In2o3 / zns hetero photoelectrocatalyst and biomass high-value conversion application thereof
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- LIAONING UNIVERSITY OF TECHNOLOGY
- Filing Date
- 2026-03-09
- Publication Date
- 2026-05-29
Smart Images
Figure CN122105491A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of photoelectrochemical synthesis and catalysis technology, specifically to an In2O3 / ZnS heterogeneous photoelectrocatalyst and its application in high-value biomass conversion. Background Technology
[0002] The selective oxidation of alcohols to their corresponding aldehydes is one of the most challenging and promising functional group transformations in organic synthesis. For example, furfural (FAL) is one of the 14 most competitive biomass platform compounds identified by the U.S. Department of Energy (DOE), and it is widely used as a key chemical in agrochemicals, plastics, pharmaceutical engineering, and oil refineries. Furfuryl alcohol (FA), as a conventional biomass, has been widely used in the synthesis of furfural. However, traditional production processes for converting FA to FAL typically require harsh reaction conditions, such as the addition of toxic oxidants and the maintenance of high temperatures, high pressures, or strong alkalinity. Photocatalysis, with its environmentally friendly, mild, and tunable input energy, is an attractive alternative for the selective oxidation of FAL, which is undoubtedly of great significance for the development of photocatalysis and the efficient utilization of biomass.
[0003] In recent years, indium oxide and transition metal sulfide semiconductors have attracted widespread attention in the field of photocatalytic organic matter conversion due to their unique electro-optical properties and band structures. However, their large band gaps limit their utilization of sunlight, and their photocatalytic performance remains unsatisfactory to date, with low target product yields and reaction rates. This is mainly due to the low efficiency of photogenerated electron-hole separation, poor transport properties, and low utilization efficiency of photogenerated carriers. Notably, heterojunction semiconductor catalysts have tunable band gaps, and the potential gradient at their interfaces facilitates charge separation and transport. Appropriate heterostructures can facilitate spatial separation of photogenerated carriers while maintaining relatively excellent redox performance, making them ideal candidate materials for the photocatalytic selective oxidation of fatty acids (FA) to fatty acids (FAL). Furthermore, the addition of electricity is expected to further promote charge separation, enhance the adsorption of reactant molecules, and improve product dissociation, showing broad application prospects in assisting the photocatalytic selective oxidation of organic matter. Therefore, constructing efficient photoelectrocatalytic systems and designing highly active photoelectrocatalysts are key approaches to improving the efficiency of photoelectrocatalytic selective oxidation. Summary of the Invention
[0004] The purpose of this invention is to provide an In2O3 / ZnS heterogeneous photoelectrocatalyst and its photoelectrocatalytic reaction system for the selective synthesis of furfural.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows: An In2O3 / ZnS heterogeneous photoelectrocatalyst is prepared by a hydrothermal method. In2O3 nanoparticles are anchored on ZnS nanosheets, and the catalyst as a whole exhibits a spherical morphology composed of many nanosheets.
[0006] An In2O3 / ZnS heteroelectrophotocatalyst with excellent photoelectrocatalytic performance was prepared by hydrothermal method using In(NO3)3·4H2O, Zn(CH3COO)2 and thiourea as precursors and by adjusting the ratio of In(NO3)3·4H2O and Zn(CH3COO)2.
[0007] The hydrothermal temperature is 120℃~180℃.
[0008] The diameter of In2O3 nanoparticles is 10~50nm.
[0009] There is electron loss on the surface of In2O3, while electron enrichment is found on the surface of ZnS. The electron binding energy of ZnS is shifted by 0.8~1 eV compared to pure In2O3 and ZnS materials.
[0010] The photoelectrocatalytic reaction uses furfuryl alcohol as the reactant and is carried out in a two-chamber electrolytic cell separated by a proton exchange membrane using a three-electrode system. The working electrode in the three-electrode system is an In2O3 / ZnS heterogeneous photoelectrocatalyst.
