title: Enhancing the water stability of Al-MIL-101-NH2 via postsynthetic modification.
abstract: The resistance of metal-organic frameworks towards water is a very critical issue concerning their practical use. Recently, it was shown for microporous MOFs that the water stability could be increased by introducing hydrophobic pendant groups. Here, we demonstrate a remarkable stabilisation of the mesoporous MOF Al-MIL-101-NH2 by postsynthetic modification with phenyl isocyanate. In this process 86 % of the amino groups were converted into phenylurea units. As a consequence, the long-term stability of Al-MIL-101-URPh in liquid water could be extended beyond a week. In water saturated atmospheres Al-MIL-101-URPh decomposed at least 12-times slower than the unfunctionalised analogue. To study the underlying processes both materials were characterised by Ar, N2 and H2 O sorption measurements, powder X-ray diffraction, thermogravimetric and chemical analysis as well as solid-state NMR and IR spectroscopy. Postsynthetic modification decreased the BET equivalent surface area from 3363 to 1555 m(2)  g(-1) for Al-MIL-101-URPh and reduced the mean diameters of the mesopores by 0.6 nm without degrading the structure significantly and reducing thermal stability. In spite of similar water uptake capacities, the relative humidity-dependent uptake of Al-MIL-101-URPh is slowed and occurs at higher relative humidity values. In combination with (1) H-(27) Al D-HMQC NMR spectroscopy experiments this favours a shielding mechanism of the Al clusters by the pendant phenyl groups and rules out pore blocking.
authors.affiliation: Department for Inorganic Chemistry III, University of Bayreuth, Universitätsstraße 30, 95440 Bayreuth (Germany).
authors.forename: Thomas
authors.initials: T
authors.lastname: Wittmann
authors.forename: Renée
authors.initials: R
authors.lastname: Siegel
authors.forename: Nele
authors.initials: N
authors.lastname: Reimer
authors.forename: Wolfgang
authors.initials: W
authors.lastname: Milius
authors.forename: Norbert
authors.initials: N
authors.lastname: Stock
authors.forename: Jürgen
authors.initials: J
authors.lastname: Senker
mesh_terms: D000535:Aluminum / Q000737:chemistry*; D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D000073396:Metal-Organic Frameworks; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D016062:Porosity; D013052:Spectrometry, X-Ray Emission; D013818:Thermogravimetry; D014867:Water / Q000737:chemistry*; D014961:X-Ray Diffraction
chemical_list: D056831:Coordination Complexes; C000589635:MIL-101; D000073396:Metal-Organic Frameworks; D009942:Organometallic Compounds; D014867:Water; D000535:Aluminum
keywords: hybrid materials; metal-organic frameworks; porosity; postsynthetic modification; water stability