High Catalytic Efficiency of a Layered Coordination Polymer to Remove Simultaneous Sulfur and Nitrogen Compounds from Fuels

An ionic lamellar coordination polymer based on a flexible triphosphonic acid linker, [Gd(H4nmp)(H2O)2]Cl2 H2O (1) (H6nmp stands for nitrilo(trimethylphosphonic) acid), presents high efficiency to remove sulfur and nitrogen pollutant compounds from model diesel. Its oxidative catalytic performance was investigated using single sulfur (1-BT, DBT, 4-MDBT and 4,6-DMDBT, 2350 ppm of S) and nitrogen (indole and quinolone, 400 ppm of N) model diesels and further, using multicomponent S/N model diesel. Different methodologies of preparation followed (microwave, one-pot, hydrothermal) originated small morphological differences that did not influenced the catalytic performance of catalyst. Complete desulfurization and denitrogenation were achieved after 2 h using single model diesels, an ionic liquid as extraction solvent ([BMIM]PF6) and H2O2 as oxidant. Simultaneous desulfurization and denitrogenation processes revealed that the nitrogen compounds are more easily removed from the diesel phase to the [BMIM]PF6 phase and consequently, faster oxidized than the sulfur compounds. The lamellar catalyst showed a high recycle capacity for desulfurization. The reusability of the diesel/H2O2/[BMIM]PF6 system catalyzed by lamellar catalyst was more efficient for denitrogenation than for desulfurization process using a multicomponent model diesel. This behavior is not associated with the catalyst performance but it is mainly due to the saturation of S/N compounds in the extraction phase.

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An Effective Hybrid Heterogeneous Catalyst to Desulfurize Diesel: Peroxotungstate@Metal–Organic Framework

Molecules ◽

10.3390/molecules25235494 ◽

2020 ◽

Vol 25 (23) ◽

pp. 5494

Author(s):

Yan Gao ◽

Fátima Mirante ◽

Baltazar de Castro ◽

Jianshe Zhao ◽

Luís Cunha-Silva ◽

...

Keyword(s):

Heterogeneous Catalyst ◽

Metal Organic Framework ◽

Oxidative Desulfurization ◽

Catalytic Efficiency ◽

Catalytic Performance ◽

Impregnation Method ◽

Extraction Solvent ◽

Metal Organic ◽

Model Diesel ◽

Organic Framework

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 PW4@MIL-101(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 PW4@MIL-101(Cr), maintaining its activity for consecutive oxidative desulfurization cycles. A comparison of the catalytic performance of this peroxotungstate composite with others previously reported tungstate@MIL-101(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.

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Membrane-Supported Layered Coordination Polymer as an Advanced Sustainable Catalyst for Desulfurization

Molecules ◽

10.3390/molecules26092404 ◽

2021 ◽

Vol 26 (9) ◽

pp. 2404

Author(s):

Fátima Mirante ◽

Ricardo F. Mendes ◽

Rui G. Faria ◽

Luís Cunha-Silva ◽

Filipe A. Almeida Paz ◽

...

Keyword(s):

Coordination Polymer ◽

Oxidative Desulfurization ◽

Liquid System ◽

Catalytic Membrane ◽

Extraction Solvent ◽

Acrylic Glass ◽

Drying Procedures ◽

Cost Efficient ◽

Model Diesel ◽

Reaction Cycles

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.

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Fast Immobilization of Human Carbonic Anhydrase II on Ni-Based Metal-Organic Framework Nanorods with High Catalytic Performance

Catalysts ◽

10.3390/catal10040401 ◽

2020 ◽

Vol 10 (4) ◽

pp. 401

Author(s):

Mengzhao Jiao ◽

Jie He ◽

Shanshan Sun ◽

Frank Vriesekoop ◽

Qipeng Yuan ◽

...

Keyword(s):

Carbonic Anhydrase ◽

High Efficiency ◽

Specific Binding ◽

Metal Organic Framework ◽

Immobilized Enzymes ◽

Catalytic Performance ◽

Carbonic Anhydrase Ii ◽

One Pot ◽

Original Activity ◽

Simple Strategy

Carbonic anhydrase (CA) has received considerable attention for its ability to capture carbon dioxide efficiently. This study reports a simple strategy for immobilizing recombinant carbonic anhydrase II from human (hCA II) on Ni-based MOFs (Ni-BTC) nanorods, which was readily achieved in a one-pot immobilization of His-tagged hCA II (His-hCA II). Consequently, His-hCA II from cell lysate could obtain an activity recovery of 99% under optimal conditions. After storing for 10 days, the immobilized His-hCA II maintained 40% activity while the free enzyme lost 91% activity. Furthermore, during the hydrolysis of p-nitrophenyl acetic acid, immobilized His-hCA II exhibited excellent reusability and still retained more than 65% of the original activity after eight cycles. In addition, we also found that Ni-BTC had no fixation effect on proteins without histidine-tag. These results show that the Ni-BTC MOFs have a great potential with high efficiency for and specific binding of immobilized enzymes.

