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An effective process to remove nitrogen-based compounds from fossil fuels without harming the process of sulfur removal is an actual gap in refineries. A success combination of desulfurization and denitrogenation processes capable of completely removing the most environmental contaminates in diesel under sustainable conditions was achieved in this work, applying polyoxometalates as catalysts, hydrogen peroxide as oxidant, and an immiscible ionic liquid as an extraction solvent. The developed process based in simultaneous oxidative desulfurization (ODS) and oxidative denitrogenation (ODN) involved initial extraction of sulfur and nitrogen compounds followed by catalytic oxidation. Keggin-type polyoxomolybdates revealed much higher reusing capacity than the related polyoxotungstate. Effectively, the first catalysts practically allowed complete sulfur and nitrogen removal only in 1 h of reaction and for ten consecutive cycles, maintaining the original catalyst and ionic liquid samples.
Dinis Silva; Alexandre Viana; Fátima Mirante; Baltazar de Castro; Luís Cunha-Silva; Salete Balula. Removing Simultaneously Sulfur and Nitrogen from Fuel under a Sustainable Oxidative Catalytic System. Sustainable Chemistry 2021, 2, 382 -391.
AMA StyleDinis Silva, Alexandre Viana, Fátima Mirante, Baltazar de Castro, Luís Cunha-Silva, Salete Balula. Removing Simultaneously Sulfur and Nitrogen from Fuel under a Sustainable Oxidative Catalytic System. Sustainable Chemistry. 2021; 2 (2):382-391.
Chicago/Turabian StyleDinis Silva; Alexandre Viana; Fátima Mirante; Baltazar de Castro; Luís Cunha-Silva; Salete Balula. 2021. "Removing Simultaneously Sulfur and Nitrogen from Fuel under a Sustainable Oxidative Catalytic System." Sustainable Chemistry 2, no. 2: 382-391.
High catalytic activity is found to be due to the combination of a chromium catalyst with large pores (MIL-101(Cr)) with aprotic solvents (γ-valerolactone−10% H2O).
Marta Lara-Serrano; Silvia Morales-Delarosa; Jose M. Campos-Martin; Víctor K. Abdelkader-Fernández; Luís Cunha-Silva; Salete S. Balula. Isomerization of glucose to fructose catalyzed by metal–organic frameworks. Sustainable Energy & Fuels 2021, 5, 3847 -3857.
AMA StyleMarta Lara-Serrano, Silvia Morales-Delarosa, Jose M. Campos-Martin, Víctor K. Abdelkader-Fernández, Luís Cunha-Silva, Salete S. Balula. Isomerization of glucose to fructose catalyzed by metal–organic frameworks. Sustainable Energy & Fuels. 2021; 5 (15):3847-3857.
Chicago/Turabian StyleMarta Lara-Serrano; Silvia Morales-Delarosa; Jose M. Campos-Martin; Víctor K. Abdelkader-Fernández; Luís Cunha-Silva; Salete S. Balula. 2021. "Isomerization of glucose to fructose catalyzed by metal–organic frameworks." Sustainable Energy & Fuels 5, no. 15: 3847-3857.
Ternary nanocomposites consisting of cobalt phosphotungstate, metal nanoparticles and a carbon matrix (Co4(PW9)[email protected][email protected]) were synthesized by decorating four different MOF-74-derived nanocarbons with the sandwich-type polyoxometalate [Co4(H2O)2(PW9O34)2]10−, Co4(PW9)2. An unprecedented strategy based on the “bulk” deposition of the POM salt nanocrystals has been persecuted on purpose, avoiding the homogeneous dispersion of POM clusters across the nanocarbon surfaces. Thereby, virtually unaltered Co4(PW9)2 nanocrystals were supported on three of the four nanocarbons, but unexpectedly the combination of bimetallic undoped Co/[email protected] support with the POM induces partial structural modifications in both materials. Consequently, the derived Co4(PW9)[email protected]/[email protected] electrocatalyst undergoes a noteworthy electroactive surface area relative increase, but at the same time, its intrinsic OER activity declines. This is not an obstacle for this nanocomposite to exhibit (along with Co4(PW9)[email protected],[email protected]) very significant nominal OER performances: low overpotentials (ca. 400 mV to develop 10 mA cm−2 of current density), fast kinetics at intermediate overpotentials (Tafel slopes ≤67 mV dec−1) and remarkable stability levels. Regardless of the specific results, this preliminary study demonstrates for the first time the POM “bulk” deposition strategy as a useful tool to prepare highly active OER catalysts, and it shows up the dramatic effect that the nanocarbon doping and metal composition has on the resultant POM loading, electrocatalytically active area and OER behavior.
Víctor K. Abdelkader-Fernández; Diana M. Fernandes; Luís Cunha-Silva; António J.S. Fernandes; Cristina Freire. Decorating MOF-74-derived nanocarbons with a sandwich-type polyoxometalate to enhance their OER activity: Exploring the underestimated bulk-deposition approach. Electrochimica Acta 2021, 389, 138719 .