[0011] The electrocatalytic reaction employs a three-electrode system, with the working electrode being the In2O3 / ZnS heterogeneous photocatalyst of claim 1, the counter electrode being a platinum wire, platinum mesh, or platinum sheet, and the reference electrode being a calomel electrode, a mercury / mercuric oxide electrode, a silver / silver chloride electrode, or a mercury / mercurous sulfate electrode. The electrocatalytic reaction is carried out in an H-type electrolytic cell, where the anode and cathode chambers are separated by a proton exchange membrane. The anode electrolyte consists of Na2CO3 and furfuryl alcohol solution, while the cathode electrolyte is a Na2CO3 solution.
[0012] The concentration of the reactant furfuryl alcohol is 3~200 mmol / L, preferably 50~100 mmol / L.
[0013] The reaction voltage is 0.8~2.5 V vs. RHE, preferably 1.0~2.0 V vs. RHE; the reaction temperature is 20~30℃, preferably 25~28℃; and the reaction time is 1~5 h, preferably 2~3 h.
[0014] Illumination intensity of 100~150 mW / cm -2 Preferred value: 100~120 mW cm -2 .
[0015] The selectivity of furfural was 80–97%, and the formation rate of furfural was 5.1–7.3 mmol / g.-1 h -1 .
[0016] The principle of this invention is as follows: The photoelectrocatalytic reaction system for the selective synthesis of furfural proposed in this invention utilizes an In₂O₃ / ZnS heterocomposite material as the photoelectrocatalyst, where In₂O₃ nanoparticles are anchored on ZnS nanosheets. By constructing the In₂O₃ / ZnS heterocatalyst, its band gap is reduced, thereby improving its utilization of sunlight. The heterostructure formed between In₂O₃ and ZnS, along with the assistance of an electric field, promotes the efficient separation and transfer of photogenerated electrons and holes, giving the In₂O₃ / ZnS heterocatalyst excellent selective oxidation catalytic performance.
[0017] The advantages of this invention compared to the prior art are as follows: 1. The photoelectrocatalytic reaction for the selective synthesis of furfural in this invention is carried out at room temperature and atmospheric pressure, using a neutral aqueous solution as the electrolyte. No organic solvents need to be added, making it non-toxic and pollution-free, and in line with green chemistry standards.
[0018] 2. In this invention, the heterostructure formed between In2O3 and ZnS promotes the accumulation of active material holes on In2O3, effectively improving the yield of furfural.
[0019] 3. Compared with electrocatalytic reaction systems, the introduction of light reduces the onset potential, thereby greatly reducing the consumption of electrical energy. At the same time, the electric field effectively promotes the efficient separation and transfer of photogenerated electrons and holes.
[0020] 4. This invention uses In2O3 / ZnS heterogeneous photoelectric material as a photoelectrochemical catalytic oxidation catalyst for furfuryl alcohol. In neutral electrolyte, it exhibits excellent selective oxidation catalytic activity, with a selectivity of up to 97% for the intermediate product furfural. Attached Figure Description
[0021] Figure 1 This is a scanning electron microscope image of the In2O3 / ZnS heteroelectrophotocatalyst prepared in this invention.
[0022] Figure 2 Transmission electron microscopy (TEM) image of the In2O3 / ZnS heteroelectrophotocatalyst prepared in this invention.
[0023] Figure 3 The furfural selectivity and formation rate were measured for In2O3, ZnS and In2O3 / ZnS catalysts in systems with a mixed solution of sodium carbonate and furfuryl alcohol as the electrolyte. Detailed Implementation
[0024] The present invention will be described in detail below with reference to the embodiments.
