Department of Chemical and Biomolecular Engineering, North Carolina State University, Raleigh, NC 27695-7905, USA.
Phys Chem Chem Phys. 2012 Aug 28;14(32):11327-32. doi: 10.1039/c2cp41511a. Epub 2012 Jul 13.
The thermal stability of a dehydrated Cu(3)(BTC)(2) (copper(II) benzene 1,3,5-tricarboxylate) metal-organic framework was studied by molecular dynamics simulation with a ReaxFF reactive force field. The results show that Cu(3)(BTC)(2) is thermally stable up to 565 K. When the temperature increases between 600 K and 700 K, the framework starts to partially collapse. The RDF analysis shows that the long range correlations between Cu dimers disappear, indicating the loss of the main channels of Cu(3)(BTC)(2). When the temperature is above 800 K, we find the decomposition of the Cu(3)(BTC)(2) framework. CO is the major product, and we also observe the release of CO(2), O(2), 1,3,5-benzenetricarboxylate (C(6)H(3)(CO(2))(3), BTC) and glassy carbon. The Cu dimer is stable up to 1100 K, but we find the formation of new copper oxide clusters at 1100 K. These results are consistent with experimental findings, and provide valuable information for future theoretical investigations of Cu(3)(BTC)(2) and its application in adsorption, separation and catalytic processes.
采用 ReaxFF 反应力场的分子动力学模拟研究了脱水 Cu(3)(BTC)(2)(铜(II)苯三甲酸酯)金属有机骨架的热稳定性。结果表明，Cu(3)(BTC)(2)在 565 K 下热稳定。当温度在 600 K 到 700 K 之间升高时，骨架开始部分坍塌。RDF 分析表明，Cu 二聚体之间的长程相关性消失，表明 Cu(3)(BTC)(2)的主要通道丧失。当温度高于 800 K 时，我们发现 Cu(3)(BTC)(2)骨架的分解。主要产物是 CO，我们还观察到 CO(2)、O(2)、1,3,5-苯三甲酸(C(6)H(3)(CO(2))(3)，BTC)和玻璃态碳的释放。Cu 二聚体在 1100 K 下稳定，但在 1100 K 下我们发现形成了新的氧化铜团簇。这些结果与实验结果一致，为 Cu(3)(BTC)(2)及其在吸附、分离和催化过程中的应用的未来理论研究提供了有价值的信息。
