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Abstract 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 CO₂electroreduction into valuable C₂chemicals (CO₂RR‐to‐C₂) over SAM‐modulated Cu. Our theoretical results show that 1/4 monolayer aminothiolates improve the stability, activity and selectivity of CO₂RR‐to‐C₂by: (1) decreasing surface energy to suppress surface reconstruction; (2) facilitating CO₂activation 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.