Dong Chaoran, Lin Cheng, Li Panjie, Park Jong Hyeok, Shen Jinyou, Zhang Kan
Key Laboratory of Environmental Remediation and Ecological Health, Ministry of Industry and Information Technology, School of Environmental and Biological Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China.
School of Materials Science and Engineering, Nanjing University of Science and Technology, Nanjing, China.
Angew Chem Int Ed Engl. 2025 Mar 17;64(12):e202423730. doi: 10.1002/anie.202423730. Epub 2025 Jan 9.
Suppressing over-oxidation is a crucial challenge for various chemical intermediate synthesis in heterogeneous catalysis. The distribution of oxidative species and the substrate coverage, governed by the direction of electron transfer, are believed to influence the oxidation extent. In this study, we presented an experimental realization of surface coverage modulation on a photoelectrode using a photo-induced charge activation method. Through the surface coverage modulation, both pre-oxidized alcohol substrates and surface coverage were increased, which not only improved the reaction kinetics but also suppressed the over-oxidation of the generated aldehydes/ketones. As a demonstration, the Faradaic efficiency for the conversion of glycerol to dihydroxyacetone increased from 31.8 % to 46.8 % (with selectivity rising from 47.6 % to 71.3 %), from 73.4 % to 87.8 % for benzyl alcohol to benzyl aldehyde (selectivity increasing from 76.7 % to 92.4 %) and from 4.2 % to 53.6 % for ethylene glycol to glycolaldehyde (selectivity increasing from 6.2 % to 62.7 %). Our findings offer a promising strategy for the production of high-value carbon products in heterogeneous catalysis.
抑制过度氧化是多相催化中各种化学中间体合成面临的关键挑战。氧化物种的分布和受电子转移方向控制的底物覆盖率被认为会影响氧化程度。在本研究中，我们展示了一种利用光诱导电荷活化方法在光电极上实现表面覆盖率调制的实验。通过表面覆盖率调制，预氧化的醇底物和表面覆盖率均增加，这不仅改善了反应动力学，还抑制了生成的醛/酮的过度氧化。作为示例，甘油转化为二羟基丙酮的法拉第效率从31.8%提高到46.8%（选择性从47.6%提高到71.3%），苯甲醇转化为苯甲醛的法拉第效率从73.4%提高到87.8%（选择性从76.7%提高到92.4%），乙二醇转化为乙醇醛的法拉第效率从4.2%提高到53.6%（选择性从6.2%提高到62.7%）。我们的研究结果为多相催化中高价值碳产品的生产提供了一种有前景的策略。
