Single-Pt-Atom-Decorated TiO 2 Nanorod Arrays for Photoelectrochemical C–H Chlorination

作者：Ying Tao, Jie Ding, Zhenyuan Teng, Qingzhu Xu, Wei Ou, Hongli Sun, Shuangjun Li, Lei Yu, Guisheng Li, Bin Liu, Chenliang Su · 发表于：Journal of the American Chemical Society · 年份：2025 · DOI：10.1021/jacs.5c02551 · 被引用次数：40 · 研究领域：Advanced Photocatalysis Techniques、Advanced Nanomaterials in Catalysis、Catalytic Processes in Materials Science

Photoelectrochemical (PEC) chloride oxidation reaction offers a green and sustainable approach for the synthesis of chlorinated chemicals, pesticides, pharmaceuticals/drugs, etc. However, until now, efficient PEC chloride activation remains highly challenging, primarily due to the lack of effective catalytically active reaction sites on the developed photoanodes. Herein, we construct a high-performance photoanode for PEC C–H chlorination by controllably embedding Pt single atoms onto positively charged TiO 2 nanorod arrays (denoted as Pt 1 - p -TiO 2 NRAs). The one-dimensional single-crystalline TiO 2 nanorods not only create a rapid electron transport pathway but also orthogonalize the light absorption and hole transport directions, effectively suppressing photogenerated electron–hole recombination. Furthermore, the positively charged TiO 2 nanorod surface induced by electrochemical reduction can facilitate the anchoring of single Pt atoms as C–H chlorination active sites onto TiO 2 and at the same time modulate the charge carrier dynamics. Consequently, high selectivity (up to 87%) and Faradaic efficiency (close to 60%) toward chlorination of organics are achieved over Pt 1 - p -TiO 2 NRAs using NaCl as the chlorine source under light illumination. PEC experiments and mechanistic investigations demonstrate that the single Pt atoms on TiO 2 nanorods can help to effectively separate photoexcited charge carriers and induce preferable chloride ions’ adsorption as well as electr...