Cabrero Antonino, María

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Instituto Universitario Mixto de Tecnología Química

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A Semiconducting Bi2O2(C4O4) Coordination Polymer Showing a Photoelectric Response
(American Chemical Society, 2020-03-16) Babaryk, Artem A.; Contreras Almengor, Oscar R.; Cabrero Antonino, María; Navalón Oltra, Sergio; García Gómez, Hermenegildo; Horcajada, Patricia; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; Generalitat Valenciana; Fundación Ramón Areces; Agencia Estatal de Investigación; Ministerio de Economía y Competitividad; Ministerio de Ciencia, Innovación y Universidades
[EN] Inorganic semiconductors are extensively considered to be among the most promising materials to convert solar light into electricity or chemical energy owing to their efficiency in the separation of photoinduced electron/hole. Bismuth oxides, and, in particular, those built up of [Bi2O2](2+) layers, show an efficient charge separation and, thus, high photocatalytic activities. To explore a possible synergetic effect of bismuth metallic nodes combined with the electron-rich linker squarate, Bi2O2(C4O4) or IEF-3 (an IMDEA Energy framework) was hydrothermally prepared and adequately characterized. As determined from the X-ray structure, [Bi2O2](2+) layers are interconnected by squarate ligands, having a pronounced effect of the 6s(2) lone pair on the bismuth local environment. IEF-3 shows high thermal and chemical robustness at industrially relevant model aggressive media. A large panel of physicochemical methods were applied to recognize IEF-3 as an UV-absorbing n-type semiconductor, showing a photocurrent response comparable to that of alpha-Bi2O3, offering further possibilities for tuning its electrochemical properties by modifying the ligand. In this way, the well-known compositional and structural versatility of coordination polymers may be applied in the future to fine-tune metal-organic semiconductor systems.
A Robust Titanium Isophthalate Metal-Organic Framework for Visible-Light Photocatalytic CO2 Methanation
(Elsevier (Cell Press), 2020-12-03) Wang, Sujing; Cabrero Antonino, María; Navalón Oltra, Sergio; Cao, Chen-chen; Tissot, Antoine; Dovgaliuk, Iurii; Marrot, Jerome; Martineau-Corcos, Charlotte; Yu, Liang; Wang, Hao; Shepard, William; García Gómez, Hermenegildo; Serre, Christian; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; Region Ile-de-France; Fundación Ramón Areces; Generalitat Valenciana; China Scholarship Council; Agencia Estatal de Investigación; Institut Universitaire de France; Agència Valenciana de la Innovació; National Natural Science Foundation of China; Fundamental Research Funds for the Central Universities; Ministère de l'Europe et des Affaires Étrangères, Francia
[EN] Isophthalic acid (IPA) has been considered to build metal-organic frameworks (MOFs), owing to its facile availability, unique connection angle-mode, and a wide range of functional groups attached. Constructing titanium-IPA frameworks that possess photoresponse properties is an alluring characteristic with respect to the challenge of synthesizing new titanium-based MOFs (Ti-MOFs) Here, we report the first Ti-IPA MOF (MIP-208) that efficiently combines the use of preformed Ti-8 oxoclusters and in situ acetylation of the 5-NH2-IPA linker. The mixed solid-solution linkers strategy was successfully applied, resulting in a series of multivariate MIP-208 structures with tunable chemical environments and sizable porosity. MIP-208 shows the best result among the pure MOF catalysts for the photocatalytic methanation of carbon dioxide. To improve the photocatalytic performance, ruthenium oxide nanoparticles were photo-deposited on MIP-208, forming a highly active and selective composite catalyst, MIP-208@RuOx, which features a notable visible-light response coupled with excellent stability and recycling ability.
