Aniline molecule modified semiconductor photo-anode, preparation method thereof and application of aniline molecule modified semiconductor photo-anode in photoelectrocatalysis of glycerol oxidation

Abstract

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

Description

Technical Field

[0001] The invention relates to the field of semiconductor photoanode materials and photoelectrocatalytic glycerol oxidation, and in particular to a semiconductor photoanode material modified at the molecular level of aniline monomers and a preparation method thereof, as well as application in photoelectrocatalytic glycerol selective oxidation reaction. Background Art

[0002] Glycerol is a major byproduct of biodiesel production ($0.24 / kg), with excess capacity and rich hydroxyl functional groups, making it a very valuable platform compound for catalytic conversion to produce high value-added fine chemicals. Glycerol can be converted into a series of aldehyde and ketone products through catalytic oxidation reactions, which have a wide range of applications in the pharmaceutical, fragrance, food additive and other industries and have high economic value.

[0003] At present, there are two main mainstream production processes for glyceraldehyde and glyceric acid: (1) Using glycerol as raw material, oxidizing with a strong oxidant to obtain glyceraldehyde and acid products, but the reaction process is cumbersome, the product is complex and will produce many glycerol derivatives, which is not conducive to the separation and extraction of the subsequent products. (2) Microbial fermentation process, with mild reaction conditions, high raw material utilization rate, and green environmental protection, but limited production efficiency, long production cycle, can not give full play to the production capacity of the production equipment; and during use, the cells in the fermentation liquid often adhere to the membrane, which greatly shortens the service life of the membrane and limits its practical application. The emerging photoelectric catalytic technology uses clean and renewable solar energy to excite semiconductor materials to generate charge-hole and other carriers. It 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 that tungsten trioxide is used as a photoanode catalyst, ITO is used as a substrate to make a photoanode, and a copper sheet is used as a cathode to assemble an electrolytic cell, and then 500mW·cm -2 (five times the standard sunlight intensity), 0.8V bias voltage for 6h, dihydroxyacetone selectivity is 30%. In addition, most of the published photoanode materials have the problems of complex synthesis process, high cost and difficulty in practical application. Patent document CN114990585A also discloses FTO with two semiconductor materials of loaded bismuth oxide and titanium dioxide as photoanode. The photoanode synthesis route is more complicated and requires repeated roasting, which is still not conducive to actual production. Patent document CN115341240A uses cyclic voltammetry scanning or constant potential pretreatment to invent a method for improving the activity of Bi-modified Pt catalyst in glycerol electro-oxidation reaction, which is applied in glycerol electro-oxidation reaction, solving the problem that the activity of existing liquid alcohol fuel cell catalysts is not high, but the use of precious metals increases the preparation cost.

[0005] In summary, traditional production technologies still have problems with complex generation methods, high losses and low yields, while emerging photoelectrocatalytic technologies either have low current density and low yields, or complex synthesis processes for photoanode semiconductor materials and high preparation costs.

[0006] The aniline molecular modification strategy of the present invention has the following advantages: 1) It is achieved by the impregnation method, and the preparation process is relatively simple, does not require multiple firing and drying, and the amount of grafted aniline monomer is controllable; 2) The preparation cost is low, and no precious metals or other expensive raw materials are required; 3) The aniline molecular modification will not affect the properties of the basic material, and the basic material can be reused; 4) Aniline molecules are grafted on the surface of the photoanode material to form a steric hindrance, avoiding a certain amount of ineffective adsorption, repeated adsorption, and multiple adsorption; 5) The amino center of aniline loses an electron and becomes positively charged, which promotes the mobility of photogenerated electrons-holes and increases the relative number and survival time. Summary of the invention

[0007] In view of the shortcomings of the existing technology and the integration of related advantages, we propose to use a simple impregnation method to graft aniline monomers on the surface of semiconductor materials to make the required photoanode, realize the regulation of steric hindrance and electronic structure, and then use platinum as the cathode and Ag / AgCl as the reference electrode to achieve photoelectrocatalytic selective oxidation of glycerol under a certain intensity of light and a certain voltage. The present invention meets the requirements of the coupling relationship of "green sustainable raw materials-energy-chemistry" and provides a new way for glycerol oxidation.

