Upgrading of primary alcohols by C–H bond breaking currently requires temperatures of >200 °C. In this work, new understanding from simulation of a temperature-programmed reaction study with methanol over a CeO₂(111) surface shows C–H bond breaking and the subsequent desorption of formaldehyde, even below room temperature. This is of particular interest because CeO₂ is a naturally abundant and inexpensive metal oxide. We combine density functional theory and kinetic Monte Carlo methods to show that the low-temperature C–H bond breaking occurs via disproportionation of adjacent methoxy species. We further show from calculations that the same transition state with comparable activation energy exists for other primary alcohols; with ethanol, 1-propanol, and 1-butanol explicitly calculated. These findings indicate a promising class of transition states to search for in seeking low-temperature C–H bond breaking over inexpensive oxides.

中文翻译：

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廉价金属氧化物上低于室温的C–H键断裂：CeO ₂（111）上的甲醇至甲醛

目前，通过C–H键断裂来升级伯醇的温度要求> 200°C。在这项工作中，通过对甲醇在CeO ₂（111）表面上进行程序升温反应研究的模拟获得的新认识表明，即使在室温以下，CH键断裂和甲醛的随后脱附也是如此。这是特别有趣的，因为CeO ₂是一种天然丰富且廉价的金属氧化物。我们结合密度泛函理论和动力学蒙特卡罗方法来证明，低温C–H键断裂是通过相邻甲氧基种类的歧化而发生的。从计算中我们进一步表明，其他伯醇存在相同的过渡态，具有可比的活化能。用乙醇，1-丙醇和1-丁醇明确计算。这些发现表明，寻求廉价的氧化物打破低温C–H键的过渡态是有前途的。