AMA StyleVíctor K. Abdelkader-Fernández, Diana M. Fernandes, Luís Cunha-Silva, António J.S. Fernandes, Cristina Freire. Decorating MOF-74-derived nanocarbons with a sandwich-type polyoxometalate to enhance their OER activity: Exploring the underestimated bulk-deposition approach. Electrochimica Acta. 2021; 389 ():138719.
Chicago/Turabian StyleVíctor K. Abdelkader-Fernández; Diana M. Fernandes; Luís Cunha-Silva; António J.S. Fernandes; Cristina Freire. 2021. "Decorating MOF-74-derived nanocarbons with a sandwich-type polyoxometalate to enhance their OER activity: Exploring the underestimated bulk-deposition approach." Electrochimica Acta 389, no. : 138719.
The application of a catalytic membrane in the oxidative desulfurization of a multicomponent model diesel formed by most refractory sulfur compounds present in fuel is reported here for the first time. The catalytic membrane was prepared by the impregnation of the active lamellar [Gd(H4nmp)(H2O)2]Cl·2H2O (UAV-59) coordination polymer (CP) into a polymethyl methacrylate (PMMA, acrylic glass) supporting membrane. The use of the catalytic membrane in the liquid–liquid system instead of a powder catalyst arises as an enormous advantage associated with the facility of catalyst handling while avoiding catalyst mass loss. The optimization of various parameters allowed to achieve a near complete desulfurization after 3 h under sustainable conditions, i.e., using an aqueous H2O2 as oxidant and an ionic liquid as extraction solvent ([BMIM]PF6, 1:0.5 ratio diesel:[BMIM]PF6). The performance of the catalytic membrane and of the powdered UAV-59 catalyst was comparable, with the advantage that the former could be recycled successfully for a higher number of desulfurization cycles without the need of washing and drying procedures between reaction cycles, turning the catalytic membrane process more cost-efficient and suitable for future industrial application.
Fátima Mirante; Ricardo Mendes; Rui Faria; Luís Cunha-Silva; Filipe Paz; Salete Balula. Membrane-Supported Layered Coordination Polymer as an Advanced Sustainable Catalyst for Desulfurization. Molecules 2021, 26, 2404 .
AMA StyleFátima Mirante, Ricardo Mendes, Rui Faria, Luís Cunha-Silva, Filipe Paz, Salete Balula. Membrane-Supported Layered Coordination Polymer as an Advanced Sustainable Catalyst for Desulfurization. Molecules. 2021; 26 (9):2404.
Chicago/Turabian StyleFátima Mirante; Ricardo Mendes; Rui Faria; Luís Cunha-Silva; Filipe Paz; Salete Balula. 2021. "Membrane-Supported Layered Coordination Polymer as an Advanced Sustainable Catalyst for Desulfurization." Molecules 26, no. 9: 2404.
The development of straightforward reproducible methods for the preparation of new photoluminescent coordination polymers (CPs) is an important goal in luminescence and chemical sensing fields. Isophthalic acid derivatives have been reported for a wide range of applications, and in addition to their relatively low cost, have encouraged its use in the preparation of novel lanthanide-based coordination polymers (LnCPs). Considering that the photoluminescent properties of these CPs are highly dependent on the existence of water molecules in the crystal structure, our research efforts are now focused on the preparation of CP with the lowest water content possible, while considering a green chemistry approach. One- and two-dimensional (1D and 2D) LnCPs were prepared from 5-aminoisophthalic acid and Sm3+/Tb3+ using hydrothermal and/or microwave-assisted synthesis. The unprecedented LnCPs were characterized by single-crystal X-ray diffraction (SCRXD), powder X-ray diffraction (PXRD), Fourier transform infrared (FT-IR) spectroscopy and scanning electron microscopy (SEM), and their photoluminescence (PL) properties were studied in the solid state, at room temperature, using the CPs as powders and encapsulated in poly(methyl methacrylate (PMMA) films, envisaging the potential preparation of devices for sensing. The materials revealed interesting PL properties that depend on the dimensionality, metal ion, co-ligand used and water content.
Carla Queirós; Chen Sun; Ana Silva; Baltazar de Castro; Juan Cabanillas-Gonzalez; Luís Cunha-Silva. Multidimensional Ln-Aminophthalate Photoluminescent Coordination Polymers. Materials 2021, 14, 1786 .
AMA StyleCarla Queirós, Chen Sun, Ana Silva, Baltazar de Castro, Juan Cabanillas-Gonzalez, Luís Cunha-Silva. Multidimensional Ln-Aminophthalate Photoluminescent Coordination Polymers. Materials. 2021; 14 (7):1786.
Chicago/Turabian StyleCarla Queirós; Chen Sun; Ana Silva; Baltazar de Castro; Juan Cabanillas-Gonzalez; Luís Cunha-Silva. 2021. "Multidimensional Ln-Aminophthalate Photoluminescent Coordination Polymers." Materials 14, no. 7: 1786.
