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

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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
Small ( IF 13.0 ) Pub Date : 2021-09-29 , DOI: 10.1002/smll.202102957
Tingxia Wang ₁ , Lulu Guo ₁ , Hao Pei ₁ , Shengtao Chen ₁ , Renjie Li ₁ , Jing Zhang ₁ , Tianyou Peng ₁

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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.

中文翻译：

具有单原子位点的富电子钳形配体偶联钴卟啉聚合物可在超低过电位下进行高效（光）电催化 CO2 还原

带有单原子催化位点 (MN ₄ ) 的卟啉和酞菁配合物已被探索为有前景的 CO ₂还原反应 (CO ₂ RR)电催化剂，其活性可以通过调节配体和/或金属中心来提高。此外，它们的光敏特性也为高效光电催化 CO ₂ RR提供了可能。在此，开发了一种新型N'NN'-钳-配体 (N ₃ )-偶联钴卟啉 (CoPor-N ₃ ) 聚合物以实现高效的（光）电催化CO ₂RR。未解开的电子结构和（光）电催化特征表明，富含电子的 N ₃配体和CoPor-N ₃聚合物中的 Co -N ₄单原子位点之间的协同作用导致 Co 中心获得更多的电子，这有利于促进电子转移到 CO ₂以进行活化和还原过程。正如预期的那样，所得的 CoPor-N ₃聚合物在超低过电位 (0.39 V) 下提供了良好的长期耐久性和高 CO 法拉第效率 (96%)，其性能优于单独的 CoPor 和迄今为止报道的大多数卟啉/酞菁基电催化剂。此外，CoPor 单元的光敏性可以进一步将过电位降低至 0.34 V，在光照下 CO 法拉第效率超过 90%。本研究结果为构建具有高效光电催化 CO ₂ RR 的卟啉基光敏电催化剂提供了一种新方法。

更新日期：2021-11-11

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