Recent studies have found that the existence of oxygen around the active sites may be essential for efficient electrochemical CO2 -to-CO conversion. Hence, this work proposes the modulation of oxygen coordination and investigates the as-induced catalytic behavior in CO2 RR. It designs and synthesizes conjugated phthalocyanine frameworks catalysts (CPF-Co) with abundant CoN4 centers as an active source, and subsequently modifies the electronic structure of CPF-Co by introducing graphene oxide (GO) with oxygen-rich functional groups. A systematic study reveals that the axial coordination between oxygen and the catalytic sites could form an optimized O-CoN4 structure to break the electron distribution symmetry of Co, thus reducing the energy barrier to the activation of CO2 to COOH*. Meanwhile, by adjusting the content of oxygen, the proper supports can also facilitate the charge transfer efficiency between the matrix layer and the catalytic sites. The optimized CPF-Co@LGO exhibits a high TOF value (2.81 s-1 ), CO selectivity (97.6%) as well as stability (24 h) at 21 mA cm-2 current density. This work reveals the modulation of oxygen during CO2 RR and provides a novel strategy for the design of efficient electrocatalysts, which may inspire new exploration and principles for CO2 RR.
Keywords: CO 2 reduction; coordination microenvironments; electrocatalysis; oxygen modulation.
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