Man Dong,Qingqing Pan,Fanfei Meng,Xiaohui Yao,Siqi You,Guogang Shan,Chunyi Sun,Xinlong Wang,Zhongmin Su
Sunlight-driven CO 2 reduction to value-added chemicals is an effective strategy to promote carbon recycling. The exploration of catalysts with efficient charge separation is crucially important for highly efficient CO 2 photoreduction. In this work, the preparation of metal-cluster-based covalent organic framework (CuABD) integrated features from both metal organic frameworks (MOFs) and covalent organic frameworks (COFs) through the condensation of diamines and functionalized trinuclear copper clusters demonstrate a thoughtful design strategy. The reported yield of 1.3 mmol g −1 h −1 for formic acid (HCOOH) under simulated solar irradiation is impressive, surpassing the performance of many COF- and MOF-based catalysts previously reported. Compared to its isomorphic metal-free structure (named BDFTD) and bare trinuclear Cu cluster which present extremely poor catalytic activities, CuABD displays remarkably enhanced CO 2 reduction activity. Experimental and theoretical investigations reveal that the efficient charge transfer between diamine monomer and cyclic trinuclear copper (I) units, and the electron delocalization of the π-conjugated framework are responsible for the appealing catalytic performance. In summary, the work presents a well-structured and scientifically sound exploration of a metal-cluster-based covalent organic framework for efficient CO 2 reduction under sunlight.
Liang Zhao,Guoying Yao,Huai Chen,Tao Zeng,Zhenyu Yang
Hybrid metal halide perovskites have attracted significant attention due to their outstanding chemical and structural versatility. Incorporating additional building blocks, such as large organic groups and organometallic clusters, provides additional pathways to manipulate the optoelectronic properties of perovskites. However, the bulky building blocks often struggle to cocrystallize with the lead halide framework, leading to undesirable crystal phase segregation or component exchange during cocrystallization. Here, we introduce a new zwitterionic-ligand-driven method for incorporating Cu-based clusters into perovskites. Mercaptoethylamine (MEA) serves as the bifunctional ligand to bridge the Cu(I) tetrahedral moieties and the perovskite scaffold, yielding a new bimetallic structure (MEA)4Cu2Pb3Br12. Combined X-ray-based characterizations and charge analysis affirm the antiferromagnetic coupling between the [CuS2Br2] tetrahedra, where the spin density is localized on the S atoms in a diradical form. The inclusion of Cu-based clusters introduces new acceptor energy levels that facilitate photocarrier separation and enable near-infrared light absorption.
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