Formaldehyde Encapsulated in Lithium-Decorated Metal-Organic Frameworks: A Density Functional Theory Study

被引:18
作者
Maihom, Thana [1 ,2 ,3 ]
Choomwattana, Saowapak [1 ,2 ,3 ]
Khongpracha, Pipat [1 ,2 ,3 ,4 ]
Probst, Michael [5 ]
Limtrakul, Jumras [1 ,2 ,3 ,4 ]
机构
[1] Kasetsart Univ, Lab Computat & Appl Chem, Dept Chem, Fac Sci, Bangkok 10900, Thailand
[2] Kasetsart Univ, Inst Res & Dev, Ctr Nanotechnol, Bangkok 10900, Thailand
[3] Kasetsart Univ, NANOTEC Ctr Excellence, Natl Nanotechnol Ctr, Bangkok 10900, Thailand
[4] Kasetsart Univ, Ctr Adv Studies Nanotechnol Applicat Chem Food &, Bangkok 10900, Thailand
[5] Univ Innsbruck, Inst Ion Phys & Appl Phys, A-6020 Innsbruck, Austria
关键词
density functional calculations; encapsulation; formaldehyde; metal-organic frameworks; zeolites; CARBONYL-ENE REACTION; HYDROGEN STORAGE; AB-INITIO; ELECTRONIC-STRUCTURE; ADSORPTION SITES; H-2; STORAGE; ZEOLITE; DESIGN; CAPACITY; METHANE;
D O I
10.1002/cphc.201100642
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The stability of monomeric formaldehyde encapsulated in the lithium-decorated metal-organic framework Li-MOF-5 was investigated by means of density functional calculations with the M06-L functional and the 6-31G(d,p) basis set. To assess the efficiency of Li-MOF-5 for formaldehyde preservation, we consider the reaction kinetics and the thermodynamic equilibrium between formaldehyde and its trimerized product, 1,3,5-trioxane. We propose that trimerization of encapsulated formaldehyde takes place in a single reaction step with an activation energy of 34.5 kcal?mol-1. This is 17.2 kcal?mol-1 higher than the corresponding activation energy in the bare system. In addition, the reaction energy of the system studied herein is endothermic by 6.1 kcal?mol-1 and the Gibbs free energy (?G) of the reaction becomes positive (11.0 kcal?mol-1). Consequently, the predicted reverse rate for the trimerization reaction in the Li-MOF-5 is significantly faster than the forward rate. The calculations show that the oligomerization of formaldehyde in Li-MOF-5 is a reversible reaction, suggesting that such a zeolite might be a good candidate material for preserving formaldehyde in its monomeric form.
引用
收藏
页码:245 / 249
页数:5
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