A Planar, Conjugated N4-macrocyclic Cobalt Complex for Heterogeneous Electrocatalytic CO2 Reduction with High Activity.
A Planar, Conjugated N4-macrocyclic Cobalt Complex for Heterogeneous Electrocatalytic CO2 Reduction with High Activity.
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DOI：
10.1002/anie.202007445
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发表时间：
2020-07
影响因子：
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通讯作者：
Libo Sun;Zhenfeng Huang;Vikas Reddu;Tan Su;A. Fisher;Xin Wang
中科院分区：
文献类型：
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作者：
Libo Sun;Zhenfeng Huang;Vikas Reddu;Tan Su;A. Fisher;Xin Wang
金属配合物作为一种有前途的CO2还原电催化剂已被广泛研究.目前的研究工作主要集中在基于吡咯亚基的配体上，所报道的活性还远不能令人满意。合成了一种新型的平面共轭N4-大环钴配合物（Co（II）CPY），该配合物在水溶液中对CO2多相电催化合成CO具有很高的活性，其电催化性能优于目前报道的大多数金属配合物.在摩尔负载量为5.93×10 - 8 molcm-2时，对CO的法拉第效率为96%，转换频率为9.59s-1（-0.70Vvs. RHE。电子结构特征的揭示表明，钴（II）CPY中的配体对钴的协同效应在提高其活性方面起着关键作用。因此，形成 *COOH的自由能差低于钴卟啉上的自由能差，导致CO产量增加。
Metal complexes have been widely investigated as promising electrocatalysts for CO 2 reduction. Most of the current research efforts mainly focus on ligands based on pyrrole subunits and the reported activities are still far from satisfactory. A novel planar and conjugated N4-macrocyclic cobalt complex (Co(II)CPY) derived from phenanthroline subunits is prepared herein, which delivers high activity for heterogeneous CO 2 electrocatalysis to CO in an aqueous medium and outperforms most of the metal complexes reported so far. At a molar loading of 5.93×10 -8 mol cm -2 , it exhibits a Faradaic efficiency of 96% and a turnover frequency of 9.59 s -1 towards CO at -0.70 V vs . RHE. The unraveling of electronic structural features suggests a synergistic effect from ligand to cobalt in Co(II)CPY plays a critical role in boosting its activity. As a result, the free energy difference for the formation of *COOH is lower than that on cobalt porphyrin, leading to enhanced CO production.