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Ammonia effects on proton conductivity properties of coordination polymers

Pérez-Colodrero, Rosario Mercedes,Salcedo, Inés R.,Bazaga-García, Montse,Olivera-Pastor, Pascual,Moreno-Real, Laureano,Losilla, Enrique R.,Cabeza-Díaz, Aurelio

Abstract

Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed.

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Book of Abstracts CPSSC 16 Challenges and Prospects for Solid State Chemistry CPSSC16: Challenges and Prospects for Solid State Chemistry, September 9-10 2016, Seville, Spain SSC - 12  Ammonia Effects on Proton Conductivity Properties of Coordination Polymers. R.M.P. Colodrero1,*, I.R. Salcedo1, M. Bazaga-García1, P. Olivera-Pastor1, L. Moreno-Real1, E.R. Losilla1, A. Cabeza1 1 Dpto Química Inorgánica, Cristalografía y Mineralogía, Facultad de Ciencias, Campus de Teatinos s/n, Málaga, 29071, Spain. *Corresponding author, email: [email protected] Research field:Solid state chemistry and applications. Abstract: Crystalline metal phosphonates are referred to as a type of structurally versatile coordination polymers [1]. Many of them contain guest molecules (H2O, heterocyclics, etc.), acidic sites and, furthermore, their structure can be also amenable for post‐synthesis modifications in order to enhance desired properties [2]. In the present work, we examine the relationships between crystal structure and proton conductivity for several metal phosphonates derive from multifunctional ligands, such as 5- (dihydroxyphosphoryl)isophthalic acid (PiPhtA) [3] and 2-hydroxyphosphonoacetic acid (H3HPAA). Crystalline divalent metal derivatives show a great structural diversity, from 1D to 3D open-frameworks, possessing hydrogen-bonded water molecules and acid groups. These solids present a proton conductivity range between 7.2·10-6 and 1.3·10−3 S·cm-1. Upon exposure to ammonia vapor, from an aqueous solution, solid state transformations are observed accompanied of enhance proton conductivities. The stability of these solids under different environment conditions (temperature and relative humidities) as well as the influence of the ammonia adsorption on the proton conduction properties of the resulting solids will be discussed. References: [1] Shimizu G. K. H., Taylor J. M. and Dawson, K.W. 2012 Metal Organophosphonate Proton Conductors. In Metal Phosphonate Chemistry: From Synthesis to Applications; Eds. Clearfield, A., Demadis, K.D. (RSC: Cambridge) Ch. 15; p 493–524. [2] Ikawa, H., 1992 Proton Conductors; Ed. P. Colomban (Cambridge University Press: Cambridge), p. 511–515. [3] Bazaga-García M., Colodrero R.M.P., Papadaki M., Garczarek P., Zoń J., Olivera-Pastor P., Losilla E.R., León-Reina L., Aranda M.A.G., Choquesillo-Lazarte D., Demadis K.D. and Cabeza A., 2014, J. Amer. Chem. Soc., 136, 5731-5739.