Nanoparticles for Catalysis

The present book is aimed at illustrating the width of applications of metal nanoparticles in catalysis. It covers aspects such as metal nanoparticles preparation using natural biomolecules to the catalytic, photocatalytic and electrocatalytic activity of supported metal nanoparticles. In catalysis, metal nanoparticles exhibit general activity in oxidation and reduction reactions and the book contains examples of both types of processes in which the nanoparticles are on carbon supports or embedded inside the voids of microporous crystalline metal organic frameworks. Metal nanoparticles are also widely used in photocatalysis to enhance light absorption through plasmon band and the efficiency of the photochemical process. Besides classical applications, the use of metal nanoparticles is expanding rapidly in the field of renewable energies, going from catalysts for solid fuels electrodes to novel Li-O2 batteries

Estudio de soluciones para la mejora de la operatividad frente a fenómenos de agitación y resonancia en el Puerto de Alicante

[ES] La existencia de indicios y evidencias que indican la existencia de fenómenos de agitación y/o resonancia tanto en las dársenas como en el propio puerto deportivo del Puerto de Alicante. Este fenómeno es muy molesto pues produce que el oleaje incidente incremente su energía por acumulación debida a las reflexiones, que están condicionadas a la geometría del puerto, pudiendo dar un oleaje superior en el interior que el que incide. Esta situación es indeseable por la merma de operatividad de los buques, así como para el confort de los usuarios del puerto deportivo. Por lo tanto, para verificar y conocer las características de dichos fenómenos se realizará un Estudio de Agitación /Resonancia. Este tipo de fenómenos requiere el uso de modelos numéricos con ecuaciones de tipo elíptico. Para poder realizar este estudio se va a considerar el régimen medio incluyendo el oleaje existente en el año medio (agitación), así como las ondas largas con periodos superiores a los 30 segundos a hasta los 3 minutos (oleaje de infragravedad). Una vez obtenidas las características de agitación y resonancia que se producirían en las dársenas y en el puerto deportivo, se propondrán una serie de alternativas para minimizar dicho efecto. Se verificará la efectividad de las alternativas propuestas y se pasará a la opción de escoger cual es la mejor alternativa. Posteriormente se desarrollará la definición de dicha alternativa, incluso gráficamente efectuándose una valoración económica y analizando su viabilidad constructiva.[EN] The existence of indications and evidences that indicate the existence of phenomena of agitation and / or resonance both in the docks and in the marina of the Port of Alicante itself. This phenomenon is very annoying because it causes the incident waves to increase their energy due to accumulation due to reflections, which are conditioned by the geometry of the port, being able to give a higher wave in the interior than the one that affects it. This situation is undesirable due to the decrease in the operation of the ships, as well as for the comfort of the users of the marina. Therefore, to verify and know the characteristics of said phenomena, an Agitation / Resonance Study will be carried out. This type of phenomenon requires the use of numerical models with elliptic-type equations. In order to carry out this study, the average regimen will be considered, including the waves existing in the average year (agitation), as well as the long waves with periods greater than 30 seconds to up to 3 minutes (infragravity waves). Once the characteristics of agitation and resonance that would occur in the docks and in the marina have been obtained, a series of alternatives will be proposed to minimize this effect. The effectiveness of the proposed alternatives will be verified and the option of choosing the best alternative will be passed. Subsequently, the definition of said alternative will be developed, including graphically making an economic assessment and analysing its constructive viability.Navalón Pinto, S. (2020). Estudio de soluciones para la mejora de la operatividad frente a fenómenos de agitación y resonancia en el Puerto de Alicante. http://hdl.handle.net/10251/155322TFG

Parámetros de calidad del agua relacionados con la presencia de materia orgánica y microorganismos

