Porous Supramolecular Crystalline Materials for Photocatalysis

Porous supramolecular crystalline materials (PSCMs), usually including hydrogen‐bonded organic frameworks (HOFs), π frameworks, and so on, can be defined as a type of porous supramolecular assemblies stabilized by hydrogen‐bonding, π‐π stacking and other non‐covalent interactions. Given the unique features of mild synthetic conditions, well‐defined and tailorable structures, easy healing and regeneration, PSCMs have captured widespread interest in molecular recognition, sensor, gas storage and separation, and so on. Moreover, they currently emerge as promising photocatalysts because it is readily to endow PSCMs with photo‐function, and the hydrogen‐bonding and π‐π stacking can serve as electron transfer channels to boost photocatalytic activity. Nevertheless, the research on PSCMs for photocatalysis is still at an early stage. A review on this topic will greatly promote the development of supramolecular chemistry. In this Minireview, we will firstly introduce the syntheses of PSCMs, and then highlight the advantages of PSCMs in photocatalysis. Following this, we will further summarize the photocatalytic applications of PSCMs toward CO2 reduction, H2 evolution, H2O2 production, organic transformation and pollution degradation, where emphasis will be placed on concluding the relationship between the catalyst performances and structures. Finally, we will discuss the remaining challenges and perspectives in developing high‐performance PSCM‐based photocatalysts.