Publicacions

@article{Barzallo2024,

title = {On-site extraction using a 3D printed device coated with Zn/Co-ZIF-derived carbon followed by an on-line SIA-HPLC-FL system for fluoroquinolones determination in wastewater},

author = {D. Barzallo and A. Están and N. Crespí and C. Palomino and G. Turnes and E. Palacio and L. Ferrer},

doi = {https://doi.org/10.1016/j.talanta.2024.125897},

year  = {2024},

date = {2024-06-01},

urldate = {2024-06-01},

journal = {Talanta},

volume = {273},

pages = {125897},

abstract = {A 3D printed device covered with Zn/Co-ZIF-derived carbon allows the on-site extraction of fluoroquinolones (FQs) from wastewater, avoiding the sample transportation to the laboratory, and the subsequent elution, separation and determination using an on-line flow system based on sequential injection analysis (SIA) coupled to HPLC-FL. Several parameters that affect the extraction efficiency and desorption were optimized including the sorption phase immobilization technique on the 3D device, extraction time, pH effect, sample volume as well as the type of eluent, eluent volume, and flow rate. Under optimum conditions, detection limits of 3–9 ng L−1 were achieved for norfloxacin, ciprofloxacin, danofloxacin, enrofloxacin and difloxacin. The precision expressed as relative standard deviation (%RSD, n = 3), showed intraday and interday ranges of 1.5–5.3% and 2.8–5.7%, respectively, demonstrating a good precision of the proposed methodology. To assess matrix effects and accuracy of the proposed method in real samples, recovery studies were performed without and with FQs spiked at different concentrations (0.5–10 μg L−1) to wastewater samples, showing good recoveries in the range of 91–104%. The results allow to confirm the applicability of MOF-derived carbons as adsorbents for on-site extraction, and the satisfactory separation and quantification of FQs by a SIA-HPLC-FL on-line system after their desorption with small eluent volumes.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Sanz2024,

title = {Boosting the activity of UiO-66 (Zr) by defect engineering: efficient aldol condensation of furfural and MIBK for the production of bio jet-fuel precursors},

author = {María Sanz and Pedro Leo and Carlos Palomino and Marta Paniagua and Gabriel Morales and Juan A Melero},

doi = {https://doi.org/10.1039/D3GC05022J},

year  = {2024},

date = {2024-05-30},

urldate = {2024-05-30},

journal = {Green Chemistry},

volume = {26},

pages = { 7337-7350},

abstract = {The production of jet-fuel precursors from furfural via aldol-condensation with methyl-isobutyl ketone (MIBK) over defect-engineered UiO-66(Zr) catalysts is presented. The catalysts are prepared using formic acid (FA), trifluoroacetic acid (TFA) and HCl as synthesis modulators, leading to the incorporation of defects on the microcrystalline structure of the metalorganic framework (MOF) material, which dramatically boosts the catalytic performance. An extensive characterization of the modified catalysts by means of X-ray diffraction (XRD), argon adsorption isotherm, thermogravimetry (TGA), transmission electron microscopy, and FTIR spectroscopy of adsorbed acetonitrile, confirmed the incorporation of missing-linker and missing-node defects within the MOF structure, enabling the explanation of the enhancement in the catalytic process. The analysis of the reaction kinetics evidences that, working under moderate temperature conditions, conversion of furfural and selectivity to the desired adduct (FuMe) close to 100% can be achieved, avoiding the formation of degradation and bulkier compounds. Finally, despite the generation of defects within the UiO-66(Zr) structure, the resultant catalyst displays good reusability in low furfural concentration mediums.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{García-Rojas2024,

title = {Catalytical advantages of Hf-MOFs in benzaldehyde acetalization},

author = {Elena García-Rojas and Jesús Tapiador and Pedro Leo and Carlos Palomino and Carmen Martos and Gisela Orcajo},

doi = {https://doi.org/10.1016/j.cattod.2024.114705},

year  = {2024},

date = {2024-05-15},

urldate = {2024-05-15},

journal = {Catalysis Today},

volume = {434},

pages = {114705},

abstract = {The potential use of acetals as bioadditives based on sustainable feedstocks in the automotive industry is of great interest. If such feedstock is a residual stream, the process would represent a dual environmental challenge, such as the valorization of glycerol obtained as a by-product of biodiesel to produce acetals. There are just scarce works about this synthetic route due to the challenge in finding efficient catalytic converters for glycerol valorization in a single process. Herein four different Metal-Organic Frameworks (MOFs) are evaluated as heterogeneous catalysts for the acetalization reaction of benzaldehyde with methanol, specifically, two structures, MOF-808 and UiO-66, containing two structural metal ions, zirconium and hafnium. The aim of this work is to investigate the influence of the MOF structure, the metallic active sites and the reaction conditions on the catalytic performance of this acetal production-type reaction. Furthermore, the recyclability of the catalyst is evaluated, and a potential reaction mechanism is suggested. As relevant results, Hf-MOFs showed higher benzaldehyde conversion than Zr-based ones, and significant improvements in reaction conditions were achieved, such as a significant reduction in catalyst loading of 99.6 % using UiO-66-Hf, and an optimization of reagent ratios reducing methanol consumption by 50 % for a 92 % of benzaldehyde conversion. The Brønsted character of UiO-66-Hf seems to enhance the reaction rate more than the metal center accessibility and larger pore volumes offered by MOF-808.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{González-Rodal2024,

title = {Amino-grafted basic mesoporous silicas: a type of highly performant catalysts for the green synthesis of 2-amino-4H-chromenes},

author = {D. González-Rodal and M. Godino-Ojer and C. Palomino-Cabello and G. Turnes-Palomino and A.J López-Peinado and E. Pérez-Mayoral},

doi = {https://doi.org/10.1016/j.cattod.2024.114515},

year  = {2024},

date = {2024-03-15},

urldate = {2024-03-15},

journal = {Catalysis Today},

volume = {430},

pages = {114515},

abstract = {Novel series of amino-grafted mesoporous silica materials applied to the green and efficient synthesis of 2-amino-4H-chromenes, from salicylaldehydes and ethyl cyanoacetate, under mild and free-solvent conditions, is herein reported for the first time. These catalysts are easily prepared by using the post-synthetic method, by functionalizing the SBA-15 silica with the corresponding amino silanes. The observed catalytic performance is mainly controlled by the type and concentration of basic sites. The methodology herein reported could be considered as an environmentally friendly alternative for the selective chromene synthesis, which allows to achieve high yields in short reaction times using notably small amounts of the catalysts. The experimental results are also supported with theoretical calculations, which suggest that the amine groups at the silica surface are behind the observed catalytic performance with the assistance of the silica matrix.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Bauzá2024,

title = {Multifunctional HKUST-1-3D-printed device for the simultaneous extraction of hydrocarbons and dyes from water},

author = {M. Bauzá and N. Munar and A. Figuerola and G. Turnes and C. Palomino},

doi = {https://doi.org/10.1016/j.jwpe.2024.104890},

year  = {2024},

date = {2024-01-29},

urldate = {2024-01-29},

journal = {Journal of Water Process Engineering},

volume = {58},

pages = {104890},

abstract = {Herein, we report a MOF polymer coating and in-situ growth mixed strategy to fabricate a multifunctional floating 3D printed device for simultaneous hydrocarbon and dye removal. Due to the superhydrophobic properties (water contact angle = 151o) of the upper part of the device, it was applied for the removal of oil from water, obtaining excellent separation efficiency (from 90 to 98.6 %) for n-hexane, decane, dodecane and hexadecane. In addition, this part of the device showed excellent reusability, maintaining its separation efficiency of hexane/water above 95 % with a relative standard deviation of 1.0 % after 25 consecutive extraction cycles. The lower part of the multifunctional device, coated with HKUST-1 synthesized by in-situ growth, was tested for methylene blue dye removal, demonstrating fast kinetics adsorption (percentage of removal higher than 90 % in 2 h) due to the combination of electrostatic and π-π interactions between HKUST-1 and the dye. Furthermore, this 3D support showed high versatility, exceeding a 92 % extraction capacity for various dyes (malachite green, crystal violet and methyl violet), with the advantage of being easily regenerated several times by a simple regrowth procedure. Finally, the complete 3D-modified device was tested for the simultaneous extraction of hydrocarbons and dyes from real groundwater sample with excellent results.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Cabello2023,

title = {Thiol-Functionalized MIL-100(Fe)/Device for the Removal of Heavy Metals in Water},

author = {D.R. Sáenz-García and Andreu Figuerola and Gemma Turnes-Palomino and Luz O. Leal and Carlos Palomino-Cabello},

doi = {https://doi.org/10.1021/acs.inorgchem.3c01544},

year  = {2023},

date = {2023-11-18},

urldate = {2023-11-18},

journal = {Inorganic Chemistry},

volume = {62},

issue = {48},

pages = {19404–19411},

abstract = {The preparation of a functional device based on a functionalized MIL-100(Fe) metal–organic framework for the solid-phase extraction of heavy metals is reported. By a simple and easy straightforward grafting procedure, a thiol-functionalized MIL-100(Fe) material (MIL-100(Fe)-SH) with a S/Fe ratio of 0.80 and a surface area of 840 m2 g–1 was obtained. MIL-100(Fe)-SH exhibited a higher Hg(II) extraction (96 ± 5%) than that of MIL-100(Fe) (78 ± 4%) due to the interaction between thiol groups and Hg(II) ions. For practical applications, the obtained MIL-100(Fe)-SH was integrated by a simple method to a 3D printed support based on a matrix of interconnected cubes using poly(vinylidene fluoride) as binder, obtaining a functional device that simultaneously acts as stirrer and sorbent. The developed device showed high efficiency for the removal of Hg(II), good reusability, and excellent performance for the simultaneous preconcentration and further detection and quantification of Hg(II), Pb(II), and As(V) in tap, well, and lake water samples.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Vargas-Muñoz2023,

title = {A sampling platform incorporating 3D-printed paddles-stirrers coated with metal-organic framework MIL-100(Fe) for in-situ extraction of phenolic pollutants in biodigester supernatant and wastewater effluent samples},

