Tuning Proton Conductivity in Alkali Metal Phosphonocarboxylates by Cation Size-Induced and Water-Facilitated Proton Transfer Pathways
| العنوان: | Tuning Proton Conductivity in Alkali Metal Phosphonocarboxylates by Cation Size-Induced and Water-Facilitated Proton Transfer Pathways |
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| المؤلفون: | Duane Choquesillo-Lazarte, Pascual Olivera-Pastor, Enrique R. Losilla, Aurelio Cabeza, Miguel A. G. Aranda, Rosario M. P. Colodrero, Belén Nieto-Ortega, Konstantinos D. Demadis, Montse Bazaga-García, Maria Papadaki |
| المصدر: | RIUMA: Repositorio Institucional de la Universidad de Málaga Universidad de Málaga RIUMA. Repositorio Institucional de la Universidad de Málaga instname |
| بيانات النشر: | American Chemical Society, 2014. |
| سنة النشر: | 2014 |
| مصطلحات موضوعية: | Metal phosphonates, Alkali Metal Phosphonocarboxylates, Proton conductivity, Ionic radius, Proton, Chemistry, General Chemical Engineering, Inorganic chemistry, Ab initio, General Chemistry, Crystal structure, Alkali metal, Química inorgánica, X-ray diffraction, R,S-hydroxyphosphonoacetate, Crystallography, X-ray crystallography, Materials Chemistry, Single crystal, Powder diffraction |
| الوصف: | The structural and functional chemistry of a family of alkali-metal ions with racemic R,S-hydroxyphosphonoacetate (M-HPAA; M = Li, Na, K, Cs) are reported. Crystal structures were determined by X-ray data (Li+, powder diffraction following an ab initio methodology; Na+, K+, Cs+, single crystal). A gradual increase in dimensionality directly proportional to the alkali ionic radius was observed. [Li3(OOCCH(OH)PO3)-(H2O)4]·H2O (Li-HPAA) shows a 1D framework built up by Li-ligand “slabs” with Li+ in three different coordination environments (4-, 5-, and 6-coordinated). Na-HPAA, Na2(OOCCH(OH)PO3H)(H2O)4, exhibits a pillared layered “house of cards” structure, while K-HPAA, K2(OOCCH(OH)PO3H)(H2O)2, and Cs-HPAA, Cs(HOOCCH(OH)-PO3H), typically present intricate 3D frameworks. Strong hydrogen-bonded networks are created even if no water is present, as is the case in Cs-HPAA. As a result, all compounds show proton conductivity in the range 3.5 × 10−5 S cm−1 (Cs-HPAA) to 5.6 × 10−3 S cm−1 (Na-HPAA) at 98% RH and T = 24 °C. Differences in proton conduction mechanisms, Grothuss (Na+ and Cs+) or vehicular (Li+ and K+), are attributed to the different roles played by water molecules and/or proton transfer pathways between phosphonate and carboxylate groups of the ligand HPAA. Upon slow crystallization, partial enrichment in the S enantiomer of the ligand is observed for Na-HPAA, while the Cs-HPAA is a chiral compound containing only the S enantiomer. Proyectos nacionales MAT2010-15175 y MAT2013-41836-R |
| الوصول الحر: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::85781f32808f3cf874842f48ae4a3552Test https://hdl.handle.net/10630/21020Test |
| حقوق: | OPEN |
| رقم الانضمام: | edsair.doi.dedup.....85781f32808f3cf874842f48ae4a3552 |
| قاعدة البيانات: | OpenAIRE |
| الوصف غير متاح. |