Synthesis of metalloporphyrin-based porous organic polymers and their functionalization for conversion of CO2 into cyclic carbonates: recent advances, opportunities and challenges

Abstract

In the context of carbon neutrality, significant progress has been made in the exploration of advanced porous organic polymers (POPs) as a promising and emerging platform for heterogeneous CO₂ catalysis in the past few decades owing to their structural designability and functional diversity, high thermal and chemical stability, and ability to accelerate the mass-transfer rate. Inspired by natural biological systems, incorporation of metalloporphyrin moieties into the porous skeletons via covalent linkages for affording metalloporphyrin-based POPs can not only facilitate strong interactions with Lewis acidic CO₂ molecules, but also can establish highly efficient biomimetic catalytic systems. In this review, we aim to summarise the recent advances made in the task-specific design and synthesis of metalloporphyrin-based POPs and their functionalization for conversion of CO₂ into cyclic carbonates. The focus mainly lies on the rational construction of targeted building blocks and the diverse synthetic strategies for preparing metalloporphyrin-based POPs with different functionalities and compositions. Single/multi-active-site synergistic catalytic models relevant to epoxide activation provide feasible theoretical guidance to the multifunctionalization of metalloporphyrin-based POPs. Finally, we discuss the key opportunities and challenges in this field and also highlight possible avenues for future directions to help researchers to fabricate ideal catalysts for industrial applications.