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Influence of UiO-66(Zr) Preparation Strategies in Its Catalytic Efficiency for Desulfurization Process

Materials ◽

10.3390/ma12183009 ◽

2019 ◽

Vol 12 (18) ◽

pp. 3009 ◽

Cited By ~ 4

Author(s):

Alexandre M. Viana ◽

Susana O. Ribeiro ◽

Baltazar de Castro ◽

Salete S. Balula ◽

Luís Cunha-Silva

Keyword(s):

Reaction Time ◽

Metal Organic Framework ◽

Oxidative Desulfurization ◽

Catalytic Efficiency ◽

Porous Metal ◽

Catalytic Performance ◽

Cooling Time ◽

High Catalytic Activity ◽

Desulfurization Process ◽

Desulfurization Efficiency

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.

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One-Pot Photochemical Synthesis of Solution-Stable TiO2-Polypyrrole Nanocomposite for the Photodegradation of Methyl Orange

Key Engineering Materials ◽

10.4028/www.scientific.net/kem.853.217 ◽

2020 ◽

Vol 853 ◽

pp. 217-222

Author(s):

Salvador C.Jr. Buenviaje ◽

Ken Aldren S. Usman ◽

Yasmin De Guzman Edañol ◽

Genes P. Maylem ◽

Leon M.Jr. Payawan

Keyword(s):

Methyl Orange ◽

Colloidal Stability ◽

Catalytic Efficiency ◽

Kinetic Studies ◽

Chemical Conversion ◽

Catalytic Performance ◽

Band Gap Energy ◽

Photochemical Synthesis ◽

One Pot ◽

Simple Method

Photocatalysis is a promising technology used in wastewater treatment. However, the practical application of this approach has been hindered by several factors. One issue is the aggregation of the photocatalyst in solution which leads to significant decrease in catalytic efficiency. Recent innovations in photochemical research have geared towards improving the colloidal stability of well-known photocatalysts such as titanium dioxide (TiO2). In this study, a simple method of imparting colloidal stability to TiO2, through one-pot photo-polymerized polypyrrole (PPy) nanoparticle coatings were demonstrated. The resulting TiO2-PPy (TP) dispersions exhibited excellent resistance to aggregation as evident in their uniform particle size distribution (diameter = 81.40 ± 6.58 nm, polydispersity index = 0.412 ± 0.037) and stable zeta-potential values (ζ = 33.15 ± 4.35). The optimum TiO2 to polymer ratio also resulted to significant lowering in band-gap energy (from 3.54 eV to 3.15 eV) which is an indicator of improved photocatalytic properties. Photodegradation of a model pollutant, methyl orange (MO) performed at optimal lightning condition and 4TP dosage showed 35% /hour photocatalytic efficiency. Lastly, kinetic studies suggest that the catalytic performance is dependent on the pollutant concentration as shown by a second-order MO degradation with rate constant of 306.856 x 10-7 M-1 s-1 and proposed rate law of R = k [MO]2. The study had also indicated the chemical conversion of MO to CO2 by measuring about 43% decrease in total organic carbon in an hour.

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Solvent-Free Desulfurization System to Produce Low-Sulfur Diesel Using Hybrid Monovacant Keggin-Type Catalyst

Molecules ◽

10.3390/molecules25214961 ◽

2020 ◽

Vol 25 (21) ◽

pp. 4961

Author(s):

Fátima Mirante ◽

Baltazar de Castro ◽

Carlos M. Granadeiro ◽

Salete S. Balula

Keyword(s):

