Density Functional Theory Studies on Photocatalysis and Photoelectrocatalysis: Challenges and Opportunities

Density functional theory (DFT) is pivotal in the advancement of photocatalysis and photoelectrocatalysis. Its capability to explore electronic structures of materials contributes significantly to clarifying the mechanisms of photocatalytic (PC) and photoelectrocatalytic (PEC) processes. DFT calculations enable a deeper understanding of how these processes work at a molecular level, which is essential for designing versatile photocatalysts and photoelectrodes and optimizing reaction pathways. In this Perspective, we highlight key PC and PEC applications, such as H2 production, CO2 reduction, dye degradation, and N2 reduction, where DFT has been instrumental in optimizing materials designs and reaction pathways. Exploration on the synergy between experimental research and DFT calculations is highlighted, which is crucial for the development of efficient and environmentally friendly energy solutions. The discussion further extends to challenges and future directions, emphasizing the need for incorporating factors, including discrepancy in scale, light illumination, electrolyte presence, and applied bias, into DFT calculations, to achieve a more comprehensive understanding of PC and PEC systems. This Perspective aims to provide a holistic view of the current state and potential advancements in photocatalyst and photoelectrode modeling, thereby guiding future research towards more effective and sustainable energy and chemical production processes in PC and PEC systems.