author = {M.A. Vargas-Muñoz and C. Palomino and G. turnes and E. Palacio},

doi = {https://doi.org/10.1016/j.jece.2023.110503},

year  = {2023},

date = {2023-10-05},

journal = {Journal of Environmental Chemical Engineering},

volume = {11},

issue = {5},

pages = {110503},

abstract = {In this work, a portable paddle stirrer platform for solid-phase extraction of chlorophenols, p-nitrophenol, and bisphenol A is presented. These compounds are important environmental pollutants and toxic inhibitors of the anaerobic treatment of wastewater. The platform integrates 3D-printed paddle stirrers coated with the metal-organic framework MIL-100(Fe), which is prepared in 10 min using a green microwave-assisted synthesis. This coated stirrer serves as an adsorbent for the preconcentration of phenols. The device is assembled with an electric motor that agitates the sample in a sample container. The sampler can be used for in-situ extraction of the analytes, eliminating the need for transporting samples to the laboratory. The analytes are eluted through ultrasonic desorption before analysis by HPLC-DAD. An exhaustive study of the stirring and extraction parameters was conducted. Under optimum conditions, the detection limits ranged from 0.3 to 1.7 μg L−1, and the precision, expressed as the relative standard deviation, showed intraday and interday ranges of 1.2–5.1% and 4.5–6.8%, respectively. The accuracy was evaluated using spiked samples of wastewater effluent and biodigester supernatant, and it provided relative recoveries in the range of 91.5–108.5%.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Gómez-Lobon2023,

title = {A study of cadmium yellow paints from Joan Miró’s paintings and studio materials preserved at the Fundació Miró Mallorca},

author = {M. Gómez-Lobon and M- Ghirardello and E. Juncosa-Darder and C. Palomino-Cabello and M. Bauzá and M. Cotte and A. Burnstock and A. Nevin and S.R. Amato and F.C. Izzo and D. Comelli},

doi = {https://doi.org/10.1186/s40494-023-00987-4},

year  = {2023},

date = {2023-07-17},

urldate = {2023-07-17},

journal = {Heritage Science},

volume = {11},

number = {145},

abstract = {The deterioration of cadmium yellow paints in artworks by Joan Miró (1893–1983) and in painting materials from his studios in Mallorca (Spain) was investigated. Analysis of samples from Miró’s paintings and from paint tubes and palettes showed that degraded paints are composed of poorly crystalline cadmium sulfide/zinc cadmium sulfide (CdS/Cd1−xZnxS) with a low percentage of zinc, in an oil binding medium. Cadmium sulfates were identified as the main deterioration products, forming superficial white crusts detected using SR µXANES and µXRD techniques. Time-resolved photoluminescence measurements demonstrated that highly degraded samples display a pink/orange emission from the paint surface with a microsecond lifetime, a phenomenon observed in other degraded cadmium yellow paints. In agreement with recent studies on altered cadmium paints, these results suggest that the stability of the paint is related to its manufacturing method, which affects the degree of crystallinity of the resulting pigment. This, together with the environmental conditions in which artworks have been exposed, have induced the degradation of yellow paints in Miró’s artworks. It was finally noted that the paints exhibiting alteration in the analysed Miró artworks have a chemical composition that is very similar to the tube paint ‘Cadmium Yellow Lemon No. 1’ produced by Lucien Lefebvre-Foinet. Indeed, paint tubes from this brand were found in the studio, linking the use of this product with Miro’s degraded artworks.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Crespí-Sánchez2023,

title = {Sulfonic-functionalized MIL-100-Fe MOF for the removal of diclofenac from water},

author = {N. Crespí-Sánchez and G. Turnes-Palomino and C. Palomino-Cabello},

doi = {https://doi.org/10.1016/j.micromeso.2022.112398},

year  = {2023},

date = {2023-01-15},

urldate = {2023-01-15},

journal = {Microporous and Mesoporous Materials},

volume = {348},

pages = {112398},

abstract = {In this work, a novel adsorbent (MIL-100-Fe-AMSA), for the removal of the nonsteroidal anti-inflammatory drug sodium diclofenac (DCF), was prepared by grafting aminomethanesulfonic acid to the open iron sites in a porous MIL-100-Fe MOF obtained by a green microwave-assisted synthesis. The obtained materials were characterized by XRD, N2 adsorption-desorption, FTIR spectroscopy of adsorbed CO, electron microscopy and EDS spectroscopy. MIL-100-Fe-AMSA showed fast adsorption kinetics and an excellent maximum adsorption capacity of 476 mg/g. Synergistic effect of H-bonding, between the electronegative ionized –SO3H groups of MIL-100-Fe-AMSA and –NH group of DCF, and π−π interactions between the aromatic rings that are present in both MOF and pollutant, is probably the main mechanism of adsorption. In addition, the developed functionalized-MOF showed excellent reusability for at least five consecutive adsorption-desorption cycles, demonstrating its stability and potential for the removal of DCF. For practical applications, the prepared MIL-100-Fe-AMSA was incorporated into a 3D printed column for flow-through solid-phase extraction of pharmaceuticals pollutants before HPLC determination. The functional device showed excellent performance for the preconcentration and further detection and quantification of ketoprofen and DCF pollutants.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Bauzá2022,

title = {Hypercrosslinked polymer derived carbon@ MIL-100 magnetic material for the enhanced extraction of diclofenac},

author = {M. Bauzá and G. {Turnes-Palomino} and C. {Palomino-Cabello}},

doi = {https://doi.org/10.1016/j.seppur.2022.122211},

year  = {2022},

date = {2022-12-15},

urldate = {2022-12-15},

journal = {Separation and Purification Technology},

volume = {303},

number = {122211},

abstract = {Herein we report for the first time the preparation of a magnetic hybrid carbon@MOF material by combining hypercrosslinked polymer-derived carbon and MIL-100(Fe) MOF. FeCl3, used as catalyst for the synthesis of the benzene-based hypercrosslinked polymer by Friedel-Crafts reaction, was reused for the preparation of a magnetic carbon with a high amount of iron particles, which in turn acted as precursor for the in situ growth of MIL-100(Fe) MOF on the carbon. The effect of the ligand amount and the transformation time in the conversion process was studied by X-ray diffraction and N2 adsorption–desorption isotherms. The developed hybrid material (C-BHCP@MIL-100(Fe)) was evaluated for the extraction of the emerging pollutant diclofenac (DCF) in dispersive mode and the adsorbent was easily retrieved by using an external magnet. The adsorption of DCF by C-BHCP@MIL-100(Fe) fitted the pseudo-second order kinetic model and the Langmuir isothermal model, with a maximum adsorption capacity of 210 mg/g, which is higher than many of the values of DCF adsorption capacity reported in the literature for magnetic adsorbents. The good extraction performance could be attributed to the high surface area and mesoporosity of the obtained hybrid material along with the coexistence of multiple π-π interactions and H-bond interactions between the DCF and the adsorbent. In addition, excellent reusability with a variation of a 2.2 % for 5 consecutive DCF extraction cycles, was obtained, demonstrating the potential of the developed carbon@MOF hybrid material for the removal of DCF and other organic pollutants. The developed synthesis approach can be extended to the preparation of other hypercrosslinked polymer derived carbon@MOFs with great potential for environmental applications.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{nokey,

title = {Carbon@ ceramic 3D printed devices for bisphenol A and other organic contaminants extraction},

author = {A. Figuerola and F. Rodríguez and C. Palomino-Cabello and G. Turnes-Palomino},

doi = {https://doi.org/10.1016/j.seppur.2022.121749},

year  = {2022},

date = {2022-10-15},

urldate = {2022-10-15},

journal = {Separation and Purification Technology},

volume = {299},

pages = {121749},

abstract = {A high efficient and versatile extraction device was prepared by coating a durable 3D printed ceramic support with a polymer-derived porous carbon. The ceramic support was coated with polyvinylidene fluoride (PVDF), which acted as binder and carbon source simultaneously, allowing to obtain a high robust and functional carbon coated device in a direct and very simple way. The so prepared device was evaluated for the extraction of the endocrine disrupting phenol, bisphenol A. It showed fast adsorption kinetics, high extraction capacity (122.5 mg g−1), and excellent reusability, keeping removal percentages above 90% after 10 consecutive extraction cycles. Carbon@ceramic 3D printed devices also showed good performance for the individual and simultaneous extraction of other phenolic compounds (4-tert-octylphenol and 4-tert-butylphenol), pharmaceutical products (ibuprofen, diclofenac and acetaminophen), and organic dyes (malachite green and methylene blue) in real water samples, demonstrating its potential for the removal of organic pollutants from water.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{delCampo2022,

title = {Boosting the sensitivity of paper-based biosensors with polymeric water-soluble reservoirs},

author = {M.M. González-Campo and Alejandra Alba-Patiño and Carlos Palomino and Marta Bauzá and Estrella Rojo-Molinero and Antonio Oliver and Gemma Turnes and Roberto {de la Rica}},

doi = {https://doi.org/10.1016/j.snb.2021.131214},

year  = {2022},

date = {2022-03-01},

urldate = {2022-03-01},

journal = {Sensors and Actuators B: Chemical},

volume = {354},

pages = { 131214},

abstract = {Storing highly concentrated reagents and releasing them with high efficiency is crucial for developing highly sensitive biosensors. However, the performance of reservoirs in biosensors made of filter paper is limited by the intrinsic physicochemical properties of untreated cellulose. In this article, the impact of 9 different polymer modifications on the storage and release of enzymes and nanoparticles in paper-based biosensors is studied for the first time. Carboxymethylcellulose, polyvinyl alcohol, carrageenan, and chitosan, which contain hydroxyl groups, yielded paper-based reservoirs with the highest concentration of reagents in them. Polymer reservoirs made of carboxymethylcellulose release enzymes rapidly and at high concentration, which results in colorimetric glucose biosensors with an ultralow limit of detection of 0.005 mM. Reservoirs made with a blend of polymers concentrate antibody-decorated nanoparticles and decrease 10 times the limit of detection of a model immunosensor. An adaption of this design was used for detecting the pathogen Klebsiella pneumoniae in urine samples from hospital patients at the infectious dose threshold rapidly and with high specificity. The fabrication of the reservoirs only requires drop-casting a polymer solution on the paper and drying. This procedure is compatible with the fabrication of origami biosensors, which are made from a single piece of filter paper.



