College of Chemistry and Chemical Engineering, Qiqihaer University, Qiqihaer 161006, Heilongjiang Province, China.
J Colloid Interface Sci. 2013 Aug 15;404:16-23. doi: 10.1016/j.jcis.2013.04.028. Epub 2013 May 10.
CuCl microcrystals with different morphologies such as tetrahedra, etched tetrahedra, tripod dendrites, and tetrapods were synthesized using CuCl2⋅2H2O as the copper precursor in the mixed solvent of acetylacetone and ethylene glycol. The samples were characterized with X-ray diffraction, scanning electron microscopy, infrared spectroscopy, and transmission electron microscope. Cu(C5H7O2)2 was identified as the key intermediate, and the morphology and structure of the CuCl microcrystals were highly dependent on the reaction time and temperature, as well as the volume of the solvents. The catalytic properties of these CuCl microcrystals were explored in the dimethyldichlorosilane synthesis via Rochow reaction. Compared to the commercial CuCl microparticles with irregular morphology and dense internal structure, the obtained CuCl microcrystals possessed regular morphology and different exposed crystal planes and showed much higher dimethyldichlorosilane selectivity and Si conversion via the Rochow reaction because of the enhanced formation of active CuxSi phase and gas transportation within the dendritic structure, demonstrating the significance of regular morphology of the copper-based catalysts in catalytic organosilane synthesis.
使用乙酰丙酮和乙二醇的混合溶剂,以 CuCl2·2H2O 为铜前体制备了不同形貌的 CuCl 微晶体,如四面体、刻蚀四面体、三脚架树枝状和四足。通过 X 射线衍射、扫描电子显微镜、红外光谱和透射电子显微镜对样品进行了表征。确定 Cu(C5H7O2)2 为关键中间体,CuCl 微晶体的形貌和结构高度依赖于反应时间和温度以及溶剂的体积。这些 CuCl 微晶体的催化性能在通过 Rochow 反应合成二甲基二氯硅烷中进行了探索。与具有不规则形貌和密集内部结构的商业 CuCl 微粒相比,由于活性 CuxSi 相的形成增强以及树枝状结构内的气体传输,所获得的 CuCl 微晶体具有规则的形貌和不同的暴露晶面,通过 Rochow 反应表现出更高的二甲基二氯硅烷选择性和 Si 转化率,这表明在催化有机硅烷合成中,基于铜的催化剂的规则形貌具有重要意义。