Plasmon-induced hot-hole generation and extraction at nano-heterointerfaces for photocatalysis

Localized surface plasmon resonance excitation presents tremendous opportunities for light-harvesting in the field of photocatalysis. Notably, the use of plasmon-generated hot carriers to drive chemical reactions offers the opportunity to control the selectivity of the reaction, unlike temperature-driven catalysis. There has been extensive development of photocatalysts based on plasmon-induced hot electron transfer. However, the equally important hole transfer process has been largely understudied mainly because of the ultrafast dynamics and shorter lifetime of holes compared to electrons. The electron and hole transport asymmetry to the catalytic site introduces additional challenges in extracting holes as oxidants for chemical adsorbents/reactants. This review provides a fundamental overview of plasmonic catalysis, emphasizing recent hot hole extraction and catalysis advancements by exploring different nano-heterointerfaces through which energetic holes can be localized to the catalytic sites. We also highlight some of the critical parameters which must be considered to address the limitations and introduce new possibilities to the field.