电化学选择性氢化脱氯反应介绍.ppt

银、钯催化的电化学选择性氢化脱氯反应 浙江工业大学/化学工程学院 绿色化学合成技术国家重点实验室培育基地 徐 颖 华、马红星、丁旭芬、马淳安 Silver, Palladium-electrocatalyzed selective hydrodechlorination 1 目录 1. 银、钯催化的电化学选择性氢化脱氯反应简介 2. 多氯吡啶甲酸的电化学选择性氢化脱氯反应 3. 其他多氯有机物的电化学选择性氢化脱氯反应 4. 总结和展望 Zhejiang University of Technology 2 1.银、钯催化的电化学选择性氢化脱氯反应简介 有机合成：合成部分氯代有机物作为药物中间体或原料药； 要求:区域选择性脱氯。 1.1. 主要用途及要求 Zhejiang University of Technology Rondinini S., et al. Electroreduction of Halogenated Organic Compounds, 2010, 279; Alonao F., et al. Chem. Rev., 2002, 102(11): 4009-4091. 环境保护：降解环境中存在的高毒、难降解氯代有机物； 要求：化学选择性脱氯。 3 1.2.催化原理 Isse A.A., et al. J. Phys. Chem. C, 2009, 113: 14983; Wang A., et al. J. Am. Chem. Soc.: 2010, 132: 9534. Dabo P., et al. Environ. Sci. Technol., 2000, 34: 1265; Chen G.,et al. J. Phys. Chem. B, 2006, 110: 4863. Fig. 1.1 The hydrodechlorination mechanism on silver electrode Fig. 1.2 The hydrodechlorination mechanism on palladium electrode 4 2.多氯吡啶甲酸的电化学选择性氢化脱氯 化工学报, 2010, 61: 699. Zhejiang University of Technology 5 Fig. 2.1 CVs of 3,5,6-T (a) at four electrodes in a N2-saturated 0.25 M PBS at pH = 3, (b) at a Ag(r) electrode in a N2-saturated 0.5 M H2SO4 (pH = 0.2), a 0.5 M NaOH (pH = 13.3) aqueous solution, and 0.25 M PBS of three different pH values (3, 7, and 11); scan rate v = 50 mV s-1, T = 297 K. Electrochim. Acta, 2015, 151: 284; ZL 201410264884.1 Zhejiang University of Technology 2.1. 银催化 Ag(p) Ag(r) pH = 3 Ag(r) 6 Table 2.1 Electrochemical reduction of 3.33 mM 3,5,6-T in a N2-saturated 0.5 M H2SO4 (pH = 0.2), a 0.5 M NaOH (pH = 13.3) aqueous solution, and 0.25 M PBS of three different pH values (3, 7, and 11) at 297 K on five cathodes. Entry Cathodes Iappa or Eappa Solution pH Final product distribution (%) Current efficiency (%)b 3,5-D selectivity (%)c 3,6-D selectivity (%) c 3,5-D 3,6-D 3,5,6-T 1 Ni 10 mA 3 0 0 98.2 0 0 0 2 Cu 10 mA 3 0 0 98.5 0 0 0 3 Ag(p) 1.0 mA 3 2.5 0.8 95.4 2.5 54.3 17.4 4 GC 1.0 mA 3 0 0 94.4 0 0 0 5 Ag(r) 10 mA 3 44.0 2.6 49.3 44.0 86.8 5.1 6 Ag(r) -1.1 V 13.3 0.4 37.8 60.7 0.4 1.0