Surface-Engineered Cesium Lead Bromide Perovskite Nanocrystals for Enabling Photoreduction Activity

In recent years, colloidal lead halide perovskite (LHP) nanocrystals (NCs) have exhibited such intriguing light absorption properties to be contemplated as promising candidates for photocatalytic conversions. However, for effective photocatalysis, the light harvesting system needs to be stable under the reaction conditions propaedeutic to a specific transformation. Unlike photoinduced oxidative reaction pathways, photoreductions with LHP NCs are challenging due to their scarce compatibility with common hole scavengers like amines and alcohols. In this contribution, it is investigated the potential of CsPbBr₃ NCs protected by a suitably engineered bidentate ligand for the photoreduction of quinone species. Using an in situ approach for the construction of the passivating agent and a halide excess environment, quantum-confined nanocubes (average edge length = 6.0 ± 0.8 nm) are obtained with a low ligand density (1.73 ligand/nm²) at the NC surface. The bifunctional adhesion of the engineered ligand boosts the colloidal stability of the corresponding NCs, preserving their optical properties also in the presence of an amine excess. Despite their relatively short exciton lifetime (τ_AV = 3.7 ± 0.2 ns), these NCs show an efficient fluorescence quenching in the presence of the selected electron accepting quinones (1,4-naphthoquinone, 9,10-phenanthrenequinone, and 9,10-anthraquinone). All of these aspects demonstrate the suitability of the NCs for an efficient photoreduction of 1,4-naphthoquinone to 1,4-dihydroxynaphthalene in the presence of triethylamine as a hole scavenger. This chemical transformation is impracticable with conventionally passivated LHP NCs, thereby highlighting the potential of the surface functionalization in this class of nanomaterials for exploring new photoinduced reactivities.