期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 142, 期 49, 页码 20763-20771出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c09727
关键词
-
资金
- NSFC [21725101, 21673213, 21521001]
- Supercomputing Center of University of Science and Technology of China
Excitonic effects caused by Coulomb interactions between electrons and holes play subtle and significant roles on photocatalysis, yet have been long ignored. Herein, porphyrinic covalent organic frameworks (COFs, specifically DhaTph-M), in the absence or presence of different metals in porphyrin centers, have been shown as ideal models to regulate excitonic effects. Remarkably, the incorporation of Zn2+' in the COF facilitates the conversion of singlet to triplet excitons, whereas the Ni2+ introduction promotes the dissociation of excitons to hot carriers under photoexcitation. Accordingly, the discriminative excitonic behavior of DhaTph-Zn and DhaTph-Ni enables the activation of O-2 to O-1(2) and O-2(center dot-), respectively, under visible light irradiation, resulting in distinctly different activity and selectivity in photocatalytic terpinene oxidation. Benefiting from these results, DhaTph-Ni exhibits excellent photocatalytic activity in O-2(center dot-)-engaged hydroxylation of boronic acid, while DhaTph-Zn possesses superior performance in O-1(2)-mediated selective oxidation of organic sulfides. This work provides indepth insights into molecular oxygen activation and opens an avenue to the regulation of excitonic effects based on COFs.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据