Parial Oxidation of Aromatics with Activated-Oxygen Cell Reactions

利用活性氧池反应对芳香族化合物进行部分氧化

• 批准号: 04453078
• 负责人: OTSUKA Kiyoshi
• 金额: $ 3.2万
• 依托单位: Tokyo Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453078/
• 关键词: Hudroxylation of benzene.; One step sunthesis of phenol.; Fuel cell.; Partial of toluene.; Selective synthesis of cresol.; Selective synthesis of benzaldehyde.; Carbon electrode.; Hydroxy radical.; 酸素酸化; ベンゼル水酸化; フェノール段合成

One step synthesis of phenol from benzene with reductivated O2 over the cathode was a success by applying an H2 cell reaction system. Cathodes of some carbon materials activated woth HNO3 aq. at refluxing were active for the hydroxylation of benzene. The order of the cathodes for the yield of products was carbon whisker a10 carbon black >> active carbon > graphite.The co-addition of Pd black and Fe2O3 and the addition of CuSO 4 to carbon whisker enhanced the catalytic acticity of the cathode for the hydroxylation of benzene. Especially, the maximum yield of phenol was obtained during generating electricity at 0.3 V for the cathode of carbon whiskeradded CuSO4. This result demonstrates that the possibility of phenol and electroricity. The oxidation of toluene occurredwith our reaction system, producing o-, m-, p-cresols and benzaldehyde, benzyl alcohol. The selectiviy to cresols was high for the cathode of carbom black and active carbon, that to benzaldehyde and benzyl alcohol was high for the cathode of carbon whisker and graphite. The selectivities of the products can be controlled by changing the oncentration of the electrolyte solutions of H3PO4. Cresols were selectively produced (90%) at low concentration of H3PO4, and benzaldehyde was selectively produced (95%) at high concentration. The synergistic effect of active carbon and carbon whisker for the oxidation of toluene was observed. The catalytic activity for the cathode of the mixture of active carbon andcarbon whisker (1 : 1) was 6 tumes of that for active carbon alone and twice of that for carbon whisker alone. These observations could be explained by a Fenton-type chemistry assuming HO・ as an active oxugen.

采用氢气电池反应系统，成功地实现了阴极上氧气还原苯一步合成苯酚。用硝酸水溶液活化某些炭材料的阴极。对苯的羟基化反应具有催化活性。结果表明，不同的阴极对产物收率的影响顺序为：碳晶须a 10炭黑>活性炭>石墨，Pd黑和Fe2 O3的共添加以及CuSO 4的添加均提高了碳晶须对苯羟基化反应的催化活性。特别是添加CuSO_4的碳晶须阴极在0.3V时产生的苯酚产率最高。这一结果说明了苯酚与电性的可能性。在本反应体系中，甲苯发生氧化反应，生成邻、间、对甲酚和苯甲醛、苯甲醇。炭黑和活性炭阴极对甲酚的选择性高，碳晶须和石墨阴极对苯甲醛和苯甲醇的选择性高。产物的选择性可以通过改变H_3PO_4电解质溶液的浓度来控制。在低浓度的H_3PO_4条件下，选择性地生成甲酚（90%），在高浓度的H_3PO_4条件下，选择性地生成苯甲醛（95%）。考察了活性炭和碳晶须对甲苯氧化的协同效应。活性炭与碳晶须（1：1）的混合物对阴极的催化活性是单独活性炭的6倍，是单独碳晶须的2倍。这些观察结果可以用假设HO·为活性氧的芬顿型化学来解释。

项目成果

Ichiro Yamanaka: "Partial oxidation of Cyclohexane with Reductively Activated Dioxygen on SmCl_3 supported on Graphite during H_2-O_2 Fuel Cell Reactions" Journal of Chemical Society,Faraday Transactions. 89. 1791-1797 (1993)

Ichiro Yamanaka：“H_2-O_2 燃料电池反应期间石墨上支持的 SmCl_3 上的还原活化分子氧对环己烷的部分氧化”《化学学会杂志》，《法拉第汇刊》。

大塚 潔: "H_2-O_2電池反応を応用した芳香族の水酸化" 化学工学. 56. 834-836 (1992)

Kiyoshi Otsuka：“使用H_2-O_2电池反应的芳香族氢氧化物”化学工程56。834-836（1992）。

Ichiro Yamanaka and Kiyoshi Otsuka: ""Partial oxidation of Cyclohexane with Reductively Activated Dioxygen on SmCl3 supported on Graphite during H2-O2 Fuel Cell Reactions"" Journal of Chemical Society, Faraday Transactions. 89[11]. 1790-1797 (1993)

Ichiro Yamanaka 和 Kiyoshi Otsuka：“H2-O2 燃料电池反应期间石墨上负载的 SmCl3 上的还原活化分子氧对环己烷的部分氧化”，《化学学会杂志》，《法拉第汇刊》。

Kiyoshi Otsuka: ""The Hydoroxylation of Aromatics Appling H2-O2 Fuel Cell Reactions"" Kagakukougaku. 56. 834-536 (1992)

Kiyoshi Otsuka：““应用 H2-O2 燃料电池反应进行芳香烃的羟基化”” Kagakukougaku。

Kiyoshi Otsuka: "Regioselective Oxidation of n-Hexane and Aromatics in the Presence of Cyclodextrins during H2-02 Fuel Cell Reactions" Electrochimica Acta. 37. 1135-1141 (1992)

Kiyoshi Otsuka：“H2-02 燃料电池反应过程中环糊精存在下正己烷和芳烃的区域选择性氧化”《电化学学报》。