Axial Modification of Cobalt Complexes on Heterogeneous Surface with Enhanced Electron Transfer for Carbon Dioxide Reduction.,Angewandte Chemie International Edition

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Axial Modification of Cobalt Complexes on Heterogeneous Surface with Enhanced Electron Transfer for Carbon Dioxide Reduction.
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2020-07-09 , DOI: 10.1002/anie.202008759
Jiong Wang ₁ , Xiang Huang ₂ , Shibo Xi ₃ , Hu Xu ₂ , Xin Wang ₁

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Efficient electron communication between molecular catalyst and support is critical for heterogeneous molecular electrocatalysis and yet it is often overlooked during the catalyst design. Taking CO₂ electro‐reduction on tetraphenylporphyrin cobalt (PCo) immobilized onto graphene as an example, we demonstrate that adding a relay molecule improves the interfacial electron communication. While the directly immobilized PCo on graphene exhibits relatively poor electron communications, it is found that diphenyl sulfide serves as an axial ligand for PCo and it improves the redox activity of PCo on the graphene surface to facilitate the generation of [PCo]^.‐ active sites for CO₂ reduction. Thus, the turnover frequencies of the immobilized Co complexes are increased. Systematic structural analysis indicates that the benzene rings of diphenyl sulfide exhibit strong face‐to‐face stacking with graphene, which is proposed as an efficient medium to facilitate the interfacial electron communication.

中文翻译：

异质表面上钴配合物的轴向修饰，并通过增强电子转移来减少二氧化碳。

分子催化剂与载体之间的有效电子通讯对于非均相分子电催化至关重要，但在催化剂设计过程中常常被忽视。以固定在石墨烯上的四苯基卟啉钴（PCo）上的CO ₂电还原为例，我们证明添加中继分子可以改善界面电子通信。虽然直接固定在石墨烯上的PCo表现出相对较差的电子通讯，但是发现二苯硫醚可作为PCo的轴向配体，并且可以提高PCo在石墨烯表面的氧化还原活性，从而促进[PCo]的生成^。‐ CO _2的活性位减少。因此，固定化的Co络合物的周转频率增加。系统结构分析表明，二苯硫醚的苯环与石墨烯具有很强的面对面堆积，被认为是促进界面电子通讯的有效介质。

更新日期：2020-07-09

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