Imaging the Self-Healing Dynamics of Single-Nanoparticle Electron Transfer Event Regulated by Local Electron Insertion.

The self-healing properties of nanomaterials to resist electron beam damage are of great concern, which is inspiring to improve the stability and electron transfer efficiency of nanoelectronic devices especially in an abnormal environment. However, the influence of electron beam insertion on the electron transfer efficiency of single nanoentities at a heterogeneous electrochemical interface is still in debate, which is a concern for the development of liquid cell transmission electron microscopy of the next generation. Herein, we employ an electro-optical imaging technique and directly visualize the controllable recovery of electron transfer ability for single Prussian blue nanoparticle (PBNP) after electron beam insertion with different electron doses. While eliminating e-beam damage by decreasing charge accumulation, the precise control of electron insertion behaviors induces a lossless chemical reduction mechanism for metal ions on the framework structure of PBNP, which leads to static imbalance and temporarily blocks the electron transfer channels. A subsequent charge rebalance process at a sub-nanoparticle level driven by electrochemical cycling controllably rebuilds the ion migration channels on the outer layer of single PBNP to repair the electron transfer path, which is confirmed by single-nanoparticle spectral characterizations. This work provides a generic methodology to study the electron-particle interplay and mechanism of electrode materials for eliminating the heterogeneity of electrochemical activity down to a sub-nanoparticle level.