TY - JOUR
T1 - Cu(II)-Schiff base covalently anchored to MIL-125(Ti)-NH2 as heterogeneous catalyst for oxidation reactions
AU - Daliran, Saba
AU - Santiago-Portillo, Andrea
AU - Navalón, Sergio
AU - Oveisi, Ali Reza
AU - Álvaro, Mercedes
AU - Ghorbani-Vaghei, Ramin
AU - Azarifar, Davood
AU - García, Hermenegildo
N1 - Funding Information:
Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa) CTQ2014-53292-R is gratefully acknowledged. Generalidad Valenciana is also thanked for funding ( Prometeo 2017/063 ). S.D., A.R.O., D.A., and R.G-V thank H.G., S.N. and M.A., S.D., D.A., and R.G-V gratefully acknowledge financial support from Bu-Ali Sina University . S.N. thanks financial support by the Fundación Ramón Areces (XVIII Concurso Nacional para la Adjudicación de Ayudas a la Investigación en Ciencias de la Vida y de la Materia, 2016).
Publisher Copyright:
© 2018 Elsevier Inc.
PY - 2018/12/15
Y1 - 2018/12/15
N2 - MIL-125(Ti)-NH2 has been modified by reaction of salicylaldehyde with the terephthalate amino groups to form a salicylideneimine that act as ligand of Cu2+. The success of the postsynthetic modification was assessed by FTIR spectroscopy of the MIL-125(Ti)-NH2-Sal-Cu and by analysis by 1H NMR spectroscopy of the organic linkers upon dissolution of MIL-125(Ti)-NH2-Sal-Cu. In comparison with parent MIL-125(Ti)-NH2 and MIL-125(Ti)-NH2-Sal, that exhibit a poor activity, the presence of the Cu-Schiff base complex in MIL-125(Ti)-NH2-Sal-Cu catalyst for the oxidation of 1-phenylethanol by tert-butylhydroperoxyde (TBHP, 3 eq.) increases notably the catalytic activity. Hot filtration test and reusability experiments confirm that the process is heterogeneous and that MIL-125(Ti)-NH2-Sal-Cu is stable under the reaction conditions. Quenching studies and EPR spectra using N-tbutylphenylnitrone indicate the generation of tBuOO[rad] and tBuO[rad] under the reaction conditions. The scope of MIL-125(Ti)-NH2-Sal-Cu as oxidation catalyst by tBuOOH was studied for benzyl alcohol as well as alicyclic and aliphatic alcohols and ethylbenzene.
AB - MIL-125(Ti)-NH2 has been modified by reaction of salicylaldehyde with the terephthalate amino groups to form a salicylideneimine that act as ligand of Cu2+. The success of the postsynthetic modification was assessed by FTIR spectroscopy of the MIL-125(Ti)-NH2-Sal-Cu and by analysis by 1H NMR spectroscopy of the organic linkers upon dissolution of MIL-125(Ti)-NH2-Sal-Cu. In comparison with parent MIL-125(Ti)-NH2 and MIL-125(Ti)-NH2-Sal, that exhibit a poor activity, the presence of the Cu-Schiff base complex in MIL-125(Ti)-NH2-Sal-Cu catalyst for the oxidation of 1-phenylethanol by tert-butylhydroperoxyde (TBHP, 3 eq.) increases notably the catalytic activity. Hot filtration test and reusability experiments confirm that the process is heterogeneous and that MIL-125(Ti)-NH2-Sal-Cu is stable under the reaction conditions. Quenching studies and EPR spectra using N-tbutylphenylnitrone indicate the generation of tBuOO[rad] and tBuO[rad] under the reaction conditions. The scope of MIL-125(Ti)-NH2-Sal-Cu as oxidation catalyst by tBuOOH was studied for benzyl alcohol as well as alicyclic and aliphatic alcohols and ethylbenzene.
KW - Heterogeneous catalysis
KW - Metal-organic frameworks: Cu(II) Schiff-base complex
KW - Tert-butylhydroperoxyde
UR - http://www.scopus.com/inward/record.url?scp=85051502696&partnerID=8YFLogxK
U2 - 10.1016/j.jcis.2018.07.140
DO - 10.1016/j.jcis.2018.07.140
M3 - Article
C2 - 30121522
AN - SCOPUS:85051502696
SN - 0021-9797
VL - 532
SP - 700
EP - 710
JO - Journal of Colloid and Interface Science
JF - Journal of Colloid and Interface Science
ER -