Desde 1974 se conoce que el cloro añadido como desinfectante en el tratamiento de aguas potables reacciona con la materia orgánica natural (MON) del agua para dar lugar a compuestos clorados entre los que se encuentran los trihalometanos (THMs), los cuales están considerados como compuestos potencialmente cancerígenos, genotóxicos y mutagénicos. La concentración de THMs está regulada en España a un nivel máximo de 100 µg L-1. Por ello, en la actualidad algunas plantas de tratamiento de aguas potables trabajan con desinfectantes alternativos al cloro (principalmente ClO2 ó O3) que tienen un mayor poder de desinfección y reducen la formación de THMs. De modo general la MON del agua está formada por una fracción hidrófoba (ácidos húmicos, fúlvicos y/o derivados de la lignina) y una fracción hidrófila (sacáridos, proteínas, compuestos de polaridad media/alta con grupos carbonílicos cetónicos y/o carboxílicos). De entre todos estos compuestos, los derivados de fenol y los compuestos [beta]-dicarbonílicos son considerados como los principales precursores de los SPDs. Además de la MON del agua están siendo detectados en las aguas de abastecimiento o potables muchos compuestos derivados de la actividad humana (ej. Compuestos farmacéuticos). Considerando estos precedentes nos propusimos realizar un estudio de los parámetros de calidad relacionados con la materia orgánica del agua y con microorganismos resistentes a la cloración. Inicialmente se caracterizó la materia orgánica disuelta del río Turia (Capítulo 3), destacando la abundancia de estructuras derivadas de polisacáridos y de ácidos grasos. Además, inesperadamente no se observa la presencia de ácidos húmicos y fúlvicos. En contraste, se ha detectado paracetamol, un compuesto considerado contaminante emergente en las aguas de abastecimiento. Posteriormente, se procedió a evaluar el comportamiento de los carbohidratos como precursores de THMs en la cloración (Capítulo 4). Los resultados indican que aunque los valores de THMs obtenidos son menores respecto a los modelos tradicionales de ácidos húmicos y fúlvicos, en aquellos sistemas en los que existan elevadas concentraciones de carbohidratos éstos pueden contribuir notablemente a la formación de THMs.Los resultados obtenidos demuestran que el sistema UV/TiO2 es eficaz para conseguir la descontaminación completa de estos protozoos trabajando en condiciones reales de tratamiento. El cloro desempeña un papel sinérgico en el sistema reduciendo considerablemente los tiempos de exposición necesarios para llevar a cabo una desinfección efectiva.Navalón Oltra, S. (2010). Parámetros de calidad del agua relacionados con la presencia de materia orgánica y microorganismos [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/8415Palanci

Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions

[EN] Metal organic frameworks (MOFs) are porous crystalline solids whose frameworks are constituted by metal ions/nodes with rigid organic linkers leading to the formation of materials having high surface area and pore volume. One of the unique features of MOFs is the presence of coordinatively unsaturated metal sites in their crystalline lattice that can act as Lewis acid sites promoting organic transformations, including aerobic oxidation reactions of various substrates such as hydrocarbons, alcohols, and sulfides. This review article summarizes the existing Co-based MOFs for oxidation reactions organized according to the nature of substrates like hydrocarbon, alcohol, olefin, and water. Both aerobic conditions and peroxide oxidants are discussed. Emphasis is placed on comparing the advantages of using MOFs as solid catalysts with respect to homogeneous salts in terms of product selectivity and long-term stability. The final section provides our view on future developments in this field.H.G. is thankful for financial assistance from the Spanish Ministry of Science and Innovation (Severo Ochoa and CTQ2018-980237-CO2-1) and Generalitat Valenciana (Prometeo 2017-083). A.D. is thankful for the University Grants Commission, New Delhi, for awarding an Assistant Professorship through the Faculty Recharge Programme. A.D. acknowledges financial assistance from the Science Engineering Research Board, India, through its Extra Mural Research project (EMR/2016/006500). S.N. is thankful for financial support by the Ministerio de Ciencia, Innovacion y Universidades (RTI 2018-099482-A-I00 project), Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016) and Agencia Valenciana de la Innovacion (AVI-GVA, Carboagua project, INNEST/2020/111).Dhakshinamoorthy, A.; Montero-Lanzuela, E.; Navalón Oltra, S.; García Gómez, H. (2021). Cobalt-Based Metal Organic Frameworks as Solids Catalysts for Oxidation Reactions. Catalysts. 11(1):1-25. https://doi.org/10.3390/catal1101009512511

Nanoparticles for Catalysis

Navalón Oltra, S.; García Gómez, H. (2016). Nanoparticles for Catalysis. Nanomaterials. 6(7):123-123. doi:10.3390/nano6070123S1231236

