Electrochemiluminescence Microscopy in Nano‐Electrochemistry Research: Unraveling the Underlying Principles, Tracing the Evolutionary Developments, and Charting the Prospective Trajectories

Abstract Electrochemical technology provides unique opportunities to create an environment‐friendly and sustainable chemical industry. Nano‐electrochemistry offers valuable insights into the comprehension of electrochemical mechanisms and behaviors at the nanoscale, as opposed to complex ensemble systems. Despite the use of various analytical tools, such as nanopore technology and scanning probe microscopy, for nano‐electrochemical research, direct operando and high‐throughput spatially resolved electrochemical measurements remain challenging. Electrochemiluminescence (ECL) is an electrochemical reactions‐dependent luminescence process without external light sources. Coupled with a microscopy configuration, a novel imaging methodology ECL microscopy (ECLM), is developed. ECLM, due to its distinctive imaging mode, holds considerable potential in the field of nano‐electrochemistry. This review will initially present an overview of the basic principles of ECL. The next section will describe the design of the ECLM apparatus and discuss its diverse applications in nano‐electrochemistry. Finally, the challenges and outline of the prospects for further development of the ECLM technique will summarized.