Mechanistic examination of the titania photocatalyzed oxidation of ethanolamines
Mechanistic examination of the titania photocatalyzed oxidation of ethanolamines
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DOI：
10.1039/b102186i
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发表时间：
2001
影响因子：
3.3
通讯作者：
S. Horikoshi;N. Watanabe;M. Mukae;H. Hidaka;N. Serpone
中科院分区：
文献类型：
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作者：
S. Horikoshi;N. Watanabe;M. Mukae;H. Hidaka;N. Serpone
在这项研究中，我们重点阐明了当存在于照明的水相二氧化钛分散体中时，乙醇胺、二乙醇胺和三乙醇胺中的伯胺、仲胺和叔胺的光催化转化机制。这些乙醇胺的光解作用通过预先形成各种中间物质导致CO2的演化。铵离子（NH4+）和硝态氮离子（NO3−）是氨基氮原子光转化的最终产物，三种乙醇胺中NH4+阳离子的生成量均大于NO3−阴离子。在完全矿化发生之前，三乙醇胺的光氧化产生各种中间体，包括3-吡咯烷酮衍生物、二乙醇胺和乙醇胺。通过计算机辅助的点电荷分子轨道（MO）计算和乙醇胺结构中所有原子的前沿电子密度预测了光降解初始步骤的性质。
In this study we focus on elucidating the mechanism of the photocatalyzed transformation of the primary, secondary and tertiary amines found in ethanolamine, diethanolamine and triethanolamine when present in illuminated aqueous titania dispersions. Photodecomposition of these ethanolamines leads to the evolution of CO2 through prior formation of various intermediate species. Ammonium (NH4+) and nitrate ions (NO3−) are the ultimate products formed in the photoconversion of the amine nitrogen atoms, with NH4+ cations produced in greater quantity than NO3− anions for all three ethanolamines. Photooxidation of triethanolamine yields various intermediates, including a 3-pyrrolidone derivative, diethanolamine, and then ethanolamine, before complete mineralization occurs. The nature of the initial steps in the photodegradation was predicted by computer-aided molecular orbital (MO) calculations of point charges, and by frontier electron densities of all atoms in the ethanolamine structures.