reaction conditions, simple production equipment, and easy product separation, but still has the problems of low current density and low conversion rate.

[0004] Patent document CN114990585A discloses an electrolytic cell assembled using tungsten trioxide as the photoanode catalyst, ITO as the substrate to fabricate the photoanode, and copper sheets as the cathode, and then irradiated with 500 mW·cm⁻¹ light. -2 (Five times the standard sunlight intensity) and a 0.8V bias voltage for 6 hours, the selectivity for dihydroxyacetone was 30%. Furthermore, most published photoanode materials suffer from complex synthesis processes, high costs, and difficulty in practical application. Patent document CN114990585A also discloses FTO supported on two semiconductor materials, bismuth oxide and titanium dioxide, as a photoanode. This photoanode synthesis route is even more complex and requires repeated calcination, still unfavorable for practical production. Patent document CN115341240A invented a method to improve the activity of Bi-modified Pt catalysts in the electro-oxidation reaction of glycerol using cyclic voltammetry or constant potential pretreatment. Its application in the electro-oxidation reaction of glycerol solves the problem of low activity in existing liquid alcohol fuel cell catalysts, but the use of precious metals increases the preparation cost.

[0005] In summary, traditional production technologies still suffer from problems such as complex generation methods, high losses, and low yields, while emerging photoelectrocatalysis technologies either have low current densities and low yields, or complex synthesis processes for photoanode semiconductor materials, resulting in high preparation costs.

[0006] The aniline molecule modification strategy of this invention has the following advantages: 1) It is achieved by impregnation, the preparation process is relatively simple, it does not require multiple firing and drying, and the amount of grafted aniline monomer is controllable; 2) The preparation cost is low, and it does not require the use of precious metals or other expensive raw materials; 3) The modification of aniline molecules does not affect the properties of the base material, and the base material can be reused; 4) When aniline molecules are grafted onto the surface of the photoanode material, they can form steric hindrance, avoiding a certain amount of ineffective adsorption, repeated adsorption, and excessive adsorption; 5) The amino center of aniline will lose an electron and become positively charged, which promotes the mobility of photogenerated electrons and holes, increases their relative number, and extends their survival time. Summary of the Invention

[0007] Addressing the shortcomings of existing technologies and integrating their advantages, we propose a simple impregnation method to graft aniline monomers onto the surface of a semiconductor material to create the desired photoanode. This allows for the control of steric hindrance and electronic structure. Using platinum as the cathode and Ag / AgCl as the reference electrode, photoelectrocatalytic selective oxidation of glycerol is achieved under specific light intensity and voltage. This invention aligns with the need for a "green and sustainable raw material-energy-chemistry" coupling relationship, providing a new pathway for glycerol oxidation.

[0008] The technical solution of the present invention is as follows:

[0009] An aniline-modified semiconductor material is prepared by the following method:

[0010] Aniline was added to an ethanol / water mixture and stirred (30 min) to prepare an impregnation solution; the basic semiconductor material was placed in the impregnation solution for 12-24 h, then removed, rinsed with deionized water, and dried (50-80 °C, 24 h) to obtain the aniline molecule modified semiconductor material.

[0011] In the preferred ethanol / water mixture, the volume ratio of ethanol to water is 3:1 to 5:1.

[0012] The preferred impregnation solution has an aniline concentration of 1–5 mol / L;

[0013] The basic semiconductor material has strong oxidation ability, and preferably one of the semiconductor materials with nanostructures such as WO3, TiO2, and BiVO4; WO3, TiO2, and BiVO4 with nanostructures can be loaded onto FTO conductive glass for preparation.

[0014] The modification method provided by this invention can not only optimize the electronic structure of the basic photoanode material to obtain higher photogenerated electron-hole pair migration efficiency and survival time, but also form steric hindrance to affect the adsorption state of glycerol molecules on the surface of the photoanode material, thereby improving selectivity.

