CO<sub>2</sub>-Based Stable Porous Metal–Organic Frameworks for CO<sub>2</sub> Utilization
Bo Song, Yuhang Liang, Yi Zhou, Liang Zhang, He Li, Neng‐Xiu Zhu, Ben Zhong Tang, Dan Zhao, Bin Liu
Abstract
The transformation of carbon dioxide (CO 2 ) into functional materials has garnered considerable worldwide interest. Metal–organic frameworks (MOFs), as a distinctive class of materials, have made great contributions to CO 2 capture and conversion. However, facile conversion of CO 2 to stable porous MOFs for CO 2 utilization remains unexplored. Herein, we present a facile methodology of using CO 2 to synthesize stable zirconium-based MOFs. Two zirconium-based MOFs CO 2 –Zr-DEP and CO 2 –Zr-DEDP with face-centered cubic topology were obtained via a sequential desilylation–carboxylation–coordination reaction. The MOFs exhibit excellent crystallinity, as verified through powder X-ray diffraction and high-resolution transmission electron microscopy analyses. They also have notable porosity with high surface area ( S BET up to 3688 m 2 g –1 ) and good CO 2 adsorption capacity (up to 12.5 wt %). The resulting MOFs have abundant alkyne functional moieties, confirmed through 13 C cross-polarization/magic angle spinning nuclear magnetic resonance and Fourier transform infrared spectra. Leveraging the catalytic prowess of Ag(I) in diverse CO 2 -involved reactions, we incorporated Ag(I) into zirconium-based MOFs, capitalizing on their interactions with carbon–carbon π-bonds of alkynes, thereby forming a heterogeneous catalyst. This catalyst demonstrates outstanding efficiency in catalyzing the conversion of CO 2 and propargylic alcohols into cyclic carbonates, achieving >99% yield at room temperature and atmospheric pressure conditions. Thus, this work provides a dual CO 2 utilization strategy, encompassing the synthesis of CO 2 -based MOFs (20–24 wt % from CO 2 ) and their subsequent application in CO 2 capture and conversion processes. This approach significantly enhances overall CO 2 utilization.