Structure-induced interfacial activation convoying the CO-relayed conversion of CO2 to dimethyl carbonate

The recognition of structure-induced interfacial activation in heterogenized molecule catalysts is essential to steer CO2 value-added electroconversion but remains inadequate. Herein, through designing three congeneric Co-N4 model molecules (Co-CPY, Co-TAA and Co-PHE) with recognizable steric configurations, we systematically investigated the impact of structure-induced interfacial activation on promoting CO2 electroconversion. Concretely, the Co-CPY/CNTs, featuring highly planar and conjugated molecules immobilized onto CNTs, delivers an ultra-high current density and enables near-unity Faradaic efficiency for CO2 electroconversion, exceeding the counterparts. The theoretical and spectrographic findings demonstrate that the Co-CPY/CNTs not only creates the adaptive interfaces with strong communication to greatly expedite electron transfer but also reconstructs the electronic structures of active Co-N4 units to effectively promote the formation of intermediates. Furthermore, the electroconversion of CO2 to dimethyl carbonate was reliably performed with a high yield of 96 μmol cm–2 h−1 through paired tandem electrosynthesis, highlighting the superior expansibility of Co-CPY/CNTs.