Dehydration Process of Hofmann-Type Layered Solids.docVIP

Materials 2013, 6, 1452-1466; doi:10.3390/ma6041452 OPEN ACCESS materials ISSN 1996-1944 /journal/materials Article Dehydration Process of Hofmann-Type Layered Solids 1 2 3, Omar Reyes-Martinez , Enelio Torres-García , Geonel Rodríguez-Gattorno * and Edilso Reguera 1 1 Centro de Investigación en Ciencia Aplicada y Tecnología Avanzada Unidad Legaria, Instituto Politécnico Nacional, Legaria 694, Colonia, Irrigación, México D.F. 11500, Mexico; E-Mails: oreyesm0621@ (O.R.-M); edilso.reguera@ (E.R.) 2 Mexican Petroleum Institute, Eje Central 152, México D.F. 07730, Mexico; E-Mail: etorresg@imp.mx 3 Center for Research and Advanced Studies of the National Polytechnic Institute, Km 6 Antigua Carretera Progreso, Cordemex, Mérida 97310, Yucatán, Mexico * Author to whom correspondence should be addressed; E-Mail: geonelr@mda.cinvestav.mx; Tel.: +52-999-942-9420; Fax: +52-999-981-2923. Received: 14 December 2012; in revised form: 8 March 2013 / Accepted: 22 March 2013 / Published: 9 April 2013 Abstract: In the present work the dehydration process of layered solids with formula unit M(H O) [Ni(CN) ]·nH O, M = Ni, Co, Mn; n = 1, 2, 4 is studied using modulated 2 2 4 2 thermogravimetry. The results show that water molecules need to overcome an energetic barrier (activation energy between 63 and 500 kJ/mol) in order to diffuse through the interlayer region. The related kinetic parameters show a dependence on the water partial pressure. On the other hand, X-ray diffraction results provide evidence that the dehydration process is accompanied by framework collapse, limiting the structural reversibility, except for heating below 80 °C where the ordered structure remains. Removal of water molecules from the interlayer region disrupts the long-range structural order of the solid. Keywords: kinetics parameters; hi-res/modulated-TG; porous lattices; dehydration of lamellar solids  Materials 2013, 6 1453 1. Introductio