TY - JOUR
T1 - MIL-101(Cr)-NO2 as efficient catalyst for the aerobic oxidation of thiophenols and the oxidative desulfurization of dibenzothiophenes
AU - Vallés-García, Cristina
AU - Santiago-Portillo, Andrea
AU - Álvaro, Mercedes
AU - Navalón, Sergio
AU - García, Hermenegildo
N1 - Funding Information:
Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21 ) and Generalitat Valenciana ( Prometeo 2017/083 ) is gratefully acknowledged. 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), Ministerio de Ciencia, Innovación y Universidades CTQ-2018 RTI2018-099482-A-I00 project and Generalitat Valenciana grupos de investigación consolidables 2019 (AICO2019/214 project).
Funding Information:
Financial support by the Spanish Ministry of Science and Innovation (Severo Ochoa and RTI2018-098237-CO21) and Generalitat Valenciana (Prometeo 2017/083) is gratefully acknowledged. S.N. thanks financial support by the Fundaci?n Ram?n Areces (XVIII Concurso Nacional para la Adjudicaci?n de Ayudas a la Investigaci?n en Ciencias de la Vida y de la Materia, 2016), Ministerio de Ciencia, Innovaci?n y Universidades CTQ-2018 RTI2018-099482-A-I00 project and Generalitat Valenciana grupos de investigaci?n consolidables 2019 (AICO2019/214 project).
Publisher Copyright:
© 2019 Elsevier B.V.
PY - 2020/1/25
Y1 - 2020/1/25
N2 - A series of MIL-101(Cr)-X functionalized with electron withdrawing (NO2, SO3H or Cl) or electron donor (NH2 or CH3) groups has been tested for the solvent-free oxidative coupling of thiophenol to disulfides. No byproducts were observed. A relationship between the catalytic activity of these MOFs with the substituent meta Hammet constant on the terephthalate ligand and with their redox potential was found, MIL-101(Cr)-NO2 being the most active catalyst. NO2-substituted MIL-101 is also more efficient than the parent MIL-101(Cr) to promote the aerobic desulfurization of dibenzothiophenes in n-dodecane or commercial Diesel as solvent. No byproduct formation was observed. Mechanistic studies reveal that MIL-101(Cr)-NO2 is acting as heterogeneous catalyst in thiophenol oxidation and as radical initiator for the aerobic desulfurization. For both reactions, the catalyst can be reused without deactivation, maintaining its crystallinity and with negligible metal leaching.
AB - A series of MIL-101(Cr)-X functionalized with electron withdrawing (NO2, SO3H or Cl) or electron donor (NH2 or CH3) groups has been tested for the solvent-free oxidative coupling of thiophenol to disulfides. No byproducts were observed. A relationship between the catalytic activity of these MOFs with the substituent meta Hammet constant on the terephthalate ligand and with their redox potential was found, MIL-101(Cr)-NO2 being the most active catalyst. NO2-substituted MIL-101 is also more efficient than the parent MIL-101(Cr) to promote the aerobic desulfurization of dibenzothiophenes in n-dodecane or commercial Diesel as solvent. No byproduct formation was observed. Mechanistic studies reveal that MIL-101(Cr)-NO2 is acting as heterogeneous catalyst in thiophenol oxidation and as radical initiator for the aerobic desulfurization. For both reactions, the catalyst can be reused without deactivation, maintaining its crystallinity and with negligible metal leaching.
KW - Aerobic oxidations
KW - Desulfurization
KW - Fuel
KW - Heterogeneous catalysis
KW - MIL-101(Cr)-NOas catalyst
KW - Thiophenol coupling
UR - http://www.scopus.com/inward/record.url?scp=85075001265&partnerID=8YFLogxK
U2 - 10.1016/j.apcata.2019.117340
DO - 10.1016/j.apcata.2019.117340
M3 - Article
AN - SCOPUS:85075001265
SN - 0926-860X
VL - 590
JO - Applied catalysis. A: General
JF - Applied catalysis. A: General
M1 - 117340
ER -