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

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

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

[0011] Preferably, the volume ratio of ethanol to water in the ethanol / water mixture is 3:1 to 5:1;

[0012] Preferably, the aniline concentration in the impregnation solution is 1 to 5 mol / L;

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

[0014] The modification method provided by the present invention can not only optimize the electronic structure of the basic photoanode material to obtain a higher migration efficiency and survival time of photogenerated electron-hole pairs, 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 molecule modified semiconductor material of the present invention can be used as a photoanode in the photoelectrocatalytic selective oxidation reaction of glycerol; the specific application method is as follows:

[0016] (i) Assembly of the photoelectrocatalytic device

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

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

[0019] The cathode material uses the platinum electrode commonly found on the market;

[0020] In the H-type electrode reaction tank, the light window side 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 a 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 has a concentration of 0.1 to 2 mol / L, and the solvent is deionized water;

[0023] (ii) Photoelectrocatalytic reaction

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

[0025] The light intensity of the light source is preferably 100 mW / cm 2 ;

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

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

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

[0029] The present invention has excellent catalytic oxidation performance of glycerol. Taking aniline-modified tungsten oxide as an example, the total yield of three-carbon products such as glyceric acid, glyceraldehyde, and dihydroxyacetone can reach up to 239mmol / m 2 ·h, of which glyceraldehyde 152.96mmol / m 2 h, glyceric acid 33.46mmol / m 2 ·h, dihydroxyacetone 52.58mmol / m 2 ·h, the selectivity of three-carbon products reaches 95%. Compared with chemical oxidation and biological oxidation, this method is environmentally friendly and has simple equipment. Compared with other photoelectrocatalytic technologies, the photoanode preparation process is simple, low-cost and reusable, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[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 produce high value-added products before and after WO3 aniline modification.

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

[0035] Figure 6 : Scanning electron microscope and transmission electron microscope images of BiVO4 material with nanosheet structure.

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

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

[0038] In order to facilitate the understanding of the present invention, the technical content of the present invention will be further described below in conjunction with specific embodiments, which are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The professional terms used are only for the purpose of describing the specific embodiments and are not intended to limit the scope of protection of the present invention.

[0039] The N117 cationic membrane used in the examples was purchased from DuPont proton exchange membrane N117 perfluorosulfonic acid ion membrane Nafion117 (10*10 cm).

[0040] Example 1: Aniline monomer modified WO3 material (FTO\A-WO3) is used as a photoanode for photoelectrocatalytic oxidation of glycerol to generate 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 ) was used as a carrier and 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 value of the solution was adjusted to 7 with 3 M hydrochloric acid. Subsequently, a hydrothermal reaction was carried out at 120 °C for 12 h. After the reaction was completed, it was repeatedly rinsed with deionized water and ethanol, and then calcined at 450 °C for 2 h to obtain a WO3 photoanode with a nanosheet structure array on a FTO conductive glass substrate (denoted as FTO / WO3).

[0043] Figure 1 In the figure, (a) and (b) are scanning electron microscope images of the prepared FTO / WO3. It can be seen that its microscopic morphology is that high-density vertically arranged WO3 nanosheets are evenly covered on the FTO carrier.

[0044] Figure 2 This is the transmission electron microscope image of FTO / WO3 material. It can be seen that its crystal structure is a monoclinic phase with (020) and (200) crystal planes as the main components.

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

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

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

[0048] Figure 4 This is a simplified diagram of a reaction device with FTO\A-WO3 as the photoanode, platinum as the cathode, and N117 cationic membrane separating the two polar chambers.

[0049] Figure 5 This is the liquid phase spectrum of FTO / WO3 and FTO\A-WO3 after photoanode electrolysis for 1 hour. It can be seen that the front intensity of the three-carbon products has increased.

