Abstract
Direct structural information of confined CO2 in a micropore is important for elucidating its specific binding or activation mechanism. However, weak gas-binding ability and/or poor sample crystallinity after guest exchange hindered the development of efficient materials for CO2 incorporation, activation and conversion. Here, we present a dynamic porous coordination polymer (PCP) material with local flexibility, in which the propeller-like ligands rotate to permit CO2 trapping. This process can be characterized by X-ray structural analysis. Owing to its high affinity towards CO2 and the confinement effect, the PCP exhibits high catalytic activity, rapid transformation dynamics, even high size selectivity to different substrates. Together with an excellent stability with turnover numbers (TON) of up to 39,000 per Zn1.5 cluster of catalyst after 10 cycles for CO2 cycloaddition to form value-added cyclic carbonates, these results demonstrate that such distinctive structure is responsible for visual CO2 capture and size-selective conversion.
Highlights
Direct structural information of confined CO2 in a micropore is important for elucidating its specific binding or activation mechanism
Direct structural information of the molecular state of captured CO2 by X-ray diffraction (XRD) techniques is invaluable despite the practical difficulties associated with its gaseous nature because this enables a thorough understanding of the specific host–guest interaction or activation mechanism and processes, and leads to the development of new and improved catalysts
porous coordination polymer (PCP) have an advantage over other catalysts with respect to CO2 chemistry because of their integration of the inherent sorptive behavior with the uniform Lewis/Brønsted acidic or basic active sites endowed by their facile tunability and modular nature, as well as their ultra-high surface area and heterogeneous nature19–21
Summary
Direct structural information of confined CO2 in a micropore is important for elucidating its specific binding or activation mechanism. We present a dynamic porous coordination polymer (PCP) material with local flexibility, in which the propeller-like ligands rotate to permit CO2 trapping This process can be characterized by X-ray structural analysis. Direct structural information of the molecular state of captured CO2 by X-ray diffraction (XRD) techniques is invaluable despite the practical difficulties associated with its gaseous nature because this enables a thorough understanding of the specific host–guest interaction or activation mechanism and processes, and leads to the development of new and improved catalysts. We report the successful design of a two-fold interpenetrated framework, Zn-DPA·2H2O (DPA = 4,4′,4′′-tricarboxyltriphenylamine and (E)-1,2-di-(pyridin-4- yl)diazene) Their propeller-like ligands 4,4′,4′′- tricarboxyltriphenylamine undergo rotational rearrangement in response to the release and capture of guest molecules, resulting in slight changes of their channels. The PCP shows a high affinity towards CO2 molecules, which is clearly verified by the single-crystal structure of the CO2-adsorbed phases and its high catalytic efficiency and size selectivity with respect to CO2 cycloaddition to epoxides
Sign-in/Register to view highlights & summary Sign-in/Register to access full text options 
Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
