Unlocking Single Particle Anisotropy in Real‐Time for Photoelectrochemistry Processes at the Nanoscale

• Published in: Angewandte Chemie International Edition 2024-08, Vol.63 (32), p.e202404170-n/a
• Main Authors: Lu, Si‐Min, Wang, Hao‐Wei, Chen, Mengjie, Xie, Bao‐Kang, Long, Yi‐Tao
• Format: Article
• Language: English
• Subjects: Anisotropy; Collision dynamics; collision photoelectrochemistry; Diffusion coefficient; Electrochemistry; Electron transfer; Mass transfer; morphological anisotropy; Nanoparticles; Photoelectrochemistry; Silver; single particle; Working conditions
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202404170

The key to rationally and rapidly designing high‐performance materials is the monitoring and comprehension of dynamic processes within individual particles in real‐time, particularly to gain insight into the anisotropy of nanoparticles. The intrinsic property of nanoparticles typically varies from one crystal facet to the next under realistic working conditions. Here, we introduce the operando collision electrochemistry to resolve the single silver nanoprisms (Ag NPs) anisotropy in photoelectrochemistry. We directly identify the effect of anisotropy on the plasmonic‐assisted electrochemistry at the single NP/electrolyte interface. The statistical collision frequency shows that heterogeneous diffusion coefficients among crystal facets facilitate Ag NPs to undergo direction‐dependent mass transfer toward the gold ultramicroelectrode. Subsequently, the current amplitudes of transient events indicate that the anisotropy enables variations in dynamic interfacial electron transfer behaviors during photothermal processes. The results presented here demonstrate that the measurement precision of collision electrochemistry can be extended to the sub‐nanoparticle level, highlighting the potential for high‐throughput material screening with comprehensive kinetics information at the nanoscale. Real‐time tracking and investigation of single particle anisotropy in the dynamic photochemistry processes at the nanoscale via collision electrochemistry is performed. This high‐throughput material screening methodology offers insights into the impact of morphological anisotropy on interfacial mass transfer and electron transfer kinetics in plasmonic‐assisted electrochemistry.