A series of porous metal–organic frameworks (MOFs) of the UiO-66 family, namely UiO-66(Zr), UiO-66(Hf) and UiO-66(Hf)-NH2, prepared by solvothermal procedures were characterized, and their catalytic efficiency for oxidative denitrification (ODN) was investigated for the first time. Sustainable denitrogenation systems combining adsorption and oxidative catalytic capacity were designed using a model diesel containing two distinct nitrogen compounds (NCs) in a solvent-free medium and using an environment-friendly oxidant (H2O2). An efficient adsorptive denitrogenation process was only achieved after long reaction times (24 h): using the Hf-based MOFs, the adsorptive denitrogenation increased from 19% to 79% at 5 to 24 h, while the UiO-66(Zr) reached 76% after 24 h, although the absence of adsorption capacity after 5 h. UiO-66(Hf) and UiO-66(Hf)-NH2 also revealed superior oxidative catalytic denitrogenation than UiO-66(Zr), attaining 97% of efficiency instead of 80%. ODN processes demonstrated to be more effective than the adsorptive denitrogenation, mainly during the first hours of the process. In addition, the metal center in the MOF structure had a larger influence than the presence of the amine-functional groups. Hf-based compounds revealed higher denitrogenation efficiency than the UiO-66(Zr) for a shorter reaction time (5 h).
Rui G. Faria; Diana Julião; Salete S. Balula; Luís Cunha-Silva. Hf-Based UiO-66 as Adsorptive Compound and Oxidative Catalyst for Denitrogenation Processes. Compounds 2021, 1, 3 -14.
AMA StyleRui G. Faria, Diana Julião, Salete S. Balula, Luís Cunha-Silva. Hf-Based UiO-66 as Adsorptive Compound and Oxidative Catalyst for Denitrogenation Processes. Compounds. 2021; 1 (1):3-14.
Chicago/Turabian StyleRui G. Faria; Diana Julião; Salete S. Balula; Luís Cunha-Silva. 2021. "Hf-Based UiO-66 as Adsorptive Compound and Oxidative Catalyst for Denitrogenation Processes." Compounds 1, no. 1: 3-14.
A peroxotungstate composite comprising the chromium terephthalate metal–organic framework MIL-101(Cr) and the Venturello peroxotungstate [PO4{WO(O2)2}4]3− (PW4) has been prepared by the impregnation method. The [email protected](Cr) composite presents high catalytic efficiency for oxidative desulfurization of a multicomponent model diesel containing the most refractory sulfur compounds present in real fuels (2000 ppm of total S). The catalytic performance of this heterogeneous catalyst is similar to the corresponding homogeneous PW4 active center. Desulfurization efficiency of 99.7% was achieved after only 40 min at 70 °C using H2O2 as an oxidant and an ionic liquid as an extraction solvent ([BMIM]PF6, 2:1 model diesel/[BMIM]PF6). High recycling and reusing capacity was also found for [email protected](Cr), maintaining its activity for consecutive oxidative desulfurization cycles. A comparison of the catalytic performance of this peroxotungstate composite with others previously reported [email protected](Cr) catalysts indicates that the presence of active oxygen atoms from the peroxo groups promotes a higher oxidative catalytic efficiency in a shorter reaction time.
Yan Gao; Fátima Mirante; Baltazar De Castro; Jianshe Zhao; Luís Cunha-Silva; Salete S. Balula. An Effective Hybrid Heterogeneous Catalyst to Desulfurize Diesel: [email protected]–Organic Framework. Molecules 2020, 25, 5494 .
AMA StyleYan Gao, Fátima Mirante, Baltazar De Castro, Jianshe Zhao, Luís Cunha-Silva, Salete S. Balula. An Effective Hybrid Heterogeneous Catalyst to Desulfurize Diesel: [email protected]–Organic Framework. Molecules. 2020; 25 (23):5494.
Chicago/Turabian StyleYan Gao; Fátima Mirante; Baltazar De Castro; Jianshe Zhao; Luís Cunha-Silva; Salete S. Balula. 2020. "An Effective Hybrid Heterogeneous Catalyst to Desulfurize Diesel: [email protected]–Organic Framework." Molecules 25, no. 23: 5494.
Increasing the POM loadings in [email protected] nanocomposites prepared in situ results in extremely modified framework electrocatalysts with highly enhanced OER performances.
Víctor K. Abdelkader-Fernández; Diana M. Fernandes; Salete S. Balula; Luís Cunha-Silva; Cristina Freire. Advanced framework-modified [email protected] nanocomposites as enhanced oxygen evolution reaction electrocatalysts. Journal of Materials Chemistry A 2020, 8, 13509 -13521.
AMA StyleVíctor K. Abdelkader-Fernández, Diana M. Fernandes, Salete S. Balula, Luís Cunha-Silva, Cristina Freire. Advanced framework-modified [email protected] nanocomposites as enhanced oxygen evolution reaction electrocatalysts. Journal of Materials Chemistry A. 2020; 8 (27):13509-13521.