Oxidative Desulfurization ◽

Catalytic Efficiency ◽

Catalytic Performance ◽

Sulfur Compounds ◽

Solvent Free ◽

Clean Diesel ◽

Liquid Liquid Extraction ◽

Model Diesel ◽

Low Sulfur ◽

Multicomponent Model

Two quaternary ammonium catalysts based on the monovacant polyoxotungstate ([PW11O39]7−, abbreviated as PW11) were prepared and characterized. The desulfurization performances of the PW11-based hybrids (of tetrabutylammonium and trimethyloctadecylammonium, abbreviated as TBA[PW11] and ODA[PW11], respectively), the corresponding potassium salt (K7PW11O39, abbreviated as KPW11) and the peroxo-compound (TBA-PO4[WO(O2)2], abbreviated as TBA[PW4]) were compared as catalysts for the oxidative desulfurization of a multicomponent model diesel (2000 ppm S). The oxidative desulfurization studies (ODS) were performed using solvent-free systems and aqueous H2O2 as oxidant. The nature of the cation in the PW11 catalyst showed to have an important influence on the catalytic performance. In fact, the PW11-hybrid catalysts showed higher catalytic efficiency than the peroxo-compound TBA[PW4], known as Venturello compound. TBA[PW11] revealed a remarkable desulfurization performance with 96.5% of sulfur compounds removed in the first 130 min. The reusability and stability of the catalyst were also investigated for ten consecutive ODS cycles without loss of activity. A treated clean diesel could be recovered without sulfur compounds by performing a final liquid/liquid extraction diesel/EtOH:H2O mixture (1:1) after the catalytic oxidative step.

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Recyclable Magnetic Cu/CuFe2O4 Nanocomposites for the Rapid Degradation of 4-NP

Catalysts ◽

10.3390/catal10121437 ◽

2020 ◽

Vol 10 (12) ◽

pp. 1437

Author(s):

Hui Zheng ◽

Jie Huang ◽

Tianxiang Zhou ◽

Yumeng Jiang ◽

Yuhong Jiang ◽

...

Keyword(s):

High Efficiency ◽

Catalytic Reduction ◽

Magnetic Measurements ◽

Catalytic Performance ◽

Magnetic Saturation ◽

One Pot ◽

Synthetic Process ◽

Catalytic Activities ◽

Molar Ratios ◽

The One

Magnetic Cu/CuFe2O4 nanocomposites were prepared by the one-pot thermal decomposition of acetylacetone compounds. Adjusting the molar ratios of Fe to Cu was used to control the content of Cu in the synthetic process. XRD, TEM, XPS and UV-Vis were employed to reveal detailed structural and catalytic activities of Cu/CuFe2O4 nanocomposites. Magnetic measurements demonstrated that Cu/CuFe2O4 nanocomposites possessed a considerable magnetic saturation. Cu/CuFe2O4 nanocomposites showed superb efficiency in the degradation of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP). 4-NP could be reduced by Cu/CuFe2O4 nanocomposites within 40 s in the attendance of NaBH4. Cu nanocrystals played an indispensable rose in the enhancement of catalytic performance. The synergistic effect of Cu and CuFe2O4 nanocrystals achieved the high-efficiency catalytic reduction for 4-NP. After six recycling experiments, the efficiency of Cu/CuFe2O4 nanocomposites was almost stable. Our work advances a straightforward strategy to synthesize efficient and recoverable Cu/CuFe2O4 nanocomposites, which has promising utilizations in the purifying of nitrophenolic contamination.

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Chlorosulfonic Acid Supported Piperidine-4-carboxylic Acid (PPCA) Functionalized Fe3O4 Nanoparticles (Fe3O4-PPCA): The Efficient, Green and Reusable Nanocatalyst for the Synthesis of Pyrazolyl Coumarin Derivatives under Solvent-Free Conditions

Combinatorial Chemistry & High Throughput Screening ◽

10.2174/1386207322666190325120715 ◽

2019 ◽

Vol 22 (2) ◽

pp. 123-128

Author(s):

Setareh Habibzadeh ◽

Hassan Ghasemnejad-Bosra ◽

Mina Haghdadi ◽

Soheila Heydari-Parastar

Keyword(s):

Carboxylic Acid ◽

Fe3o4 Nanoparticles ◽

High Efficiency ◽

Reaction Times ◽

Chlorosulfonic Acid ◽

Aromatic Aldehydes ◽

Solvent Free ◽

Magnetic Nanocatalyst ◽

One Pot ◽

Solvent Free Conditions

Background: In this study, we developed a convenient methodology for the synthesis of coumarin linked to pyrazolines and pyrano [2,3-h] coumarins linked to 3-(1,5-diphenyl-4,5- dihydro-1H-pyrazol-3-yl)-chromen-2-one derivatives using Chlorosulfonic acid supported Piperidine-4-carboxylic acid (PPCA) functionalized Fe3O4 nanoparticles (Fe3O4-PPCA) catalyst. Materials and Methods:: Fe3O4-PPCA was investigated as an efficient and magnetically recoverable Nanocatalyst for the one-pot synthesis of substituted coumarins from the reaction of coumarin with a variety of aromatic aldehydes in high to excellent yield at room temperature under solvent-free conditions. The magnetic nanocatalyst can be easily recovered by applying an external magnet device and reused for at least 10 reaction runs without considerable loss of reactivity. Results and Conclusion: The advantages of this protocol are the use of commercially available materials, simple and an inexpensive procedure, easy separation, and an eco-friendly procedure, and it shows good reaction times, good to high yields, inexpensive and practicability procedure, and high efficiency.

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