Effects of Multiple Promotion of the Direct Synthesis Contact Mass with P, Zn, and Sn on the Synthesis of Methylchlorosilanes

Gordon, Alexander D.; Hinch, B. J.; Strongin, Daniel R.

doi:10.1007/s10562-009-0172-z

Cited by 27 publications

(27 citation statements)

References 24 publications

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“…However, when the addition was dropped to several hundred ppm of coppers, the promoting effect began to show up . Many researchers found that Sn has a promoting effect synergistically with Zn by reducing the melting points and surface tensions of Cu 3 Si, thus increasing surface transfer of Cl and accelerating formation of the active SiCl x sites . Sn‐promoted Cu can increase the concentration of surface methyl species .…”

Section: Chemistry: State‐of‐the‐artmentioning

confidence: 99%

Recent Advances in Rochow‐Müller Process Research: Driving to Molecular Catalysis and to A More Sustainable Silicone Industry

et al. 2019

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The Rochow‐Müller process, an old process that has been known for more than seventy years, is for the direct synthesis of methylchlorosilane. However, due to its unique economic efficiency, it is still extremely important in silicone industry, e. g., about 90 % of starting materials for producing silicones are obtained by this route. Although significant progress has been made in exploring high‐efficient catalysts and understanding its mechanism, a quantitative description of this reaction is still far‐fetched due to its high complexity. In addition, sustainable use and recycling of by‐products and waste solid have become imperative nowadays due to the increasing demands for atom economy and environmental protection. This paper provides a comprehensive overview and insights into Rochow‐Müller process from its catalysis to sustainable issues, including the catalyst development and reaction mechanism investigation, waste reutilization and their derived products. In addition, several emerging novel processes originated from Rochow‐Müller process are summarized. Lastly, challenges and perspectives with respect to this reaction are discussed. We hope this work has accurately reflected and recorded the transition of Rochow‐Müller process to modern molecular catalysis, and can promote a much more sustainable silicone industry.

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Section: Chemistry: State‐of‐the‐artmentioning

confidence: 99%

Recent Advances in Rochow‐Müller Process Research: Driving to Molecular Catalysis and to A More Sustainable Silicone Industry

et al. 2019

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“…The composite of Cu x Ag nanoparticles can be easily controlled by adjusting the ratio of metal precursors. These bimetallic Cu x Ag (such as Cu 50 Ag, Cu 20 Ag, Cu 10 Ag, Cu 5 Ag, CuAg, and CuAg 2 ) nanoparticles are used as model catalysts for Rochow reaction. Compared with the Si conversion for monometallic Cu (35.4% for Cu) and Ag (0% for Ag) nanoparticles, these bimetallic Cu x Ag nanoparticles exhibit much enhanced Si conversion (65.4% for Cu 50 Ag, 68.6% for Cu 20 Ag, 71.1% for Cu 10 Ag, 73.0% for Cu 5 Ag, and 70.3% for CuAg), demonstrating the synergistic electronic effect between Cu and Ag atoms in the AgCu bimetallic nanoparticles, which led to the lower electron density for Cu atoms, in the Rochow reaction.…”

Section: Introductionmentioning

confidence: 99%

“…XRD patterns for samples Cu, Cu50 Ag, Cu 20 Ag, Cu 10 Ag, Cu 5 Ag, CuAg, CuAg 2 , and Ag nanoparticles.…”

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confidence: 99%

Synergistic effect in bimetallic copper–silver (Cu_xAg) nanoparticles enhances silicon conversion in Rochow reaction

Zhang

et al. 2015

RSC Adv.

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The oleylamine thermal reduction process was employed to prepare bimetallic copper-silver (Cu x Ag (0 # x # 50)) nanoparticles, such as Cu, Cu 50 Ag, Cu 20 Ag, Cu 10 Ag, Cu 5 Ag, CuAg, CuAg 2 , and Ag, by using Cu(CH 3 COO) 2 and AgNO 3 as the precursors. The samples were characterized by X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, and X-ray photoelectron spectroscopy. The Cu x Ag hybrid nanostructure showed good particle dispersion, and Cu and Ag metals were well mixed. The catalytic properties of these bimetallic Cu x Ag nanoparticles as model catalysts for the Rochow reaction were explored. Compared to monometallic Cu and Ag nanoparticles, bimetallic Cu x Ag nanoparticles resulted in a much higher silicon conversion, which is attributed to the synergistic electronic effect between Cu and Ag metals. For example, the Cu atom was observed to have a lower electron density in the Cu x Ag bimetallic nanoparticle than that in monometallic Cu nanoparticles, which enhanced the formation of methylchlorosilanes on the silicon surface with chloromethane, demonstrating the significance of the Cu x Ag bimetallic catalysts in catalytic reactions during organosilane synthesis. The insights gained in this study should be conducive to the design of good Cubased catalysts for the Rochow reaction.