Chicago/Turabian StyleVíctor K. Abdelkader-Fernández; Diana M. Fernandes; Salete S. Balula; Luís Cunha-Silva; Cristina Freire. 2020. "Advanced framework-modified [email protected] nanocomposites as enhanced oxygen evolution reaction electrocatalysts." Journal of Materials Chemistry A 8, no. 27: 13509-13521.
An unprecedented and straightforward strategy towards the activation of metal-organic frameworks UiO-66(Zr) and UiO-66(Hf) in oxidative desulfurization reactions was developed. Post-synthetic treatment of poor-defect pristine UiO-66 materials with chloride-based salts (for example TiCl4) leaded to the preparation of more active and recyclable heterogeneous catalysts for oxidative desulfurization processes. The pristine UiO-66(Hf) showed to be an inactive catalyst; however, after activation treatment 80% of total desulfurization was achieved after 1 h. Also, UiO-66 (Zr) increased appreciably its activity after treatment with chloride-based salts (from 62% from 97% after treatment with TiCl4). The insertion of chloride in UiO-66 framework did not retained the counter-cation Ti(IV). The possible interaction of chloride with UiO-66 framework enhances catalytic activity without structural degradation of catalyst, even after consecutive reaction cycles. Chloride activation method opened a new route to activate efficiently catalytic UiO-66 MOFs. This is a cost-effective method capable to be feasible to other MOFs structures, promoting their catalytic capacities and enlarging their catalytic application.
Alexandre Viana; Diana Julião; Fátima Mirante; Rui G. Faria; Baltazar de Castro; Salete S. Balula; Luís Cunha-Silva. Straightforward activation of metal-organic framework UiO-66 for oxidative desulfurization processes. Catalysis Today 2020, 362, 28 -34.
AMA StyleAlexandre Viana, Diana Julião, Fátima Mirante, Rui G. Faria, Baltazar de Castro, Salete S. Balula, Luís Cunha-Silva. Straightforward activation of metal-organic framework UiO-66 for oxidative desulfurization processes. Catalysis Today. 2020; 362 ():28-34.
Chicago/Turabian StyleAlexandre Viana; Diana Julião; Fátima Mirante; Rui G. Faria; Baltazar de Castro; Salete S. Balula; Luís Cunha-Silva. 2020. "Straightforward activation of metal-organic framework UiO-66 for oxidative desulfurization processes." Catalysis Today 362, no. : 28-34.
The self-assembly reaction between NiI2, benzoic acid (PhCO2H) and the Schiff base chelate, N-naphthalidene-2-amino-5-chlorobenzoic acid (nacbH2), in the presence of the organic base triethylamine (NEt3), has resulted in the isolation and the structural, spectroscopic, and physicochemical characterization of the dodecanuclear [Ni12I2(OH)6(O2CPh)5(nacb)5(H2O)4(MeCN)4]I (1) cluster compound in ~30% yield. Complex 1 has a cage-like conformation, comprising twelve distorted, octahedral NiII ions that are bridged by five μ3-OH−, one μ-OH−, an I− in 55% occupancy, five PhCO2− groups (under the η1:η1:μ, η1:η2:μ3 and η2:η2:μ4 modes), and the naphthoxido and carboxylato O-atoms of five doubly deprotonated nacb2− groups. The overall {Ni12} cluster exhibits a nanosized structure with a diameter of ~2.5 nm and its metallic core can be conveniently described as a series of nine edge- or vertex-sharing {Ni3} triangular subunits. Complex 1 is the highest nuclearity coordination compound bearing the nacbH2 chelate, and a rare example of polynuclear NiII complex containing coordinating I− ions. Direct current (DC) magnetic susceptibility studies revealed the presence of predominant antiferromagnetic exchange interactions between the NiII ions, while photophysical studies of 1 in the solid-state showed a cyan-to-green centered emission at 520 nm, upon maximum excitation at 380 nm. The reported results demonstrate the rich coordination chemistry of the deprotonated nacb2− chelate in the presence of NiII metal ions, and the ability of this ligand to adopt a variety of different bridging modes, thus fostering the formation of high-nuclearity molecules with rare, nanosized dimensions and interesting physical (i.e., magnetic and optical) properties.
Panagiota S. Perlepe; Konstantinos N. Pantelis; Luís Cunha-Silva; Vlasoula Bekiari; Albert Escuer; Theocharis C. Stamatatos. Rare Nuclearities in Ni(II) Cluster Chemistry: An Unprecedented {Ni12} Nanosized Cage from the Use of N-Naphthalidene-2-Amino-5-Chlorobenzoic Acid. Inorganics 2020, 8, 32 .
AMA StylePanagiota S. Perlepe, Konstantinos N. Pantelis, Luís Cunha-Silva, Vlasoula Bekiari, Albert Escuer, Theocharis C. Stamatatos. Rare Nuclearities in Ni(II) Cluster Chemistry: An Unprecedented {Ni12} Nanosized Cage from the Use of N-Naphthalidene-2-Amino-5-Chlorobenzoic Acid. Inorganics. 2020; 8 (5):32.
