Deciphering the Promoting Effect of Zn on CuO for Dimethyldichlorosilane Production via the Rochow-Müller Reaction

IF 3.8 3区 工程技术 Q2 ENGINEERING, CHEMICAL Industrial & Engineering Chemistry Research Pub Date : 2024-10-13 DOI:10.1021/acs.iecr.4c02149
Yuanlong Cui, Yongxia Zhu, Baofang Jin, Kangjun Wang, Jiajian Gao, Lili Zhang, Guangwen Xu, Ziyi Zhong, Fabing Su
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Abstract

Zinc (Zn) is commonly used as a promoter in Cu-based catalysts to boost the production of organosilane monomers during the Rochow-Müller reaction. However, the effect of Zn on the phase change of Cu-based catalysts in the reaction process is not yet fully understood. In this study, we prepared two Zn-modified CuO catalysts using simple ball milling (Zn–CuO) and physical mixing (Zn+CuO) methods. We found that adding Zn into CuO enhanced the adsorption of methyl chloride on the CuO surface, thereby promoting the sequential phase transformation of CuO to Cu2O and then to Cu and further to CuCl. Moreover, CuCl, as a key intermediate phase, could diffuse into Si powder and form Cu3Si under high-temperature conditions. Compared to CuO and Zn+CuO, Zn–CuO underwent a faster phase transformation, facilitating the generation of the active Cu3Si phase and enhancing the dimethyldichlorosilane selectivity and Si conversion. This study has clarified the role of the Zn promoter in the phase transformation of CuO catalysts in the Rochow-Müller reaction. Understanding this mechanism is crucial to designing more efficient catalysts.

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解密 Zn 对通过 Rochow-Müller 反应生产二甲基二氯硅烷的 CuO 的促进作用
锌(Zn)通常被用作铜基催化剂的促进剂,以提高罗考夫-缪勒反应过程中有机硅单体的产量。然而,锌在反应过程中对铜基催化剂相变的影响尚未完全清楚。在本研究中,我们采用简单球磨法(Zn-CuO)和物理混合法(Zn+CuO)制备了两种 Zn 改性 CuO 催化剂。我们发现,在 CuO 中添加 Zn 可增强 CuO 表面对氯化甲烷的吸附,从而促进 CuO 向 Cu2O、Cu 以及 CuCl 的顺序相变。此外,CuCl 作为一种关键的中间相,在高温条件下可扩散到硅粉中并形成 Cu3Si。与 CuO 和 Zn+CuO 相比,Zn-CuO 的相变速度更快,从而促进了活性 Cu3Si 相的生成,提高了二甲基二氯硅烷的选择性和硅转化率。这项研究阐明了 Zn 促进剂在 Rochow-Müller 反应中 CuO 催化剂相变过程中的作用。了解这一机制对于设计更高效的催化剂至关重要。
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来源期刊
Industrial & Engineering Chemistry Research
Industrial & Engineering Chemistry Research 工程技术-工程:化工
CiteScore
7.40
自引率
7.10%
发文量
1467
审稿时长
2.8 months
期刊介绍: ndustrial & Engineering Chemistry, with variations in title and format, has been published since 1909 by the American Chemical Society. Industrial & Engineering Chemistry Research is a weekly publication that reports industrial and academic research in the broad fields of applied chemistry and chemical engineering with special focus on fundamentals, processes, and products.
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