Nitro functionalized chromium terephthalate metal-organic framework as multifunctional solid acid for the synthesis of benzimidazoles
(Elsevier, 2020-02-15) Vallés-García, Cristina; Cabrero Antonino, María; Navalón Oltra, Sergio; Álvaro Rodríguez, María Mercedes; Dhakshinamoorthy, Amarajothi; García Gómez, Hermenegildo; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; Generalitat Valenciana; Fundación Ramón Areces; University Grants Commission, India; Department of Science and Technology, Ministry of Science and Technology, India; Agencia Estatal de Investigación
[EN] In the present work, nitro functionalized chromium terephthalate [MIL-101(Cr)-NO2] metal-organic framework is prepared and characterized by powder X-ray diffraction (XRD), elemental analysis, infrared spectroscopy (IR), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and Brun auer-Emmett-Teller (BET) surface area. The inherent Lewis acidity of MIL-101(Cr)-NO2 is confirmed by FT-IR spectroscopy using CD3CN as a probe molecule. The performance of MIL-101(Cr)-NO2 as bifunctional catalyst (acid and redox) promoting the synthesis of wide range of benzimidazoles has been examined by catalyzed condensation on acid sites and subsequent oxidative dehydrogenation. The catalytic activity of MIL-101(Cr)-NO2 is found to be superior than analogues catalysts like MIL-101(Cr)-S0(3)H, MIL-101(Cr)-NH2, U10-66(Zr), Ui0-66(Zr)-NO2, MIL-100(Fe) and Cu-3(BTC)(2) (BTC: 1,35-benzenetricarboxylate) under identical reaction conditions, The structural stability of MIL-101(Cr)-NO2 is supported by leaching analysis and reusability tests. MIL-101(Cr)-NO2 solid is used five times without decay in its activity. Comparison of the fresh and five times used MIL-101(Cr)-NO2 solids by powder XRD, SEM and elemental analysis indicate identical crystallinity, morphology and the absence of chromium leaching, respectively. (C) 2019 Elsevier Inc. All rights reserved.
Influence of co-catalysts on the photocatalytic activity of MIL-125(Ti)-NH2 in the overall water splitting
(Elsevier, 2019-10-05) Remiro Buenamañana, Sonia; Cabrero Antonino, María; Martínez-Guanter, Marcos; Álvaro Rodríguez, María Mercedes; Navalón Oltra, Sergio; García Gómez, Hermenegildo; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; Generalitat Valenciana; Fundación Ramón Areces; Ministerio de Economía y Competitividad
[EN] Titanium containing aminoterephthalate metal organic framework promotes the photocatalytic overall water splitting into H-2 and O-2 at a rate that depends on the presence of Pt, RuOx and CoOx co-catalyst. The best values of have been obtained for the MIL-125-NH2 material that contains Pt and RuOx, reaching a production of 218 and 85 mu mol/g (-1)(photocataly)(st) at 24 h for H-2 and O-2, respectively.
Nickel phosphonate MOF as efficient water splitting photocatalyst
(Springer-Verlag, 2021-02) Salcedo-Abraira, Pablo; Vilela, Sérgio M. F.; Babaryk, Artem A.; Cabrero Antonino, María; Salles, Fabrice; Navalón Oltra, Sergio; García Gómez, Hermenegildo; Horcajada, Patricia; Gregorio, Pedro; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; Fundación Ramón Areces; Generalitat Valenciana; Agencia Estatal de Investigación; European Regional Development Fund; Agencia Valenciana de la Innovación
[EN] A novel microporous two-dimensional (2D) Ni-based phosphonate metal-organic framework (MOF; denoted as IEF-13) has been successfully synthesized by a simple and green hydrothermal method and fully characterized using a combination of experimental and computational techniques. Structure resolution by single-crystal X-ray diffraction reveals that IEF-13 crystallizes in the triclinic space group P-i having bi-octahedra nickel nodes and a photo/electroactive tritopic phosphonate ligand. Remarkably, this material exhibits coordinatively unsaturated nickel(II) sites, free-PO3H2 and-PO3H acidic groups, a CO2 accessible microporosity, and an exceptional thermal and chemical stability. Further, its in-deep optoelectronic characterization evidences a photoresponse suitable for photocatalysis. In this sense, the photocatalytic activity for challenging H-2 generation and overall water splitting in absence of any co-catalyst using UV-Vis irradiation and simulated sunlight has been evaluated, constituting the first report for a phosphonate-MOF photocatalyst. IEF-13 is able to produce up to 2,200 mu mol of H-2 per gram using methanol as sacrificial agent, exhibiting stability, maintaining its crystal structure and allowing its recycling. Even more, 170 mu mol of H-2 per gram were produced using IEF-13 as photocatalyst in the absence of any co-catalyst for the overall water splitting, being this reaction limited by the O-2 reduction. The present work opens new avenues for further optimization of the photocatalytic activity in this type of multifunctional materials.
