Bifunctional Porphyrin-Based Nano-Metal-Organic Frameworks: Catalytic and Chemosensing Studies


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.






Pereira, CF; Figueira, F; Mendes, RF; Rocha, J; Hupp, JT; Farha, OK; Simoes, MMQ; Tome, JPC; Paz, FAA

nossos autores


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.

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