Electrocatalysis: From Planar Surfaces to Nanostructured Interfaces.

The reactions critical for the energy transition center on the chemistry of hydrogen, oxygen, carbon, and the heterogeneous catalyst surfaces that make up electrochemical energy conversion systems. Together, the surface-adsorbate interactions constitute the electrochemical interphase and define reaction kinetics of many clean energy technologies. Practical devices introduce high levels of complexity where surface roughness, structure, composition, and morphology combine with electrolyte, pH, diffusion, and system level limitations to challenge our ability to deconvolute underlying phenomena. To make significant strides in materials design, a structured approach based on well-defined surfaces is necessary to selectively control distinct parameters, while complexity is added sequentially through careful application of nanostructured surfaces. In this review, we cover advances made through this approach for key elements in the field, beginning with the simplest hydrogen oxidation and evolution reactions and concluding with more complex organic molecules. In each case, we offer a unique perspective on the contribution of well-defined systems to our understanding of electrochemical energy conversion technologies and how wider deployment can aid intelligent materials design.