Developments and Perspectives on Robust Nano‐ and Microstructured Binder‐Free Electrodes for Bifunctional Water Electrolysis and Beyond

Abstract The development of robust nano‐ and microstructured catalysts on highly conductive substrates is an effective approach to produce highly active binder‐free electrodes for energy conversion and storage applications. As a result, nanostructured electrodes with binder‐free designs have abundant advantages that provide superior electrocatalytic performance; these include more exposed active sites, large surface area, strong adhesion to substrates, facile charge transfer, high conductivity, high intrinsic catalytic activity, and fine‐tuning of its electronic nature through nanostructure modification. Notably, the interface chemistry of an electrocatalyst plays a significant role in their optimized electrocatalytic activity and stability. This review provides an overview of recent progress in nano‐ and microstructured catalysts, such as one, two, and 3D catalysts as binder‐free electrodes for electrocatalytic water splitting via the hydrogen evolution reaction and oxygen evolution reaction, and beyond. Furthermore, this review focuses on the current challenges and synthesis strategies of binder‐free electrodes, with a focus on the impact of nanostructure on their functional property relationships and enhanced bifunctional electrocatalytic performance. Finally, an outlook for their future advances in energy conversion and storage is provided.