[0025] Example 1
[0026] An In₂O₃ / ZnS photoelectroanode catalyst was synthesized via a one-step hydrothermal method. First, 3 mmol of zinc acetate (Zn(CH₃COO)₂), 1 mmol of In(NO₃)₃·4H₂O, and 6 mmol of thiourea were dissolved in 50 mL of deionized water and transferred to a Teflon-lined stainless steel autoclave. The autoclave was sealed and the reaction was carried out hydrothermally at 160 °C for 10 h. After the reaction, the container was cooled to room temperature, the precursor was removed, and subjected to multiple centrifugations and washings, followed by drying in a 60 °C oven. Finally, the catalyst was annealed at 400 °C for 2 h under an argon atmosphere to obtain the In₂O₃ / ZnS catalyst. Figure 1 2). Prepare conductive glass with a size of 1*1.5 cm coated with conductive fluorine-doped tin oxide (FTO), and then ultrasonically clean the glass with acetone, ethanol, and deionized water. Prepare a slurry by taking 3 mL of 0.5% Nafion solution and 6 mg of In₂O₃ / ZnS catalyst. Drop the slurry onto the conductive glass and dry it in a 60 °C oven for later use. Photoelectrochemical measurements were performed on an electrochemical workstation (CH Instruments, CHI 920D) using a three-electrode system. The photoelectrochemical anode catalyst was directly used as the working electrode, and the counter electrode and reference electrode were a Pt sheet and a Hg / HgO reference electrode, respectively. 1.5 M Na₂CO₃ solution was used as the electrolyte. According to the Nernst equation E RHE = E Hg / HgO +0.0591pH +0.095V converts the applied potential into a reversible hydrogen potential (RHE), where E RHE and E Hg / HgO These represent the potentials relative to the RHE and Hg / HgO reference electrodes, respectively. Before testing, the electrolyte was purged with argon gas for 30 minutes. All working areas were 1 cm². 2 The photoanodes all use simulated sunlight (100 mW cm⁻¹). -2 The electrode front was irradiated with a 300 W xenon lamp (AM 1.5G filter). High-performance liquid chromatography (HPLC) was used for quantitative analysis to evaluate the photoelectrocatalytic performance of the catalyst in the oxidation of furfuryl alcohol. Figure 3 ).
[0027] Comparative Example 1 An In₂O₃ photoanode catalyst was synthesized via a one-step hydrothermal method. First, 4 mmol of In(NO₃)₃·4H₂O was annealed at 400 °C for 2 h in air to obtain a powder sample. Then, the sample was repeatedly centrifuged and washed with acetone, ethanol, and deionized water, and dried in a 60 °C oven to obtain the In₂O₃ catalyst. A 1*1.5 cm conductive glass coated with conductive fluorine-doped tin oxide (FTO) was prepared and ultrasonically cleaned with acetone, ethanol, and deionized water. A slurry was prepared by mixing 3 mL of 0.5% Nafion solution and 6 mg of In₂O₃ catalyst. The slurry was drop-coated onto the conductive glass and dried in a 60 °C oven for later use. Photoelectrochemical measurements were performed on an electrochemical workstation (CH Instruments, CHI 920D) using a three-electrode system. The photoanode catalyst was used directly as the working electrode, with a Pt sheet as the counter electrode and a Hg / HgO reference electrode as the reference electrode. A 1.5 M Na₂CO₃ solution was used as the electrolyte. According to the Nernst equation, E... RHE = E Hg / HgO +0.0591pH +0.095V converts the applied potential into a reversible hydrogen potential (RHE), where E RHE and E Hg / HgO These represent the potentials relative to the RHE and Hg / HgO reference electrodes, respectively. Before testing, the electrolyte was purged with argon gas for 30 minutes. All working areas were 1 cm². 2 The photoanodes all use simulated sunlight (100 mW cm⁻¹). -2 The electrode front was irradiated with a 300 W xenon lamp (AM 1.5G filter). High-performance liquid chromatography (HPLC) was used for quantitative analysis to evaluate the photoelectrocatalytic performance of the catalyst in the oxidation of furfuryl alcohol. Figure 3 ).
