Ma Wenjie, Mao Junjie, He Chun-Ting, Shao Leihou, Liu Ji, Wang Ming, Yu Ping, Mao Lanqun
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Analytical Chemistry for Living Biosystems, Institute of Chemistry, The Chinese Academy of Sciences (CAS) Beijing 100190 China
University of Chinese Academy of Sciences Beijing 100049 China.
Chem Sci. 2022 Apr 19;13(19):5606-5615. doi: 10.1039/d2sc01110g. eCollection 2022 May 18.
Singlet oxygen (O) as an excited electronic state of O plays a significant role in ubiquitous oxidative processes from enzymatic oxidative metabolism to industrial catalytic oxidation. Generally, O can be produced through thermal reactions or the photosensitization process; however, highly selective generation of O from O without photosensitization has never been reported. Here, we find that single-atom catalysts (SACs) with atomically dispersed MN sites on hollow N-doped carbon (M/HNC SACs, M = Fe, Co, Cu, Ni) can selectively activate O into O without photosensitization, of which the Fe/HNC SAC shows an ultrahigh single-site kinetic value of 3.30 × 10 min mol, representing top-level catalytic activity among known catalysts. Theoretical calculations suggest that different charge transfer from MN sites to chemisorbed O leads to the spin-flip process and spin reduction of O with different degrees. The superior capacity for highly selective O generation enables the Fe/HNC SAC as an efficient non-radiative therapeutic agent for inhibition of tumor cell proliferation.
单线态氧（O）作为O的一种激发电子态，在从酶促氧化代谢到工业催化氧化等普遍存在的氧化过程中发挥着重要作用。一般来说，O可以通过热反应或光敏化过程产生；然而，从未有过关于在无光敏化条件下从O高选择性生成O的报道。在此，我们发现具有原子分散的MN位点的单原子催化剂（SACs）负载在空心氮掺杂碳上（M/HNC SACs，M = Fe、Co、Cu、Ni）能够在无光敏化条件下将O选择性地活化成O，其中Fe/HNC SAC表现出3.30×10 min mol的超高单位点动力学值，代表了已知催化剂中的顶级催化活性。理论计算表明，从MN位点到化学吸附的O的不同电荷转移导致了O不同程度的自旋翻转过程和自旋降低。高选择性生成O的卓越能力使Fe/HNC SAC成为一种抑制肿瘤细胞增殖的高效非辐射治疗剂。