[0015] The aniline-modified semiconductor material described in this invention can be used as a photoanode in the photoelectrocatalytic selective oxidation of glycerol; the specific application method is as follows:

[0016] (i) Assembly of photoelectrocatalytic devices

[0017] In an H-type electrode reaction cell with a quartz light window on one side, an N117 cation membrane is used to separate the electrolyte in the anode and cathode chambers. An aniline-modified semiconductor material is used as the photoanode, a platinum sheet as the cathode, and Ag / AgCl as the reference electrode. An electrolyte containing the reaction substrate glycerol is added to the side of the light window, and a normal electrolyte is added to the other side to complete the assembly.

[0018] The N117 cation exchange membrane only allows cations such as hydrogen ions to pass through;

[0019] The cathode material uses platinum sheet electrodes commonly found in the market;

[0020] In the H-type electrode reaction cell, the side with the light window is the anode chamber, and the opposite side is the cathode chamber;

[0021] The electrolyte in the anode chamber is a sodium sulfate solution containing the reaction substrate glycerol, with a pH of 2 to 4; preferably, the concentration of glycerol in the electrolyte is 0.05 to 2 mol / L; preferably, the concentration of the sodium sulfate solution is 0.1 to 2 mol / L, and the solvent is deionized water;

[0022] The common electrolyte in the cathode chamber is a sodium sulfate solution with a pH of 2 to 4; preferably, the sodium sulfate solution concentration is 0.1 to 2 mol / L, and the solvent is deionized water.

[0023] (ii) Photocatalytic reaction

[0024] Using sunlight simulated by a xenon lamp equipped with an AM1.5G filter as the light source, the light shines onto the surface of the photoanode through a quartz window. A voltage of 0.8 to 2V is applied between the cathode and anode, and the photoelectrocatalytic oxidation reaction is carried out at 15 to 50°C (preferably 30°C) for 1 to 8 hours under stirring conditions to generate high-value-added three-carbon products.

[0025] The preferred light source has an illuminance of 100 mW / cm². 2 ;

[0026] High-value-added three-carbon products include glyceraldehyde, glyceric acid, and dihydroxyacetone.

[0027] Compared with the prior art, the beneficial effects of the present invention are:

[0028] This invention uses low-cost aniline as a modifying material, avoiding the use of precious metals such as palladium, platinum, and gold, and heavy metals such as lead and cesium. Furthermore, the reaction conditions are relatively mild, and the material preparation and reaction equipment are simple. The photoanode material improved by this method exhibits excellent catalytic activity and stability in the photoelectrocatalytic oxidation of glycerol to high-value-added three-carbon products such as glyceraldehyde, glyceric acid, and dihydroxyacetone.

[0029] This invention exhibits excellent catalytic oxidation performance of glycerol. Taking aniline-modified tungsten oxide as an example, the total yield of three-carbon products, including glyceric acid, glyceraldehyde, and dihydroxyacetone, reaches a maximum of 239 mmol / m³. 2 •h, of which glyceraldehyde 152.96mmol / m 2 • h, glyceric acid 33.46 mmol / m 2 • h, dihydroxyacetone 52.58 mmol / m 2 The selectivity for three-carbon products reaches 95%. Compared with chemical oxidation and biological oxidation methods, this method is environmentally friendly and requires simple equipment. Compared with other photoelectrocatalytic technologies, the photoanode preparation process is simple, low-cost, and reusable, showing broad application prospects. Attached Figure Description

[0030] Figure 1 Scanning electron microscope image and X-ray diffraction pattern of nano-WO3 material.

[0031] Figure 2 Transmission electron microscopy image of nano-WO3 aniline modified material.

[0032] Figure 3 Mapping diagram of nano-WO3 aniline modified material.

[0033] Figure 4 Schematic diagram of the device for photoelectrocatalytic oxidation of glycerol to generate high-value-added products before and after modification with WO3 aniline.

[0034] Figure 5 : Liquid phase results of photoelectrocatalytic oxidation of aniline monomer-modified nano-WO3 material as photoanode.

[0035] Figure 6 Scanning electron microscope (SEM) and transmission electron microscope (TEM) images of BiVO4 materials with nanosheet structures.

[0036] Figure 7 Mapping diagram of nano-BiVO4 aniline modified material.

