abstract
The use of 5,10,15,20-tetrakis(p-phenylphosphonic acid)porphyrin (H(10)TPPA) as a linker in the preparation of porphyrin-based metal-organic frameworks (Por-MOFs) through coordination to lanthanides cations is reported. The resulting unprecedented materials, formulated as [M(H(9)TPPA)(H2O)(x)]Cl-2 center dot yH(2)O [x + y = 7; M3+ = La3+ (1), Yb3+ (2), and Y3+ (3)], prepared using hydrothermal synthesis, were extensively characterized in the solid-state, for both their structure and thermal robustness, using a myriad of solid-state advanced techniques. Materials were evaluated as heterogeneous catalysts in the oxidation of thioanisole by H2O2 and as chemosensors for detection of nitroaromatic compounds (NACs). Nano-Por-MOFs 1-3 proved to be effective as heterogeneous catalysts in the sulfoxidation of thioanisole, with Por-MOF 1 exhibiting the best catalytic performance with a conversion of thioanisole of 89% in the first cycle and with a high selectivity for the sulfoxide derivative (90%). The catalyst maintained its activity roughly constant in three consecutive runs. Por-MOFs 1-3 can be employed as chemosensors because of a measured fluorescence quenching up to 70% for nitrobenzene, 1,4-dinitrobenzene, 4-nitrophenol, and phenol, with 2,4,6-trinitrophenol exhibiting a peculiar fluorescence profile.
keywords
ORGANOSULFUR COMPOUNDS; OXIDATION; DESULFURIZATION; CHEMISTRY
subject category
Chemistry
authors
Pereira, CF; Figueira, F; Mendes, RF; Rocha, J; Hupp, JT; Farha, OK; Simoes, MMQ; Tome, JPC; Paz, FAA
our authors
Carla Patrícia Fernandes Pereira
PhD Student
Filipe Alexandre Almeida Paz
Principal Researcher
Flávio Alberto da Silva Figueira
Junior Researcher
João Rocha
Full Professor
Ricardo Faria Mendes
Junior Researcheracknowledgements
Funding Agencies and Projects: We wish to thank Fundacao para a Ciencia e a Tecnologia (FCT, Portugal), the European Union, QREN, FEDER through Programa Operational Factores de Competitividade (COMPETE), CICECO - Aveiro Institute of Materials (POCI-01-0145-FEDER-007679; FCT ref. UID/CTM/50011/2013), QOPNA (FCT UID/QUI/00062/2013), and CQE (FCT UID/QUI/0100/2013) research units, financed by national funds through the FCT/MEC and when appropriate cofinanced by FEDER under the PT2020 Partnership Agreement. We also thank FCT for funding the R&D project FCOMP-01-0124-FEDER-041282 (ref. FCT EXPL/CTM-NAN/0013/2013). Individual Grants and Scholarships: FCT is also gratefully acknowledged for the Ph.D. grant no. SFRH/BD/86303/2012 (to C.F.P.), SFRH/BD/84231/2012 (RFM) and FCT UID/QUI/00062/2013 (F.F.). F.F. and R.F.M. acknowledge the project "Smart Green Homes - BOSCH" (POCI-010247-FEDER-007678) for the postdoctoral and Masters scholarships (refs. BPD/CICECO/5508/2017 and BIM-SGH/CICECO-UA/174-01/2017, respectively). We also thank Dr. Venkatramaiah Nutalapati for insightful discussions concerning the chemosensing studies.