Jiang De-en, van Duin Adri C T, Goddard William A, Dai Sheng
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA.
J Phys Chem A. 2009 Jun 25;113(25):6891-4. doi: 10.1021/jp902986u.
Pyrolysis of phenolic resins leads to carbon formation. Simulating this resin-to-carbon process atomistically is a daunting task. In this paper, we attempt to model the initial stage of this process by using the ReaxFF reactive force field, which bridges quantum mechanical and molecular mechanical methods. We run molecular dynamics simulations to examine the evolution of small molecules at different temperatures. The main small-molecule products found include H(2)O, H(2), CO, and C(2)H(2). We find multiple pathways leading to H(2)O formation, including a frequent channel via beta-H elimination, which has not been proposed before. We determine the reaction barrier for H(2)O formation from the reaction rates obtained at different temperatures. We also discuss the relevance of our simulations to previous experimental observations. This work represents a first attempt to model the resin-to-carbon process atomistically.
酚醛树脂的热解会导致碳的形成。从原子层面模拟这种从树脂到碳的过程是一项艰巨的任务。在本文中，我们尝试使用ReaxFF反应力场对该过程的初始阶段进行建模，该反应力场架起了量子力学方法和分子力学方法之间的桥梁。我们进行分子动力学模拟，以研究不同温度下小分子的演化情况。发现的主要小分子产物包括H₂O、H₂、CO和C₂H₂。我们发现了多种导致H₂O形成的途径，包括一条之前未被提出的通过β-H消除的常见通道。我们根据在不同温度下获得的反应速率确定了H₂O形成的反应势垒。我们还讨论了我们的模拟与先前实验观察结果的相关性。这项工作代表了从原子层面模拟树脂到碳过程的首次尝试。
