(Invited) Theoretical Insights in the Design of Active Sites and Environments to Guide Electrocatalytic Transformations for Sustainable Energy and Chemicals Production

Future strategies for sustainable energy and chemicals production will undoubtedly require the design of electrocatalytic systems that actively and selectively convert wastes such as CO 2 emissions and biomass into chemicals and fuels. While enzymes elegantly integrate highly active centers together with adaptive nanoscale environments to selectively control catalytic transformations, they are limited industrially by their durability. The design of robust electrocatalytic materials and systems that can mimic the activity and selectivity of enzymes, however, has been hindered by our understanding of how such transformations proceed over inorganic materials and complex environments. Advances in theory, simulations, spectroscopy and characterization begin to allow us to track the molecular transformations and how they proceed in electrocatalytic systems at specific sites and within particular environments. This information can enable the design of unique surface ensembles and nanoscale environments that can efficiently catalyze specific molecular transformations. Herein we develop and use ab initio methods to examine the influence of anions, cations and solvents in complex electrochemical environments to carry out selective molecular transformations. More specifically, we discuss the electrocatalytic reduction of CO 2 and aromatics to valuable chemical and pharmaceutical intermediates. We draw direct analogies between the elementary processes that govern these seemingly different systems. We explore the manipulation of different solvents (ionic liquids and water), electrolytes (effects of anions and cations), pH as well as different metals and electrochemical potential to drive the formation of 3D environments that aid in controlling these transformations. We expand the discussion to selective oxidation reactions and examine the design of mediators to enable the selective C-H bond activation.