Stabilizing Silver Single‐Atom Site via A Pore‐Confined Triphenylphosphine for CO <sub>2</sub> Conversion With High Substrate‐Specificity
Abstract
ABSTRACT Ensuring the dispersion and anti‐aggregation of single‐atom sites under catalytic conditions remains a critical challenge in heterogeneous catalysis. Here, we report a dual‐confinement strategy for constructing a metal–organic framework (MOF) based catalyst, MEC‐88, by spatially confining triphenylphosphine (PPh 3 ) within the pores of MOF‐808 to anchor silver single‐atom sites. MEC‐88 exhibits exceptional activity and pronounced substrate selectivity for the carboxylative cyclization of CO 2 with benzyl‐substituted propargylamines under mild, additive‐free aqueous conditions, achieving a turnover frequency up to 1051.3 ± 0.7 h −1 . Moreover, PPh 3 , as a soft‐base ligand, provides robust coordination to silver atoms, effectively inhibiting their aggregation to endow the catalyst with good recyclability. Mechanistic studies reveal that the PPh 3 ‐coordinated silver site synergizes with the Zr 6 O 8 cluster to activate both the alkyne substrate and CO 2 , substantially lowering the energy barriers for CO 2 insertion and cyclization. This work presents a molecule‐enhanced confinement approach for designing stable and efficient single‐atom catalysts with controllable substrate‐specificity.
Article Details
Authors (12)
Jing Li
Zhao‐Cheng Shi
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China
Xiao‐Xiao Deng
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China
Xue‐Feng Zhang
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China
Zhonggao Zhou
College of Chemistry and Materials Science Analysis and Testing Center Key Laboratory of Jiangxi University for Functional Materials Chemistry Jiangxi Provincial Key Laboratory of Bamboo Fiber Composite Gannan Normal University Ganzhou China
Ping‐Ping Xu
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China
Ming‐Ming Wu
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China
Jia Zhang
Li‐Dong Wang
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China
Jia‐Jun Zeng
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China
Yan‐Tong Xu
School of Advanced Energy and IGCME Sun Yat‐sen University (Shenzhen) Shenzhen Guangdong China
Chun‐Ting He
Key Lab of Fluorine and Silicon for Energy Materials and Chemistry/College of Chemistry and Materials Jiangxi Normal University Nanchang China