Tuning the Microenvironment of Gold Nanoparticles Encapsulated within MIL-101(Cr) for the Selective Oxidation of Alcohols with O-2: Influence of the Amino Terephthalate Linker
(John Wiley & Sons, 2019-07-11) Santiago-Portillo, Andrea; Cabrero Antonino, María; Álvaro Rodríguez, María Mercedes; Navalón Oltra, Sergio; García Gómez, Hermenegildo; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; Generalitat Valenciana; Fundación Ramón Areces; Ministerio de Economía y Competitividad
[EN] This manuscript reports a comparative study of the catalytic performance of gold nanoparticles (NPs) encapsulated within MIL-101(Cr) with or without amino groups in the terephthalate linker. The purpose is to show how the amino groups can influence the microenvironment and catalytic stability of incorporated gold nanoparticles. The first influence of the presence of this substituent is the smaller particle size of Au NPs hosted in MIL-101(Cr)-NH2 (2.45 +/- 0.19 nm) compared with the parent MIL-101(Cr)-H (3.02 +/- 0.39 nm). Both materials are highly active to promote the aerobic alcohol oxidation and exhibit a wide substrate scope. Although both catalysts can achieve turnover numbers as high as 10(6) for the solvent-free aerobic oxidation of benzyl alcohol, Au@MIL-101(Cr)-NH2 exhibits higher turnover frequency values (12 000 h(-1)) than Au@MIL-101(Cr)-H (6800 h(-1)). Au@MIL-101(Cr)-NH2 also exhibits higher catalytic stability, being recyclable for 20 times with coincident temporal conversion profiles, in comparison with some decay observed in the parent Au@MIL-101(Cr)-H. Characterization by transmission electron microscopy of the 20-times used samples shows a very minor particle size increase in the case of Au@MIL-101(Cr)-NH2 (2.97 +/- 0.27 nm) in comparison with the Au@MIL-101(Cr)-H analog (5.32 +/- 0.72 nm). The data presented show the potential of better control of the microenvironment to improve the performance of encapsulated Au nanoparticles.
Enhancing visible-light photocatalytic activity for overall water splitting in UiO-66 by controlling metal node composition
(Elsevier, 2020-12-05) Melillo, Arianna; Cabrero Antonino, María; Navalón Oltra, Sergio; Álvaro Rodríguez, María Mercedes; Ferrer Ribera, Rosa Belén; García Gómez, Hermenegildo; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; Fundación Ramón Areces; Generalitat Valenciana; Agencia Estatal de Investigación
[EN] The photocatalytic activity of a series of five UiO-66 (M: Zr, Zr/Ti, Zr/Ce, Zr/Ce/Ti, Ce) materials for overall water splitting with generation of hydrogen and oxygen has been herein measured. The most efficient photocatalyst for the overall water splitting is the trimetallic MOF UiO-66(Zr/Ce/Ti) which achieves 230 mu mol.g(-1) of H-2 and 110 mu mol.g(-1) of O-2, upon UV light irradiation, and 210 mu mol.g(-1) of H-2 and 70 mu mol.g(-1) of O-2, under visible light irradiation. These productivity data indicate that a considerable percentage of its photocatalytic activity derives from the visible region of the spectrum (lambda > 450 nm). The photocatalytic activity of trimetallic UiO-66(Zr/Ce/Ti) was maintained upon reuse. Kinetics of the charge separated state monitored by transient absorption spectroscopy shows similar deactivation profiles for the five UiO-66 samples, suggesting that it is the charge separation efficiency the main factor responsible for the differences in the photocatalytic activity. The use of methanol as sacrificial agent during the photocatalytic experiments indicated that the high photocatalytic efficiency for overall water splitting in UiO-66(Zr/Ce/Ti) derives from the favorable kinetics of oxygen evolution. These results show the potential of multimetallic metal-organic frameworks as solar photocatalysts by tuning light absorption towards the visible region.
Base-Controlled Heck, Suzuki, and Sonogashira Reactions Catalyzed by Ligand-Free Platinum or Palladium Single Atom and Sub-Nanometer Clusters
(American Chemical Society, 2019-02-06) Fernández, Estefanía; Rivero-Crespo, Miguel Á.; Domínguez, Irene; Rubio-Marqués, Paula; Oliver Meseguer, Judit; Liu, Lichen; Cabrero Antonino, María; Gavara Clemente, Rafael José; Hernández-Garrido, Juan C.; Boronat Zaragoza, Mercedes; Leyva Perez, Antonio; Corma Canós, Avelino; Departamento de Tecnología de Alimentos; Instituto Universitario Mixto de Tecnología Química; Escuela Técnica Superior de Ingeniería Agronómica y del Medio Natural; Agencia Estatal de Investigación; Ministerio de Economía y Competitividad
[EN] The assumption that oxidative addition is the key step during the cross-coupling reaction of aryl halides has led to the development of a plethora of increasingly complex metal catalysts, thereby obviating in many cases the exact influence of the base, which is a simple, inexpensive, and necessary reagent for this paramount transformation. Here, a combined experimental and computational study shows that the oxidative addition is not the single kinetically relevant step in different cross-coupling reactions catalyzed by sub-nanometer Pt or Pd species, since the reactivity control is shifted toward subtle changes in the base. The exposed metal atoms in the cluster cooperate to enable an extremely easy oxidative addition of the aryl halide, even chlorides, and allow the base to bifurcate the coupling. With sub-nanometer Pd species, amines drive to the Heck reaction, carbonate drives to the Sonogahira reaction, and phosphate drives to the Suzuki reaction, while for Pt clusters and single atoms, good conversion is only achieved using acetate as a base. This base-controlled orthogonal reactivity with ligand-free catalysts opens new avenues in the design of cross-coupling reactions in organic synthesis.