General aspects in the use of graphenes in catalysis

[EN] This perspective is aimed at presenting some issues that, in our opinion, have still to be better addressed in the field of graphenes as catalysts. After an introductory section, the article comments on how the number of layers present on the catalyst, termed frequently as graphene, could be in some cases in contradiction with good practices about what should be or not considered as graphene. It will also be commented that some of the characterization tools that are employed in some cases for graphenes as catalysts, like specific surface area measurements based on isothermal gas adsorption on powders or XRD patterns are not well suited to characterizing graphenes. The potential role of impurities and structural defects in graphene catalysis has been highlighted showing the importance of providing exhaustive analysis of the materials. This perspective includes a final section with our view on future progress and wider consensus in the use of graphene in catalysis.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2014-53292-R) is gratefully acknowledged. Generalidad Valenciana is also thanked for funding (Prometeo 2013/014). SN is thankful for financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016). Financial support by Fundacion Ramon Areces (XVII Concurso Nacional para la adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia).Navalón Oltra, S.; Herance, JR.; Alvaro Rodríguez, MM.; García Gómez, H. (2018). General aspects in the use of graphenes in catalysis. Materials Horizons (Online). 5(3):363-378. https://doi.org/10.1039/c8mh00066bS3633785

Photocatalytic Hydrogen Production from Glycerol Aqueous Solutions as Sustainable Feedstocks Using Zr-Based UiO-66 Materials under Simulated Sunlight Irradiation

[EN] There is an increasing interest in developing cost-effective technologies to produce hydrogen from sustainable resources. Herein we show a comprehensive study on the use of metal-organic frameworks (MOFs) as heterogeneous photocatalysts for H-2 generation from photoreforming of glycerol aqueous solutions under simulated sunlight irradiation. The list of materials employed in this study include some of the benchmark Zr-MOFs such as UiO-66(Zr)-X (X: H, NO2, NH2) as well as MIL-125(Ti)-NH2 as the reference Ti-MOF. Among these solids, UiO-66(Zr)-NH2 exhibits the highest photocatalytic H-2 production, and this observation is attributed to its adequate energy level. The photocatalytic activity of UiO-66(Zr)-NH2 can be increased by deposition of small Pt NPs as the reference noble metal co-catalyst within the MOF network. This photocatalyst is effectively used for H-2 generation at least for 70 h without loss of activity. The crystallinity of MOF and Pt particle size were maintained as revealed by powder X-ray diffraction and transmission electron microscopy measurements, respectively. Evidence in support of the occurrence of photoinduced charge separation with Pt@UiO-66(Zr)-NH2 is provided from transient absorption and photoluminescence spectroscopies together with photocurrent measurements. This study exemplifies the possibility of using MOFs as photocatalysts for the solar-driven H-2 generation using sustainable feedstocks.Y S.N. is gracious for the financial support from the Agencia Valenciana de la Innovacio (AVI, INNEST/2020/111) project and Grant PID2021-123856OB-I00 fundedby MCIN/AEI/10.13039/501100011033 and by "ERDF A way of making Europe".Rueda-Navarro, CM.; Ferrer Ribera, RB.; Garcia-Baldovi, H.; Navalón Oltra, S. (2022). Photocatalytic Hydrogen Production from Glycerol Aqueous Solutions as Sustainable Feedstocks Using Zr-Based UiO-66 Materials under Simulated Sunlight Irradiation. Nanomaterials. 12(21):1-17. https://doi.org/10.3390/nano12213808117122

Metal Node Control of Brønsted Acidity in Heterobimetallic Titanium–Organic Frameworks

Compared to indirect framework modification, synthetic control of cluster composition can be used to gain direct access to catalytic activities exclusive of specific metal combinations. We demonstrate this concept by testing the aminolysis of epoxides with a family of isostructural mesoporous frameworks featuring five combinations of homometallic and heterobimetallic metal-oxo trimers (Fe3, Ti3, TiFe2, TiCo2, and TiNi2). Only TiFe2 nodes display activities comparable to benchmark catalysts based on grafting of strong acids, which here originate from the combination of Lewis Ti4+ and Brønsted Fe3+–OH acid sites. The applicability of MUV-101(Fe) to the synthesis of β-amino alcohols is demonstrated with a scope that also includes the gram scale synthesis of propranolol, a natural β-blocker listed as an essential medicine by the World Health Organization, with excellent yield and selectivity

Generating and optimizing the catalytic activity in UiO-66 for aerobic oxidation of alkenes by post-synthetic exchange Ti atoms combined with ligand substitution