[0050] The electrolyte of the cathode and anode tanks was 0.5 mol / L sodium sulfate, the pH value was adjusted to 2, the substrate was 0.1 M glycerol, and the intensity was 100 mW / cm 2 The xenon lamp was continuously irradiated, and a voltage of 0.8V was applied between the cathode and anode. After the photoelectrocatalytic reaction was carried out for 1 hour at room temperature and under stirring conditions, the experimental results were obtained by quantitative detection using liquid chromatography:

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

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

[0053] Example 2: Catalysis of FTO\A-WO3 photoanode material as photoanode at different voltages.

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

[0055] With FTO\A-WO3 as the photoanode, platinum as the cathode, and N117 cationic membrane separating the two polar chambers, the schematic diagram of the reaction device is shown in Figure 4 The cathode electrolyte is a sodium sulfate solution with a concentration of 0.5 mol / L, the anode electrolyte is a sodium sulfate solution with a concentration of 0.5 mol / L and contains 0.1 mol / L glycerol, and the pH value of the cathode electrolyte is adjusted to about 2. The intensity is 100 mW / cm2 The xenon lamp was continuously irradiated, and a voltage of 1.0V was applied between the cathode and anode. After the photoelectrocatalytic reaction was carried out at room temperature and under stirring conditions for 1 hour, the experimental results were obtained by quantitative detection using liquid chromatography:

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

[0057] Example 3: Aniline monomer modified BiVO4 material (FTO\A-BiVO4) is 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 3.32 g of potassium iodide in 50 ml of deionized water, add an appropriate amount of nitric acid to adjust the pH to about 1.7, then add 0.9701 g of bismuth nitrate pentahydrate (0.4 M), and quickly stir and mix to obtain solution A; add 0.5126 g of p-benzoquinone into 20 ml of anhydrous ethanol (p-benzoquinone concentration is 0.4 mol / 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 Pt metal sheet as the counter electrode. The A\B mixed solution was poured into the electrolytic cell, the electrolysis potential was -0.1V, the electrolysis time was 300s, and the BiOI film was electrodeposited on the working electrode.

[0062] b. Calcination to fix the crystal form

[0063] A dimethyl sulfoxide (DMSO) solution of vanadium acetylacetonate (wherein the concentration of vanadium acetylacetonate is 0.06 g / mL) is prepared and evenly added to the surface of the BiOI film prepared in step a; then it is placed in a muffle furnace and calcined at 450°C for 2 hours; after cooling to room temperature with the furnace, it is taken out and immersed in a 1M NaOH solution for 30 minutes, rinsed with deionized water, and dried at room temperature to obtain FTO\BiVO4 NPs.

[0064] Figure 6This is the scanning electron microscope image of the prepared FTO\BiVO4. It can be seen that its microscopic morphology is a porous, interconnected nanosheet array, and most of the microscopically active (112) crystal planes.

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

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

[0067] Figure 7 This is the mapping diagram of aniline-modified bismuth vanadate. It can be seen that aniline is evenly distributed on the surface of bismuth vanadate.

[0068] Figure 8 The liquid phase result of electrolysis for 1 hour when FTO\A-BiVO4 is used as the photoanode (other conditions are the same as those in Example 1), with an intensity of 100mW / cm 2 The xenon lamp was continuously irradiated, and a voltage of 1V was applied between the positive and negative electrodes. After the photoelectrocatalytic reaction was carried out for 1 hour at room temperature and under stirring conditions, 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 122mmol / m 2 ·h, of which glyceraldehyde 47mmol / m 2 h, dihydroxyacetone 75mmol / m 2 h, the selectivity of three-carbon products reached 60%, including 24% glyceraldehyde and 36% dihydroxyacetone.