[0037] Figure 8 Liquid phase results of photoelectrocatalytic oxidation of glycerol to produce high-value-added products before and after BiVO4 aniline modification. Detailed Implementation

[0038] To facilitate understanding of the present invention, the technical content of the present invention will be further described below with reference to specific embodiments. These embodiments are only used to illustrate the present invention and do not limit the scope of the present invention. The technical terms used are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0039] The N117 cation exchange membrane used in the examples was purchased from DuPont N117 perfluorosulfonic acid ion exchange membrane Nafion 117 (10*10cm).

[0040] Example 1: Aniline monomer-modified WO3 material (FTO\A-WO3) was used as a photoanode for photoelectrocatalytic oxidation of glycerol to produce high-value-added three-carbon products.

[0041] (1) Preparation of FTO / WO3 photoanode by hydrothermal method

[0042] FTO conductive glass (27*15mm, 7Ω / cm) 2 Using sodium tungstate as a carrier, the sample was immersed in 6.75 mL of an aqueous solution containing 0.03825 g of sodium tungstate and 0.049 g of citric acid. The pH of the solution was adjusted to 7 with 3 M hydrochloric acid. The reaction was then carried out at 120 °C for 12 h. After the reaction was completed, the sample was repeatedly rinsed with deionized water and ethanol. The sample was then calcined at 450 °C for 2 h to obtain a WO3 photoanode with a nanosheet structure array (denoted as FTO / WO3) on an FTO conductive glass substrate.

[0043] Figure 1 In the image, (a) and (b) are scanning electron microscope images of the prepared FTO / WO3. It can be seen that its microstructure consists of high-density vertically arranged WO3 nanosheets uniformly covering the FTO support.

[0044] Figure 2 The image shows a transmission electron microscope (TEM) image of FTO / WO3 material, which reveals that its crystal structure is a monoclinic phase dominated by (020) and (200) crystal planes.

[0045] (2) Preparation of FTO\A-WO3 photoanode by impregnation method

[0046] The prepared tungsten oxide substrate was immersed in a 3:1 mixture of aniline and ethanol / water (aniline concentration 3 mol / L) for 12 hours. After immersion, it was rinsed repeatedly with deionized water and ethanol, and then dried in an oven at 70°C for 24 hours.

[0047] Figure 3 This is a mapping diagram of the FTO / A-WO3 photoanode. It can be seen that aniline molecules are uniformly grafted onto the surface of the tungsten oxide material.

[0048] Figure 4 This is a simplified diagram of a reaction apparatus using FTO / A-WO3 as the photoanode, platinum as the cathode, and an N117 cation exchange membrane to separate the two electrode chambers.

[0049] Figure 5 The liquid phase spectra of FTO / WO3 and FTO\A-WO3 after 1 hour of photoanodic electrolysis show that the peak intensity of the three carbon products is enhanced.

[0050] The electrolyte in both the anode and cathode cells was 0.5 mol / L sodium sulfate, with the pH adjusted to 2. The substrate was 0.1 M glycerol, and the electrolyte concentration was 100 mW / cm². 2 Under continuous xenon lamp irradiation and with a 0.8V voltage applied between the anode and cathode, the photoelectrocatalytic reaction was carried out for 1 hour at room temperature and with stirring. The experimental results were obtained by quantitative detection using liquid chromatography.

[0051] a. FTO / WO3 photoanode: The total yield of the three-carbon products glyceric acid, glyceraldehyde, and dihydroxyacetone reached 102 mmol / m³. 2 ·h, of which glyceraldehyde 75mmol / m 2 •h, glyceric acid 5mmol / m 2 • h, dihydroxyacetone 22 mmol / m 2 •h; The selectivity of the three-carbon products reached 96%, including 64% glyceraldehyde, 5% glyceric acid, and 27% dihydroxyacetone.

[0052] b. FTO / A-WO3 photoanode: The total yield of the three-carbon products glyceric acid, glyceraldehyde, and dihydroxyacetone reached a maximum of 132 mmol / m³. 2 ·h, of which glyceraldehyde 87mmol / m 2 •h, Glyceric acid 8mmol / m 2 • h, dihydroxyacetone 37 mmol / m 2 •h; The selectivity of the three-carbon products reached 98%, including 66% glyceraldehyde, 3% glyceric acid, and 29% dihydroxyacetone.

