Mechanistic Study of the Electrocatalytic Oxidation of Alcohols by TEMPO and NHPI
Mechanistic Study of the Electrocatalytic Oxidation of Alcohols by TEMPO and NHPI
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DOI：
10.1002/celc.201300016
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发表时间：
2014-02-11
期刊：
影响因子：
4
通讯作者：
Alizadeh, Saber
中科院分区：
文献类型：
--
作者：
Rafiee, Mohammad;Karimi, Babak;Alizadeh, Saber
动力学研究和优化是催化领域的重要步骤。我们进行了补充的研究（2，2，6，6-四甲基哌啶-1-基）氧基（克里思）和N-羟基邻苯二甲酰亚胺（NHPI）对醇氧化的电催化性能，通过使用伏安法作为一个通用的和信息丰富的技术。两种有机催化剂在水溶液中均表现出良好且明确的电催化活性。对反应条件的有效性的研究表明，催化性能受溶液pH值的影响很大，并且这些表面上相似的系统之间的反应性存在根本差异。克里思在温和的碱性碳酸盐缓冲液中是有效的催化剂，而NHPI在稀乙酸溶液中有效地起作用。此外，醇的类型和取代基的影响进行了评估，为一个完整的系列的醇，并通过伏安分析和数字模拟的循环伏安图获得新的动力学数据。在最佳条件下考察了几种醇的电化学转化，得到了令人鼓舞的结果。
Kinetic studies and optimization are of interest as essential steps in the field of catalysis. We performed a complementary study of the electrocatalytic performances of (2,2,6,6-tetramethylpiperidin-1-yl) oxyl (TEMPO) and N-hydroxyphthalimide (NHPI) towards alcohol oxidation by using voltammetry as a versatile and informative technique. Both organocatalysts exhibited a good and well-defined electrocatalytic activity in aqueous solution. Investigations of the efficacy of the reaction conditions revealed that the catalytic performance is greatly affected by the pH of the solution-and that there is a fundamental difference in reactivity between these apparently similar systems. TEMPO is an efficient catalyst in mild basic carbonate buffer, whereas NHPI acts efficiently in diluted acetic acid solution. Moreover, the effects of the alcohol type and the substituents were evaluated for a complete series of alcohols, and new kinetic data were obtained by means of voltammetric analyses and digital simulations of the cyclic voltammograms. Preparative electrocatalytic conversions of some alcohols were also examined under optimum conditions, and the results were encouraging.