},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{delRio2022,

title = {Zinc/Iron mixed-metal MOF-74 derived magnetic carbon nanorods for the enhanced removal of organic pollutants from water},

author = {M. del Rio and J. C. Grimalt-Escarabajal and G. Turnes-Palomino and C. Palomino-Cabello},

doi = {https://doi.org/10.1016/j.cej.2021.131147},

year  = {2022},

date = {2022-01-15},

urldate = {2022-01-15},

journal = {Chemical Engineering Journal},

volume = {428},

pages = {131147},

abstract = {The preparation of magnetic porous carbon from a mixed-metal-organic framework by a two steps simple method is reported. By taking advantage that the calcination process at high temperature under inert atmosphere of zinc and iron MOFs results in the formation of carbons with excellent porosity and magnetic properties, respectively, MOF-74(Zn/Fe) prepared at room temperature was used as precursor for the synthesis of high porous magnetic carbons. The prepared materials were characterized by XRD, FTIR spectroscopy of adsorbed CO, SEM, TEM, N2 adsorption-desorption, Zeta potential analysis and energy dispersive X-ray spectroscopy. To check the potential as sorbent of the MOF-74(Zn/Fe)-derived magnetic porous carbon, adsorption isotherms of methylene blue and methyl orange were recorded and compared with those obtained using a non-magnetic MOF-74(Zn)-derived porous carbon. The maximum adsorption capacity for methylene blue and methyl orange was 370 and 239 mg g−1, which are higher than those reported for other magnetic adsorbents. The study of the extraction performance of the dyes at different pH, along with Zeta potential analysis, revealed that electrostatic and π-π interactions might be involved in the dyes removal. C-MOF-74(Zn/Fe) material showed good reusability with no apparent loss in dye extraction capacity after five cycles and the ability to treat large volume of dye polluted water. In addition, the developed C-MOF-74(Zn/Fe) showed excellent performance for the simultaneous removal of different endocrine disrupting phenols (bisphenol A, 4-tert-butylphenol and 4-tert-octylphenol) from water, demonstrating that mixed-metal-organic frameworks are promising precursors for the preparation of a wide number of new porous materials.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Leo2021,

title = {Catalytic activity and stability of sulfonic-functionalized UiO-66 and MIL-101 materials in friedel-crafts acylation reaction},

author = {P. Leo and N. Crespí and C. Palomino and A. Martín and G. Orcajo and G. Calleja and F. Martinez},

doi = {https://doi.org/10.1016/j.cattod.2021.10.007},

year  = {2021},

date = {2021-10-12},

urldate = {2021-10-12},

journal = {Catalysis Today},

abstract = {Sulfonic-containing UiO-66 and MIL-101 MOF materials, prepared by direct synthesis with a sulfonic acid-including benzene dicarboxylate (SO3H-BDC) linker, have been evaluated as acid catalysts in Friedel–Crafts acylation of anisole with acetic anhydride. The catalytic activity of these materials was compared to other conventional acidic sulfonic heterogeneous catalysts, such as commercial Nafion-SAC-13 and Amberlyst-15. The catalytic performance of MOF materials was significantly dependent on their textural properties and the availability of sulphonic acid groups. MIL-101-SO3H material displayed a remarkable anisole conversion and specific activity per sulfonic acid centre due to its open structure and multimodal pore size distribution. The inherent properties of MIL-101-SO3H material allowed a more sustainable catalyst regeneration than those used for conventional heterogeneous catalysts due to the deposition of reagents and products, in particular poly-acetylated compounds. MIL-101-SO3H proved an easy recovery and reusability in successive runs without any loss of activity. These promising results evidenced the potential of MIL-101-SO3H as an alternative catalyst for acid-catalyzed reactions.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Sánchez2021,

title = {TiO2 derived from NTU-9 metal-organic framework as highly efficient photocatalyst},

author = {N. Crespí-Sánchez and G. Turnes-Palomino and C. Palomino-Cabello},

doi = {https://doi.org/10.1016/j.mseb.2021.115424},

year  = {2021},

date = {2021-08-26},

urldate = {2021-08-26},

journal = {Materials Science and Engineering: B},

volume = {273},

pages = { 115424},

abstract = {Sulfonic-containing UiO-66 and MIL-101 MOF materials, prepared by direct synthesis with a sulfonic acid-including benzene dicarboxylate (SO3H-BDC) linker, have been evaluated as acid catalysts in Friedel–Crafts acylation of anisole with acetic anhydride. The catalytic activity of these materials was compared to other conventional acidic sulfonic heterogeneous catalysts, such as commercial Nafion-SAC-13 and Amberlyst-15. The catalytic performance of MOF materials was significantly dependent on their textural properties and the availability of sulphonic acid groups. MIL-101-SO3H material displayed a remarkable anisole conversion and specific activity per sulfonic acid centre due to its open structure and multimodal pore size distribution. The inherent properties of MIL-101-SO3H material allowed a more sustainable catalyst regeneration than those used for conventional heterogeneous catalysts due to the deposition of reagents and products, in particular poly-acetylated compounds. MIL-101-SO3H proved an easy recovery and reusability in successive runs without any loss of activity. These promising results evidenced the potential of MIL-101-SO3H as an alternative catalyst for acid-catalyzed reactions.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{delRio2021,

title = {Zinc/Iron mixed-metal MOF-74 derived magnetic carbon nanorods for the enhanced removal of organic pollutants from water},

author = {M. del Rio and J.C. Grimalt-Escarabajal and G. Turnes-Palomino and C. Palomino-Cabello},

doi = {https://doi.org/10.1016/j.cej.2021.131147},

year  = {2021},

date = {2021-07-06},

urldate = {2021-07-06},

journal = {Chemical Engineering Journal },

pages = {131147},

abstract = {The preparation of magnetic porous carbon from a mixed-metal-organic framework by a two steps simple method is reported. By taking advantage that the calcination process at high temperature under inert atmosphere of zinc and iron MOFs results in the formation of carbons with excellent porosity and magnetic properties, respectively, MOF-74(Zn/Fe) prepared at room temperature was used as precursor for the synthesis of high porous magnetic carbons. The prepared materials were characterized by XRD, FTIR spectroscopy of adsorbed CO, SEM, TEM, N2 adsorption-desorption, Zeta potential analysis and energy dispersive X-ray spectroscopy. To check the potential as sorbent of the MOF-74(Zn/Fe)-derived magnetic porous carbon, adsorption isotherms of methylene blue and methyl orange were recorded and compared with those obtained using a non-magnetic MOF-74(Zn)-derived porous carbon. The maximum adsorption capacity for methylene blue and methyl orange was 370 and 239 mg g-1, which are higher than those reported for other magnetic adsorbents. The study of the extraction performance of the dyes at different pH, along with Zeta potential analysis, revealed that electrostatic and π-π interactions might be involved in the dyes removal. C-MOF-74(Zn/Fe) material showed good reusability with no apparent loss in dye extraction capacity after five cycles and the ability to treat large volume of dye polluted water. In addition, the developed C-MOF-74(Zn/Fe) showed excellent performance for the simultaneous removal of different endocrine disrupting phenols (bisphenol A, 4-tert-butylphenol and 4-tert-octylphenol) from water, demonstrating that mixed-metal-organic frameworks are promising precursors for the preparation of a wide number of new porous materials.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Pérez-Mayoral2021,

title = {Amino-grafted Cu and Sc Metal-Organic Frameworks involved in the green synthesis of 2-amino-4H-chromenes. Mechanistic understanding},

author = {D. González-Rodal and G. Turnes-Palomino and C. Palomino-Cabello and E. Pérez-Mayoral},

doi = {https://doi.org/10.1016/j.micromeso.2021.111232},

year  = {2021},

date = {2021-06-10},

urldate = {2021-06-10},

journal = {Microporous and Mesoporous Materials},

volume = {323},

pages = {111232},

abstract = {In this work, we report for the first time a new methodology for the eco-synthesis of 2-amino-4H-chromenes 1, from salycilaldehydes and cyano compounds, under solvent-free and mild conditions, using amino-grafted MOFs as catalysts. The selected MOFs − commercial CuBTC and MIL-100(Sc) previously synthetized in our laboratories − can be easily functionalyzed with amines of different nature showing notable differences in their composition and textural properties. The total or partial functionalization of the metal centers in starting MOFs is strongly depending on the functionalization method used. Our results indicate that the catalytic performance is mainly conditioned by the type and concentration of basic sites, porosity of the samples barely showing any influence. The methodology herein reported could be considered as an environmental friendly alternative to the selective chromene synthesis, which allows to achieve high yields in relatively short reaction times (up to 90% over 1 h), using notably small amounts of easily prepared catalysts.



Furthermore, our experiments in combination with theoretical calculations strongly suggest that free-amine groups in ethylenediamine (EN) functionalized catalysts can act either as individual catalytic sites, as for EN-M/CuBTC sample, in which all metal centers are functionalized with EN ligands and shows the highest concentration of basic catalytic sites, or acting in cooperation with the closest metal centers in samples partially functionalized, as in the case of EN/CuBTC sample.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Bauza2021,

title = {MIL-100(Fe)-derived carbon sponge as high-performance material for oil/water separation},

author = {M. Bauza and G. Turnes-Palomino and C. Palomino-Cabello },

doi = {https://doi.org/10.1016/j.seppur.2020.117951},

year  = {2021},

date = {2021-02-15},

urldate = {2021-02-15},

journal = {Separation and Purification Technology},

volume = {257},

pages = {117951-117958},

abstract = {High hydrophobic and oleophilic hybrid porous sponges were prepared by coating low cost commercial melamine-formaldehyde sponges with a metal-organic framework (MOF) derived porous carbon. A mesoporous metal-organic framework MIL-100(Fe), obtained under mild conditions, was used as precursor material to obtain highly porous carbon, which was incorporated by a simple method onto the three-dimensional skeleton of the commercial sponge. Due to the porous structure and high hydrophobic (water contact angle of 145 ± 6°) and oleophilic (oil contact angle of 0°) properties of the developed hybrid sponges, they were successfully applied for oil-water separation. The carbon coated sponge exhibited excellent selectivity, good absorption capacity of different oils and the advantage of being easily regenerable. Moreover, the hybrid sponge was used in conjunction with a vacuum system for continuous separation of oil pollutants from the water surface showing excellent oil-absorption abilities even in the case of real saltwater samples.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Mendiola-Álvarez2021,

title = {Comparison of photocatalytic activity of αFe2O3-TiO2/P on the removal of pollutants on liquid and gaseous phase},

author = {S. Y. Mendiola-Álvarez and J. Araña and J.M. Doña-Rodríguez and A. Hernández-Ramírez and G. Turnes-Palomino and C. Palomino-Cabello and L. Hinojosa-Reyes},

doi = {https://doi.org/10.1016/j.jece.2020.104828},

year  = {2021},

date = {2021-02-01},

urldate = {2021-02-01},

journal = { Journal of Environmental Chemical Engineering},

volume = {9},

number = {1},

pages = {104828},

abstract = {The photocatalytic activity of mixed oxide α-Fe2O3/TiO2 doped with P (αFe-Ti/P) was evaluated on diuron degradation in aqueous solution and NOx oxidation under UV and visible light irradiation. The microwave-assisted sol-gel route was used to prepare the αFe-Ti/P catalyst. The TiO2 doped with P (Ti/P), α-Fe2O3/TiO2 (αFe-Ti) and TiO2 (Ti) were also synthesized under similar conditions as reference catalysts. The samples were characterized by different instrumental techniques (XRD, UV–VIS with DRS, PL, N2 adsorption, pHPZC, XPS, HRTEM, and FTIR). The photocatalytic activity on diuron degradation in aqueous media under UV and visible light followed the tendency Ti/P > αFe-Ti/P > αFe-Ti > Ti. The characteristics of the catalysts that enhanced photocatalytic reaction in liquid media were the low value of point of zero charge associated with Brønsted surface acid sites, narrow band-gap, small crystallite size, reduced e-/h+ recombination rate, and large surface area attributed to the P incorporation on the TiO2. On the other hand, the NOx oxidation on the gas-phase reaction under UV and visible light followed the trend αFe-Ti > Ti > Ti/P > αFe-Ti/P. These results could be related to the assemble of αFe2O3 nanoparticles with TiO2 to form αFe2O3/TiO2 heterostructure that extended the optical absorption in the visible range and increased the basicity of the prepared TiO2 based material (Lewis basic surface sites).},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Martínez-Pérez-Cejuelaa2020,

