Formulation of porous hetero-frameworks via incorporating poly(ionic liquid)s with porphyrin derivative-functionalized organosilicas for boosting in-situ CO2 capture and conversion.

Robust Zn-TPMO x @PIL-C n hetero-frameworks are developed and exhibit excellent performance for in-situ flue gas CO 2 capture and transformation. [Display omitted] • Robust Zn-TPMO x @PIL-C n hetero-frameworks with multiple active sites are developed. • The catalyst shows excellent dual functions of in-situ CO 2 capture and conversion. • The optimal Zn-TPMO 20 @PIL-C 6 exhibits excellent recyclability and versatility. • A novel strategy is presented for the effective utilization of low-concentration CO 2. Chemical utilization of CO 2 has garnered significant attention in response to the growing environmental and energy challenges. Novel porous hetero-frameworks, Zn-TPMO x @PIL-C n , are developed herein via in-situ polymerization of [VImC n ]Br (n = 2, 4, 6) onto porphyrin derivative-functionalized organosilicas (Zn-TPMO x , x = 10, 15, 20). The structures of Zn-TPMO x @PIL-C n are characterized and found to possess high specific surface area as well as multiple active sites including Lewis acid/base groups, dual hydrogen bond donors and nucleophilic groups. These hetero-frameworks are then utilized for the synthesis of cyclic carbonates through in-situ capture and conversion of CO 2 from simulated flue gas. The catalytic performance of different Zn-TPMO x @PIL-C n and technological conditions are investigated, revealing that the optimal Zn-TPMO 20 @PIL-C 6 catalyst achieves a 96 % yield of chloropropene carbonate with 99 % selectivity under reaction conditions of 110 °C, 1 MPa flue gas for 6 h. Through an assessment of the recyclability and versatility of Zn-TPMO 20 @PIL-C 6 catalyst, it is observed that the robust Zn-TPMO 20 @PIL-C 6 maintains its high activity even after five cycles. Furthermore, this catalyst exhibits satisfactory performance in promoting reactions between various epoxides and flue gas CO 2. Based on the synergistic activation of multiple active sites, the cycloaddition mechanism between CO 2 and epoxide under the catalysis of Zn-TPMO x @PIL-C n is proposed. [ABSTRACT FROM AUTHOR]