Tuning the photosensitization efficiency of atomically precise metal nanoclusters by super-efficient and exquisite interface modulation

Abstract

Atomically precise metal nanoclusters (NCs) are distinct from conventional metal nanocrystals (NYs) in terms of unique discrete electronic structure and atomic stacking mode, rendering emerging light-harvesting antennas. However, the intrinsic correlation of metal NCs and non-plasmonic metal NYs in mediating anisotropic photoinduced charge separation and migration in photoredox catalysis is yet to be elucidated. Herein, using a self-designed automatic machine-based assembly apparatus, we conceptually reveal the generic charge correlation of metal NCs and non-plasmonic metal NYs enabled by a super-efficient ligand-triggered self-assembly on a metal-oxide substrate with an ultra-short processing time of 10 seconds under ambient conditions. The integration mode of such multilayered heterostructures is finely tuned by a self-assembly order induced interface configuration, thereby establishing multichannel vectorial charge transfer pathways and exposing enriched active sites on the metal NY surface to maximize the photosensitization effect and stability of metal NCs. This work is anticipated to fill the long-term missing gap between metal NCs and metal NYs in manipulating charge transfer to design robust, stable and emerging metal NC-based photosystems for solar energy conversion.