Thornton A W, Babarao R, Jain A, Trousselet F, Coudert F-X
Manufacturing, Commonwealth Scientific and Industrial Research Organisation, Private Bag 10, Clayton Sth, VIC 3169, Australia.
PSL Research University, Chimie ParisTech - CNRS, Institut de Recherche de Chimie Paris, 75005 Paris, France.
Dalton Trans. 2016 Mar 14;45(10):4352-9. doi: 10.1039/c5dt04330a.
Defect engineering has arisen as a promising approach to tune and optimise the adsorptive performance of metal-organic frameworks. However, the balance between enhanced adsorption and structural stability remains an open question. Here both CO2 adsorption capacity and mechanical stability are calculated for the zirconium-based UiO-66, which is subject to systematic variations of defect scenarios. Modulator-dependence, defect concentration and heterogeneity are explored in isolation. Mechanical stability is shown to be compromised at high pressures where uptake is enhanced with an increase in defect concentration. Nonetheless this reduction in stability is minimised for reo type defects and defects with trifluoroacetate substitution. Finally, heterogeneity and auxeticity may also play a role in overcoming the compromise between adsorption and stability.
缺陷工程作为一种调节和优化金属有机框架吸附性能的有前景的方法应运而生。然而，增强吸附与结构稳定性之间的平衡仍然是一个悬而未决的问题。在此，针对基于锆的UiO-66计算了二氧化碳吸附容量和机械稳定性，该材料存在缺陷情况的系统变化。分别探讨了调节剂依赖性、缺陷浓度和不均匀性。结果表明，在高压下，随着缺陷浓度的增加吸附增强，但机械稳定性会受到损害。尽管如此，reo型缺陷和三氟乙酸取代的缺陷使稳定性的降低最小化。最后，不均匀性和负泊松比效应也可能在克服吸附与稳定性之间的矛盾中发挥作用。
