Metal‐Decorated Porous Organic Polymers: Bridged the Gap between Organic and Inorganic Scaffolds†

Abstract

Comprehensive SummaryAdvanced functionalization‐decorated porous organic polymers (POPs) are emerging as a prominent research focus, spanning from their construction to applications in gas storage and separation, catalysis, energy storage, electrochemistry, and other areas. Furthermore, the inherent organic nature, tailored pore structures, and adjustable chemical components of POPs offer a versatile platform for the incorporation of various metal active sites. Meticulously designed molecular building blocks can serve as organic ligands uniformly distributed throughout POPs, leading to the effective isolation of inorganic metal active sites at the molecular level. In this manner, POPs containing active metal centers bridge the gap between organic and inorganic scaffolds. This review aims to provide an overview of recent research progress on metal‐decorated POPs, focusing on strategies for incorporating metal active sites into POPs and their applications in adsorption, separation, catalysis, and photoelectrochemistry. Finally, current challenges and future prospects are discussed for further research. Key ScientistsAdvanced functionalized porous organic polymers have become a new research hotspot, ranging from their construction to their use in gas storage and separation, catalysis, energy storage, electrochemistry, and other applications. In 2002, the McKeown group was the first to report phthalocyanine‐based MPOPs with permanent porosity and a moderate surface area. In 2010, the Yu group prepared nanoporous polyporphyrin materials P(Fe‐TTPP) from the metallated porphyrin with functionalized thiophenyl groups by the FeCl3 catalyzed oxidation couple reaction showing the surface area of 1522 m2·g–1. Subsequently, in 2013, the Deng group was the first to use metalated salens as the original building blocks for preparing MPOPs. The Morin group was the first to produce a series of ferrocene‐based nanoporous frameworks via radical polymerization, with surface areas ranging from 385 to 899 m2·g–1. In 2016, the Han group synthesized two N‐pyridinylphenylcarbazole (PPC) ligands to produce a series of metalized polycarbazole networks. Recently, the Tan group reported a solvent‐knitting hyper‐cross‐linking reaction to produce HUST‐1, which contains a porphyrin unit. The porphyrin moiety provides a centered square‐planar metal post‐coordination site, resulting in the metalated HUST‐1‐Co, which exhibits high efficiency in the catalytic conversion of CO2. Additionally, the Kegnæs group combined the decomposition of the palladium complex with an in situ catalyzed polymerization reaction, enabling the confinement of nascent Pd particles in the developing polymer network. This review focuses on recent research progress in metal‐decorated POPs, emphasizing strategies for incorporating metal active sites into POPs and their applications.