title = {Determination of benzomercaptans in environmental complex samples by combining zeolitic imidazolate framework-8-based solid-phase extraction and high-performance liquid chromatography with UV detection},

author = {H. Martínez-Pérez-Cejuelaa and O. Mompó-Roselló and N. Crespí-Sánchez and C. Palomino-Cabello and M. Catalá-Icardo and E. Simó-Alfonso and J. M. Herrero-Martínez},

doi = {https://doi.org/10.1016/j.chroma.2020.461580},

year  = {2020},

date = {2020-11-08},

urldate = {2020-11-08},

journal = {Journal of Chromatography A},

volume = {1631},

pages = {461580-461588},

abstract = {In this work, the synthesis of zeolitic imidazolate framework-8 (ZIF-8) crystals and their subsequent application as effective sorbents for extraction and preconcentration of several benzomercaptans from environmental complex samples is described. These materials were prepared by solvothermal approach varying the concentration of n-butylamine modulator to modify the surface of the metal-organic framework. The resulting materials were characterized by scanning and transmission electron microscopy, powder X-ray diffraction and Fourier transform infrared spectroscopy. The ZIF-8 material that gave the best features was selected as extractive phase and the influence of various parameters (sample pH and elution solvent composition, among others) on the extraction efficiency of target compounds were investigated. Under the optimal conditions of the method, the tested analytes (2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercapto-6-nitrobenzothiazole) were retained and eluted quantitatively with alkaline 50:50 (v:v) methanol-water mixture. Using the proposed method, low limits of detection, in the range of 16–21 ng L−1 for aqueous samples and 0.4–0.5 µg kg−1 for soil samples, were achieved whereas the precision (expressed as relative standard deviation) was lower than 7%. The resulting solid-phase extraction protocol, using the zeolitic material as sorbent, was combined with liquid chromatography and ultraviolet-vis detector and successfully applied to determine traces of these organic pollutants in environmental samples.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Peña-Velasco2020,

title = {Iron metal-organic framework supported in a polymeric membrane for solid-phase extraction of anti-inflammatory drugs},

author = {G. Peña-Velasco and L. Hinojosa-Reyes and M. Escamilla-Coronado and G. Turnes-Palomino and C. Palomino-Cabello and J. L. Guzmán-Mara},

doi = {https://doi.org/10.1016/j.aca.2020.09.049},

year  = {2020},

date = {2020-09-26},

journal = {Analytica Chimica Acta},

abstract = {A solid-phase extraction methodology using a MIL-101(Fe)/PVDF membrane was proposed as a useful alternative for the simultaneous determination of naproxen, diclofenac, and ibuprofen, three anti-inflammatory drugs (NSAIDs), in wastewater samples by HPLC-CCD analysis. The MIL-101(Fe) was prepared by a rapid microwave-assisted method and supported in a polymeric PVDF membrane. The prepared material was characterized by X-ray diffraction (XRD), nitrogen adsorption-desorption, scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy (FT-IR). The factors that affect the extraction of the NSAIDs using the MIL-101(Fe)/PVDF membrane as the sample volume, the solution pH and the elution solvent were studied in detail. The selected conditions were 50 mL of sample solution at pH 3 and 5 mL of methanol: acetone (30:70, v/v) acidified with formic acid at 2% as elution solvent. The analytical method was linear with determination coefficients (r2 ≥ 0.998) in the calibration ranges from 2-100 ng mL-1 for naproxen, 20-200 ng mL-1 for diclofenac, and 100-300 ng mL-1 for ibuprofen. The intra and inter-day precision (repeatability and reproducibility, respectively) of the method (RSD%, n = 5) were lower than 4.8% and 7.1%, respectively. The accuracy reported as recovery percentages ranged from 82 to 118%, and the limits of detection were between 1.7 and 32.3 ng mL-1. Moreover, MIL-101(Fe)/PVDF membrane exhibited improved adsorption efficiency compared to that of its analog MIL-101(Cr)/PVDF and the pristine PVDF membranes, obtaining in an easy and rapid (60 min) way a low-cost and low-toxic adsorbent with excellent stability, reusability, mechanic resistance, and simple operation which shows excellent performance.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Mediola-Alvarez2020,

title = {Magnetic porous carbons derived from cobalt(ii)-based metal–organic frameworks for the solid-phase extraction of sulfonamides},

author = {S. Y. Mediola-Alvarez and G. Turnes-Palomino and J. Guzmán-Mar and A. Hernández-Ramírez and L. Hinojosa-Reyes and C. Palomino-Cabello},

doi = {https://doi.org/10.1039/D0DT01215G},

year  = {2020},

date = {2020-06-05},

urldate = {2020-06-05},

journal = {Dalton Transactions},

volume = {49},

number = {26},

pages = {8959-8966},

abstract = {In this work, the dispersive solid-phase extraction of sulfonamide antibiotics was evaluated using magnetic porous carbons derived from cobalt(II)-based metal–organic frameworks. By direct carbonization under the inert atmosphere of Co-SIM-1, Co-MOF-74 and Co-DABCO MOFs, different magnetic porous carbons were prepared and characterized to study their structural, morphological, chemical and textural properties. Their performance for the simultaneous extraction of three sulfonamides (sulfadiazine, sulfamerazine and sulfamethazine), prior to HPLC analysis, was also evaluated, obtaining the best results (>95%) in the case of C/Co-SIM-1 carbon, probably due to its bimodal pore structure, high surface area and large amount of surface defects. Using this adsorbent, the effect of the solution pH and contact time on the adsorption of the sulfonamides, and the reusability of the carbon were studied.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Mendiola-Alvarez2020,

title = {Coupled heterogeneous photocatalysis using a P-TiO2-αFe2O3 catalyst and K2S2O8 for the efficient degradation of a sulfonamide mixture},

author = {S. Y. Mendiola-Alvarez and C. Palomino-Cabello and A. Hernández-Ramírez and G. Turnes-Palomino and J. L. Guzmán-Mar and L. Hinojosa-Reyes},

doi = {https://doi.org/10.1016/j.jphotochem.2020.112485},

year  = {2020},

date = {2020-05-01},

urldate = {2020-05-01},

journal = {Journal of Photochemistry and Photobiology A: Chemistry},

volume = {394},

pages = {112485-112461},

abstract = {Phosphorous-doped Ti-Fe mixed oxide (P-TiO2-αFe2O3) catalysts were prepared by the microwave-assisted sol-gel route and characterized using XRD, SEM, N2 physisorption, UV–vis diffuse reflectance, FTIR, and XPS. P-TiO2-αFe2O3 was evaluated during the degradation of a sulfonamide mixture (5 mg/L, each) under visible light. The photocatalytic process was optimized with a face-centered central composite design. Under optimal conditions (0.5 wt% of αFe2O3, pH 10, and 0.75 g/L of catalyst loading), the sulfate radical advanced oxidation process was carried out using 5 mM K2S2O8 (PS). P doping shifted the light absorption of P-TiO2-αFe2O3 in the visible light range owing to substitutional doping, while the coupling of P-TiO2 with α-Fe2O3 enhanced the absorption in the visible range, which resulted in an increase in the lifetime of the charge carriers and in a superior photoactivity of the P-TiO2-αFe2O3 catalyst in comparison to that of TiO2. The mineralization yield of the sulfonamides (SNs) mixture was enhanced in the presence of an electron acceptor (SO4−), allowing nearly 69 % within 300 min with the P-TiO2-αFe2O3/PS system, while P-TiO2-αFe2O3 and K2S2O8 oxidation achieved only 27 % and 21 %, respectively. The biodegradability index was 0.48 using the P-TiO2-αFe2O3/PS system, indicating a less toxic effluent than the original compounds. Recycling tests demonstrated that P-TiO2-αFe2O3 exhibits good stability in activating PS for SNs degradation during three cycles. Two main intermediates (pyrimidine and hydroquinone) and their hydroxylated re-arrangements were detected during the degradation of the SNs by the coupled process. Oxalic, oxamic, sulfonic, and acetic acids were also identified as by-products from the degradation of the SNs.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Safont2020,

title = {Brønsted acidity of H-[Ga]-ZSM-5 zeolites as determined by variable-temperature IR spectroscopy},

author = {A.C. Safont and C.P. Cabello and C.O. Areán and G.T. Palomino},

doi = {https://doi.org/10.1016/j.cattod.2019.10.015},

year  = {2020},

date = {2020-04-01},

urldate = {2020-04-01},

journal = {Catalysis Today},

volume = {345},

pages = {71-79},

abstract = {Protonic gallosilicates H-[Ga]-ZSM-5 were synthesized, following a hydrothermal procedure, from gels having Si/Ga ratios of 25, 50 and 75. Likewise, for comparison, protonic zeolites H-[Al]-ZSM-5 having Si/Al ratios of 25 and 50 were also prepared. Brønsted acidity of the structural Si(OH)Ga groups in the gallosilicates was studied by means of IR spectroscopy at a variable temperature (VTIR) using CO and N2 as probe molecules. This instrumental technique enables one simultaneous measurement of the bathochromic shift of the stretching OH mode, Δυ(OH), of the Brønsted acid group interacting (through hydrogen bonding) with the probe molecule and the corresponding standard enthalpy change, ΔH⁰, in the adsorption process. The results obtained clearly showed that the gallosilicates are distinctively less acidic than the aluminosilicates, whichever acidity indicator is used: Δυ(OH) either or ΔH⁰. Nevertheless, no change of Brønsted acid strength was found when changing the Si/Ga ratio.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{delRio2020,

title = {Metal–Organic Framework@Carbon Hybrid Magnetic Material as an Efficient Adsorbent for Pollutant Extraction},

