ZnO supported on Cu2O{100} enhances charge transfer in dimethyldichlorosilane synthesis
ZnO supported on Cu2O{100} enhances charge transfer in dimethyldichlorosilane synthesis
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Cu2O{100} 负载的 ZnO 增强二甲基二氯硅烷合成中的电荷转移
DOI：
10.1016/j.jcat.2019.02.029
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发表时间：
2019
影响因子：
7.3
通讯作者：
Su Fabing
中科院分区：
文献类型：
--
作者：
Li Jing;Ni Zibin;Ji Yongjun;Zhu Yongxia;Liu Hezhi;Zhang Yu;Gong Xue Qing;Zhong Ziyi;Su Fabing
本工作通过在Cu 2 O立方体、Cu 2 O八面体和Cu 2 O十二面体载体上沉积ZnO纳米粒子，制备了三种不同类型的ZnO/Cu 2 O异质结构。这些催化剂被用于Rochow反应，这是一个重要的工业过程，用于合成有机硅聚合物。结果表明，Cu 2 O立方负载ZnO催化剂对二甲基二氯硅烷的生成活性最高，而Cu 2 O十二面体负载ZnO催化剂的活性最低。实验结果和密度泛函理论计算均表明，在这3种情况下，ZnO纳米粒子与Cu 2 O {1 0 0}面之间的电荷转移效率最高，这促进了氯甲烷在Cu 2 O {1 0 0}面上的解离吸附，进而促进了Cu+还原为Cu 0，最终形成Cu 3Si活性相.本工作揭示了Rochow反应在ZnO/Cu 2 O催化剂上如何进行的基本信息，并为合理设计高效的多相催化体系提供了一种实用的策略。
In this work, three types of ZnO/Cu2O heterostructures were synthesized by depositing ZnO nanoparticles on the supports of Cu2O cubes, Cu2O octahedrons and Cu2O dodecahedrons with different exposed facets. These catalysts were used for the Rochow reaction, which is an important industrial process for the synthesis of organosilicon polymers. It was demonstrated that Cu2O cubes-supported ZnO catalyst is the most active toward dimethyldichlorosilane formation, while Cu2O dodecahedrons-supported ZnO catalyst is the least active. Both experimental results and density functional theory calculations show that, in the three cases, the charge transfer efficiency between the ZnO nanoparticle and the Cu2O{1 0 0} plane is the highest, which enhances the dissociative adsorption of methylchloride at Cu2O{1 0 0}, the subsequent reduction of Cu+into Cu0and the final formation of the Cu3Si active phases. This work reveals essential information about how the Rochow reaction proceeds on the ZnO/Cu2O catalyst and demonstrates a practical strategy to rationally design highly efficient catalytic system in heterogeneous catalysis.