Leveraging co-operative redox enhancement (CORE) for efficient electrochemical production.

The shift from traditional fossil-fuel-based chemical production to a renewable e-chemical industry requires innovation in the design of catalytic and electrocatalytic systems for both initial production of platform hydrocarbons and their subsequent upgrading to a core suite of feedstocks and chemical intermediates. To this end, we require selective and efficient catalytic systems that operate under relatively mild conditions. We have recently developed a new approach, termed Co-Operative Redox Enhancement (CORE), to the design of catalytic systems that leverage electrocatalytic driving forces to substantially enhance the activity of what, at first glance, would be considered a thermal catalytic process. Dissimilar, physically separated but electrochemically connected catalytic nanoparticles will establish a spontaneous, nanoscale, electrochemical gradient between them due to differences in the electrocatalytic selectivity of each particle towards the desired half reactions. This leads to polarization of the nanoparticles and associated enhancement in their selectivity and activity towards the half reactions, driving an overall increase in catalytic turnover. The extent of polarization is quantifiable and the impact on overall catalytic turnover is predictable through an electrochemical approach based on modified corrosion theory. This new approach to the design of catalytic systems has wide-ranging implications for the design of thermal and electrocatalytic systems for the e-chemical industry and beyond. In this work, we discuss the oxidative dehydrogenation of benzyl alcohol utilizing coupled Au/C and Pd/C catalysts as an exemplar of CORE. The role of CORE is demonstrated through a combination of thermocatalytic and electrocatalytic experiments, pointing towards CORE as an approach to design and implement both thermal and electrochemical catalytic systems for efficient e-chemical production.