[0053] Example 2: FTO\A-WO3 photoanode material as a photoanode for catalysis at different voltages.

[0054] The preparation of the photoanode material is the same as in Example 1.

[0055] Using FTO / A-WO3 as the photoanode and platinum as the cathode, the two electrode chambers are separated by an N117 cation exchange membrane. A simplified diagram of the reaction apparatus is shown below. Figure 4 The cathode electrolyte is a 0.5 mol / L sodium sulfate solution, and the anode electrolyte is also a 0.5 mol / L sodium sulfate solution containing 0.1 mol / L glycerol. The pH of the anode and cathode electrolytes is adjusted to approximately 2. An intensity of 100 mW / cm² is used.2 The xenon lamp was continuously irradiated, and a voltage of 1.0V was applied between the anode and cathode. After a photoelectrocatalytic reaction was carried out at room temperature and with stirring for 1 hour, the experimental results were obtained by quantitative detection using liquid chromatography.

[0056] The total yield of the three-carbon products, glyceric acid, glyceraldehyde, and dihydroxyacetone, reached a maximum of 175 mmol / m³. 2 ·h, of which glyceraldehyde 110 mmol / m 2 • h, glyceric acid 15 mmol / m 2 • h, dihydroxyacetone 50 mmol / m 2 •h; The selectivity of the three-carbon products reached 96%, including 67% glyceraldehyde, 4% glyceric acid, and 25% dihydroxyacetone.

[0057] Example 3: Aniline monomer-modified BiVO4 material (FTO\A-BiVO4) was used as a photoanode for photoelectrocatalytic oxidation of glycerol to produce high-value-added three-carbon products.

[0058] (1) Preparation of FTO / BiVO4 photoanode by precipitation method:

[0059] a. Electrodeposition of BiOI

[0060] Dissolve 3.32g of potassium iodide in 50ml of deionized water, add an appropriate amount of nitric acid to adjust the pH to about 1.7, then add 0.9701g of bismuth nitrate pentahydrate (0.4M), and stir quickly to obtain solution A; add 0.5126g of p-benzoquinone to 20ml of anhydrous ethanol (p-benzoquinone concentration is 0.4mol / L) to obtain solution B.

[0061] Solution B was introduced into solution A and stirred to mix. A typical three-electrode system was used for constant potential electrodeposition, with FTO as the working electrode, Ag / AgCl as the reference electrode, and a Pt metal sheet as the counter electrode. The A / B mixed solution was poured into an electrolytic cell, with an electrolysis potential of -0.1V and an electrolysis time of 300s, and a BiOI thin film was electrodeposited on the working electrode.

[0062] b. Calcination to fix the crystal form

[0063] A dimethyl sulfoxide (DMSO) solution of vanadium acetylacetonate (with a vanadium acetylacetonate concentration of 0.06 g / mL) was prepared and uniformly dropped onto the surface of the BiOI film obtained in step a. The film was then placed in a muffle furnace and calcined at 450 °C for 2 hours. After cooling to room temperature in the furnace, the film was removed, immersed in 1 M NaOH solution for 30 minutes, rinsed with deionized water, and dried at room temperature to obtain FTO\BiVO4 NPs.

[0064] Figure 6The scanning electron microscope image of the prepared FTO\BiVO4 shows that its microstructure is a porous, interconnected array of nanosheets, with most of them being highly active (112) crystal planes.

[0065] (2) Preparation of FTO\A-BiVO4 photoanode by impregnation method

[0066] The prepared bismuth vanadate substrate was immersed in a 3:1 mixture of aniline and ethanol / water (aniline concentration 3 mol / L) for 12 hours. After immersion, it was repeatedly rinsed with deionized water and ethanol, and then dried in an oven at 70°C for 24 hours.

[0067] Figure 7 The image shows a mapping diagram of aniline-modified bismuth vanadate, which indicates that aniline is uniformly distributed on the surface of bismuth vanadate.

[0068] Figure 8 The liquid phase results after 1 hour of electrolysis with FTO / A-BiVO4 as the photoanode (other conditions are the same as in Example 1) are shown in the figure, with an intensity of 100 mW / cm². 2 The xenon lamp was continuously irradiated, and a 1V voltage was applied between the anode and cathode. After the photoelectrocatalytic reaction was carried out for 1 hour at room temperature and with stirring, the experimental results were obtained by quantitative detection using liquid chromatography.

