Kochubei, Alena S.Marianov, Aleksei N.Conquest, Oliver J.Lu, TengLiu, YunStampfl, CatherineJiang, Yijiao2025-05-232025-05-232050-7488ORCID:/0000-0002-7866-1859/work/184104637http://www.scopus.com/inward/record.url?scp=85208067858&partnerID=8YFLogxKhttps://hdl.handle.net/1885/733752454Cobalt(ii) phthalocyanine (CoPc) complexes are some of the most active catalysts for the CO2 electroreduction reaction (CO2ERR). However, these organic complexes are non-conductive, thus the CO2ERR rate is hindered by the slow electron delivery to the active centers. Herein, our recently developed variable frequency square wave voltammetry (VF-SWV) was employed to directly image the charge transfer between the covalently ligated polymeric CoPc and the carbon fiber paper electrode. The VF-SWV shows that the conjugated structure of the covalently ligated CoPc provides a direct path for the charge migration between the active centers and the electrode. Combined with the density-functional theory (DFT) calculations, our mechanistic studies show that CoI is the catalyst resting state and the doubly reduced Co0 is the key catalytically active species driving the CO2ERR. The conductive nature of the macromolecular framework evidenced by VF-SWV allows for faster replenishing of dianionic Co0 species and, subsequently, boosts the CoPc-cov catalyst performance with a high selectivity to carbon monoxide (CO) evolution with the Faradaic efficiency up to 85% and turnover frequency TOF(CO) of up to 38.1 s−1, which is nearly double that of the noncovalently ligated counterpart. The immobilization strategy developed in this work provides an opportunity for the development of cheap, efficient, and stable heterogeneous molecular catalysts for the CO2ERR.Funding support of the ARC (Discovery Project DP1901013720, DP200100159, and Laureate Fellowship Program FL210100017) and Macquarie University (iMQRTP Scholarship) is gratefully acknowledged. The authors would like to express gratitude to Macquarie University Analytical and Fabrication Facility for access to the instrumentation and technical support. The authors also thank Mengxin Liu and Dr Yuming Wu from Macquarie University, and Haoyue Sun from the University of Sydney for NMR and XPS experiments.13enPublisher Copyright: © 2025 The Royal Society of Chemistry.2024-10-1610.1039/d4ta03220a85208067858