Chicago/Turabian StylePanagiota S. Perlepe; Konstantinos N. Pantelis; Luís Cunha-Silva; Vlasoula Bekiari; Albert Escuer; Theocharis C. Stamatatos. 2020. "Rare Nuclearities in Ni(II) Cluster Chemistry: An Unprecedented {Ni12} Nanosized Cage from the Use of N-Naphthalidene-2-Amino-5-Chlorobenzoic Acid." Inorganics 8, no. 5: 32.
A relatively unexplored synthetic route in redox-active Mn(II/III) coordination chemistry has been employed toward the preparation of a new mixed-valence MnII/III 1-D linear chain from the reaction of [MnIII(sacb)2]− precursor with a MnII source, where sacbH2 is the Schiff base ligand N-salicylidene-2-amino-5-chlorobenzoic acid. The mononuclear (Pr2NH2)[MnIII(sacb)2] (1) compound was obtained in excellent yields (>85%) from the 1:2:3 reaction of Mn(O2CMe)2∙4H2O, sacbH2 and Pr2NH, respectively. In 1, the two doubly deprotonated sacb2− ligands act as Ocarboxylate,Nimine,Ophenoxide-tridentate chelates, while the second carboxylate O atom of sacb2− is dangling and H-bonded to the Pr2NH2+ countercation. Complex 1 was subsequently used as a ‘ligand’ to react stoichiometrically with the ‘metal’ Mn(NO3)2∙4H2O, thus leading to the 1-D coordination polymer {[MnIIMnIII(sacb)2(H2O)2(MeOH)2](NO3)}n (2) in good yields (~50%). The removal of Pr2NH2+ from the vicinity of the [MnIII(sacb)2]− metalloligand has rendered possible (vide infra) the coordination of the second Ocarboxylate of sacb2− to neighboring {MnII(H2O)2(MeOH)2}2+ units, and consequently the formation of the 1-D polymer 2. Direct-current (dc) magnetic susceptibility studies revealed the presence of very weak antiferromagnetic exchange interactions between alternating MnIII and MnII atoms with a coupling constant of J = −0.08 cm−1 for g = 2.00. The combined results demonstrate the potential of the ‘metal complexes as ligands’ approach to yield new mixed-valence Mn(II/III) coordination polymers with interesting structural motifs and physicochemical properties.
Konstantinos N. Pantelis; Georgios Karotsis; Christos Lampropoulos; Luís Cunha-Silva; Albert Escuer; Theocharis C. Stamatatos. ‘Metal Complexes as Ligands’ for the Synthesis of Coordination Polymers: A MnIII Monomer as a Building Block for the Preparation of an Unprecedented 1-D {MnIIMnIII}n Linear Chain. Materials 2020, 13, 1352 .
AMA StyleKonstantinos N. Pantelis, Georgios Karotsis, Christos Lampropoulos, Luís Cunha-Silva, Albert Escuer, Theocharis C. Stamatatos. ‘Metal Complexes as Ligands’ for the Synthesis of Coordination Polymers: A MnIII Monomer as a Building Block for the Preparation of an Unprecedented 1-D {MnIIMnIII}n Linear Chain. Materials. 2020; 13 (6):1352.
Chicago/Turabian StyleKonstantinos N. Pantelis; Georgios Karotsis; Christos Lampropoulos; Luís Cunha-Silva; Albert Escuer; Theocharis C. Stamatatos. 2020. "‘Metal Complexes as Ligands’ for the Synthesis of Coordination Polymers: A MnIII Monomer as a Building Block for the Preparation of an Unprecedented 1-D {MnIIMnIII}n Linear Chain." Materials 13, no. 6: 1352.
A series of metal–organic coordination complexes based on alkaline-earth metal centers [Mg(II), Ca(II), and Ba(II)] and the ligand 5-aminoisophthalate (aip2−) revealed notable structural diversity, both in the materials’ dimensionality and in their hydrogen bonding networks: [Mg(H2O)6]∙[Mg2(Haip)(H2O)10]∙(Haip)∙3(aip)∙10(H2O) (1) and [Mg(aip)(phen)(H2O)2]∙(H2O) (2) were isolated as discrete complexes (0D); [Ca(aip)(H2O)2]∙(H2O) (3), [Ca(aip)(phen)(H2O)2]∙(phen)∙(H2O) (4), and [Ba2(aip)2(phen)2(H2O)7]∙2(phen)∙2(H2O) (5) revealed metal–organic chain (1D) structures, while the [Ba(aip)(H2O)] (6) showed a metal–organic layered (2D) arrangement. Furthermore, most of these metal–organic coordination materials revealed interesting thermal stability properties, being stable at temperatures up to 450 °C.
Carla Queirós; Ana Silva; Baltazar De Castro; Luís Cunha-Silva. From Discrete Complexes to Metal–Organic Layered Materials: Remarkable Hydrogen Bonding Frameworks. Molecules 2020, 25, 1353 .
AMA StyleCarla Queirós, Ana Silva, Baltazar De Castro, Luís Cunha-Silva. From Discrete Complexes to Metal–Organic Layered Materials: Remarkable Hydrogen Bonding Frameworks. Molecules. 2020; 25 (6):1353.
