Electrocatalytic CO${}_2$ Reduction: Role of the Cross-Talk at Organic-Inorganic Interfaces

Abstract

Electrocatalytic CO${}_2$RR is an interfacial process, involving a minimum of three phases at the contact point of gaseous CO${}_2$ with the electrodic surface and the liquid electrolyte. As a consequence, surface chemistry at composite interfaces plays a central role for CO${}_2$RR selectivity and catalysis. Each interface defines a functional boundary, where active sites are exposed to a unique environment with respect to distal sites in the bulk or organic and inorganic materials. While the individual role of each component-type is hardly predictable a-solo, the interface ensemble works via a strategic interplay of individual effects, including: (i) enhanced electrical conductivity, (ii) high surface area and exposure of the interfacial catalytic sites, (iii) favorable transport and feeding of reactants, (iv) complementary interactions for the on/off stabilization of cascade intermediates, (v) a secondary sphere assistance to lower the activation energy of bottleneck steps, (vi) a reinforced robustness and long-term operation stability by mutual protection and/or healing mechanisms. Selected CO${}_2$RR case studies are compared and contrasted to highlight how the organic domains of carbon nanostructures merge with metal and metal-oxide active sites to separate tasks but also to turn them into a cooperative asset of mutual interactions, thus going beyond the classic Divide et Impera rule.

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