Deciphering the Photocatalysis Mechanism of Semimetallic Bismuth Nanoparticles.

Metallic nanoparticle photocatalysts have been developed in various catalytic systems over the past few decades, including diverse noble and non-noble metals with plasmonic properties. The hot-carrier-induced mechanism is one of the most appealing pathways as it can provide energetic electrons or holes for driving thermodynamically unfavorable reactions or increasing the reaction rate. In this work, we evaluate the photocatalytic performance of semimetallic bismuth nanoparticles and offer detailed mechanistic interpretations in terms of hot carriers and interband transitions. The photocatalyzed nitrophenol reduction with sodium borohydride serves as a model reaction, and a wavelength-dependent study reveals the contribution of hot carriers. It is demonstrated that light irradiation under shorter wavelengths could produce deeper hot holes in bismuth nanoparticles, which can be quenched more effectively by hole scavengers, thus facilitating the electron-transfer process and resulting in larger apparent reaction rate constants. The observed photocatalysis enhancement accounts for the unique band structure with an extremely small band gap and exclusive interband absorption in the visible region. This proof-of-concept work offers a different perspective on the photocatalysis mechanism of bismuth nanoparticles and could help us better understand the role of hot carriers involved in photocatalysis, especially with interband transitions.