Hybrid Organic-Inorganic Heterogeneous Interfaces for Electrocatalysis: A Theoretical Study of CO2 Reduction to C2

Hybrid organic-inorganic heterogeneous catalytic interfaces, where traditional catalytic materials are modified with self-assembled monolayers (SAMs), create promising features to control a wide range of catalytic processes through the design of dual organic-inorganic active sites and the induced confinement effect. To provide a fundamental insight, we investigated CO2 electroreduction into valuable C-2 chemicals (CO2RR-to-C-2) over SAM-modulated Cu. Our theoretical results show that 1/4 monolayer aminothiolates improve the stability, activity and selectivity of CO2RR-to-C-2 by: (1) decreasing surface energy to suppress surface reconstruction; (2) facilitating CO2 activation and C-C coupling through dual organic-inorganic (i. e., -NH, Cu) active sites; (3) promoting C-C coupling via confinement effects that enlarge the adsorption energy difference between CO* and COH*; (4) inducing local electric fields to Cu surface and changing its dipole moment and polarizability to be in favor of C-C coupling under electrode/electrolyte interfacial electric field.

Automated summary

By modifying Cu surface with SAM, the stability, activity, and selectivity of CO2 electroreduction to C-2 chemicals can be improved, mainly through decreasing surface energy, facilitating CO2 activation and C-C coupling, as well as inducing confinement effects and charge transfer.