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Electron‐Rich Pincer Ligand‐Coupled Cobalt Porphyrin Polymer with Single‐Atom Sites for Efficient (Photo)Electrocatalytic CO2 Reduction at Ultralow Overpotential

Porphyrin and phthalocyanine complexes bearing single‐atom catalytic sites (M‐N4) have been explored as promising electrocatalysts for CO2 reduction reaction (CO2RR), whose activity can be improved by regulating the ligands and/or the metal centers. Moreover, their photosensitive features also provi...

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Published in:Small (Weinheim an der Bergstrasse, Germany) Germany), 2021-11, Vol.17 (45), p.e2102957-n/a
Main Authors: Wang, Tingxia, Guo, Lulu, Pei, Hao, Chen, Shengtao, Li, Renjie, Zhang, Jing, Peng, Tianyou
Format: Article
Language:English
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Summary:Porphyrin and phthalocyanine complexes bearing single‐atom catalytic sites (M‐N4) have been explored as promising electrocatalysts for CO2 reduction reaction (CO2RR), whose activity can be improved by regulating the ligands and/or the metal centers. Moreover, their photosensitive features also provide the possibility for highly efficient photoelectrocatalytic CO2RR. Herein, a novel N′NN′‐pincer‐ligand (N3)‐coupled cobalt porphyrin (CoPor‐N3) polymer is developed for realizing efficient (photo)electrocatalytic CO2RR. The unraveled electronic structure and (photo)electrocatalytic features suggest that a synergistic effect between the electron‐rich N3 ligands and the Co‐N4 single‐atom sites in the CoPor‐N3 polymer results in the Co centers attaining more electrons, which is beneficial to facilitating the electron transfer to CO2 for the activation and reduction processes. As expected, the resultant CoPor‐N3 polymer delivers a good long‐term durability and high CO faradaic efficiency (96%) at an ultralow overpotential (0.39 V), which outperforms the CoPor alone and most porphyrin‐/phthalocyanine‐based electrocatalysts reported so far. Moreover, the photosensitivity of CoPor units can further reduce the overpotential to 0.34 V with a CO faradaic efficiency over 90% under light illumination. The present findings offer a new approach to constructing porphyrin‐based photosensitive electrocatalysts with high‐efficiency photoelectrocatalytic CO2RR. A novel electron‐rich pincer ligand‐coupled cobalt porphyrin polymer (CoPor‐N3) with single‐atom sites that delivers a good long‐term durability and high CO faradaic efficiency (96%) at an ultralow overpotential (0.39 V) is designed and synthesized. The photosensitivity of CoPor unit can further reduce the overpotential to 0.34 V with a CO faradaic efficiency over 90% under illumination.
ISSN:1613-6810
1613-6829
DOI:10.1002/smll.202102957