The Role of a Three Dimensionally Ordered Defect Sublattice on the Acidity of a Sulfonated Metal鈥揙rganic Framework

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• 作者：Jared M. Taylor ; Tokutaro Komatsu ; Shun Dekura ; Kazuya Otsubo ; Masaki Takata ; Hiroshi Kitagawa
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：September 9, 2015
• 年：2015
• 卷：137
• 期：35
• 页码：11498-11506
• 全文大小：556K
• ISSN：1520-5126

文摘

Understanding the role that crystal imperfections or defects play on the physical properties of a solid material is important for any application. In this report, the highly unique crystal structure of the metal鈥搊rganic framework (MOF) zirconium 2-sulfoterephthalate is presented. This MOF contains a large number of partially occupied ligand and metal cluster sites which directly affect the physical properties of the material. The partially occupied ligand positions give rise to a continuum of pore sizes within this highly porous MOF, supported by N₂ gas sorption and micropore analysis. Furthermore, this MOF is lined with sulfonic acid groups, implying a high proton concentration in the pore, but defective zirconium clusters are found to be effective proton trapping sites, which was investigated by a combination of AC impedance analysis to measure the proton conductivity and DFT calculations to determine the solvation energies of the protons in the pore. Based on the calculations, methods to control the pK_a of the clusters and improve the conductivity by saturating the zirconium clusters with strong acids were utilized, and a 5-fold increase in proton conductivity was achieved using these methods. High proton conductivity of 5.62 脳 10^鈥? S cm^鈥? at 95% relative humidity and 65 掳C could be achieved, with little change down to 40% relative humidity at room temperature.