title: Capture of nerve agents and mustard gas analogues by hydrophobic robust MOF-5 type metal-organic frameworks.
abstract: 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.
authors.affiliation: Departamento de Química Inorgánica, Universidad de Granada, Av. Fuentenueva S/N, 18071 Granada, Spain.
authors.forename: Carmen
authors.initials: C
authors.lastname: Montoro
authors.forename: Fátima
authors.initials: F
authors.lastname: Linares
authors.forename: Elsa Quartapelle
authors.initials: EQ
authors.lastname: Procopio
authors.forename: Irena
authors.initials: I
authors.lastname: Senkovska
authors.forename: Stefan
authors.initials: S
authors.lastname: Kaskel
authors.forename: Simona
authors.initials: S
authors.lastname: Galli
authors.forename: Norberto
authors.initials: N
authors.lastname: Masciocchi
authors.forename: Elisa
authors.initials: E
authors.lastname: Barea
authors.forename: Jorge A R
authors.initials: JA
authors.lastname: Navarro
mesh_terms: D002619:Chemical Warfare Agents / Q000737:chemistry*; D057927:Hydrophobic and Hydrophilic Interactions; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000737:chemistry*; D055549:Volatile Organic Compounds / Q000737:chemistry*
chemical_list: D002619:Chemical Warfare Agents; D009942:Organometallic Compounds; D055549:Volatile Organic Compounds