Conte Marco, Wilson Karen, Chechik Victor
Department of Chemistry, University of York, Heslington, York, YO10 5DD, United Kingdom.
Rev Sci Instrum. 2010 Oct;81(10):104102. doi: 10.1063/1.3492247.
A catalytic reactor for the trapping of free radicals originating from gas phase catalytic reactions is described and discussed. Radical trapping and identification were initially carried out using a known radical generator such as dicumyl peroxide. The trapping of radicals was further demonstrated by investigating genuine radical oxidation processes, e.g., benzaldehyde oxidation over manganese and cobalt salts. The efficiency of the reactor was finally proven by the partial oxidation of cyclohexane over MoO(3), Cr(2)O(3), and WO(3), which allowed the identification of all the radical intermediates responsible for the formation of the products cyclohexanol and cyclohexanone. Assignment of the trapped radicals was carried out using spin trapping technique and X-band electron paramagnetic resonance spectroscopy.
本文描述并讨论了一种用于捕获源自气相催化反应的自由基的催化反应器。自由基捕获和鉴定最初是使用已知的自由基发生器（如过氧化二异丙苯）进行的。通过研究真正的自由基氧化过程（例如在锰盐和钴盐上进行苯甲醛氧化）进一步证明了自由基的捕获。该反应器的效率最终通过在MoO(3)、Cr(2)O(3)和WO(3)上进行环己烷的部分氧化得以证明，这使得能够鉴定出负责生成产物环己醇和环己酮的所有自由基中间体。使用自旋捕获技术和X波段电子顺磁共振光谱对捕获的自由基进行了归属。
