Approach to generating the right active phase in the “Direct” synthesis of trimethoxysilanes using the CuCl-Cu2O catalyst

Ji, Yongjun; Zhou, Xiwen; Jiang, Xingyu; Li, Huifang; Zhu, Yongchun; Li, Jing; Liu, Hezhi; Xiao, Junping; Zhong, Ziyi; Su, Fabing

doi:10.1016/j.apsusc.2020.148915

Cited by 16 publications

(9 citation statements)

References 37 publications

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“…To better understand the dependence of the yield on the Cu mole fraction and pre-treatment time, we considered the results of several previous non-mechanochemical alkoxysilane synthesis studies and arrived at the following three key conclusions. First, thermal treatment of Si and Cu increases alkoxysilane yields. ,,, Second, copper silicide Cu 3 Si acts as an active center for alkoxysilane synthesis. Third, larger amounts of Cu 3 Si result in larger amounts of alkoxysilanes; specifically, a 3.5-fold increase in the amount of Cu 3 Si was found to result in a 4.5-fold increase in the conversion of Si to alkoxysilanes .…”

Section: Resultsmentioning

confidence: 99%

“…First, thermal treatment of Si and Cu increases alkoxysilane yields. 9,11,38,39 Second, copper silicide Cu 3 Si acts as an active center for alkoxysilane synthesis. Third, larger amounts of Cu 3 Si result in larger amounts of alkoxysilanes; specifically, a 3.5-fold increase in the amount of Cu 3 Si was found to result in a 4.5-fold increase in the conversion of Si to alkoxysilanes.…”

Section: ■ Experimental Methodsmentioning

confidence: 99%

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Near-Room-Temperature Synthesis of Alkoxysilanes and H₂ via Mechanochemical Ball Milling

Miura

Kashiwagi

Fukuda

et al. 2022

ACS Sustainable Chem. Eng.

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Alkoxysilanes are important precursors of silicone materials for which various synthesis methods have been reported. However, these approaches are not without problems, and hence, halogen-free, HF-free, and room-temperature reactions producing alkoxysilanes are required. In this study, we demonstrated a direct low-temperature (∼40 °C) alkoxysilane synthesis method that did not involve halogens or HF. Si, Cu, and ethanol were milled in a planetary ball mill for 2 h, and a 50% yield of tetraethoxysilane (TEOS) was obtained; in addition, analysis revealed negligible contamination (<50 ppm) and a TEOS purity of 99.9%. Gas-, liquid-, and solid-phase mechanochemical products were identified. The alkoxysilane yield depended significantly on the mechanochemical pre-treatment, and seven transition metals were investigated as catalysts. Specifically, mechanochemical pre-treatment of a Si–Cu mixture produced silicide (Cu3Si), which was responsible for the high yields. The alkoxysilane yields and silicide formation mechanism were examined by calculating the local temperature upon impact between colliding balls. We also observed high-volume H2 production and demonstrated that the stainless-steel milling medium acted as a mechanocatalyst. Thus, a near-room-temperature, halogen-free green one-pot synthesis method, involving milling Si and Cu powders in alcohol, was discovered and demonstrated as a novel strategy for high-purity alkoxysilane and H2 production.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Experimental Methodsmentioning

confidence: 99%

Near-Room-Temperature Synthesis of Alkoxysilanes and H₂ via Mechanochemical Ball Milling

Miura

Kashiwagi

Fukuda

et al. 2022

ACS Sustainable Chem. Eng.

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“…The spectra showed the peak at a binding energy of 855.2 eV, which can be assigned to Ni 2+ in NiCl 2 20%, while the Cu 10%-Ni 10% catalyst presented obviously down-shifted peaks of 853.8 eV. [33][34][35] In addition, it must be mentioned that the ratio of Ni 0 fitted by Gaussian curves was increased in Cu 10%-Ni 10%. All these indicated that there was an interaction between copper and nickel, and the same phenomenon also existed in the bimetallic Cu 10%-Co 10% catalyst.…”

Section: Effect Of Bimetal Chloride On the Hydrogenation Of Stcmentioning

confidence: 99%

Bimetal chloride catalyzed hydrogenation of silicon tetrachloride in the presence of silicon

Wang

Jia

et al. 2023

New J. Chem.

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“…In that study, CuO failed to provide good results. At the same time, copper oxides are widely used in the direct synthesis of both alkoxy- , and chlorosilanes, are relatively stable, and are commercially available precatalysts. Using CuO as an alternative to CuCl allows to completely eliminate chlorine from the synthesis of alkoxysilanes .…”

Section: Introductionmentioning

confidence: 99%

Study of the Effect of Zn, Sn, and Pb Additives on the Direct Mechanochemical Synthesis of Tetramethoxysilane in the Presence of CuCl and CuO Catalysts

Kryzhanovskii,

Temnikov,

Anisimov

et al. 2024

Ind. Eng. Chem. Res.

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This article presents the results of our study on the direct mechanochemical synthesis of tetramethoxysilane in a high-pressure reactor using CuO and CuCl as catalysts and some promoters. The rate of the reaction of silicon with methanol in the presence of CuO is significantly lower than that in the presence of CuCl. A method for studying the influence of promoters (SnCl2, Zn, and PbCl2) on different process steps (formation of an active silicide and the reaction of silicon with methanol) has been proposed. It has been shown that the addition of 5000 ppm of SnCl2 [or the same amount of Sn as Sn(0)] improves the rate of the reaction between silicon and methanol in the presence of a low-active copper source (CuO) to the level provided by CuCl. Scanning electron microscopy, powder X-ray diffraction, and X-ray photoelectron spectroscopy studies of the contact masses (CM) carried out at different steps of the process showed that tin promotes the reduction of CuO to Cu by silicon. The term “mechanochemical contact mass” was proposed because in traditional systems without in situ milling (fixed bed, slurry, and fluidization), the CMs are static, resulting in uneven formation of active reaction sites.

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Approach to generating the right active phase in the “Direct” synthesis of trimethoxysilanes using the CuCl-Cu2O catalyst

Cited by 16 publications

References 37 publications

Near-Room-Temperature Synthesis of Alkoxysilanes and H₂ via Mechanochemical Ball Milling

Near-Room-Temperature Synthesis of Alkoxysilanes and H₂ via Mechanochemical Ball Milling

Bimetal chloride catalyzed hydrogenation of silicon tetrachloride in the presence of silicon

Study of the Effect of Zn, Sn, and Pb Additives on the Direct Mechanochemical Synthesis of Tetramethoxysilane in the Presence of CuCl and CuO Catalysts

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Approach to generating the right active phase in the “Direct” synthesis of trimethoxysilanes using the CuCl-Cu2O catalyst

Cited by 16 publications

References 37 publications

Near-Room-Temperature Synthesis of Alkoxysilanes and H2 via Mechanochemical Ball Milling

Near-Room-Temperature Synthesis of Alkoxysilanes and H2 via Mechanochemical Ball Milling

Bimetal chloride catalyzed hydrogenation of silicon tetrachloride in the presence of silicon

Study of the Effect of Zn, Sn, and Pb Additives on the Direct Mechanochemical Synthesis of Tetramethoxysilane in the Presence of CuCl and CuO Catalysts

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Product

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Near-Room-Temperature Synthesis of Alkoxysilanes and H₂ via Mechanochemical Ball Milling

Near-Room-Temperature Synthesis of Alkoxysilanes and H₂ via Mechanochemical Ball Milling