Achieving Diverse CO<sub>2</sub> Conversions through On-Demand Installation of Multivariate Catalytic Sites into One Prototypical Metal–Organic Framework
Songlin Deng, Yang‐Yang Xiong, Cheng‐Xia Chen, Qi Dai, Yin-Xian Chen, Wei Geng, Zi-Ying Liang, Wei-Lun Ruan, Zhang‐Wen Wei, Mihail Bãrboiu, Cheng‐Yong Su
Abstract
The programmable design and construction of multirole or swing-role metal–organic frameworks (MR/SR-MOFs) for variable CO 2 conversions are appealing for green and sustainable chemistry. Herein, we describe a facile MR/SR-MOF synthetic strategy for on-demand engineering of the catalytic pore spaces in a primitive MOF for diverse CO 2 chemical fixation. Distinct functional groups can be precisely and quantitively immobilized into prototypical LIFM-28 ( proto -LIFM-28) by virtue of postsynthesis based on its solid-state dynamic attribute, generating different catalytic pore spaces suitable for hydrosilylation, N -methylation, cycloaddition, and cyclization reactions of CO 2 . Remarkably, the resultant LIFM-DSL-3 carrying amino and CO 2 -masked N -heterocyclic carbene (NHC–CO 2 ) sites presents an excellent hydrosilylation performance with complete Ph 2 SiH 2 conversion (>99%) and high silyl methoxide (SMO) selectivity (95%) under atmospheric CO 2 pressure, achieving an extraordinary turnover number (TON) of 4367 and a turnover frequency (TOF) of 6221 h –1 beneficial for efficient methanol release upon hydrolysis. Moreover, an exceptionally high N -methylation efficiency is obtained for CO 2 transformation via N -methylation. This work demonstrates how to design MR/SR-MOFs as a multivariate catalytic platform for the cost-saving multirole and swing-role applications through on-demand manipulation and installation of active sites into a single MOF matrix without de novo synthesis.