Chicago/Turabian StyleCarla Queirós; Ana Silva; Baltazar De Castro; Luís Cunha-Silva. 2020. "From Discrete Complexes to Metal–Organic Layered Materials: Remarkable Hydrogen Bonding Frameworks." Molecules 25, no. 6: 1353.
A bidirectional synergy involving Co-based polyoxometalates (POMs) incorporated in the Co-containing zeolitic imidazolate framework, ZIF-67, that promoted a notable improvement in the oxygen evolution reaction (OER) performance was unveiled for the first time. Two [email protected] nanocomposite materials—[email protected] and [email protected]—were successfully prepared via a room temperature ‘in situ’ approach, by the immobilization of POM anions [SiW9Co3(H2O)3O37]10− (SiW9Co3) in the cages of two isostructural ZIFs: ZIF-8 and ZIF-67, formed with Zn2+ and Co2+, respectively. Despite both [email protected] and [email protected] revealed similar and low occupancy degrees (ca. 6 POM units per 100 ZIF-cages), an intense synergy has been detected in the ZIF-67 based nanocomposite, while no synergistic interaction was found for POMs and ZIF-8. Due to this synergetic effect, the OER activity of [email protected] is significantly enhanced in comparison with that of ZIF-67: ~110 mV decreased overpotential and double current density. Additionally, this nanocomposite exhibits excellent stability in the alkaline electrolyte. Insights into the nature and magnitude of the SiW9Co3–ZIF-67 synergy have shown up its interesting ZIF ↔ POM bidirectional nature that involves activation of the Co-based active sites in POM clusters as a consequence of a ZIF-67 → SiW9Co3 electron transfer, along with POM-induced generation of more active unsaturated Co-nodes in the ZIF-67 frameworks. These findings represent a promising ‘proof of concept’ for the development of more efficient [email protected] electrocatalysts in the future.
Víctor Karim Abdelkader Fernández; Diana Mesquita Fernandes; Salete Balula; Luís Cunha-Silva; Cristina Freire. Oxygen Evolution Reaction Electrocatalytic Improvement in [email protected] Nanocomposites: A Bidirectional Synergistic Effect. ACS Applied Energy Materials 2020, 3, 2925 -2934.
AMA StyleVíctor Karim Abdelkader Fernández, Diana Mesquita Fernandes, Salete Balula, Luís Cunha-Silva, Cristina Freire. Oxygen Evolution Reaction Electrocatalytic Improvement in [email protected] Nanocomposites: A Bidirectional Synergistic Effect. ACS Applied Energy Materials. 2020; 3 (3):2925-2934.
Chicago/Turabian StyleVíctor Karim Abdelkader Fernández; Diana Mesquita Fernandes; Salete Balula; Luís Cunha-Silva; Cristina Freire. 2020. "Oxygen Evolution Reaction Electrocatalytic Improvement in [email protected] Nanocomposites: A Bidirectional Synergistic Effect." ACS Applied Energy Materials 3, no. 3: 2925-2934.
A selective luminescent sensor was fabricated by simply mixing a Tb(iii)-based MOF with polymethylmetahacrylate enabling to detect sub-ppb range of nitroaromatic vapours.
Francisco Javier G Moscoso; José Almeida; Ahmad Sousaraei; Tânia Lopes-Costa; Ana M. G. Silva; Juan Cabanillas-Gonzalez; Luís Cunha-Silva; José M. Pedrosa. A lanthanide MOF immobilized in PMMA transparent films as a selective fluorescence sensor for nitroaromatic explosive vapours. Journal of Materials Chemistry C 2020, 8, 3626 -3630.
AMA StyleFrancisco Javier G Moscoso, José Almeida, Ahmad Sousaraei, Tânia Lopes-Costa, Ana M. G. Silva, Juan Cabanillas-Gonzalez, Luís Cunha-Silva, José M. Pedrosa. A lanthanide MOF immobilized in PMMA transparent films as a selective fluorescence sensor for nitroaromatic explosive vapours. Journal of Materials Chemistry C. 2020; 8 (11):3626-3630.
Chicago/Turabian StyleFrancisco Javier G Moscoso; José Almeida; Ahmad Sousaraei; Tânia Lopes-Costa; Ana M. G. Silva; Juan Cabanillas-Gonzalez; Luís Cunha-Silva; José M. Pedrosa. 2020. "A lanthanide MOF immobilized in PMMA transparent films as a selective fluorescence sensor for nitroaromatic explosive vapours." Journal of Materials Chemistry C 8, no. 11: 3626-3630.
Transparent polymeric matrices serve as efficient platforms to immobilize Tb(BTC) crystals whose fluorescence is quenched in the presence of NO2.
Francisco García Moscoso; José Almeida; Ahmad Sousaraei; Tânia Lopes-Costa; Ana M. G. Silva; Juan Cabanillas-Gonzalez; Luís Cunha-Silva; José M. Pedrosa. Luminescent MOF crystals embedded in PMMA/PDMS transparent films as effective NO2 gas sensors. Molecular Systems Design & Engineering 2020, 5, 1048 -1056.
