Porous (CuO)_xZnO hollow spheres as efficient Rochow reaction catalysts

TY - JOUR

T1 - Porous (CuO)xZnO hollow spheres as efficient Rochow reaction catalysts

AU - Zhang, Zailei

AU - Ji, Yongjun

AU - Li, Jing

AU - Zhu, Yongxia

AU - Zhong, Ziyi

AU - Su, Fabing

N1 - Publisher Copyright: © The Royal Society of Chemistry 2016.

PY - 2016/4/28

Y1 - 2016/4/28

N2 - Nowadays, how to achieve both high dimethyldichlorosilane selectivity and silicon conversion in the Rochow reaction still remains a major challenge in the organosilane industry, in which silicon and chloromethane are converted into methylchlorosilanes on Cu-based catalysts mixed with ZnO promoter. Therefore, this calls for the development of outstanding catalysts with both high activity and selectivity for the Rochow reaction and also for a deep fundamental understanding of the catalytic mechanism. In this work, we designed and synthesized a series of copper oxide-zinc oxide catalysts ((CuO)xZnO (0 ≤ x ≤ 49)) with a distinct porous hollow spherical structure for the reaction. These porous hollow spherical catalysts composed of CuO and ZnO nanoparticles were prepared through co-adsorption of Cu2+ and Zn2+ in the interior and outer surfaces of the hydrothermally synthesized carbonaceous spheres, followed by a new hydrothermal treatment and calcination in air. The catalytic properties of the (CuO)xZnO hollow spheres for dimethyldichlorosilane synthesis via the Rochow reaction was investigated, and a deeper understanding of the catalytic mechanism was obtained. As compared to pure CuO hollow spheres, the prepared (CuO)19ZnO hollow spheres exhibited much higher dimethyldichlorosilane selectivity and silicon conversion, which are clearly related to the synergistic electronic effect between Cu and ZnO and to the distinct catalyst structures which allow intimate contact of the reactant molecules with the active component and the efficient transport of the molecules. This work opens a new way for the fabrication of efficient and integrated Cu-based catalysts for the Rochow reaction.

AB - Nowadays, how to achieve both high dimethyldichlorosilane selectivity and silicon conversion in the Rochow reaction still remains a major challenge in the organosilane industry, in which silicon and chloromethane are converted into methylchlorosilanes on Cu-based catalysts mixed with ZnO promoter. Therefore, this calls for the development of outstanding catalysts with both high activity and selectivity for the Rochow reaction and also for a deep fundamental understanding of the catalytic mechanism. In this work, we designed and synthesized a series of copper oxide-zinc oxide catalysts ((CuO)xZnO (0 ≤ x ≤ 49)) with a distinct porous hollow spherical structure for the reaction. These porous hollow spherical catalysts composed of CuO and ZnO nanoparticles were prepared through co-adsorption of Cu2+ and Zn2+ in the interior and outer surfaces of the hydrothermally synthesized carbonaceous spheres, followed by a new hydrothermal treatment and calcination in air. The catalytic properties of the (CuO)xZnO hollow spheres for dimethyldichlorosilane synthesis via the Rochow reaction was investigated, and a deeper understanding of the catalytic mechanism was obtained. As compared to pure CuO hollow spheres, the prepared (CuO)19ZnO hollow spheres exhibited much higher dimethyldichlorosilane selectivity and silicon conversion, which are clearly related to the synergistic electronic effect between Cu and ZnO and to the distinct catalyst structures which allow intimate contact of the reactant molecules with the active component and the efficient transport of the molecules. This work opens a new way for the fabrication of efficient and integrated Cu-based catalysts for the Rochow reaction.

UR - http://www.scopus.com/inward/record.url?scp=84966359044&partnerID=8YFLogxK

U2 - 10.1039/c6ce00173d

DO - 10.1039/c6ce00173d

M3 - 文章

AN - SCOPUS:84966359044

SN - 1466-8033

VL - 18

SP - 2808

EP - 2819

JO - CrystEngComm

JF - CrystEngComm

IS - 16

ER -