Capture of Nerve Agents and Mustard Gas Analogues by Hydrophobic Robust MOF-5 Type Metal鈥揙rganic Frameworks

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• 作者：Carmen Montoro ; F谩tima Linares ; Elsa Quartapelle Procopio ; Irena Senkovska ; Stefan Kaskel ; Simona Galli ; Norberto Masciocchi ; Elisa Barea ; Jorge A. R. Navarro
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：August 10, 2011
• 年：2011
• 卷：133
• 期：31
• 页码：11888-11891
• 全文大小：771K
• 年卷期：v.133,no.31(August 10, 2011)
• ISSN：1520-5126

文摘

In this communication, a series of observations and data analyses coherently confirms the suitability of the novel metal鈥搊rganic framework (MOF) [Zn₄(渭₄-O)(渭₄-4-carboxy-3,5-dimethyl-4-carboxy-pyrazolato)₃] (1) in the capture of harmful volatile organic compounds (VOCs). It is worthy of attention that 1, whose crystal structure resembles that of MOF-5, exhibits remarkable thermal, mechanical, and chemical stability, as required if practical applications are sought. In addition, it selectively captures harmful VOCs (including models of Sarin and mustard gas, which are chemical warfare agents), even in competition with ambient moisture (i.e., under conditions mimicking operative ones). The results can be rationalized on the basis of Henry constant and adsorption heat values for the different essayed adsorbates as well as H₂O/VOC partition coefficients as obtained from variable-temperature reverse gas chromatography experiments. To further strengthen the importance of 1, its performance in the capture of harmful VOCs has been compared with those of well-known materials, namely, a MOF with coordinatively unsaturated metal sites, [Cu₃(btc)₂] and the molecular sieve active carbon Carboxen. The results of this comparison show that coordinatively unsaturated metal sites (preferential guest-binding sites) are ineffective for the capture of VOCs in the presence of ambient moisture. Consequently, we propose that the driving force of the VOC鈥揗OF recognition process is mainly dictated by pore size and surface hydrophobicity.