Proton/Electron Donors Enhancing Electrocatalytic Activity of Supported Conjugated Microporous Polymers for CO₂...

Metal phthalocyanines (MePc) hold great promise in electrochemical reduction of CO₂ 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 H₂ Pc via the Scholl reaction. Given the H₂ 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 H₂ Pc moieties as proton/electron donors, the composites can selectively reduce CO₂ 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.