[0028] Comparative Example 2 A ZnS photoanode catalyst was synthesized via a one-step hydrothermal method. First, 3 mmol of zinc acetate and 6 mmol of thiourea were dissolved in 50 mL of deionized water and transferred to a Teflon-lined stainless steel autoclave. The autoclave was sealed and the reaction was carried out hydrothermally at 160 °C for 10 h. After the reaction, the container was cooled to room temperature, the precursor was removed, and subjected to multiple centrifugations and washings, followed by drying in a 60 °C oven. Finally, the catalyst was annealed at 400 °C for 2 h under an argon atmosphere to obtain the ZnS catalyst. Conductive glass with dimensions of 1 × 1.5 cm coated with conductive fluorinated tin oxide (FTO) was prepared and ultrasonically cleaned with acetone, ethanol, and deionized water. A slurry was prepared by mixing 3 mL of 0.5% Nafion solution and 6 mg of ZnS catalyst. The slurry was drop-coated onto the conductive glass and dried in a 60 °C oven for later use. Photoelectrochemical measurements were performed on an electrochemical workstation (CHInstruments, CHI 920D) using a three-electrode system. The photoelectrochemical anode catalyst was used directly as the working electrode, with a Pt sheet as the counter electrode and a Hg / HgO reference electrode as the reference electrode. A 1.5 M Na₂CO₃ solution was used as the electrolyte. The measurements were performed according to the Nernst equation E. RHE = E Hg / HgO +0.0591 pH +0.095V converts the applied potential into a reversible hydrogen potential (RHE), where E RHE and E Hg / HgO The potentials are relative to the RHE and Hg / HgO reference electrodes, respectively. Before testing, the electrolyte was purged with argon gas for 30 minutes. All working areas were 1 cm². 2 The photoanodes all use simulated sunlight (100 mW cm⁻¹). -2 The electrode front was irradiated with a 300 W xenon lamp (AM1.5G filter). High-performance liquid chromatography (HPLC) was used for quantitative analysis to evaluate the photoelectrocatalytic performance of the catalyst in the oxidation of furfuryl alcohol. Figure 3 ).
Claims
1. An In₂O₃ / ZnS heterogeneous photoelectrocatalyst, characterized in that: The In2O3 / ZnS heterogeneous photoelectrocatalyst was prepared by a hydrothermal method. In2O3 nanoparticles were anchored on ZnS nanosheets, and the catalyst as a whole exhibited a spherical morphology composed of many nanosheets.
2. The In₂O₃ / ZnS heterogeneous photocatalyst according to claim 1, characterized in that: The hydrothermal preparation conditions were as follows: In(NO3)3·4H2O, Zn(CH3COO)2 and thiourea were used as precursors. By adjusting the ratio of In(NO3)3·4H2O and Zn(CH3COO)2, an In2O3 / ZnS heteroelectrophotocatalyst with excellent photoelectrocatalytic performance was prepared.
3. The In₂O₃ / ZnS heterogeneous photocatalyst according to claim 1, characterized in that: The hydrothermal temperature is 120℃~180℃.
4. The In₂O₃ / ZnS heterogeneous photocatalyst according to claim 1, characterized in that: The diameter of In2O3 nanoparticles is 10~50nm.
5. The In₂O₃ / ZnS heterogeneous photocatalyst according to claim 1, characterized in that: There is electron loss on the surface of In2O3, while electron enrichment is found on the surface of ZnS. The electron binding energy of ZnS is shifted by 0.8~1 eV compared to pure In2O3 and ZnS materials.
6. A photoelectrocatalytic reaction system for the selective synthesis of furfural, characterized in that: The photoelectrocatalytic reaction uses furfuryl alcohol as the reactant and is carried out in a two-chamber electrolytic cell separated by a proton exchange membrane using a three-electrode system. The working electrode in the three-electrode system is the In2O3 / ZnS heterogeneous photoelectrocatalyst of claim 1.
7. The photoelectrocatalytic reaction system according to claim 6, characterized in that: The electrocatalytic reaction employs a three-electrode system. The working electrode is the In2O3 / ZnS heterogeneous photoelectrocatalyst of claim 1, the counter electrode is a platinum wire, platinum mesh, or platinum sheet, and the reference electrode is a calomel electrode, a mercury / mercuric oxide electrode, a silver / silver chloride electrode, or a mercury / mercurous sulfate electrode. The electrocatalytic reaction is carried out in an H-type electrolytic cell, where the anode and cathode chambers are separated by a proton exchange membrane. The anolyte consists of Na2CO3 and furfuryl alcohol solution, and the cathode electrolyte is a Na2CO3 solution.
8. The photoelectrocatalytic reaction system according to claim 6, characterized in that: The concentration of furfuryl alcohol as a reactant was 3–200 mmol / L, the reaction voltage was 0.8–2.5 V vs. RHE, the reaction temperature was 20–30 °C, the reaction time was 1–5 h, and the light intensity was 100–150 mW / cm². -2 .
9. The photoelectrocatalytic reaction system according to claim 6, characterized in that: The selectivity of furfural was 80–97%, and the formation rate of furfural was 5.1–7.3 mmol / g. -1 h -1 .