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“…1,2 In this reaction, gaseous methyl chloride (MeCl) reacts with silicon (Si) in the presence of Cu-based catalysts as following: [3][4][5] Among these products, dimethyldichlorosilane ((CH 3 ) 2 SiCl 2 , M2) is the most important monomer for the production of organosilane products in industry. 1,2 In this reaction, gaseous methyl chloride (MeCl) reacts with silicon (Si) in the presence of Cu-based catalysts as following: [3][4][5] Among these products, dimethyldichlorosilane ((CH 3 ) 2 SiCl 2 , M2) is the most important monomer for the production of organosilane products in industry.…”

Section: Introductionmentioning

confidence: 99%

“…6 Therefore, a high M2 yield is always demanded. 5,14 In the past few years, porous cubic structures such as Cu microparticles, 15 mesoporous Cu 2 O microspheres, 10 flower-like, 16 and hierarchical dandelion-like 5 Copper nitrate trihydrate (Cu(NO 3 5,14 In the past few years, porous cubic structures such as Cu microparticles, 15 mesoporous Cu 2 O microspheres, 10 flower-like, 16 and hierarchical dandelion-like 5 Copper nitrate trihydrate (Cu(NO 3 …”

Section: Introductionmentioning

confidence: 99%

Heterojunctions generated in SnO₂–CuO nanocatalysts for improved catalytic property in the Rochow reaction

Shanying

Wang

et al. 2015

RSC Adv.

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We report the improved catalytic performance of SnO 2 -CuO hybrid nanocatalysts synthesized by rationally designing and controlling the local heterojunctions structure. The SnO 2 nanoparticles (NPs) decorated CuO nanorods (NRs) (SnO 2 -CuO) with a mace-like structure and with various CuO : SnO 2 ratios were prepared via depositing pre-synthesized SnO 2 NPs on CuO NRs in the presence of polyvinylpyrrolidone molecules. The CuO NRs were obtained by a facile hydrothermal reaction using Cu(NO 3 ) 2 •3H 2 O as the precursor. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, and temperature-programmed reduction analyses. The results indicated that in the SnO 2 -CuO hybrid nanostructures, the heterojunctions were well generated as the SnO 2 NPs were well dispersed on the CuO NRs. Their catalytic performances were then explored via the Rochow reaction, in which solid silicon (Si) reacts with gaseous methyl chloride (MeCl) to produce dimethyldichlorosilane (M2). Compared to discrete CuO and SnO 2 as well as their physical mixture, the SnO 2 -CuO hybrids exhibit significantly enhanced M2 selectivity and Si conversion because of the enhanced synergistic interaction between SnO 2 and CuO due to the generated heterojunctions.This work demonstrates that the performance of heterogeneous catalysts can be improved by carefully designing and controlling its structures even maintaining the composition unchanged.CuO microspheres 17 have been prepared in our group as model catalysts for the Rochow reaction, and found that their catalytic performance mainly depends on the chemical composition, 18 particles size, 19 and surface structure. 16 However, the above catalysts still suffer from low M2 selectivity and/or Si conversion, which seriously hinder their further application. Therefore, more efficient Cu-based catalysts should be developed.Recently, CuO-based hetero-structured hybrid materials have caused strong attention owing to their distinct properties and high diversity in structure and composition. For instance, Avgouropoulos et al. prepared a series of CuO-CeO 2 catalysts which exhibited much better catalytic performance for the selective oxidation of CO than CuO alone. 20 Li et al. observed that the CuO-ZnO-ZrO 2 catalysts synthesized by a surfactant-assisted coprecipitation method showed higher catalytic activity than that of sole CuO as a result of more intimate contact at the interface between Cu species and ZnO and/or ZrO 2 . 21 More recently, we have grown flower-like ZnO on urchin-like CuO microspheres using a simple solvothermal method, and the hierarchical structure displayed better catalytic properties in M2 synthesis in comparison with the single CuO phase, probably because of the enhanced synergistic effect between ZnO and CuO. 22 However, the composite particles were still in the micrometer scale with limited particle contact and weak synergistic effect.On the other hand, to date there are few reports on preparing Cu...

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Effects of Multiple Promotion of the Direct Synthesis Contact Mass with P, Zn, and Sn on the Synthesis of Methylchlorosilanes

Cited by 27 publications

References 24 publications

Recent Advances in Rochow‐Müller Process Research: Driving to Molecular Catalysis and to A More Sustainable Silicone Industry

Recent Advances in Rochow‐Müller Process Research: Driving to Molecular Catalysis and to A More Sustainable Silicone Industry

Synergistic effect in bimetallic copper–silver (Cu_xAg) nanoparticles enhances silicon conversion in Rochow reaction

Heterojunctions generated in SnO₂–CuO nanocatalysts for improved catalytic property in the Rochow reaction

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Effects of Multiple Promotion of the Direct Synthesis Contact Mass with P, Zn, and Sn on the Synthesis of Methylchlorosilanes

Cited by 27 publications

References 24 publications

Recent Advances in Rochow‐Müller Process Research: Driving to Molecular Catalysis and to A More Sustainable Silicone Industry

Recent Advances in Rochow‐Müller Process Research: Driving to Molecular Catalysis and to A More Sustainable Silicone Industry

Synergistic effect in bimetallic copper–silver (CuxAg) nanoparticles enhances silicon conversion in Rochow reaction

Heterojunctions generated in SnO2–CuO nanocatalysts for improved catalytic property in the Rochow reaction

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Product

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Synergistic effect in bimetallic copper–silver (Cu_xAg) nanoparticles enhances silicon conversion in Rochow reaction

Heterojunctions generated in SnO₂–CuO nanocatalysts for improved catalytic property in the Rochow reaction