Guest Molecule-Responsive Functional Calcium Phosphonate Frameworks for Tuned Proton Conductivity

化学 单斜晶系 结晶学 水溶液 结构精修 分子 结晶度 膦酸盐 粉末衍射 X射线晶体学 结晶 晶体结构 无机化学 衍射 物理化学 有机化学 物理 光学
作者
Montse Bazaga-García,Rosario M. P. Colodrero,Maria Papadaki,Piotr Garczarek,Jerzy Zoń,Pascual Olivera‐Pastor,Enrique R. Losilla,Laura León‐Reina,Miguel Á. G. Aranda,Duane Choquesillo‐Lazarte,Konstantinos D. Demadis,Aurelio Cabeza
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:136 (15): 5731-5739 被引量:208
标识
DOI:10.1021/ja500356z
摘要

We report the synthesis, structural characterization, and functionality (framework interconversions together with proton conductivity) of an open-framework hybrid that combines Ca2+ ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]·5H2O (Ca-PiPhtA-I) is obtained by slow crystallization at ambient conditions from acidic (pH ≈ 3) aqueous solutions. It possesses a high water content (both Ca coordinated and in the lattice), and importantly, it exhibits water-filled 1D channels. At 75 °C, Ca-PiPhtA-I is partially dehydrated and exhibits a crystalline diffraction pattern that can be indexed in a monoclinic cell with parameters close to the pristine phase. Rietveld refinement was carried out for the sample heated at 75 °C, Ca-PiPhtA-II, using synchrotron powder X-ray diffraction data, which revealed the molecular formula Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]. All connectivity modes of the "parent" Ca-PiPhtA-I framework are retained in Ca-PiPhtA-II. Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous NH3) a new derivative is obtained (Ca-PiPhtA-NH3) containing 7 NH3 and 16 H2O molecules according to elemental and thermal analyses. Ca-PiPhtA-NH3 exhibits a complex X-ray diffraction pattern with peaks at 15.3 and 13.0 Å that suggest partial breaking and transformation of the parent pillared structure. Although detailed structural identification of Ca-PiPhtA-NH3 was not possible, due in part to nonequilibrium adsorption conditions and the lack of crystallinity, FT-IR spectra and DTA-TG analysis indicate profound structural changes compared to the pristine Ca-PiPhtA-I. At 98% RH and T = 24 °C, proton conductivity, σ, for Ca-PiPhtA-I is 5.7 × 10–4 S·cm–1. It increases to 1.3 × 10–3 S·cm–1 upon activation by preheating the sample at 40 °C for 2 h followed by water equilibration at room temperature under controlled conditions. Ca-PiPhtA-NH3 exhibits the highest proton conductivity, 6.6 × 10–3 S·cm–1, measured at 98% RH and T = 24 °C. Activation energies (Ea) for proton transfer in the above-mentioned frameworks range between 0.23 and 0.4 eV, typical of a Grothuss mechanism of proton conduction. These results underline the importance of internal H-bonding networks that, in turn, determine conductivity properties of hybrid materials. It is highlighted that new proton transfer pathways may be created by means of cavity "derivatization" with selected guest molecules resulting in improved proton conductivity.

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