Engineering Active Sites and Their Environments to Guide Catalytic Transformations for Sustainable Energy and Selective Chemicals Production

Future strategies for energy and chemicals production will undoubtedly require the design of catalysts that can actively and selectively convert sustainable resources in into fuels and chemicals. While enzymes elegantly integrate highly active centers together with adaptive nanoscale environments to exquisitely control catalytic transformations,  they are limited industrially by their durability and stability. The design of robust heterogeneous catalytic materials that can mimic the activity and selectivity of enzymes, however, has been hindered by our understanding of how such transformations proceed over inorganic materials. Advances in theory, simulations, spectroscopy and characterization begin to allow us to track the molecular transformations and how they proceed in heterogeneous catalytic systems at specific sites and within particular environments.  This information is enabling the design of unique atomic surface ensembles and nanoscale environments that can efficiently catalyze different molecular transformations. Herein we examine the influence of solvents and electrochemical environments on heterogeneously catalyzed reactions to carry out selective molecular transformations. More specifically, we discuss the acid-catalyzed dehydration of oxygenates derived from biomass, the electrocatalytic reduction of CO₂ to CO and electrochemical reductions of aromatics to chemical and pharmaceutical intermediates. We draw direct analogies between the elementary processes that govern these seemingly different systems and explore the manipulation of solvents, electrolytes and electrochemical potential to create 3D environments that can aid in controlling these transformations.