AMA StyleFrancisco García Moscoso, José Almeida, Ahmad Sousaraei, Tânia Lopes-Costa, Ana M. G. Silva, Juan Cabanillas-Gonzalez, Luís Cunha-Silva, José M. Pedrosa. Luminescent MOF crystals embedded in PMMA/PDMS transparent films as effective NO2 gas sensors. Molecular Systems Design & Engineering. 2020; 5 (6):1048-1056.
Chicago/Turabian StyleFrancisco García Moscoso; José Almeida; Ahmad Sousaraei; Tânia Lopes-Costa; Ana M. G. Silva; Juan Cabanillas-Gonzalez; Luís Cunha-Silva; José M. Pedrosa. 2020. "Luminescent MOF crystals embedded in PMMA/PDMS transparent films as effective NO2 gas sensors." Molecular Systems Design & Engineering 5, no. 6: 1048-1056.
Porous metal-organic framework (MOF) materials UiO-66(Zr) obtained by solvothermal and microwave advanced synthesis (MWAS) procedures were characterized, and their catalytic efficiency was investigated for oxidative desulfurization (ODS) processes using a multicomponent model diesel containing benzothiophene and dibenzothiophene derivatives. The preparation parameters as the cooling time after oven use in the solvothermal procedure, and also the reaction time in the MWAS method seemed to play an important role in the catalytic performance of the UiO-66(Zr) material, as well as in its recycle capacity. The material prepared by the solvothermal procedure with a fast cooling time showed the best catalytic performance (desulfurization efficiency of 99.5% after 3 h). However, the application of the UiO-66(Zr) material prepared by the MWAS method (desulfurization efficiency of 96% after 3 h) conciliated a higher number of advantages, such as shorter reaction time preparation (15 min) and high catalytic activity for a higher number of reaction cycles. The UiO-66(Zr) prepared by the MWAS method was used for the first time in an oxidative desulfurization process, and according to the catalytic results obtained (high recycle capacity and stability) and shorter reaction time preparation, seems to be a promising material for industrial application.
Alexandre Viana; Susana O. Ribeiro; Baltazar De Castro; Salete S. Balula; Luís Cunha-Silva. Influence of UiO-66(Zr) Preparation Strategies in Its Catalytic Efficiency for Desulfurization Process. Materials 2019, 12, 3009 .
AMA StyleAlexandre Viana, Susana O. Ribeiro, Baltazar De Castro, Salete S. Balula, Luís Cunha-Silva. Influence of UiO-66(Zr) Preparation Strategies in Its Catalytic Efficiency for Desulfurization Process. Materials. 2019; 12 (18):3009.
Chicago/Turabian StyleAlexandre Viana; Susana O. Ribeiro; Baltazar De Castro; Salete S. Balula; Luís Cunha-Silva. 2019. "Influence of UiO-66(Zr) Preparation Strategies in Its Catalytic Efficiency for Desulfurization Process." Materials 12, no. 18: 3009.
The employment of N-(2-carboxyphenyl)salicylideneimine in 4f metal chemistry has led to two families of dinuclear complexes depending on the lanthanide(III) used. Representative members exhibit interesting magnetic, optical, and catalytic properties.
Nikolaos C. Anastasiadis; Carlos M. Granadeiro; Julia Mayans; Catherine P. Raptopoulou; Vlasoula Bekiari; Luís Cunha-Silva; Vassilis Psycharis; Albert Escuer; Salete S. Balula; Konstantis F. Konidaris; Spyros P. Perlepes. Multifunctionality in Two Families of Dinuclear Lanthanide(III) Complexes with a Tridentate Schiff-Base Ligand. Inorganic Chemistry 2019, 58, 9581 -9585.
AMA StyleNikolaos C. Anastasiadis, Carlos M. Granadeiro, Julia Mayans, Catherine P. Raptopoulou, Vlasoula Bekiari, Luís Cunha-Silva, Vassilis Psycharis, Albert Escuer, Salete S. Balula, Konstantis F. Konidaris, Spyros P. Perlepes. Multifunctionality in Two Families of Dinuclear Lanthanide(III) Complexes with a Tridentate Schiff-Base Ligand. Inorganic Chemistry. 2019; 58 (15):9581-9585.
Chicago/Turabian StyleNikolaos C. Anastasiadis; Carlos M. Granadeiro; Julia Mayans; Catherine P. Raptopoulou; Vlasoula Bekiari; Luís Cunha-Silva; Vassilis Psycharis; Albert Escuer; Salete S. Balula; Konstantis F. Konidaris; Spyros P. Perlepes. 2019. "Multifunctionality in Two Families of Dinuclear Lanthanide(III) Complexes with a Tridentate Schiff-Base Ligand." Inorganic Chemistry 58, no. 15: 9581-9585.
