Electrically driven proton transfer promotes Brempty setnsted acid catalysis by orders of magnitude

• 成果类型: Article
• 署名作者: Westendorff, Karl S.; Hulsey, Max J.; Wesley, Thejas S.; Roman-Leshkov, Yuriy; Surendranath, Yogesh
• 署名单位: Massachusetts Institute of Technology (MIT); Massachusetts Institute of Technology (MIT)
• 刊物名称: SCIENCE
• ISSN/ISSBN: 0036-10801
• DOI: 10.1126/science.adk4902
• 发表日期: 2024-02-16
• 页码: 757-763
• 关键词: coupled electron-transfer; tert-butyl alcohol; tafel slope; dehydration; carbon; corrosion; SURFACES; titanium; site

摘要

Electric fields play a key role in enzymatic catalysis and can enhance reaction rates by 100,000-fold, but the same rate enhancements have yet to be achieved in thermochemical heterogeneous catalysis. In this work, we probe the influence of catalyst potential and interfacial electric fields on heterogeneous Bronsted acid catalysis. We observed that variations in applied potential of similar to 380 mV led to a 100,000-fold rate enhancement for 1-methylcyclopentanol dehydration, which was catalyzed by carbon-supported phosphotungstic acid. Mechanistic studies support a model in which the interfacial electrostatic potential drop drives quasi-equilibrated proton transfer to the adsorbed substrate prior to rate-limiting C-O bond cleavage. Large increases in rate with potential were also observed for the same reaction catalyzed by Ti/TiOyHx and for the Friedel Crafts acylation of anisole with acetic anhydride by carbon-supported phosphotungstic acid.