Direct synthesis of phenol from benzene during O[sub 2]-H[sub 2] fuel cell reactions
Direct synthesis of phenol from benzene during O[sub 2]-H[sub 2] fuel cell reactions
复制标题
O[sub 2]-H[sub 2]燃料电池反应中苯直接合成苯酚
DOI：
10.1149/1.2221235
复制
发表时间：
1992
影响因子：
3.9
通讯作者：
H. Yamagata
中科院分区：
文献类型：
--
作者：
K. Otsuka;M. Kunieda;H. Yamagata
在本文中，苯部分氧化为苯酚在阴极在室温下证明在O[sub 2]-H[sub 2]燃料电池反应。探索了该反应的最佳阴极。研究了石墨、炭黑、活性炭和碳晶须作为阴极。在373 K下用HNO[sub 3]水溶液（6/7 M）预处理这些碳材料显著提高了苯酚的产率。在这些碳材料中，碳晶须表现出最好的结果。羟基自由基是苯羟基化反应的活性氧物种。提出了以羟基己二烯自由基为反应中间体的反应机理。钯黑和铁离子的共同添加到碳显示出市场协同作用的苯酚的形成。Pd黑增加了分子氧的还原速率。Fe ~（2+）离子增强了羟基自由基的生成，同时也增强了苯酚的选择性。这些效果的组合解释了Pd黑和Fe阳离子的协同作用。将上述反应体系和最佳阴极用于甲苯和环己烷的部分氧化。
In this paper partial oxidation of benzene to phenol at the cathode is demonstrated at room temperature during O[sub 2]-H[sub 2] fuel cell reactions. The best cathode for this reaction was explored. Graphite, carbon black, active carbon, and carbon whisker were examined as the cathodes. Pretreatment of these carbon materials with HNO[sub 3] aqueous solution (6/7M) at 373 K improved the rate of phenol production remarkably. Among these carbon materials, the carbon whisker showed the best results. Hydroxyl radical was suggested to be the active oxygen species responsible for hydroxylation of benzene. The reaction mechanism assuming hydroxyhexadienyl radical as a reaction intermediate has been proposed. Coaddition of Pd black and Fe-cation to the carbons showed a market synergism for the formation of phenol. Pd black increases the rate of reduction of dioxygen. Fe-cation enhances the generation of hydroxyl radical as well as the selectivity to phenol. The combination of these effects explains the synergism of Pd black and Fe-cation. The same reaction system and the best cathode described above have been applied to the partial oxidations of toluene and cyclohexane.