A supramolecular cucurbit[6]uril/MoVI hydrogen-bonded assembly displays dual-function (oxidation/acid) catalytic behavior for the one-pot conversion of olefins to alkoxy products.
Lucie S. Nogueira; Margarida M. Antunes; Ana C. Gomes; Luís Cunha-Silva; Martyn Pillinger; André D. Lopes; Anabela A. Valente; Isabel S. Gonçalves. A hydrogen-bonded assembly of cucurbit[6]uril and [MoO2Cl2(H2O)2] with catalytic efficacy for the one-pot conversion of olefins to alkoxy products. Dalton Transactions 2019, 48, 11508 -11519.
AMA StyleLucie S. Nogueira, Margarida M. Antunes, Ana C. Gomes, Luís Cunha-Silva, Martyn Pillinger, André D. Lopes, Anabela A. Valente, Isabel S. Gonçalves. A hydrogen-bonded assembly of cucurbit[6]uril and [MoO2Cl2(H2O)2] with catalytic efficacy for the one-pot conversion of olefins to alkoxy products. Dalton Transactions. 2019; 48 (30):11508-11519.
Chicago/Turabian StyleLucie S. Nogueira; Margarida M. Antunes; Ana C. Gomes; Luís Cunha-Silva; Martyn Pillinger; André D. Lopes; Anabela A. Valente; Isabel S. Gonçalves. 2019. "A hydrogen-bonded assembly of cucurbit[6]uril and [MoO2Cl2(H2O)2] with catalytic efficacy for the one-pot conversion of olefins to alkoxy products." Dalton Transactions 48, no. 30: 11508-11519.
A new family of ferromagnetically-coupled {Cu4Ln2} complexes is reported. The compounds exhibit SMM and magnetocaloric properties.
Dimitris I. Alexandropoulos; Luis Cunha-Silva; Jinkui Tang; Theocharis C. Stamatatos. Heterometallic Cu/Ln cluster chemistry: ferromagnetically-coupled {Cu4Ln2} complexes exhibiting single-molecule magnetism and magnetocaloric properties. Dalton Transactions 2018, 47, 11934 -11941.
AMA StyleDimitris I. Alexandropoulos, Luis Cunha-Silva, Jinkui Tang, Theocharis C. Stamatatos. Heterometallic Cu/Ln cluster chemistry: ferromagnetically-coupled {Cu4Ln2} complexes exhibiting single-molecule magnetism and magnetocaloric properties. Dalton Transactions. 2018; 47 (34):11934-11941.
Chicago/Turabian StyleDimitris I. Alexandropoulos; Luis Cunha-Silva; Jinkui Tang; Theocharis C. Stamatatos. 2018. "Heterometallic Cu/Ln cluster chemistry: ferromagnetically-coupled {Cu4Ln2} complexes exhibiting single-molecule magnetism and magnetocaloric properties." Dalton Transactions 47, no. 34: 11934-11941.
This work proposes an efficient desulfurization system to produce low sulfur diesel under sustainable and moderate experimental conditions. Treatment of a real diesel with a sulfur content of 2300 ppm led to 80% desulfurization after 2 h. The processes used conciliate liquid-liquid extraction and sulfur oxidative catalysis. The catalytic performance of the commercial Keggin-polyoxomolybdate H3[PMo12O40] (PMo12) was strategically increased by simple cation exchange, using a long carbon chain (ODAPMo12, ODA = CH3(CH2)17(CH3)3N), and by its incorporation into the Metal-Organic Framework (MOF) NH2-MIL-101(Cr), forming a new active heterogeneous [email protected] composite catalyst. Activity of both catalysts was similar; however, the solid catalyst could be easily recovered and reused, and its stability was confirmed after multiple continuous cycles.
Carlos M. Granadeiro; Pedro M. C. Ferreira; Diana Julião; Luís A. Ribeiro; Rita Valença; Jorge C. Ribeiro; Isabel S. Gonçalves; Baltazar De Castro; Martyn Pillinger; Luís Cunha-Silva; Salete S. Balula. Efficient Oxidative Desulfurization Processes Using Polyoxomolybdate Based Catalysts. Energies 2018, 11, 1696 .
AMA StyleCarlos M. Granadeiro, Pedro M. C. Ferreira, Diana Julião, Luís A. Ribeiro, Rita Valença, Jorge C. Ribeiro, Isabel S. Gonçalves, Baltazar De Castro, Martyn Pillinger, Luís Cunha-Silva, Salete S. Balula. Efficient Oxidative Desulfurization Processes Using Polyoxomolybdate Based Catalysts. Energies. 2018; 11 (7):1696.
Chicago/Turabian StyleCarlos M. Granadeiro; Pedro M. C. Ferreira; Diana Julião; Luís A. Ribeiro; Rita Valença; Jorge C. Ribeiro; Isabel S. Gonçalves; Baltazar De Castro; Martyn Pillinger; Luís Cunha-Silva; Salete S. Balula. 2018. "Efficient Oxidative Desulfurization Processes Using Polyoxomolybdate Based Catalysts." Energies 11, no. 7: 1696.