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6545788 
Journal Article 
Capture of nerve agents and mustard gas analogues by hydrophobic robust MOF-5 type metal-organic frameworks 
Montoro, C; Linares, F; Procopio, EQ; Senkovska, I; Kaskel, S; Galli, S; Masciocchi, N; Barea, E; Navarro, JA 
2011 
Yes 
Journal of the American Chemical Society
ISSN: 0002-7863
EISSN: 1520-5126 
133 
31 
11888-11891 
English 
21761835 
WOS:000293768400020 
In this communication, a series of observations and data analyses coherently confirms the suitability of the novel metal-organic framework (MOF) [Zn(4)(μ(4)-O)(μ(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 H(2)O/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, [Cu(3)(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-MOF recognition process is mainly dictated by pore size and surface hydrophobicity.