Electrons Mediate the Gas-Phase Oxidation of Formic Acid with Ozone

被引：14
作者：
van der Linde, Christian [1 ]
Tang, Wai-Kit [2 ]
Siu, Chi-Kit [2 ]
Beyer, Martin K. [1 ]
机构：
[1] Leopold Franzens Univ Innsbruck, Inst Ionenphys & Angew Phys, Technikerstr 25, A-6020 Innsbruck, Austria
[2] City Univ Hong Kong, Dept Biol & Chem, 83 Tat Chee Ave, Kowloon Tong, Hong Kong, Peoples R China
来源：
CHEMISTRY-A EUROPEAN JOURNAL | 2016年 / 22卷 / 36期
关键词：
electron; gas-phase reactions; radical ions; reaction mechanisms; reactive intermediates; CLUSTER ANIONS; PHOTODISSOCIATION SPECTROSCOPY; IONS; KINETICS; THERMOCHEMISTRY; CO2; ATTACHMENT; CHEMISTRY; HYDRATION; ISOMERS;
D O I：
10.1002/chem.201603080
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Gas-phase reactions of CO3 center dot- with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38% of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O-2, which in turn transfer the electron to O-3 center dot O-3(center dot-) reacts with CO2 to form CO3 center dot-. The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.
引用
收藏
页码：12684 / 12687
页数：4
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