{"title":"多功能co3o4修饰ZnIn2S4光催化剂选择性氧化生物质衍生5-羟甲基糠醛的研制","authors":"Shan Jiang , Zhenpan Chen , Shaofeng Xiong , Hongxin Zhao , Xishun Xiao , Zhigang Shen","doi":"10.1016/j.jechem.2025.06.032","DOIUrl":null,"url":null,"abstract":"<div><div>The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) offers a sustainable alternative to thermal catalysis. However, the efficiency of this process is significantly limited by inadequate light absorption efficiency and the rapid recombination of photogenerated charge carriers in conventional photocatalysts. Herein, we developed a Co<sub>3</sub>O<sub>4</sub>/ZnIn<sub>2</sub>S<sub>4</sub> (Co<sub>3</sub>O<sub>4</sub>/ZIS) photocatalyst, in which Co<sub>3</sub>O<sub>4</sub> functions as a multifunctional cocatalyst. This photocatalyst significantly enhances the chemisorption and activation of HMF molecules through interfacial oxygen-hydroxyl interactions. Additionally, the incorporation of narrow-band gap Co<sub>3</sub>O<sub>4</sub> broadens the optical absorption range of the composite photocatalyst. Besides, integrating Co<sub>3</sub>O<sub>4</sub> with ZnIn<sub>2</sub>S<sub>4</sub> leads to a 5.9-fold increase in charge separation efficiency compared to pristine ZnIn<sub>2</sub>S<sub>4</sub>. The optimized Co<sub>3</sub>O<sub>4</sub>/ZIS-3 photocatalyst (3 wt% Co<sub>3</sub>O<sub>4</sub> loading) exhibits exceptional selectivity and yield for 2,5-diformylfuran (DFF) under visible light irradiation, achieving 70.4% DFF selectivity with a 5.4-fold enhancement compared to pristine ZnIn<sub>2</sub>S<sub>4</sub>. Scavenger experiments and electron spin resonance (ESR) spectroscopy indicate that superoxide radicals (⋅O<sub>2</sub><sup>−</sup>) and h<sup>+</sup> are the main active species driving the photocatalytic oxidation of HMF. Molecular simulations reveal that the activation of HMF and the transformation of the intermediate *MF to *DFF are more favorable over the Co<sub>3</sub>O<sub>4</sub>/ZIS composite due to lower activation barriers compared to those over ZnIn<sub>2</sub>S<sub>4</sub>. Through this work, we aim to design highly efficient and affordable photocatalysts for biomass valorization and contribute valuable insights into the mechanisms of photocatalytic oxidation of HMF.</div></div>","PeriodicalId":15728,"journal":{"name":"Journal of Energy Chemistry","volume":"109 ","pages":"Pages 830-838"},"PeriodicalIF":14.9000,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Development of multifunctional Co3O4-modified ZnIn2S4 photocatalyst for the selective oxidation of biomass-derived 5-hydroxymethylfurfural\",\"authors\":\"Shan Jiang , Zhenpan Chen , Shaofeng Xiong , Hongxin Zhao , Xishun Xiao , Zhigang Shen\",\"doi\":\"10.1016/j.jechem.2025.06.032\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) offers a sustainable alternative to thermal catalysis. However, the efficiency of this process is significantly limited by inadequate light absorption efficiency and the rapid recombination of photogenerated charge carriers in conventional photocatalysts. Herein, we developed a Co<sub>3</sub>O<sub>4</sub>/ZnIn<sub>2</sub>S<sub>4</sub> (Co<sub>3</sub>O<sub>4</sub>/ZIS) photocatalyst, in which Co<sub>3</sub>O<sub>4</sub> functions as a multifunctional cocatalyst. This photocatalyst significantly enhances the chemisorption and activation of HMF molecules through interfacial oxygen-hydroxyl interactions. Additionally, the incorporation of narrow-band gap Co<sub>3</sub>O<sub>4</sub> broadens the optical absorption range of the composite photocatalyst. Besides, integrating Co<sub>3</sub>O<sub>4</sub> with ZnIn<sub>2</sub>S<sub>4</sub> leads to a 5.9-fold increase in charge separation efficiency compared to pristine ZnIn<sub>2</sub>S<sub>4</sub>. The optimized Co<sub>3</sub>O<sub>4</sub>/ZIS-3 photocatalyst (3 wt% Co<sub>3</sub>O<sub>4</sub> loading) exhibits