Porous Supramolecular Crystalline Materials for Photocatalysis

Abstract Porous supramolecular crystalline materials (PSCMs), such as hydrogen‐bonded organic frameworks (HOFs), π frameworks, can be defined as a type of porous supramolecular assemblies stabilized by hydrogen‐bonding, π ‐ π stacking and other non‐covalent interactions. Benefiting from the unique features of mild synthesis conditions, well‐defined and synthetically tailorable structures, easy healing and regeneration, PSCMs have garnered widespread interest in research fields including molecular recognition, sensor, gas storage and separation. Moreover, they have emerged as promising photocatalysts because these PSCMs could be readily endowed with optical function, and the hydrogen‐bonding and π‐π stacking can offer channels for electron transfer to boost the photocatalytic activity. However, the research on PSCMs for photocatalysis is still at an early stage, and a review on this topic would help to promote the development of supramolecular chemistry. In this Minireview, we first introduce the synthesis methods for PSCMs, and then highlight their advantages in photocatalysis. Subsequently, we summarize the applications of PSCMs in photocatalysis including CO 2 reduction, H 2 evolution, H 2 O 2 production, organic transformation and pollutant degradation, and we put particular emphasis on delineating the structure‐performance relationship. At the end, we discuss the challenges and perspectives in developing high‐performance PSCM‐based photocatalysts.