author = {M. del Rio and G. T. Palomino and C. P. Cabello},

doi = {https://doi.org/10.1021/acsami.9b19722},

year  = {2020},

date = {2020-01-08},

journal = {ACS Applied Materials & Interfaces},

volume = {12},

number = {5},

pages = {6419-6425},

abstract = {The preparation of a hybrid magnetic metal–organic framework (MOF)@carbon from a MOF-derived porous carbon is reported. MOF-74(Co) is used as a precursor for the synthesis of a magnetic carbon with homogeneous cobalt particle distribution (C-MOF-74) by a direct carbonization step. The cobalt particles present in the carbon are partially converted to zeolitic imidazolate framework (ZIF)-67 by reaction with 2-methylimidazole to obtain a core–shell ZIF-67@C-MOF-74. The effect of the reaction time and 2-methylimidazole concentration in the conversion procedure is studied by X-ray diffraction and scanning microscopy. Because of its high surface area, dual porosity, and magnetic properties, ZIF-67@C-MOF-74 exhibits high extraction capacity (180 mg g–1), fast adsorption rate, and excellent recyclability for Congo red adsorption. In addition, the prepared material shows high efficiency in the extraction of different phenolic compounds. The developed procedure can be easily adapted to different carbons and MOFs, thus potentially enabling the preparation of a wide number of new hybrid materials.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Sánchez2019b,

title = {Carbon composite membrane derived from MIL-125-NH2 MOF for the enhanced extraction of emerging pollutants},

author = {Crespí-Sánchez, N. and Guzmán-Mar, J. L. and Hinojosa-Reyes, L. and Turnes-Palomino, G. and Palomino-Cabello, C.},

doi = {https://doi.org/10.1016/j.chemosphere.2019.05.173},

year  = {2019},

date = {2019-09-02},

urldate = {2019-09-02},

journal = {Chemosphere},

volume = {231},

pages = {510-517},

abstract = {Porous carbon derived from amine-functionalized MIL-125 metal-organic framework (C-MIL-125-NH2) was prepared by carbonization at high temperature under inert atmosphere, and used for adsorption of bisphenol A (BPA) and 4-tert-butylphenol (4-tBP). The obtained carbon showed bimodal porosity and fast extraction of both pollutants in batch conditions following a pseudo-second-order model. The adsorption mechanism was studied by the measurement of zeta potential, and the results suggested that π-π stacking interactions between the carbon material and the phenol molecules probably are the main sorption mechanism. The prepared C-MIL-125-NH2 was incorporated into mechanically stable membranes for flow-through solid-phase extraction of studied phenols prior to HPLC analysis. The hybrid material showed excellent permeance to flow, easy regeneration and good performance for the simultaneous enrichment of mixtures of BPA and 4-tBP, facilitating their determination when present at low concentration levels.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{D.2019,

title = {Hyperporous carbon-coated 3D printed devices},

author = {A. V. Medina D. and Figuerola, A. and Rodriguez, F. and Santos-Neto, A.J. and Palomino-Cabello, C and Turnes-Palomino, G. and Cerdá, V. and Maya, F. },

doi = {https://doi.org/10.1016/j.apmt.2018.11.001},

year  = {2019},

date = {2019-09-01},

urldate = {2019-09-01},

journal = {Applied materials today},

volume = {14},

pages = {29-34},

abstract = {3D printing by stereolithography (SLA) typically leads to low surface area materials, limiting the application of this advanced manufacturing technique for the extraction of environmental pollutants. Here, a simple and efficient procedure to immobilize highly porous materials on SLA 3D printed devices has been developed using a hypercrosslinked pyrrole-derived hyperporous carbon (HCP-carbon) with a surface area of 3361 m2·g−1. The HCP-carbon is directly immobilized to the soft and sticky surface of non-post cured SLA 3D printed devices. The HCP-carbon becomes permanently immobilized to the 3D printed device after UV post curing, obtaining a highly robust and efficient support for the removal of pollutants from water.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Maya2019,

title = {Immobilization of metal-organic frameworks on supports for sample preparation and chromatographic separation},

author = {Maya, F. and Palomino-Cabello, C. and Figuerola, A. and Turnes-Palomino, G. and Cerdà, V. },

doi = {https://dx.doi.org/10.1007/s10337-018-3616-z},

issn = {0009-5893},

year  = {2019},

date = {2019-09-01},

urldate = {2019-09-01},

journal = {Chromatographia},

volume = {82},

number = {1},

pages = {361-375},

abstract = {Metal–organic frameworks (MOFs) are porous crystalline materials with large surface areas, uniform pore size, and tunable selectivity. In the last few years, the number of analytical applications of MOFs has been growing constantly. However, the direct use of as-synthesized MOFs in packed column format is rather limited for analytical separations because of the small size and non-spherical shape of MOF crystals. In this review, we outline and critically discuss the advantages and limitations of the different methods described to immobilize MOFs into functional supports for analytical separations, including beads, monoliths, and fibers. These methods are based on embedding MOF crystals into functional supports, in situ MOF growth, controlled layer-by-layer MOF growth, or the in situ conversion of immobilized MOF metal oxide precursors. Representative examples of immobilized MOFs for sample preparation and chromatographic separation are overviewed. We also overview recent progress on the use of MOFs as precursors to obtain other functional materials such as layered double hydroxides or porous carbons.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Salazar-Beltrán2019,

title = {Automated on-line monitoring of the TiO2-based photocatalytic degradation of dimethyl phthalate and diethyl phthalate},

author = {Salazar-Beltrán, D. and Hinojosa-Reyes, L. and Maya-Alejandro, F. and Turnes-Palomino, G. and Palomino-Cabello, C and Hernández-Ramírez, A. and Guzmán-Mar, J.},

doi = {10.1039/c8pp00307f},

year  = {2019},

date = {2019-04-01},

urldate = {2019-04-01},

journal = {Photochemical & Photobiological Sciences},

volume = {18},

number = {4},

pages = {863-870},

abstract = {A fully automated on-line system for monitoring the TiO2-based photocatalytic degradation of dimethyl phthalate (DMP) and diethyl phthalate (DEP) using sequential injection analysis (SIA) coupled to liquid chromatography (LC) with UV detection was proposed. The effects of the type of catalyst (sol–gel, Degussa P25 and Hombikat), the amount of catalyst (0.5, 1.0 and 1.5 g L−1), and the solution pH (4, 7 and 10) were evaluated through a three-level fractional factorial design (FFD) to verify the influence of the factors on the response variable (degradation efficiency, %). As a result of FFD evaluation, the main factor that influences the process is the type of catalyst. Degradation percentages close to 100% under UV-vis radiation were reached using the two commercial TiO2 materials, which present mixed phases (anatase/rutile), Degussa P25 (82%/18%) and Hombikat (76%/24%). 60% degradation was obtained using the laboratory-made pure anatase crystalline TiO2 phase. The pH and amount of catalyst showed minimum significant effect on the degradation efficiencies of DMP and DEP. Greater degradation efficiency was achieved using Degussa P25 at pH 10 with 1.5 g L−1 catalyst dosage. Under these conditions, complete degradation and 92% mineralization were achieved after 300 min of reaction. Additionally, a drastic decrease in the concentration of BOD5 and COD was observed, which results in significant enhancement of their biodegradability obtaining a BOD5/COD index of 0.66 after the photocatalytic treatment. The main intermediate products found were dimethyl 4-hydroxyphthalate, 4-hydroxy-diethyl phthalate, phthalic acid and phthalic anhydride indicating that the photocatalytic degradation pathway involved the hydrolysis reaction of the aliphatic chain and hydroxylation of the aromatic ring, obtaining products with lower toxicity than the initial molecules.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Maya2019b,

title = {Zeolitic imidazolate framework dispersions for the fast and highly efficient extraction of organic micropollutants},

author = {Maya, F. and Palomino-Cabello, C. and Clavijo, S. and Estela, J. M. and Cerdà, V. and Turnes-Palomino, G.},

doi = {10.1039/C5RA01079A},

year  = {2019},

date = {2019-03-12},

urldate = {2019-03-12},

journal = {Rsc Advances},

volume = {5},

number = {36},

pages = {28203-28210},

abstract = {Development of advanced strategies for the extraction and preconcentration of trace levels of pollutants is essential for the quality control of water resources. A new procedure for the fast and highly efficient extraction of organic micropollutants from water using dispersions of zeolite imidazolate framework-8 (ZIF-8) crystals in a mixture of solvents is reported. The synergistic effect of using ZIF-8 dispersions in mixtures of water miscible and immiscible solvents enhances mass transfer and greatly improves extraction kinetics and capacity in comparison with the use of porous crystals or solvent microextraction separately. The effect of the ZIF-8 crystal size and surface composition has been evaluated using four different ZIF-8 samples spanning the micro- to nanometer range. The relevant parameters involved in the extraction such as the composition of the dispersion medium, the amount of ZIF-8 crystals, the extraction time, or the volume of dispersion required to ensure the maximum extraction efficiency, has also been studied using diethyl phthalate as a model compound. The use of 26 nm ZIF-8 crystals obtained using n-butylamine modulated synthesis has shown very fast extraction kinetics and excellent enrichment factors ranging from 150 to 380 for a mixture of six phthalate esters listed as priority pollutants by the United States EPA, allowing detection limits below the ng L−1 to be reached.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Medina2019,

title = {Metal-organic framework mixed-matrix coatings on 3D printed devices},

author = {A. V. Medina, D. and Figuerola, A. and Rodriguez, F. and Santos-Neto, A.J. and Palomino Cabello, C. and Turnes Palomino, G. and Cerdà, V. and Maya, F.},

doi = {https://doi.org/10.1016/j.apmt.2019.04.011},

year  = {2019},

date = {2019-03-01},

journal = {Applied materials today},

volume = {16},

pages = {21-27},

abstract = {Strategies to incorporate porous coatings on 3D printed devices with intricate geometries are critical to expanding the scope of application of this type of manufacturing technique. Herein, the preparation of metal–organic framework (MOF)/polymer dispersions to be applied as coatings for 3D printed devices is described. As a proof of concept, submicrometric crystals of a zeolitic imidazolate framework (ZIF-67) were dispersed in a binary mixture comprising a polymer and an organic solvent. The resulting dispersion is dispensed through the structure of 3D printed devices, and after gentle heating for a short time, a homogeneous and robust MOF/polymer mixed-matrix coating (MMC) is formed on the effective area of the 3D printed device. The developed MOF–MMC procedure is simple, fast, and does not require specific instrumentation, or synthetic skills. The resulting MOF–MMC 3D printed devices were evaluated for the peroxymonosulfate activation to enhance the degradation of organic dyes in water. After a degradation time of 30 min using rhodamine B (5 mg L−1) as a model dye, the MOF–MMC 3D printed devices showed excellent reusability and reproducibility, degrading an average of 97–98% of the rhodamine B after 10 consecutive degradation cycles comparing three different devices. Dye degradation was evaluated in stirred-tank and flow-through column formats, demonstrating that the developed MOF–MMC procedure is a versatile, safe and convenient way to implement micro/nanoparticulated materials for water pollutant degradation applications.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Ghani2019,

title = {Automated solid-phase extraction of phenolic acids using layered double hydroxide-alumina-polymer disks},

author = {Ghani, M. and Palomino Cabello, C. and Saraji, M. and Estela, J.M. and Cerdà, V. and Turnes Palomino, G. and Maya, F.},

