TY - JOUR
T1 - Influence of functionalization of terephthalate linker on the catalytic activity of UiO-66 for epoxide ring opening
AU - Blandez, Juan F.
AU - Santiago-Portillo, Andrea
AU - Navalón, Sergio
AU - Giménez-Marqués, Mónica
AU - Álvaro, Mercedes
AU - Horcajada, Patricia
AU - García, Hermenegildo
N1 - Funding Information:
Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2015-69153 and CTQ2014-53292-R and Generalitat Valenciana (Prometeo 2013/14) and is grateful acknowledged. We also thank EU under the Being Energy contract for partial funding . J.F.B. thanks the Universitat Politécnica de Valencia for a postgraduate scholarship . S.N. thanks the Spanish Ministerio de Educación, Cultura y Deporte for José Castillejo mobility programme (CAS14/00067).
Publisher Copyright:
© 2016 Elsevier B.V.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2016/12/15
Y1 - 2016/12/15
N2 - A series of five isostructural zirconium terephthalate UiO-66 metal organic frameworks bearing different functional groups on the terephthalate linker (UiO-66-X; X = H, NH2, NO2, Br, Cl,) have been successfully prepared and characterized. UiO-66-X materials were evaluated as heterogeneous catalysts for the epoxide ring opening of styrene oxide by methanol, observing an increase in the initial reaction rate from UiO-66-H to UiO-66-Br, over one order of magnitude. The reactivity order, however, does not follow a linear relationship between the Hammett constant value of the substituent and the initial reaction rate. UiO-66-Br exhibits a wide scope, its activity depending on the structure of epoxide and nucleophile. The absence of Zr leaching to the solution together with the preservation of the UiO-66-X crystallinity confirms the stability of the framework under the reaction conditions. Nevertheless, UiO-66 undergoes a progressive deactivation upon reuse that was attributed to a strong adsorption of the reaction product.
AB - A series of five isostructural zirconium terephthalate UiO-66 metal organic frameworks bearing different functional groups on the terephthalate linker (UiO-66-X; X = H, NH2, NO2, Br, Cl,) have been successfully prepared and characterized. UiO-66-X materials were evaluated as heterogeneous catalysts for the epoxide ring opening of styrene oxide by methanol, observing an increase in the initial reaction rate from UiO-66-H to UiO-66-Br, over one order of magnitude. The reactivity order, however, does not follow a linear relationship between the Hammett constant value of the substituent and the initial reaction rate. UiO-66-Br exhibits a wide scope, its activity depending on the structure of epoxide and nucleophile. The absence of Zr leaching to the solution together with the preservation of the UiO-66-X crystallinity confirms the stability of the framework under the reaction conditions. Nevertheless, UiO-66 undergoes a progressive deactivation upon reuse that was attributed to a strong adsorption of the reaction product.
KW - Epoxide ring opening
KW - Heterogeneous catalysis
KW - Metal organic frameworks
KW - UiO-66
UR - http://www.scopus.com/inward/record.url?scp=85000400682&partnerID=8YFLogxK
U2 - 10.1016/j.molcata.2016.10.022
DO - 10.1016/j.molcata.2016.10.022
M3 - Article
AN - SCOPUS:85000400682
SN - 1381-1169
VL - 425
SP - 332
EP - 339
JO - Journal of Molecular Catalysis A: Chemical
JF - Journal of Molecular Catalysis A: Chemical
ER -