Adsorbate Effect on AlO4(OH)2 Centers in the Metal−Organic Framework MIL-53 Investigated by Solid-State NMR Spectroscopy

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• 作者：Christian Lieder ; Sabine Opelt ; Michael Dyballa ; Harald Henning ; Elias Klemm ; Michael Hunger
• 刊名：Journal of Physical Chemistry C
• 出版年：2010
• 出版时间：October 7, 2010
• 年：2010
• 卷：114
• 期：39
• 页码：16596-16602
• 全文大小：210K
• 年卷期：v.114,no.39(October 7, 2010)
• ISSN：1932-7455

文摘

¹H and ²⁷Al MAS NMR spectroscopies have been applied for studying the effect of water molecules, nitrogen bases, and o-xylene on the hydroxyl protons of bridging AlOH groups and framework aluminum atoms in the metal−organic framework (MOF) MIL-53. For water molecules adsorbed on the low-temperature form MIL-53lt, two ¹H MAS NMR signals were found indicating the formation of different O−H···O hydrogen bonds to neighboring oxygen atoms, such as to carboxylic oxygens. Upon adsorption of the nitrogen bases acetonitrile, ammonia, and pyridine, a linear increase of the quadrupole coupling constant, C_Q, of the framework aluminum atoms in dehydrated MIL-53 from C_Q = 8.5 MHz (unloaded material) to maximum 10.8 MHz (pyridine-loaded material) as a function of the proton affinity of the adsorbates was observed. Adsorption of o-xylene led to three stepwise changes of the quadrupole coupling constants, C_Q, of framework aluminum atoms in dehydrated MIL-53. While the first two stepwise changes of the C_Q values (C_Q = 8.0 and 8.7 MHz) occur for o-xylene loadings of lower than 4 molecules per unit cell and for all AlO₄(OH)₂ centers, the third change of the C_Q value to 9.4 MHz was observed for o-xylene loadings higher than 4 o-xylene molecules per unit cell and for maximum 50% of the framework aluminum atoms. This third adsorbate-induced change of the C_Q value of framework aluminum atoms in MIL-53 is accompanied by a significant decrease of the adsorbate mobility.