Zhou Xiaoyu, Cao Kuanhong, Huang Shouqiang, Wu Haonan, Cao Zhen, Liu Hang, Chen Peng, Su Dawei, Wang Guoxiu, Wang Tianyi, Wang Chengyin, Pang Huan
Institute for Innovative Materials and Energy, School of Chemistry and Chemical Engineering, Yangzhou University, Yangzhou, 225002, China.
Ciechanover Institute of Precision and Regenerative Medicine, School of Medicine, The Chinese University of Hong Kong, Shenzhen, Guangdong, 518172, China.
Angew Chem Int Ed Engl. 2025 Jun 17;64(25):e202505532. doi: 10.1002/anie.202505532. Epub 2025 Apr 21.
This study reports the synthesis of silver single-atom-loaded thiophene-conjugated carbon nitride (Ag@T─CN), a material with high carrier concentration and efficient carrier separation. Under visible light, Ag@T─CN catalyzes hydrogen peroxide (HO) production and benzyl alcohol oxidation to benzaldehyde, achieving production rates of 4729.82 µmol·g·h for HO and 19.71 mmol·g·h for benzaldehyde. The synergy between thiophene conjugation and silver atoms extends visible light absorption and accelerates the 2-electron oxygen reduction reaction (ORR), enhancing HO yield. Photogenerated holes oxidize benzyl alcohol to benzaldehyde, while the biphasic benzaldehyde-water system enables spontaneous product separation. In situ Raman spectroscopy, rotating disk electrode testing, EPR, GC-MS, and DFT calculations highlight the critical role of thiophene-silver synergy in optimizing reaction pathways, enhancing catalyst-intermediate interactions, and reducing Gibbs free energy, improving HO and benzaldehyde synthesis. This study provides new insights for designing carbon nitride-based photocatalysts and offers a strategy for co-producing value-added chemicals.
本研究报道了负载银单原子的噻吩共轭氮化碳（Ag@T─CN）的合成，该材料具有高载流子浓度和高效的载流子分离性能。在可见光下，Ag@T─CN催化过氧化氢（HO）的生成以及苄醇氧化为苯甲醛，HO的产率为4729.82 µmol·g·h，苯甲醛的产率为19.71 mmol·g·h。噻吩共轭与银原子之间的协同作用扩展了可见光吸收范围，并加速了2电子氧还原反应（ORR），提高了HO的产率。光生空穴将苄醇氧化为苯甲醛，而双相苯甲醛-水体系能够实现产物的自发分离。原位拉曼光谱、旋转圆盘电极测试、电子顺磁共振、气相色谱-质谱联用以及密度泛函理论计算突出了噻吩-银协同作用在优化反应路径、增强催化剂-中间体相互作用以及降低吉布斯自由能方面的关键作用，从而提高了HO和苯甲醛的合成效率。本研究为设计基于氮化碳的光催化剂提供了新的见解，并为联产增值化学品提供了一种策略。
