Au-activated N motifs in non-coherent cupric porphyrin metal organic frameworks for promoting and stabilizing ethylene production
Year: 2022
Type: article
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.
Source: Nature Communications
Authors: Xulan Xie, Xiang Zhang, Miao Xie, Likun Xiong, Hao Sun, Yongtao Lu, Qiaoqiao Mu, Mark H. Rummeli, Jiabin Xu, Shuo Li, Jun Zhong, Zhao Deng, Bingyun Ma, Tao Cheng, William A. Goddard, Yang Peng
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: gold
Estimated APC paid: $5,890
Funders: U.S. Department of Energy, National Natural Science Foundation of China, Government of Jiangsu Province, Natural Science Foundation of Jiangsu Province, Soochow University, Six Talent Peaks Project in Jiangsu Province, Priority Academic Program Development of Jiangsu Higher Education Institutions, Office of Science, Basic Energy Sciences
OpenAlex ID: W4205984286