[0069] a. FTO / BiVO4 photoanode: The total yield of three-carbon products such as glyceric acid, glyceraldehyde, and dihydroxyacetone reached 122 mmol / m³. 2 ·h, of which glyceraldehyde 47mmol / m 2 •h, dihydroxyacetone 75mmol / m 2 The selectivity of the three-carbon products reached 60%, including 24% glyceraldehyde and 36% dihydroxyacetone.

[0070] b. FTO / A-BiVO4 photoanode: The total yield of three-carbon products, including glyceric acid, glyceraldehyde, and dihydroxyacetone, reached 161.46 mmol / m³. 2 ·h, of which glyceraldehyde 75mmol / m 2 • h, glyceric acid 4.46 mmol / m 2 • h, dihydroxyacetone 82 mmol / m 2 The selectivity of the three-carbon products reached 60%, including 25% glyceraldehyde, 1% glyceric acid, and 34% dihydroxyacetone.

[0071] Bismuth vanadate has a higher current density due to its relatively small band gap. Some of the three-carbon products and some undetectable products are further oxidized to formic acid (the selectivity of formic acid is about 33%), which ultimately leads to bismuth vanadate having lower selectivity for three-carbon products than tungsten oxide.

[0072] Example 4: Aniline monomer-modified TiO2 NPs material was used as a photoanode for photoelectrocatalytic oxidation of glycerol to produce high-value-added three-carbon products.

[0073] (1) Preparation of FTO / TiO2 photoanode by hydrothermal method

[0074] 12 mL of deionized water was thoroughly mixed with an equal volume of concentrated hydrochloric acid. Then, 0.35 mL of tetrabutyl titanate was added dropwise to the solution, and the mixture was stirred continuously for 30 min. Subsequently, the mixture was transferred to a 100 mL stainless steel autoclave lined with polytetrafluoroethylene (PTFE), and a clean piece of FTO matrix was poured into the solution. The autoclave was maintained at 150 °C for 5 hours. After cooling to room temperature, the sample with a white film was removed and washed several times with deionized water. The sample was annealed in air at 450 °C for 3 hours.

[0075] (2) Preparation of FTO / A-TiO2 photoanode by impregnation method

[0076] The prepared titanium dioxide substrate was immersed in a 4:1 mixture of aniline and ethanol / water (aniline concentration 3 mol / L) for 12 hours. After immersion, it was rinsed repeatedly with deionized water and ethanol, and then dried in an oven at 70°C for 24 hours.

[0077] Using FTO / A-TiO2 NPs as the photoanode and platinum as the cathode, with an N117 cation exchange membrane separating the two electrode chambers, a simplified diagram of the reaction apparatus is shown below. Figure 4 The anode electrolyte is a 0.5 mol / L sodium sulfate solution containing 0.1 mol / L glycerol, while the cathode electrolyte is a 0.5 mol / L sodium sulfate solution. The pH of the anode and cathode electrolytes is adjusted to approximately 2. An intensity of 100 mW / cm² is used. 2 Under continuous xenon lamp irradiation, with a voltage of 1.85V applied between the anode and cathode, and after a photoelectrocatalytic reaction was carried out at room temperature and with stirring for 1 hour, the results were quantitatively detected by liquid chromatography.

[0078] a. FTO / TiO2 photoanode: The total yield of three-carbon products such as glyceric acid, glyceraldehyde, and dihydroxyacetone reached 181 mmol / m³. 2 ·h, of which glyceraldehyde 113mmol / m 2 •h, glyceric acid 50mmol / m 2 • h, dihydroxyacetone 18 mmol / m 2 The selectivity for three-carbon products reached 63%, including 39% glyceraldehyde, 18% glyceric acid, and 6% dihydroxyacetone.

