摘要
本文以醋酸钯为钯源,二甲基亚砜为硫源,在乙二醇和醋酸存在的条件下通过一步法制备了一种六核钯–甲硫醇团簇化合物[Pd(SCH_3)_2]_6.其具有特征的类花冠形结构.对其反应机制进行了探讨,首先二甲基亚砜分解生成甲硫醇和甲醛,钯与甲硫醇反应原位生成钯–甲硫醇团簇.这些生成的团簇分子进一步组装成微米尺寸大小的棱柱.通过向反应体系中引入一种表面活性剂,产物的形貌从微米棱柱转变为纳米球.350°C下,[Pd(SCH_3)_2]_6的微米棱柱在空气中分解得到金属钯单质.对其热解产物进行电镜表征,发现其在保持原有棱柱形貌的基础上形成了孔道结构.在不同的热解条件下可以得到钯或硫化钯热解产物.
A novel one-pot approach to synthesize the tiara-like Pd(II) thiolate complex compound, [Pd(SCH_3)_2]_6, was developed. In this strategy, dimethyl sulfoxide(DMSO) was used as a thiolate source instead of methyl mercaptan(CH_3SH). DMSO was first decomposed into CH_3SH and formaldehyde(HCHO); then, the in situ as-formed CH_3SH molecules reacted with palladium acetate, and formed [Pd(SCH_3)_2]_6. By tuning the reaction condition, the morphology of the [Pd(SCH_3)_2]_6 assemblies can change from microprism to nanosphere. The characterization of the pyrolysis product demonstrated that these two kinds of [Pd(SCH_3)_2]_6 assemblies with different shapes could further decompose into palladium or palladium sulfides through different pyrolysis conditions.
基金
supported by the State Key Project of Fundamental Research for Nanoscience and Nanotechnology (2012CB224802)
the National Natural Science Foundation of China (21573119,21221062,21131004,21390393,U1463202 and 21325101)
Beijing Municipal Commission of Science and Technology (Z141100003814017)