[EN] The catalytic activity for the aerobic epoxidation of cyclooctene of UiO-66 has been introduced by post synthetic ion exchange of Zr4+ by Ti4+ at the nodes and the performance optimized by nitro substitution in the terephthalate ligand. In this way a TON value of 16,600 (1660 considering Zr + Ti content) was achieved, comparing favorably with the highest catalytic activity reported in homogeneous for the same reaction (10,000 for gamma-SiW10{(Fe3+(OH2)}(O-38(6-)). Kinetic studies have shown that the most likely reactive oxygen species involved in the oxidation is superoxide, with hydroxyl radicals also contributing to the reaction. UiO-66(Zr-5.4 Ti-0.6)-NO2 is stable under catalytic conditions, being used six times without any change in the conversion temporal profile and in the X-ray diffractogram. The scope of UiO-66(Zr-5.4 Ti-0.6)-NO2 promoted aerobic oxidation of alkenes was expanded by including smaller rings cycloalkenes, as well as acyclic and aryl conjugated alkenes. (C) 2018 Elsevier Inc. All rights reserved.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2014-53292-R and CTQ2015-69563-CO2-14) is gratefully acknowledged. Generalidad Valenciana is also thanked for funding (Prometeo 2017/018). SN thanks financial support by the Fundacion Ramon Areces (XVIII Concurso Nacional para la Adjudicacion de Ayudas a la Investigacion en Ciencias de la Vida y de la Materia, 2016).Santiago-Portillo, A.; Navalón Oltra, S.; Alvaro Rodríguez, MM.; García Gómez, H. (2018). Generating and optimizing the catalytic activity in UiO-66 for aerobic oxidation of alkenes by post-synthetic exchange Ti atoms combined with ligand substitution. Journal of Catalysis. 365:450-463. https://doi.org/10.1016/j.jcat.2018.07.032S45046336

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

This is the peer reviewed version of the following article: Chem. Eur. J. 2019, 25, 9280 9286, which has been published in final form at https://doi.org/10.1002/chem.201901361. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.[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.Financial support by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa, CTQ2015-65963-CQ-R1 and CTQ2014-53292-R) is gratefully acknowledged. Generalidad Valenciana is also thanked for funding (Prometeo 2017/083). S.N. thanks financial support by the Fundacijn Ramjn Areces (XVIII Concurso Nacional para la Adjudicacijn de Ayudas a la Investigacijn en Ciencias de la Vida y de la Materia, 2016).Santiago-Portillo, A.; Cabrero-Antonino, M.; Alvaro Rodríguez, MM.; Navalón Oltra, S.; García Gómez, H. (2019). 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. Chemistry - A European Journal. 25(39):9280-9286. https://doi.org/10.1002/chem.201901361S928092862539H�ft, E., Kosslick, H., Fricke, R., & Hamann, H.-J. (1996). Titanhaltige Molekularsiebe als Katalysatoren f�r selektive Oxidationsreaktionen mit Wasserstoffperoxid. Journal f�r Praktische Chemie/Chemiker-Zeitung, 338(1), 1-15. doi:10.1002/prac.19963380102Matsumoto, T., Ueno, M., Wang, N., & Kobayashi, S. (2008). 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Catalysis by metal nanoparticles embedded on metal–organic frameworks. Chemical Society Reviews, 41(15), 5262. doi:10.1039/c2cs35047eAlhumaimess, M., Lin, Z., He, Q., Lu, L., Dimitratos, N., Dummer, N. F., … Hutchings, G. J. (2014). Oxidation of Benzyl Alcohol and Carbon Monoxide Using Gold Nanoparticles Supported on MnO2Nanowire Microspheres. Chemistry - A European Journal, 20(6), 1701-1710. doi:10.1002/chem.201303355Buonerba, A., Cuomo, C., Ortega Sánchez, S., Canton, P., & Grassi, A. (2011). Gold Nanoparticles Incarcerated in Nanoporous Syndiotactic Polystyrene Matrices as New and Efficient Catalysts for Alcohol Oxidations. Chemistry - A European Journal, 18(2), 709-715. doi:10.1002/chem.201101034Costa, V. V., Estrada, M., Demidova, Y., Prosvirin, I., Kriventsov, V., Cotta, R. F., … Gusevskaya, E. V. (2012). Gold nanoparticles supported on magnesium oxide as catalysts for the aerobic oxidation of alcohols under alkali-free conditions. 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