[0079] b. FTO / A-TiO2 photoanode: The total yield of three-carbon products such as glyceric acid, glyceraldehyde, and dihydroxyacetone reached a maximum of 227.4 mmol / m³. 2·h, of which glyceraldehyde 142 mmol / m 2 • h, glyceric acid 60 mmol / m 2 • h, dihydroxyacetone 25.4 mmol / m 2 The selectivity of the three-carbon products reached 60%, including 38% glyceraldehyde, 16% glyceric acid, and 6% dihydroxyacetone.

[0080] In pursuit of high yield, a voltage of 1.85V was applied between the anode and cathode, resulting in a higher current density in the system and an increased proportion of formic acid in the product, approximately 35%.

[0081] The above examples illustrate the embodiments of the present invention. The present invention uses inexpensive aniline-modified nanostructured semiconductor materials such as WO3, BiVO4, and TiO2 as photoanodes, enabling their initial application in the selective oxidation of glycerol. This method utilizes an impregnation method, resulting in a relatively simple preparation process that eliminates the need for multiple firing and drying processes. The preparation cost is low, requiring no precious metals or other expensive raw materials. The modification of aniline molecules does not affect the properties of the base material, allowing for its reuse. The grafting of aniline molecules onto the surface of the photoanode material creates steric hindrance, preventing a certain amount of ineffective adsorption, repeated adsorption, and excessive adsorption. The amino center of aniline loses an electron, becoming positively charged, which affects the mobility, relative number, and survival time of photogenerated electrons and holes. Aniline modification offers numerous advantages, providing new insights into material technology for the photoelectrocatalytic oxidation of glycerol.

Claims

1. An aniline-modified semiconductor material, characterized in that, Prepared as follows: Aniline was added to an ethanol / water mixture and stirred to prepare an impregnation solution; the basic semiconductor material was placed in the impregnation solution for 12-24 hours, then removed, rinsed with deionized water, and dried to obtain the aniline molecule modified semiconductor material. The basic semiconductor material is selected from WO3, TiO2 or BiVO4, which have nanostructures.

2. The aniline-modified semiconductor material as described in claim 1, characterized in that, In the ethanol / water mixture, the volume ratio of ethanol to water is 3:1 to 5:

1.

3. The aniline molecule-modified semiconductor material as described in claim 1, characterized in that, The aniline concentration in the impregnation solution is 1–5 mol / L.

4. The application of the aniline molecule-modified semiconductor material as described in claim 1 as a photoanode in the photoelectrocatalytic selective oxidation of glycerol.

5. The application as described in claim 4, characterized in that, The method is as follows: (i) Assembly of photoelectrocatalytic devices In an H-type electrode reaction cell with a quartz light window on one side, an N117 cation membrane is used to separate the electrolyte in the anode and cathode chambers. An aniline-modified semiconductor material is used as the photoanode, a platinum sheet as the cathode, and Ag / AgCl as the reference electrode. An electrolyte containing the reaction substrate glycerol is added to the side of the light window, and a normal electrolyte is added to the other side to complete the assembly. In the H-type electrode reaction cell, the side with the light window is the anode chamber, and the opposite side is the cathode chamber; The electrolyte in the anode chamber is a sodium sulfate solution containing the reaction substrate glycerol, with a pH of 2 to 4; The common electrolyte in the cathode chamber is a sodium sulfate solution with a pH of 2–4. (ii) Photocatalytic reaction Using sunlight simulated by a xenon lamp equipped with an AM1.5G filter as the light source, the light shines onto the surface of the photoanode through a quartz window. A voltage of 0.8–2V is applied between the cathode and anode, and the photoelectrocatalytic oxidation reaction is carried out at 15–50°C for 1–8 hours under stirring conditions to generate high-value-added three-carbon products.

6. The application as described in claim 5, characterized in that, In step (i), the concentration of glycerol in the electrolyte of the anode chamber is 0.05–2 mol / L.

7. The application as described in claim 5, characterized in that, The sodium sulfate solution in step (i) has a concentration of 0.1–2 mol / L and uses deionized water as the solvent.

8. The application as described in claim 5, characterized in that, In step (ii), the illuminance of the light source is 100 mW / cm². 2 .

9. The application as described in claim 5, characterized in that, In step (ii), the high-value three-carbon products are glyceraldehyde, glyceric acid, and dihydroxyacetone.

Images