Proton/Electron Donors Enhancing Electrocatalytic Activity of Supported Conjugated Microporous Polymers for CO2Reduction

Abstract Metal phthalocyanines (MePc) hold great promise in electrochemical reduction of CO 2 to value‐added chemicals, whereas the catalytic activity of MePc‐containing polymers often suffers from a limited molecular modulation strategy. Herein, we synthesize an ultrathin conjugated microporous polymer sheath around carbon nanotubes by an ionothermal copolymerization of CoPc and H 2 Pc via the Scholl reaction. Given the H 2 Pc‐mediated regulation in the synthesis, Co II metal is well preserved in the form of single atoms on the polymer sheath of the carbon nanotubes. With the synergistic effect of H 2 Pc moieties as proton/electron donors, the composites can selectively reduce CO 2 to CO with a high Faradaic efficiency (max. 97 % at −0.9 V) in broad potential windows, exceptional turnover frequency (97 592 h −1 at −0.65 V) and large current density (>200 mA cm −2 ). It is thus desirable to develop a family of heterogeneous polymerized MePc with molecularly regulating electrocatalytic activity.