Chen Yao, Guan Shuhui, Ge Hao, Chen Xiang, Xu Zhenming, Yue Yinghong, Yamashita Hiromi, Yu Han, Li Hexing, Bian Zhenfeng
MOE Key Laboratory of Resource Chemistry and Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Normal University, Shanghai, 200234, China.
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University, Shanghai, 200438, China.
Angew Chem Int Ed Engl. 2022 Dec 12;61(50):e202213640. doi: 10.1002/anie.202213640. Epub 2022 Nov 17.
Exploring the pathways for photocatalytic dissolution of precious metals (PMs) is crucial for optimizing recovery. In this work, we systematically investigated the selectivity and solvation effects observed for dissolution by focusing on photocatalysis, precious metals and solvents. By combining transient characterization, reaction kinetics, and density functional theory, we determined that the radicals generated in photocatalysis were the key active species in the entire reaction. The cyano functional group in the solvent was the driving factor for dissolution of gold, and the importance of chlorine radicals for dissolution of platinum group precious metals was further confirmed. In addition, the catalytic properties of different precious metals can promote different transformations of functional groups, leading to selective dissolution. The structures of photocatalytic precious metal leaches also precisely explains the special coordination forms of precious metals and functional group ligands.
探索贵金属（PMs）光催化溶解的途径对于优化回收至关重要。在这项工作中，我们通过聚焦光催化、贵金属和溶剂，系统地研究了溶解过程中观察到的选择性和溶剂化效应。通过结合瞬态表征、反应动力学和密度泛函理论，我们确定光催化过程中产生的自由基是整个反应中的关键活性物种。溶剂中的氰基官能团是金溶解的驱动因素，并且进一步证实了氯自由基对铂族贵金属溶解的重要性。此外，不同贵金属的催化性质可以促进官能团的不同转化，从而导致选择性溶解。光催化贵金属浸出物的结构也精确地解释了贵金属与官能团配体的特殊配位形式。