exceptional selectivity and yield for 2,5-diformylfuran (DFF) under visible light irradiation, achieving 70.4% DFF selectivity with a 5.4-fold enhancement compared to pristine ZnIn<sub>2</sub>S<sub>4</sub>. Scavenger experiments and electron spin resonance (ESR) spectroscopy indicate that superoxide radicals (⋅O<sub>2</sub><sup>−</sup>) and h<sup>+</sup> are the main active species driving the photocatalytic oxidation of HMF. Molecular simulations reveal that the activation of HMF and the transformation of the intermediate *MF to *DFF are more favorable over the Co<sub>3</sub>O<sub>4</sub>/ZIS composite due to lower activation barriers compared to those over ZnIn<sub>2</sub>S<sub>4</sub>. Through this work, we aim to design highly efficient and affordable photocatalysts for biomass valorization and contribute valuable insights into the mechanisms of photocatalytic oxidation of HMF.</div></div>\",\"PeriodicalId\":15728,\"journal\":{\"name\":\"Journal of Energy Chemistry\",\"volume\":\"109 \",\"pages\":\"Pages 830-838\"},\"PeriodicalIF\":14.9000,\"publicationDate\":\"2025-06-23\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Energy Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2095495625005091\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"Energy\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Energy Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2095495625005091","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"Energy","Score":null,"Total":0}
Development of multifunctional Co3O4-modified ZnIn2S4 photocatalyst for the selective oxidation of biomass-derived 5-hydroxymethylfurfural
The photocatalytic selective oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) offers a sustainable alternative to thermal catalysis. However, the efficiency of this process is significantly limited by inadequate light absorption efficiency and the rapid recombination of photogenerated charge carriers in conventional photocatalysts. Herein, we developed a Co3O4/ZnIn2S4 (Co3O4/ZIS) photocatalyst, in which Co3O4 functions as a multifunctional cocatalyst. This photocatalyst significantly enhances the chemisorption and activation of HMF molecules through interfacial oxygen-hydroxyl interactions. Additionally, the incorporation of narrow-band gap Co3O4 broadens the optical absorption range of the composite photocatalyst. Besides, integrating Co3O4 with ZnIn2S4 leads to a 5.9-fold increase in charge separation efficiency compared to pristine ZnIn2S4. The optimized Co3O4/ZIS-3 photocatalyst (3 wt% Co3O4 loading) exhibits exceptional selectivity and yield for 2,5-diformylfuran (DFF) under visible light irradiation, achieving 70.4% DFF selectivity with a 5.4-fold enhancement compared to pristine ZnIn2S4. Scavenger experiments and electron spin resonance (ESR) spectroscopy indicate that superoxide radicals (⋅O2−) and h+ are the main active species driving the photocatalytic oxidation of HMF. Molecular simulations reveal that the activation of HMF and the transformation of the intermediate *MF to *DFF are more favorable over the Co3O4/ZIS composite due to lower activation barriers compared to those over ZnIn2S4. Through this work, we aim to design highly efficient and affordable photocatalysts for biomass valorization and contribute valuable insights into the mechanisms of photocatalytic oxidation of HMF.
期刊介绍:
The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies.
This journal focuses on original research papers covering various topics within energy chemistry worldwide, including:
Optimized utilization of fossil energy
Hydrogen energy
Conversion and storage of electrochemical energy
Capture, storage, and chemical conversion of carbon dioxide
Materials and nanotechnologies for energy conversion and storage
Chemistry in biomass conversion
Chemistry in the utilization of solar energy