ReaxFF molecular dynamics simulation of thermal stability of a Cu3(BTC)2 metal―organic framework

• Published in: Physical chemistry chemical physics : PCCP Vol. 14; no. 32; pp. 11327 - 11332
• Main Authors: LIANGLIANG HUANG, JOSHI, Kaushik L, DUIN, Adri C. T. Van, BANDOSZ, Teresa J, GUBBINS, Keith E
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 28.08.2012
• Subjects: Catalysis; Chemistry; Copper - chemistry; Exact sciences and technology; General and physical chemistry; Molecular Dynamics Simulation; Organometallic Compounds - chemistry; Surface physical chemistry; Temperature; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry; Tricarboxylic Acids - chemistry; Copper II; Correlation; Catalytic reaction; Force; Transition element compounds; Molecular dynamics method; Decomposition; Carbon; Thermal stability; Adsorption; Benzene; Separation process; Dimer; Copper oxide; Release
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/C2CP41511A

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.