doi = { https://doi.org/10.1002/jssc.201701420},

year  = {2019},

date = {2019-01-26},

journal = {Journal of Separation Science},

volume = {41},

number = {9},

pages = {2012-2019},

abstract = {The application of layered double hydroxide–Al2O3–polymer mixed‐matrix disks for solid‐phase extraction is reported for the first time. Al2O3 is embedded in a polymer matrix followed by an in situ metal‐exchange process to obtain a layered double hydroxide–Al2O3–polymer mixed‐matrix disk with excellent flow‐through properties. The extraction performance of the prepared disks is evaluated as a proof of concept for the automated extraction using sequential injection analysis of organic acids (p‐hydroxybenzoic acid, 3,4‐dihydroxybenzoic acid, gallic acid) following an anion‐exchange mechanism. After the solid‐phase extraction, phenolic acids were quantified by reversed‐phase high‐performance liquid chromatography with diode‐array detection using a core–shell silica–C18 stationary phase and isocratic elution (acetonitrile/0.5% acetic acid in pure water, 5:95, v/v). High sensitivity and reproducibility were obtained with limits of detection in the range of 0.12–0.25 μg/L (sample volume, 4 mL), and relative standard deviations between 2.9 and 3.4% (10 μg/L, n = 6). Enrichment factors of 34–39 were obtained. Layered double hydroxide–Al2O3–polymer mixed‐matrix disks had an average lifetime of 50 extractions. Analyte recoveries ranged from 93 to 96% for grape juice and nonalcoholic beer samples.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Mediola-Alvarez2019,

title = {Synthesis of Cr3+-doped TiO2 nanoparticles: characterization and evaluation of their visible photocatalytic performance and stability},

author = {S. Y. Mediola-Alvarez and J. L. Guzmán-Mar and G. Turnes-Palomino and F. Maya-Alejandro and A. Caballero-Quintero and A. Hernández-Ramírez and L. Hinojosa-Reyes},

doi = {https://doi.org/10.1080/09593330.2017.1380715},

year  = {2019},

date = {2019-01-15},

journal = {Environmental Technology },

volume = {40},

number = {2},

pages = {144-153},

abstract = {Cr3+-doped TiO2 nanoparticles (Ti-Cr) were synthesized by microwave-assisted sol-gel method. The Ti-Cr catalyst was characterized by X-ray diffraction, ultraviolet-visible diffuse reflectance spectroscopy, N2 adsorption-desorption analysis, Raman spectroscopy, scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy (XPS) and zetametry. The anatase mesoporous Ti-Cr material exhibited a specific surface area of 54.5 m2/g. XPS analysis confirmed the proper substitution of Ti4+ cations by Cr3+ cations in the TiO2 matrix. The particle size was of average size of 17 nm for the undoped TiO2 but only 9.5 nm for Ti-Cr. The Cr atoms promoted the formation of hydroxyl radicals and modified the surface adsorptive properties of TiO2 due to the increase in surface acidity of the material. The photocatalytic evaluation demonstrated that the Ti-Cr catalyst completely degraded (4-chloro-2-methylphenoxy) acetic acid under visible light irradiation, while undoped TiO2 and P25 allowed 45.7% and 31.1%, respectively. The rate of degradation remained 52% after three cycles of catalyst reuse. The higher visible light photocatalytic activity of Ti-Cr was attributed to the beneficial effect of Cr3+ ions on the TiO2 surface creating defects within the TiO2 crystal lattice, which can act as charge-trapping sites, reducing the electron−hole recombination process.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Delgado2018,

title = {Non-Linear Enthalpy-Entropy Correlation for Nitrogen Adsorption in Zeolites},

author = {M. R. Delgado and C. O Areán},

doi = {https://doi.org/10.3390/molecules23112978},

year  = {2018},

date = {2018-11-15},

journal = {Molecules},

volume = {23},

number = {11},

pages = {2978-2985},

abstract = {The thermodynamics of dinitrogen adsorption in faujasite-type zeolites, Na-Y, Ca-Y and Sr-Y, were investigated by means of variable-temperature infrared spectroscopy, a technique that affords determination of the standard adsorption enthalpy (∆H0) and entropy (∆S0) from an analysis of the IR spectra recorded over a range of temperatures. The results obtained, taken together with previously reported values for N2 adsorption on protonic zeolites, revealed a non-linear correlation between ∆H0 and ∆S0. Implications of such a correlation for gas separation and purification by adsorption in porous solids are highlighted.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Salazar-Beltrán2018b,

title = {Nanoparticle@Metal-organic frameworks as a template for hierarchical porous carbon sponges},

author = {Salazar-Beltrán, D. and Palomino Cabello, C and Guzmán-Mar, J. L. and Hinojosa-Reyes, L. and Turnes Palomino, G. and Maya, F.},

doi = { https://doi.org/10.1002/chem.201802545},

year  = {2018},

date = {2018-09-04},

journal = {Chemistry A European Journal},

volume = {24},

number = {51},

pages = {13450-13456},

abstract = {The preparation of hierarchical porous carbon sponges (HCS) from metal oxide nanoparticle@metal-organic frameworks is reported. ZnO nanoparticles are partially converted to zeolitic imidazolate framework-8 (ZIF-8) crystals in presence of n-butylamine to obtain ZnO@ZIF-8 porous hybrids. After direct carbonization, followed by ZnO acidic etching, ZnO@ZIF-8 crystals were converted to submicrometric HCS. Due to the high surface area and accessible porosity, combining micro- and mesoporosity of HCS, their application for the extraction of water pollutants was studied by preparing HCS/polymer membranes, and showed a high efficiency for the fast (650 L m-2  h-1 ) removal of plastic degradation by-products (DBP, dibutyl phthalate. DEHP, bis(2-n-ethylhexyl)phthalate). DBP and DEHP breakthroughs were lower than 3 % after the filtration of 100 mL of water containing simultaneously both phthalates at a high concentration level (300 μg L-1 , each). HCS/polymer membranes were reusable up to 5 times, maintaining their extraction capacity, with relative errors of 6 % for DBP, and <1 % for DEHP.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Cabello2018,

title = {UiO-66 derived etched carbon/polymer membranes: High-performance supports for the extraction of organic pollutants from water},

author = {Palomino Cabello, C. and Font Picó, M.F. and Maya, F. and del Río, M. and Turnes Palomino, G.},

doi = {https://doi.org/10.1016/j.cej.2018.04.019},

issn = {1385-8947},

year  = {2018},

date = {2018-08-15},

journal = {Chemical Engineering Journal},

volume = {346},

pages = {85-93},

abstract = {Herein we report the use of the zirconium metal–organic framework (UiO-66) as precursor to prepare porous carbons by a direct carbonization step (carbon-ZrO2). By applying a post-carbonization acidic etching treatment with hydrofluoric acid (HF), the initial surface area of the carbon-ZrO2 sample increased from 270 m2 g−1 to 1550 m2 g−1 (carbon-ZrO2-HF). This increase is attributed to the partial removal of the ZrO2 present in the UiO-66-derived carbon. Carbon-ZrO2-HF exhibited fast adsorption kinetics and an outstanding maximum adsorption capacity of 510 mg g−1 for the dye rhodamine B. For practical applications, the obtained porous carbon-ZrO2-HF material was used to fabricate a carbon composite membrane using polyvinylidene fluoride. The prepared membranes were applied as water filtration supports for the extraction of toxic phenols from water, including an endocrine disrupting phenol with widespread exposure: bisphenol A. High efficiency for the simultaneous extraction of phenolic pollutants, and an excellent reusability with a variation of a 2% for 10 consecutive bisphenol A extraction cycles, were obtained. Due to their high and accessible porosity, small particles size, and facile processability into membranes, the UiO-66 derived etched carbons are promising materials for environmental applications, such as the extraction of organic toxic pollutants.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Salazar-Beltrán2018,

title = {Determination of phthalate acid esters plasticizers in polyethylene terephthalate bottles and its correlation with some physicochemical properties},

author = {Salazar-Beltrán, D. and Hinojosa-Reyes, L. and Palomino Cabello, C. and Turnes Palomino, G. and Hernández Ramírez, A. and Guzmán-Mar, J.},

doi = {https://doi.org/10.1016/j.polymertesting.2018.04.002},

year  = {2018},

date = {2018-07-02},

journal = {Polymer Testing},

volume = {68},

pages = {87-94},

abstract = {A method for the analysis of phthalic acid esters or phthalates (PAEs) in polyethylene terephthalate (PET) bottles based on the use of microwave-assisted extraction (MAE) and liquid chromatography with UV detection (LC-UV) was developed. The microwave-assisted extraction procedure was optimized by a three factors Box–Behnken response surface design. High PAEs recoveries were obtained by microwave-assisted extraction using 70% of acetonitrile at 140 °C during 30 min.



Moreover, some physical properties of PET samples as thickness, and crystallization and melting temperatures were determined by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), respectively. Those parameters were correlated, through Pearson correlation coefficient, with the content of PAEs determined in PET containers (dimethyl phthalate (DMP), diethyl phthalate (DEP) and dibutyl phthalate (DBP)) and with the content of PAEs in water obtained from a migration test in PET. The migration procedure was based on a standardized procedure (EU 82/711/EEC and 85/572/EEC directives) stipulated by the European Union (EU). The concentrations of PAEs found in PET bottles were between 1.1 and 14.8 mg kg−1 for DMP, 9.3 and 63.6 mg kg−1 for DBP and DEP was only detected in one of the 10 analyzed samples at a concentration of 3.1 mg kg−1. The analysis of the samples obtained by applying the migration test showed that DBP was found in five of the ten analyzed samples reaching concentrations from 14.5 up to 25.6 μg L−1. DMP was found in five of the ten analyzed samples, with concentrations from 4.1 to 50.6 μg L−1, whereas DEP was not detected in any of the analyzed samples. The results of the Pearson correlation coefficient indicated that there was a significant correlation between the thickness and the total concentration of PAEs in the PET samples (95% confidence interval), as well as the DBP content in PET samples and the concentration of DBP migrated from bottles to the water (90% confidence interval), indicating that the content of PAEs in the samples and the migration rate of these compounds was related to the physical characteristics of PET bottles.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Maya2018,

title = {Emerging materials for sample preparation},

author = {Maya, F. and Palomino Cabello, C. and Ghani, M. and Turnes Palomino, G. and Cerdà, V.},

