Synthesis of ethane from CO2 by a methyl transferase-inspired molecular catalyst

• 成果类型: Article
• 署名作者: Patra, Suman; Dinda, Souvik; Ghosh, Soumili; Roy, Triparna; Dey, Abhishek
• 署名单位: Department of Science & Technology (India); Indian Association for the Cultivation of Science (IACS) - Jadavpur
• 刊物名称: PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
• ISSN/ISSBN: 0027-9935
• DOI: 10.1073/pnas.2417764122
• 发表日期: 2025-01-14
• 关键词: carbon-dioxide; electrochemical reduction; electroreductive alkylation; porphyrin complexes; iron; methane; selectivity; electrodes; conversion; iron(iii)

摘要

Molecular catalysts with a single metal center are reported to reduce CO2 to a wide range of valuable single-carbon products like CO, HCOOH, CH3OH, etc. However, these catalysts cannot reduce CO2 to two carbon products like ethane or ethylene and the ability to form C-C from CO2 remains mostly limited to heterogeneous material-based catalysts. We report a set of simple iron porphyrins with pendant thiol group can catalyze the reduction of CO2 to ethane (C2H6) with H2O as the proton source with a Faradaic yield >40% the rest being CO. The mechanism involves a CO2-derived methyl group transfer to the pendant thiol akin to the proposal forwarded for methyl transferases and a follow-up C-C bond formation of the thioether thus formed and a Fe(II)-CH3 species generated by the reduction of a second molecule of CO2. The availability of a parking space in the molecular framework for the first reduced C-1 product from CO2 reduction allows C-C bond formation resulting in a unique case where a component of natural gas can be generated from direct electrochemical reduction of CO2.