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- Title
Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production.
- Authors
Xie, Xulan; Zhang, Xiang; Xie, Miao; Xiong, Likun; Sun, Hao; Lu, Yongtao; Mu, Qiaoqiao; Rummeli, Mark H.; Xu, Jiabin; Li, Shuo; Zhong, Jun; Deng, Zhao; Ma, Bingyun; Cheng, Tao; Goddard III, William A.; Peng, Yang
- Abstract
Direct implementation of metal-organic frameworks as the catalyst for CO2 electroreduction has been challenging due to issues such as poor conductivity, stability, and limited > 2e− products. In this study, Au nanoneedles are impregnated into a cupric porphyrin-based metal-organic framework by exploiting ligand carboxylates as the Au3+ -reducing agent, simultaneously cleaving the ligand-node linkage. Surprisingly, despite the lack of a coherent structure, the Au-inserted framework affords a superb ethylene selectivity up to 52.5% in Faradaic efficiency, ranking among the best for metal-organic frameworks reported in the literature. Through operando X-ray, infrared spectroscopies and density functional theory calculations, the enhanced ethylene selectivity is attributed to Au-activated nitrogen motifs in coordination with the Cu centers for C-C coupling at the metalloporphyrin sites. Furthermore, the Au-inserted catalyst demonstrates both improved structural and catalytic stability, ascribed to the altered charge conduction path that bypasses the incoherent framework. This study underlines the modulation of reticular metalloporphyrin structure by metal impregnation for steering the CO2 reduction reaction pathway. Metal-organic frameworks are promising catalysts for CO2 electroreduction, yet limited by their poor conductivity and stability. Here, Au nanoneedles are inserted into the metalloporphyrin framework to activate C-C coupling and stabilize the structure for much enhanced ethylene production.
- Subjects
METAL-organic frameworks; METALLOPORPHYRINS; COUPLING reactions (Chemistry); ETHYLENE; DENSITY functional theory; NEAR infrared spectroscopy; CARBOXYLATES
- Publication
Nature Communications, 2022, Vol 13, Issue 1, p1
- ISSN
2041-1723
- Publication type
Article
- DOI
10.1038/s41467-021-27768-6