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烧结碳化硅:一种用于单模反应器中微波化学的新型陶瓷容器材料。

Sintered silicon carbide: a new ceramic vessel material for microwave chemistry in single-mode reactors.

机构信息

Christian Doppler Laboratory for Microwave Chemistry (CDLMC) and Institute of Chemistry, Karl-Franzens-University Graz, Heinrichstrasse 28, 8010 Graz, Austria.

出版信息

Chemistry. 2010 Oct 25;16(40):12182-94. doi: 10.1002/chem.201001703.

Abstract

Silicon carbide (SiC) is a strongly microwave absorbing chemically inert ceramic material that can be utilized at extremely high temperatures due to its high melting point and very low thermal expansion coefficient. Microwave irradiation induces a flow of electrons in the semiconducting ceramic that heats the material very efficiently through resistance heating mechanisms. The use of SiC carbide reaction vessels in combination with a single-mode microwave reactor provides an almost complete shielding of the contents inside from the electromagnetic field. Therefore, such experiments do not involve electromagnetic field effects on the chemistry, since the semiconducting ceramic vial effectively prevents microwave irradiation from penetrating the reaction mixture. The involvement of electromagnetic field effects (specific/nonthermal microwave effects) on 21 selected chemical transformations was evaluated by comparing the results obtained in microwave-transparent Pyrex vials with experiments performed in SiC vials at the same reaction temperature. For most of the 21 reactions, the outcome in terms of conversion/purity/product yields using the two different vial types was virtually identical, indicating that the electromagnetic field had no direct influence on the reaction pathway. Due to the high chemical resistance of SiC, reactions involving corrosive reagents can be performed without degradation of the vessel material. Examples include high-temperature fluorine-chlorine exchange reactions using triethylamine trihydrofluoride, and the hydrolysis of nitriles with aqueous potassium hydroxide. The unique combination of high microwave absorptivity, thermal conductivity, and effusivity on the one hand, and excellent temperature, pressure and corrosion resistance on the other hand, makes this material ideal for the fabrication of reaction vessels for use in microwave reactors.

摘要

碳化硅(SiC)是一种强烈吸收微波的化学惰性陶瓷材料,由于其熔点高和极低的热膨胀系数,可在极高温度下使用。微波辐射会在半导体陶瓷中诱导电子流动,通过电阻加热机制非常有效地加热材料。碳化硅(SiC)反应容器与单模微波反应器结合使用,几乎可以完全将容器内的内容物屏蔽在电磁场之外。因此,此类实验不会涉及电磁场对化学的影响,因为半导体陶瓷小瓶有效地阻止了微波辐射穿透反应混合物。通过将在微波透明的 Pyrex 小瓶中获得的结果与在相同反应温度下在 SiC 小瓶中进行的实验进行比较,评估了电磁场效应(特定/非热微波效应)对 21 种选定化学转化的影响。对于大多数 21 种反应,使用两种不同小瓶类型的转化率/纯度/产物收率的结果几乎相同,这表明电磁场对反应途径没有直接影响。由于 SiC 的高化学抗性,可在不降解容器材料的情况下进行涉及腐蚀性试剂的反应。例如,使用三乙胺三氢氟酸盐进行高温氟氯交换反应,以及用水合氢氧化钾水解腈。一方面是高微波吸收率、热导率和扩散率的独特组合,另一方面是出色的温度、压力和耐腐蚀性,使得这种材料成为用于微波反应器的反应容器制造的理想选择。

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