Atomically thin layered structures open plethora of opportunities in various fields, including electrochemistry. Since all the atoms of a two-dimensional (2D) layer is exposed to its environment, local electronic and hence electrochemical properties of an atomic layer are highly influenced by physisorption and/or chemisorption of molecules. Though 2D materials have high surface area, the sorption processes of molecules/radicals/ligands may not favour in certain cases and/or may not be selective. The challenges are underlying in the engineering of these layers to make them adaptable for electrochemical applications, so that they will be beneficial for electrochemical sensors and devices.

This chapter deals with the electrochemical catalytic and sensing aspects of various atomic layers, and discusses the engineering aspects of these layers to make them useful for certain electrochemical applications. Experimental aspects of these atomic layers based measurements are discussed, and new trends in atomic layers such as van der Waals heterostructures based electrochemistry and the importance of atomic layer interface tuning are also discussed.