Unifying Solution and Surface Electrochemistry: Limitations and Opportunities in Surface Electrocatalysis

The electrochemical transformations involving small molecules could play a key role in energy storage and utilization. In this work, we develop a link between surface and solution electrochemistry and this is accomplished by relating the correlated binding of hydrogenated species on metal surfaces to their formation energy in solution. This link provides a semi-quantitative treatment of the thermodynamic landscape of multi-electron electrochemical reactions. Using this simple analysis, we identify some of the fundamental limits of oxygen, nitrogen and carbon electrochemistry. This analysis points to new avenues of electrocatalyst design and two such avenues are discussed in detail.