Plasma-Induced Defects Enhance the Visible-Light Photocatalytic Activity of MIL-125(Ti)-NH2 for Overall Water Splitting
(John Wiley & Sons, 2020-12-01) Cabrero Antonino, María; Albero Sancho, Josep; García-Vallés, Cristina; Álvaro Rodríguez, María Mercedes; Navalón Oltra, Sergio; García Gómez, Hermenegildo; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; European Commission; Generalitat Valenciana; Fundación Ramón Areces; Agencia Estatal de Investigación; Agència Valenciana de la Innovació
[EN] Defect engineering in metal-organic frameworks is commonly performed by using thermal or chemical treatments. Herein we report that oxygen plasma treatment generates structural defects on MIL-125(Ti)-NH2, leading to an increase in its photocatalytic activity. Characterization data indicate that plasma-treated materials retain most of their initial crystallinity, while exhibiting somewhat lower surface area and pore volume. XPS and FT-IR spectroscopy reveal that oxygen plasma induces MIL-125(Ti)-NH2 partial terephthalate decarboxylation and an increase in the Ti-OH population. Thermogravimetric analyses confirm the generation of structural defects by oxygen plasma and allowed an estimation of the resulting experimental formula of the treated MIL-125(Ti)-NH2 solids. SEM analyses show that oxygen plasma treatment of MIL-125(Ti)-NH2 gradually decreases its particle size. Importantly, diffuse reflectance UV/Vis spectroscopy and valence band measurements demonstrate that oxygen plasma treatment alters the MIL-125(Ti)-NH2 band gap and, more significantly, the alignment of highest occupied and lowest unoccupied crystal orbitals. An optimal oxygen plasma treatment to achieve the highest efficiency in water splitting with or without methanol as sacrificial electron donor under UV/Vis or simulated sunlight was determined. The optimized plasma-treated MIL-125(Ti)-NH2 photocatalyst acts as a truly heterogeneous photocatalyst and retains most of its initial photoactivity and crystallinity upon reuse.
Two Cu-Based Phosphonate Metal-Organic Frameworks as Efficient Water-Splitting Photocatalysts
(American Chemical Society, 2023-06-01) Salcedo-Abraira, Pablo; Serrano Nieto, Rubén; Biglione, Catalina; Cabrero Antonino, María; Vilela, Sérgio M.F.; Babaryk, Artem A.; Tilve-Martínez, David; Rodriguez-Diéguez, Antonio; Navalón Oltra, Sergio; García Gómez, Hermenegildo; Horcajada, Patricia; Instituto Universitario Mixto de Tecnología Química; Departamento de Química; Escuela Técnica Superior de Ingeniería Industrial; Grupo de Fotoquímica Heterogénea y Medioambiental; Comunidad de Madrid; AGENCIA ESTATAL DE INVESTIGACION; Agencia Estatal de Investigación; European Regional Development Fund
[EN] Two novel three-dimensional metal-organic frameworks(MOFs)based on the photoactive pyrene tetraphosphonate ligand and copper(denoted as IEF-8 and IEF-9) have been hydrothermally synthesizedand fully characterized (XRD, FTIR, TGA, SEM, XPS, etc.). Their crystalstructures were unveiled by single-crystal X-ray diffraction. Remarkably,these materials exhibit coordinatively unsaturated copper (II) sites,free -PO3H2 and -PO3H acidic groups, and good thermal and chemical stability. Further,their optoelectronic characterization evidenced a photoresponse suitablefor photocatalysis. In this sense, the photocatalytic activity ofpyrene phosphonate MOFs was evaluated for the first time for the challenginghydrogen evolution reaction. In particular, IEF-8 exhibited a catalyticefficiency higher than that of the benchmarked Ti carboxylate photocatalystMIL-125-(Ti)-NH2, producing 1800 mu mol center dot g(-1) after 22 h under UV-vis irradiation in theabsence of any co-catalyst. Furthermore, this material presented goodreusability (at least up to 4 cycles), preserving its activity andstructural integrity.