NSF-DFG Echem: Cooperativity between immobilized redox mediators for selective anodic biomass valorization

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A long-standing goal of catalysis science is the at-will design of active sites that exhibit substrate specificity, rate, and product selectivity on par with what is afforded by natural enzymatic catalysts. The performance of such structures, having tailored substrate binding environments with multiple participant functional groups, is difficult to imitate with homogeneous molecular catalysts, and arguably even more challenging using heterogeneous catalyst materials, desirable for their ease of separability. Nonetheless, increasing efforts to design heterogeneous, three-dimensional catalytic environments with multiple “cooperative” catalytically participating moieties have seen great progress in recent years. This proposal aims to understand and develop cooperative electrocatalytic sites, comprised of an organic redox mediator and redox-active metal center, both performing electron transfer to achieve multi-electron oxidation reactions at smaller driving potential than what the constituent moieties can achieve alone. We seek to develop the fundamental understanding and methodologies to effectively immobilize cooperative catalysts onto (a) soluble (but easily separated) polymers and (b) heterogeneous electrodes. These two platforms will provide complementary means to identify constraints imposed by immobilization and understand how best to retain cooperativity.