Since the discovery of graphene, two-dimensional ultrathin nanomaterials with an atomic thickness (typically <5 nm) have attracted tremendous interest due to their fascinating chemical and physical properties. These ultrathin nanomaterials, referred to as atomically thin materials (ATMs), possess inherent advantages such as a high specific area, highly exposed surface-active sites, efficient atom utilization, and unique electronic structures. While substantial efforts have been devoted to advancing ATMs through structural chemistry, the potential of heterointerface engineering to enhance their properties has not yet been fully recognized. Indeed, the introduction of bi- or multi-components to construct a heterointerface has emerged as a crucial strategy to overcome the limitations in property enhancement during ATM design. In this review, we aim to summarize the design principles of heterointerfacial ATMs, present general strategies for manipulating their interfacial structure and catalytic properties, and provide an overview of their application in energy conversion and storage, including the hydrogen evolution reaction (HER), the oxygen evolution reaction (OER), the oxygen reduction reaction (ORR), the CO2 electroreduction reaction (CO2RR), photocatalysis, and rechargeable batteries. The central theme of this review is to establish correlations among interfacial modulation, structural and electronic properties, and ATMs' major applications. Finally, based on the current research progress, we propose future directions that remain unexplored in interfacial ATMs for enhancing their properties and introducing novel functionalities in practical applications.
Keywords: atomically thin materials; electrocatalysis; electronic structure; energy conversion; energy storage; heterointerface engineering.