TY - JOUR
T1 - Scandium/Alkaline Metal-Organic Frameworks
T2 - Adsorptive Properties and Ionic Conductivity
AU - Cepeda, Javier
AU - Pérez-Yáñez, Sonia
AU - Beobide, Garikoitz
AU - Castillo, Oscar
AU - Goikolea, Eider
AU - Aguesse, Frederic
AU - Garrido, Leoncio
AU - Luque, Antonio
AU - Wright, Paul A.
N1 - Funding Information:
This work was funded by Ministerio de Econom?a y Competitividad (MAT2013-46502-C2-1-P). J. C. and S. P. Y. thank the Universidad del Pa?s Vasco/Euskal Herriko Unibertsitatea for their postdoctoral fellowships.
Publisher Copyright:
© 2016 American Chemical Society.
Copyright:
Copyright 2016 Elsevier B.V., All rights reserved.
PY - 2016/5/10
Y1 - 2016/5/10
N2 - Several synthetic approaches have been employed to obtain novel {[ScM(μ4-pmdc)2(H2O)2]·solv}n [EHU1(Sc,M)] (where M = Li, Na; pmdc = pyrimidine-4,6-dicarboxylate; solv = corresponding solvent) compounds. The synthesis method is crucial to determine the type of alkaline that could be hosted in the structure as well as the crystallinity, adsorption performance, and ionic conductivity of the resulting materials. Compared with other synthetic methods, a heat-assisted solvent-free procedure has proven to be the most effective route, giving materials with adsorption capacities close to those expected from GCMC (Grand Canonical Monte Carlo) calculations. Despite the presence of alkaline ions in the framework, the pristine materials exhibit rather low conductivity values of ca. 10-7 S cm-1. The concentration of charge carriers has been increased by means of a doping approach that incorporates divalent transition metal ions to the structure and forces an increase of the alkaline ions, thus raising the ionic conductivity by 1 order of magnitude. Additionally, soaking the samples in solutions containing alkaline salts led to materials possessing an even higher number of carriers achieving conductivity values among the best results reported for MOFs at room temperature, i.e., 4.2 × 10-4 and 9.2 × 10-5 S cm-1 for EHU1(Sc,Li) and EHU1(Sc,Na) obtained by the solvent-free procedure, respectively.
AB - Several synthetic approaches have been employed to obtain novel {[ScM(μ4-pmdc)2(H2O)2]·solv}n [EHU1(Sc,M)] (where M = Li, Na; pmdc = pyrimidine-4,6-dicarboxylate; solv = corresponding solvent) compounds. The synthesis method is crucial to determine the type of alkaline that could be hosted in the structure as well as the crystallinity, adsorption performance, and ionic conductivity of the resulting materials. Compared with other synthetic methods, a heat-assisted solvent-free procedure has proven to be the most effective route, giving materials with adsorption capacities close to those expected from GCMC (Grand Canonical Monte Carlo) calculations. Despite the presence of alkaline ions in the framework, the pristine materials exhibit rather low conductivity values of ca. 10-7 S cm-1. The concentration of charge carriers has been increased by means of a doping approach that incorporates divalent transition metal ions to the structure and forces an increase of the alkaline ions, thus raising the ionic conductivity by 1 order of magnitude. Additionally, soaking the samples in solutions containing alkaline salts led to materials possessing an even higher number of carriers achieving conductivity values among the best results reported for MOFs at room temperature, i.e., 4.2 × 10-4 and 9.2 × 10-5 S cm-1 for EHU1(Sc,Li) and EHU1(Sc,Na) obtained by the solvent-free procedure, respectively.
UR - http://www.scopus.com/inward/record.url?scp=84969264333&partnerID=8YFLogxK
U2 - 10.1021/acs.chemmater.5b03458
DO - 10.1021/acs.chemmater.5b03458
M3 - Article
AN - SCOPUS:84969264333
SN - 0897-4756
VL - 28
SP - 2519
EP - 2528
JO - Chemistry of Materials
JF - Chemistry of Materials
IS - 8
ER -