[0070] b. FTO\A-BiVO4 photoanode: The total yield of three-carbon products such as glyceric acid, glyceraldehyde, and dihydroxyacetone reached 161.46 mmol / m 2 ·h, of which glyceraldehyde 75mmol / m 2 h, glyceric acid 4.46mmol / m 2 h, dihydroxyacetone 82mmol / m 2 h, the selectivity of 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 the selectivity of bismuth vanadate for three-carbon products being lower than that of 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] 12mL of deionized water was thoroughly mixed with an equal volume of concentrated hydrochloric acid. Then, 0.35mL of tetrabutyl titanate was dropped into the above solution and stirred for 30min. Subsequently, the mixture was transferred to a polytetrafluoroethylene-lined stainless steel autoclave (100mL) and a clean FTO substrate was poured into the solution. The autoclave was kept at 150°C for 5 hours. After cooling to room temperature, the sample with a white film was taken out 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 immersion method

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

[0077] FTO\A-TiO2 NPs was used as the photoanode, platinum was used as the cathode, and the two polar chambers were separated by N117 cationic membrane. The schematic diagram of the reaction device is shown in Figure 4 The electrolyte in the anode tank is 0.5 mol / L sodium sulfate and contains 0.1 mol / L glycerol. The electrolyte in the cathode chamber is 0.5 mol / L sodium sulfate solution. The pH value of the cathode and cathode electrolytes is adjusted to about 2. The intensity is 100 mW / cm 2 The xenon lamp was continuously irradiated, and a voltage of 1.85V was applied between the cathode and anode. After the photoelectrocatalytic reaction was carried out for 1 hour at room temperature and under stirring conditions, the following was 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 181mmol / m 2 ·h, of which glyceraldehyde 113mmol / m 2 h, glyceric acid 50mmol / m 2 h, dihydroxyacetone 18mmol / m 2 h, the selectivity of 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 up to 227.4mmol / m 2·h, of which glyceraldehyde 142mmol / m 2 h, glyceric acid 60mmol / m 2 ·h, dihydroxyacetone 25.4mmol / m 2 h, the selectivity of 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 larger current density in the system and an increase in the proportion of formic acid in the product to about 35%.

[0081] The above examples are illustrations of the embodiments of the present invention. The present invention uses cheap aniline-modified nanostructured semiconductor materials such as WO3, BiVO4, TiO2, etc. as photoanodes, so that they are initially applied in the selective oxidation of glycerol. This scheme is implemented by the impregnation method, and the preparation process is relatively simple, and does not require multiple firing and drying. The preparation cost is low, and there is no need to use precious metals or other expensive raw materials. The modification of aniline molecules will not affect the properties of the basic materials, and the basic materials can be reused. Aniline molecules are grafted on the surface of the photoanode material to form steric hindrance, avoiding a certain amount of ineffective adsorption, repeated adsorption, and multiple adsorption. The amino center of aniline will lose an electron and become positively charged, affecting the mobility, relative number and survival time of photogenerated electrons-holes. Aniline modification has many advantages and provides new ideas for material technology in the photoelectrocatalytic oxidation of glycerol.

Claims

1. A semiconductor material modified by aniline molecules, It is characterized in that Prepare as follows: Adding aniline to an ethanol / water mixture and stirring to obtain an impregnation solution; placing a base semiconductor material in the impregnation solution for 12 to 24 hours, then taking it out, rinsing it with deionized water, and drying it to obtain the aniline molecule modified semiconductor material; The basic semiconductor material is selected from WO with nanostructure 3 、TiO 2 or BiVO 4 .

2. The aniline molecule modified semiconductor material according to claim 1, It is 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 according to claim 1, It is characterized in that The aniline concentration in the impregnation solution is 1-5 mol / L.

4. Use of the aniline molecule modified semiconductor material as claimed in claim 1 as a photoanode in the photoelectrocatalytic selective oxidation reaction of glycerol.

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

6. The use according to claim 5, It is 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 use according to claim 5, It is characterized in that The sodium sulfate solution in step (i) has a concentration of 0.1-2 mol / L, and the solvent is deionized water.

8. The use according to claim 5, It is characterized in that In step (ii), the light intensity of the light source is 100 mW / cm 2 .

9. The use according to claim 5, It is characterized in that In step (ii), the three-carbon products with high added value are glyceraldehyde, glyceric acid and dihydroxyacetone.

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