doi = { https://doi.org/10.1002/jssc.201700836},

issn = {1615-9306},

year  = {2018},

date = {2018-01-01},

journal = {Journal of Separation Science},

volume = {41},

number = {1},

pages = {262-287},

abstract = {This review provides an update on the implementation of emerging materials as sorbents for sample preparation in combination with chromatographic separation. We have focused on recent applications of metal–organic frameworks, layered double hydroxides, porous carbons obtained from polymers or biomass precursors, and silicates (clays and zeolites). The review is directed toward the strategies followed by the authors to engineer suitable supports enabling the application of materials with unconventional size and shape as high‐performance sorbents to explore new boundaries in sample pretreatment in manual or automated modes.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{H.2017,

title = {Surfactant-directed mesoporous zeolites with enhanced catalytic activity in tetrahydropyranylation of alcohols: Effect of framework type and morphology},

author = {Sun S. H. and Opanasenko, M. and Palomino Cabello, C. and Ryoo, R. and Cejka, J.},

doi = {https://doi.org/10.1016/j.apcata.2017.02.019},

year  = {2017},

date = {2017-05-05},

journal = {Applied Catalysis A: General},

volume = {537},

number = {5},

pages = {24-32},

abstract = {Nanosponge zeolite beta was hydrothermally synthesized using multi-quarternary ammonium surfactant as a meso-micro hierarchical structure directing agent. The nanosponge morphology of the beta zeolite consisted of randomly interconnected nanocrystals with thickness of 10–20 nm. The beta nanosponges with highly mesoporous structure exhibited enhanced catalytic activity in tetrahydropyranylation of alcohols (methanol, 1-octanol, cyclohexanol and 2-adamantanol) when compared with the conventional beta zeolites and nanosponge zeolites of MTW and MFI framework types. The enhanced catalytic performance (∼60% conversion with 90–100% selectivity towards tetrahydropyranyl ether and over two times higher initial rate compared to other zeolites) of hierarchical beta nanosponges can be attributed to the high accessibility of acid sites and facile diffusion of reactants and products through the mesopores.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Mendiola-Alvarez2017,

title = {UV and visible activation of Cr(III)-doped TiO2 catalyst prepared by a microwave-assisted sol-gel method during MCPA degradation},

author = {Mendiola-Alvarez, S. Y. and Guzmán-Mar, J. L. and Turnes-Palomino, G. and Maya-Alejandro, F. and Hernández-Ramírez, A. and Hinojosa-Reyes, L.},

doi = {http://dx.doi.org/10.1007/s11356-016-8034-x},

issn = {0944-1344},

year  = {2017},

date = {2017-05-01},

journal = {Environmental Science and Pollution Research},

volume = {24},

number = {14},

pages = {12673–12682},

abstract = {Photocatalytic degradation of 4-chloro-2-methylphenoxyacetic acid (MCPA) in aqueous solution using Cr(III)-doped TiO2 under UV and visible light was investigated. The semiconductor material was synthesized by a microwave-assisted sol–gel method with Cr(III) doping contents of 0.02, 0.04, and 0.06 wt%. The catalyst was characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), nitrogen physisorption, UV–Vis diffuse reflectance spectroscopy (DRS), and atomic absorption spectroscopy (AAS). The photocatalytic activity for the photodegradation of MCPA was followed by reversed-phase high-performance liquid chromatography (HPLC) and total organic carbon (TOC) analysis. The intermediates formed during degradation were identified using gas chromatography–mass spectrometry (GC–MS). Chloride ion evolution was measured by ion chromatography. Characterization results showed that Cr(III)-doped TiO2 materials possessed a small crystalline size, high surface area, and mesoporous structure. UV–Vis DRS showed enhanced absorption in the visible region as a function of the Cr(III) concentration. The Cr(III)-doped TiO2 catalyst with 0.04 wt% of Cr(III) was more active than bare TiO2 for the degradation of MCPA under both UV and visible light. The intermediates identified during MCPA degradation were 4-chloro-2-methylphenol (CMP), 2-(4-hydroxy-2-methylphenoxy) acetic acid (HMPA), and 2-hydroxybuta-1,3-diene-1,4-diyl-bis (oxy)dimethanol (HBDM); the formation of these intermediates depended on the radiation source.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Alejandro2017,

title = {Magnetic solid-phase extraction using metal-organic frameworks (MOFs) and their derived carbons},

author = {Maya Alejandro, F. and Palomino Cabello, C. and Mara Frizzarin, R. and Estela, J. M. and Turnes Palomino, G. and Cerdà, V.},

doi = { https://doi.org/10.1016/j.trac.2017.03.004},

year  = {2017},

date = {2017-05-01},

journal = {TrAC Trends in Analytical Chemistry},

volume = {90},

pages = {142-152},

abstract = {Magnetic solid-phase extraction (MSPE) is a useful sample preparation technique, enabling the dispersion of solid sorbents in liquid sample matrices followed by the magnetic retrieval of the sorbent. MSPE can be implemented using any kind of magnetic materials independently of their size and shape, and is a powerful tool for the application of micro/nanomaterials for analytical sample preparation. Metal-organic frameworks (MOFs) have emerged recently as highly valuable sorbents for solid-phase extraction (SPE) due to their large surface area, chemical selectivity, and versatility for tuning their chemical composition and pore size. For MSPE applications, MOFs can be magnetized, or used as precursors for the preparation of MOF-derived magnetic porous carbons (MPCs).



In this review, we outline and discuss the different approaches for the preparation of magnetic MOFs and their conversion to MPCs. The applications of magnetic MOFs and MPCs as sorbents for MSPE are critically discussed and oriented to the type of MOF used and the extracted analytes. Recent efforts on the automation of MSPE procedures using magnetic MOFs and MPCs are also described.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Carrasco-Correa2017,

title = {Incorporation of zeolitic imidazolate framework (ZIF-8)-derived nanoporous carbons in methacrylate polymeric monoliths for capillary electrochromatography},

author = {Carrasco-Correa, E. J. and Martínez-Vilata, A. and Herrero-Martínez, J. M. and Parra, J. B. and Maya, F. and Cerdà, V. and Palomino Cabello, C. and Turnes Palomino, G. and Svec, F. },

doi = {10.1016/j.talanta.2016.11.027},

year  = {2017},

date = {2017-03-01},

journal = {Talanta},

volume = {164},

number = {1},

pages = {348-354},

abstract = {A series of metal organic frameworks-derived nanoporous carbons originating from zeolitic imidazolate framework-8 (ZIF-8) crystals as precursors have been prepared via varying the preparation conditions. The ZIF-8-derived carbons were subsequently admixed in the methacrylate monomers containing polymerization mixtures and polymerized to obtain monolithic columns for capillary electrochromatography (CEC). The effect of particle size and content of the ZIF-8-derived carbon materials in the polymerization mixture on the performance of the hybrid monolithic columns was investigated in detail. The resulting composites were characterized using scanning electron microscopy. Using short time UV-initiated polymerization, monolithic beds with homogenously dispersed ZIF-8-derived carbons were obtained. The chromatographic performance of these composites was demonstrated with separations of polycyclic aromatic hydrocarbons and non-steroidal anti-inflammatory drugs as test solutes. The incorporation of the ZIF-8-derived carbons into the organic polymer monoliths led to an increase in the retention of all the analytes compared to the parent monolith. Finally, the hybrid monolithic columns exhibited satisfactory run-to-run and batch-to-batch reproducibility.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Cordero-García2017,

title = {Photocatalytic behaviour of WO3/TiO2-N for diclofenac degradation using simulated solar radiation as an activation source},

author = {Cordero-García, A. and Turnes Palomino, G. and Hinojosa-Reyes, L. and Guzmán-Mar, J. L. and Maya-Teviño, L. and Hernández-Ramírez, A. },

doi = {10.1007/s11356-016-8157-0},

issn = {0944-1344},

year  = {2017},

date = {2017-02-01},

journal = {Environmental Science and Pollution Research},

volume = {24},

number = {5},

pages = {4613–4624},

abstract = {In this study, the photocatalytic removal of an emerging contaminant, diclofenac (DCF) sodium, was performed using the nitrogen-doped WO3/TiO2-coupled oxide catalyst (WO3/TiO2-N). The catalyst synthesis was accomplished by a sol–gel method using tetrabutyl orthotitanate (C16H36O4Ti), ammonium p-tungstate [(NH4)10H2W12O42·4H2O] and ammonium nitrate (NH4NO3) as the nitrogen source. For comparison, TiO2 and WO3/TiO2 were also prepared under similar conditions. Analysis by X-ray diffraction (XRD), N2 adsorption–desorption, scanning electron microscopy (SEM), transmission electron microscopy (TEM), diffuse reflectance UV–Vis spectroscopy (DRS) and X-ray photoelectron spectroscopy (XPS) were conducted to characterize the synthesized materials. The photocatalytic efficiency of the semiconductors was determined in a batch reactor irradiated with simulated solar light. Residual and mineralized DCF were quantified by high-performance liquid chromatography, total organic carbon analysis and ion exchange chromatography. The results indicated that the tungsten atoms were dispersed on the surface of TiO2 as WO3. The partial substitution of oxygen by nitrogen atoms into the lattice of TiO2 was an important factor to improve the photocatalytic efficiency of WO3/TiO2. Therefore, the best photocatalytic activity was obtained with the WO3/TiO2-N0.18 catalyst, reaching 100% DCF transformation at 250 kJ m−2 and complete mineralization at 400 kJ m−2 of solar-accumulated energy.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Darder2017,

title = {Nanoparticle-Directed Metal-Organic Framework/Porous Organic Polymer Monolithic Supports for Flow-Based Applications},

author = {Darder, M. del M. and Salehinia, S. and Parra, J. and Herrero-Martinez, J. M. and Svec, F. and Cerdà, V. and Turnes Palomino, G. and Maya, F.},

doi = {https://doi.org/10.1021/acsami.6b10999},

issn = {1944-8252},

year  = {2017},

date = {2017-01-04},

journal = {Acs Applied Materials & Interfaces},

volume = {9},

number = {2},

pages = {1728-1736},

abstract = {A two-step nanoparticle-directed route for the preparation of macroporous polymer monoliths for which the pore surface is covered with a metal–organic framework (MOF) coating has been developed to facilitate the use of MOFs in flow-based applications. The flow-through monolithic matrix was prepared in a column format from a polymerization mixture containing ZnO-nanoparticles. These nanoparticles embedded in the precursor monolith were converted to MOF coatings via the dissolution–precipitation equilibrium after filling the pores of the monolith with a solution of the organic linker. Pore surface coverage with the microporous zeolitic imidazolate framework ZIF-8 resulted in an increase in surface area from 72 to 273 m² g–¹. Monolithic polymer containing ZIF-8 coating was implemented as a microreactor catalyzing the Knoevenagel condensation reaction and also in extraction column format enabling the preconcentration of trace levels of toxic chlorophenols in environmental waters. Our approach can be readily adapted to other polymers and MOFs thus enabling development of systems for flow-based MOF applications.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{González2017,

title = {In-syringe dispersive μ-SPE of estrogens using magnetic carbon microparticles obtained from zeolitic imidazolate frameworks.},

