Citation: Yinghong Zhu, Jianqing Zhang, Ziying Chen, Anlun Zhang, Chunan Ma. Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol[J]. Chinese Journal of Catalysis, 2016, 37(4): 533-538. doi: 10.1016/S1872-2067(15)61047-6
含硝基咔唑类有机电催化剂的合成及其对醇的电催化氧化
我们合成了三种含硝基咔唑类有机电催化剂, 通过1H NMR对其结构进行了鉴定. 采用循环伏安法测试了该类有机电催化剂的电化学氧化还原性能. 发现取代基的电子效应对有机电催化剂的氧化还原电位及电化学氧化还原可逆性有很大的影响, 供电子基(-OCH3)的引入使氧化电位负移(0.717 V), 吸电子基(-Br)的引入使氧化电位明显正移(1.282 V). 同时, 取代基的引入有效改善了有机电催化剂的电化学可逆性, 从而可以作为有效的电氧化还原媒质应用于电化学氧化反应中. 而当把化合物中的NO2还原为NH2后, 咔唑类化合物的电化学氧化还原可逆性完全消失, 表明硝基的引入对咔唑类有机电催化剂的电化学性能有很大的影响.
循环伏安结果发现, 在咔唑类硝基化合物的作用下, 对甲氧基苯甲醇(p-MBzOH)的电化学氧化峰电位从1.350 V降至1.286 V, 表明可以在较低电位下进行电解, 有效降低了电氧化反应的能耗, 同时氧化峰电流明显增加, 说明该类有机电催化剂对p-MBzOH具有良好的电催化性能. 随着p-MBzOH浓度的增加, 氧化峰电流也明显增大, 说明在咔唑类有机电催化剂的作用下, p-MBzOH可以在比较高的浓度下进行电化学氧化电解. 通过对不同对位取代基的苯甲醇类化合物进行循环伏安研究, 发现含硝基咔唑类化合物对具有较高氧化电位的反应底物均表现出良好的电催化氧化性能.
在含硝基咔唑类有机电催化剂的氧化电位(1.28 V)和室温下, 对不同浓度的p-MBzOH进行恒电位电解6 h, 发现当催化剂的用量为底物的2.5 mol%时, p-MBzOH可以完全转化为相应的醛类目标产物. 而且恒电位电解后分离回收的含硝基咔唑类有机电催化剂仍具有良好的电化学氧化还原可逆性.
English
Synthesis of nitrocarbazole compounds and their electrocatalytic oxidation of alcohol
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