Abstract
The use of 5,10,15,20-tetrakis(p-phenylphosphonic acid)porphyrin (H10TPPA) 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(H9TPPA)(H2O)x]Cl2·yH2O [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.
| Original language | English |
|---|---|
| Pages (from-to) | 3855-3864 |
| Number of pages | 10 |
| Journal | Inorganic Chemistry |
| Volume | 57 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - Apr 2 2018 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
Cite this
Bifunctional porphyrin-based nano-metal-organic frameworks : Catalytic and chemosensing studies. / Pereira, Carla F.; Figueira, Flávio; Mendes, Ricardo F.; Rocha, Joaão; Hupp, Joseph T; Farha, Omar K.; Simoães, Mário M.Q.; Tomé, Joaão P.C.; Paz, Filipe A.Almeida.
In: Inorganic Chemistry, Vol. 57, No. 7, 02.04.2018, p. 3855-3864.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Bifunctional porphyrin-based nano-metal-organic frameworks
T2 - Catalytic and chemosensing studies
AU - Pereira, Carla F.
AU - Figueira, Flávio
AU - Mendes, Ricardo F.
AU - Rocha, Joaão
AU - Hupp, Joseph T
AU - Farha, Omar K.
AU - Simoães, Mário M.Q.
AU - Tomé, Joaão P.C.
AU - Paz, Filipe A.Almeida
PY - 2018/4/2
Y1 - 2018/4/2
N2 - The use of 5,10,15,20-tetrakis(p-phenylphosphonic acid)porphyrin (H10TPPA) 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(H9TPPA)(H2O)x]Cl2·yH2O [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.
AB - The use of 5,10,15,20-tetrakis(p-phenylphosphonic acid)porphyrin (H10TPPA) 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(H9TPPA)(H2O)x]Cl2·yH2O [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.
UR - http://www.scopus.com/inward/record.url?scp=85044918831&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85044918831&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.7b03214
DO - 10.1021/acs.inorgchem.7b03214
M3 - Article
VL - 57
SP - 3855
EP - 3864
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 7
ER -