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

TL;DR

This paper explores how the interplay at organic-inorganic interfaces influences electrocatalytic CO2 reduction, emphasizing the importance of interface chemistry and cooperative effects for improving catalysis and stability.

Contribution

It provides a detailed analysis of the role of composite interfaces in CO2RR, highlighting the cooperative effects and strategies for enhancing selectivity and durability.

Findings

Interfaces enhance electrical conductivity and surface area.

Organic-inorganic synergy improves catalytic activity.

Interfacial effects contribute to long-term stability.

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.