author = {González, A. and Avivar, J. and Maya, F. and Palomino Cabello, C. and Turnes Palomino, G. and Cerdà, V.},

doi = {10.1007/s00216-016-9988-8},

issn = {1618-2642},

year  = {2017},

date = {2017-01-02},

journal = {Analytical and Bioanalytical Chemistry},

volume = {409},

number = {1},

pages = {225-234},

abstract = {Herein, we propose for the first time the use of magnetic porous carbons (MPCs) derived from zeolitic imidazolate frameworks (ZIFs) for the automated in-syringe magnetic dispersive micro-solid phase extraction (D-μ-SPE) of environmental pollutants prior to their analysis using GC-MS. MPCs with dual porosity are obtained from the direct combustion of the ZIF-67, obtaining robust and magnetic porous carbons on the micrometer scale. As proof of concept, this material has been applied for the automated D-μ-SPE of estrogens (estrone, 17β-estradiol, and 17α-ethynylestradiol) cataloged as Contaminants of Emergent Concern by the Environmental Protection Agency of the United States (US-EPA). The automation of the system provided a good precision given the low relative standard deviations (RSDs) obtained, ranging from 2.70 to 5.90 % for intra-day precision and from 4.6 to 9.55 % for inter-day precision. Furthermore, the clean-up and preconcentration of the sample is easy and quick, as the in-syringe magnetic D-μ-SPE is carried out in less than 20 min. The high porosity, magnetism, and good stability of the MPCs facilitated the automation of the SPE in dispersive mode enabling the analysis of samples with a complex matrix without backpressure or problems related with the clogging of the instrumentation conduits. The applicability of the method to wastewater samples has been demonstrated given the good recoveries attained ranging from 86 to 115 %.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Gómez-Pozuelo2017,

title = {Superior activity of isomorphously substituted MOFs with MIL-100(M) structure in Prins reaction: Impact of metal nature},

author = {Gómez-Pozuelo, G. and Palomino Cabello, C. and Opanasenko, M. and Horacek, M. and Cejka, J. },

doi = {https://doi.org/10.1002/cplu.201600456},

year  = {2017},

date = {2017-01-02},

journal = {Chempluschem},

volume = {82},

number = {1},

pages = {152-159},

abstract = {The catalytic behavior of isomorphously substituted MIL‐100(M) (M=Al, Cr, Fe, In, Sc, V) is investigated for the synthesis of nopol through the Prins condensation of β‐pinene with paraformaldehyde. The large mesoporous cages of the metal–organic frameworks provide a sustainable confinement for the formation of the target product (100 % selectivity for nopol over all materials studied). MIL‐100(Sc) and MIL‐100(V) exhibit the highest yields (up to 90 %) of nopol after just 20 min from the beginning of the reaction, owing to their high concentrations of accessible Lewis sites possessing intermediate acidity. The high catalytic activity (reaching almost 90 % β‐pinene conversion) even upon decreasing the amount of catalyst from 100 to 25 mg (0.025 and 0.0063 gcatalyst mmolsubstrate−1, respectively), the stability of its structure, and the possibility to use it several times, make MIL‐100(V) a promising material for applications in acid‐catalyzed reactions under mild reaction conditions.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{delRio2016,

title = {Metal Oxide Assisted Preparation of Core-Shell Beads with Dense Metal-Organic Framework Coatings for the Enhanced Extraction of Organic Pollutants.},

author = {del Rio, M. and Palomino Cabello, C. and Gonzalez, V. and Maya, F. and Parra, J. and Cerdà, V. and Turnes Palomino, G.},

doi = {https://doi.org/10.1002/chem.201601329},

year  = {2016},

date = {2016-07-08},

journal = {Chemistry-A European Journal},

volume = {22},

number = {33},

pages = {11770-11777},

abstract = {Dense and homogeneous metal–organic framework (MOF) coatings on functional bead surfaces are easily prepared by using intermediate sacrificial metal oxide coatings containing the metal precursor of the MOF. Polystyrene (PS) beads are coated with a ZnO layer to give ZnO@PS core–shell beads. The ZnO@PS beads are reactive in the presence of 2‐methylimidazole to transform part of the ZnO coating into a porous zeolitic imidazolate framework‐8 (ZIF‐8) external shell positioned above the internal ZnO precursor shell. The obtained ZIF‐8@ZnO@PS beads can be easily packed in column format for flow‐through applications, such as the solid‐phase extraction of trace priority‐listed environmental pollutants. The prepared material shows an excellent permeance to flow when packed as a column to give high enrichment factors, facile regeneration, and excellent reusability for the extraction of the pollutant bisphenol A. It also shows an outstanding performance for the simultaneous enrichment of mixtures of endocrine disrupting chemicals (bisphenol A, 4‐tert‐octylphenol and 4‐n‐nonylphenol), facilitating their analysis when present at very low levels (<1 μg L−1) in drinking waters. For the extraction of the pollutant bisphenol A, the prepared ZIF‐8@ZnO@PS beads also show a superior extraction and preconcentration capacity to that of the PS beads used as precursors and the composite materials obtained by the direct growth of ZIF‐8 on the surface of the PS beads in the absence of metal oxide intermediate coatings.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Frizzarin2016,

title = {Submicrometric Magnetic Nanoporous Carbons Derived from Metal-Organic Frameworks Enabling Automated Electromagnet-Assisted Online Solid-Phase Extraction},

author = {Frizzarin, R. and Palomino Cabello, C. and Bauzà, M. del M. and Portugal, L. and Maya, F. and Cerdà, V. and Estela, J. and Turnes Palomino, G.},

doi = {https://doi.org/10.1021/acs.analchem.6b02065},

year  = {2016},

date = {2016-06-23},

journal = {Analytical Chemistry},

volume = {88},

number = {44},

pages = {6990-6995},

abstract = {We present the first application of submicrometric magnetic nanoporous carbons (μMNPCs) as sorbents for automated solid-phase extraction (SPE). Small zeolitic imidazolate framework-67 crystals are obtained at room temperature and directly carbonized under an inert atmosphere to obtain submicrometric nanoporous carbons containing magnetic cobalt nanoparticles. The μMNPCs have a high contact area, high stability, and their preparation is simple and cost-effective. The prepared μMNPCs are exploited as sorbents in a microcolumn format in a sequential injection analysis (SIA) system with online spectrophotometric detection, which includes a specially designed three-dimensional (3D)-printed holder containing an automatically actuated electromagnet. The combined action of permanent magnets and an automatically actuated electromagnet enabled the movement of the solid bed of particles inside the microcolumn, preventing their aggregation, increasing the versatility of the system, and increasing the preconcentration efficiency. The method was optimized using a full factorial design and Doehlert Matrix. The developed system was applied to the determination of anionic surfactants, exploiting the retention of the ion-pairs formed with Methylene Blue on the μMNPC. Using sodium dodecyl sulfate as a model analyte, quantification was linear from 50 to 1000 μg L–1, and the detection limit was equal to 17.5 μg L–1, the coefficient of variation (n = 8; 100 μg L–1) was 2.7%, and the analysis throughput was 13 h–1. The developed approach was applied to the determination of anionic surfactants in water samples (natural water, groundwater, and wastewater), yielding recoveries of 93% to 110% (95% confidence level).},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Cabello2016,

title = {Metal-Organic Frameworks M-MOF-74 and M-MIL-100: Comparison of Textural, Acidic, and Catalytic Properties},

author = {Palomino Cabello, C. and Gomez-Pozuelo, G. and Opanasenko, M. and Nachtigall, P. and Cejka, J.},

doi = {https://doi.org/10.1002/cplu.201600168},

year  = {2016},

date = {2016-05-26},

journal = {Chempluschem},

volume = {81},

number = {8},

pages = {828-835},

abstract = {The impact of the metal nature and framework type on the textural, acidic, and catalytic properties of M‐MOF‐74 (M=Co, Cu, Mg, Ni) and M‐MIL‐100 (M=Al, Cr, Sc, V) materials was evaluated. Both metal–organic framework (MOF) families showed 100 % selectivity to the tetrahydropyranyl ether for all alcohols (methanol, 1‐propanol, 1‐octanol, 2‐adamantanol, 1‐octadecanol) applied. Independently of the metal employed in the synthesis of M‐MOF‐74, the conversions were lower than those obtained with M‐MIL‐100. This result can be attributed to the combination of superior textural properties, accessibility, and strength of open metal sites in M‐MIL‐100 that improve the accessibility/diffusion of reactant and products. The variation of the size and shape of the alcohols on the activity and selectivity showed that the yield of tetrahydropyranyl ether decreased with increase of the alcohol size (methanol<1‐propanol<1‐octanol<2‐adamantanol<1‐octadecanol). The best catalytic results were achieved with V‐MIL‐100, and were even maintained after several cycles; this could be related to the superior polarizing power of V‐containing units, which enhanced the activation of 3,4‐dihydro‐2H‐pyran and, consequently, the yield of the target ether.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{Maya2015b,

title = {Automatic In-Syringe Dispersive Microsolid Phase Extraction Using Magnetic-Metal Organic Frameworks},

author = {Maya, F. and Palomino Cabello, C. and Estela, J. M. and Cerda, V. and Turnes Palomino, G.},

doi = {10.1021/acs.analchem.5b01993},

year  = {2015},

date = {2015-08-04},

journal = {Analytical Chemistry},

volume = {87},

number = {15},

pages = {7545-7549},

abstract = {A novel automatic strategy for the use of micro- and nanomaterials as sorbents for dispersive microsolid phase extraction (D-μ-SPE) based on the lab-in-syringe concept is reported. Using the developed technique, the implementation of magnetic metal-organic framework (MOF) materials for automatic solid-phase extraction has been achieved for the first time. A hybrid material based on submicrometric MOF crystals containing Fe3O4 nanoparticles was prepared and retained in the surface of a miniature magnetic bar. The magnetic bar was placed inside the syringe of an automatic bidirectional syringe pump, enabling dispersion and subsequent magnetic retrieval of the MOF hybrid material by automatic activation/deactivation of magnetic stirring. Using malachite green (MG) as a model adsorption analyte, a limit of detection of 0.012 mg/L and a linear working range of 0.04-2 mg/L were obtained for a sample volume equal to the syringe volume (5 mL). MG preconcentration was linear up to a volume of 40 mL, obtaining an enrichment factor of 120. The analysis throughput is 18 h(-1), and up to 3000 extractions/g of material can be performed. Recoveries ranging between 95 and 107% were obtained for the analysis of MG in different types of water and trout fish samples. The developed automatic D-μ-SPE technique is a safe alternative for the use of small-sized materials for sample preparation and is readily implementable to other magnetic materials independent of their size and shape and can be easily hyphenated to the majority of detectors and separation techniques.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}