化学学报 ›› 2004, Vol. 62 ›› Issue (4): 414-417. 上一篇    下一篇

研究论文

电化学合成系列锡配合物及纳米SnO2的制备

周幸福, 赵俊峰, 褚道葆   

  1. 安徽师范大学化学与材料科学学院, 芜湖, 241000
  • 投稿日期:2003-04-22 修回日期:2003-10-08 发布日期:2014-01-26
  • 通讯作者: 周幸福,E-mail:xfzhu@263.net E-mail:xfzhu@263.net
  • 基金资助:
    国家自然科学基金(No.29873039)、安徽省自然科学基金(No.00046112)和安徽省教育委员会自然科学基金(No.2002Kj116)资助项目

Electrochemical Synthesis of Tin Complexes and Preparation of Nano-sized SnO2

ZHOU Xing-Fu, ZHAO Jun-Feng, CHU Dao-Bao   

  1. School of Chemistry and Materials Science, Anhui Normal University, Wuhu 241000
  • Received:2003-04-22 Revised:2003-10-08 Published:2014-01-26

采用锡金属为"牺牲"阳极,首次在无隔膜电解槽中,电化学一步法制备了纳米SnO2前驱体锡配合物Sn(OEt)4, Sn(OBu)4, Sn(OCH2CH2OCH3)4, Sn(OEt)2(acac)2, Sn(OBu)2(acac)2, Sn(OCH2CH2OCH3)2(acac)2[acac为乙酰丙酮基],产物通过红外光谱(FT-IR)、拉曼光谱和核磁共振进行表征.同时采用含Sn(OR)2(acac)2>的电解液直接水解制备纳米SnO2粉体,纳米SnO2通过X射线粉末衍射(XRD)和透射电子显微镜(TEM)进行表征.实验表明,电解时防止阳极钝化,控制温度在40~60℃之间,采用有机胺溴化物为导电盐,可以提高电合成效率;电解合成Sn(OCH2CH2OCH3)4, Sn(OEt)2(acac)2, Sn(OBu)2(acac)2, Sn(OCH2CH2OCH3)2(acac)2的电流效率比Sn(OEt)4, Sn(OBu)4高,适宜作为溶胶-凝胶(Sol-gel)法制备纳米SnO2的原料,制备得到的纳米SnO2经600℃煅烧后呈球形单分散结构,晶型为四方锡石型,平均粒径在(10±0.4) nm左右.

关键词: 锡配合物, 锡阳极, 有机电解合成, 溶胶-凝胶, 纳米SnO2

Tin complexes were directly prepared by using tin metal as sacrificial anode in a cell without separating the cathode and anode spaces. The products were characterized by using FT-IR, NMR and Raman spectra. The influence of temperature and conductive additives on product yield was also investigated. The study shows that direct electrochemical preparation of tin complexes such as Sn(OCH2CH2OCH3) 4, Sn(OEt)2(acac)2, Sn(OBu)2(acac)2 and Sn(OCH2CH2OC3)2(acac)2 have high current efficiency and electrolysis yield than those of Sn(OR)4, and these tin complexes have high purity and can be directly used as sol gel precursor for preparation of nanometer SnO2. The experiment shows that the temperature controlling in the range of 40~60℃, selecting R4NBr as conductive additives and preventing tin anode from being passivated or covered by electrochemical products can improve product yield. The study also shows that nano sized SnO2 prepared by this method has tetragonal cassiterite structure with a narrow size distribution of (10±0 4) nm.

Key words: tin complex, tin anode, organic electrolysis, sol2gel, nano-sized SnO2