Persona: Guerrero Ruiz, Antonio R
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Guerrero Ruiz
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Publicación Formic Acid Dehydration Using Mechanochemically Prepared TiO2-Graphite Composites(Wiley, 2024-07-27) Yruela Garrido, Marta; Martín Rodríguez, Nuria; Castillejos López, Eva; Campos Castellanos, Eduardo; Conesa, José María; Rodríguez Ramos, Inmaculada; Guerrero Ruiz, Antonio RCommercial high surface area graphite (HSAG300) and commercial TiO2 were used to produce composite materials through a simple mechanochemical method involving milling and ultrasonic treatments. The acid and basic sites exposed on the surfaces of these materials were characterized by temperature-programmed desorption (TPD) of ammonia and carbon dioxide. The catalytic materials were tested in the dehydration reaction of formic acid to produce hydrogen-free CO. While HSAG300 is practically inactive under reaction conditions (continuous gas flow at temperatures in the range of 100–250 °C), all samples containing TiO2 are active, exhibiting high selectivity to CO without significant deactivation at moderate reaction temperatures. It is demonstrated that the presence of graphite in the catalysts enhances the specific catalytic activity of TiO2. Assuming that the dehydration reaction is catalyzed by acid sites on the TiO2 surfaces, a comparative evaluation of the surface sites reveals that the graphite-TiO2 interactions not only change the density of surface sites but also modify the strength of the acid centers of TiO2. In summary, the interaction of HSAG300 with TiO2 modulates the surface properties of the prepared composite catalysts, decreasing the total number of basic surface sites and increasing the strength of acidic sites compared to bare TiO2.Publicación Critical Factors Affecting the Selective Transformation of 5-Hydroxymethylfurfural to 3-Hydroxymethylcyclopentanone Over Ni Catalysts(Chemistry Europe, 2024-06-11) Conesa, José M.; Campos Castellanos, Eduardo; Guerrero Ruiz, Antonio R; Rodríguez Ramos, Inmaculada; Morales Vargas, Mª Virtudes; https://orcid.org/0000-0003-2834-0296; https://orcid.org/0000-0001-5470-7958; https://orcid.org/0000-0003-4622-6008The ring-rearrangement of 5-hydroxymethylfurfural (HMF) to 3-hydroxymethylcyclopentanone (HCPN) was investigated over Ni catalysts supported on different carbon supports and metallic oxides with different structure and acid-base properties. Their catalytic performance was tested in a batch stirred reactor in aqueous solution at 180 °C and 30 bar of H2. Under these conditions, the HMF hydrogenation proceeds through three possible competitive routes: (i) a non-water path leading to the total hydrogenation product, 2,5-di-hydroxymethyl-tetrahydrofuran (DHMTHF), and two parallel acid-catalyzed water-mediated routes responsible for (ii) ring-opening and (iii) ring-rearrangement reaction products. All catalyst systems primarily produced HCPN, but reaction rates and product distribution were influenced by several variables, some of them intensely analyzed in this work. The most proper conditions resulted to be the presence of the medium/strong Lewis's acidity of a Ni/ZrO2 catalyst (initial TOF=5.99 min−1 and 73 % HCPN selectivity) or the Brønsted acidity originated by an oxidized high surface area graphite, Ni/HSAG-ox (initial TOF=5.92 min−1 and 87 % HCPN selectivity). However, too high density of acidic sites on the catalyst support (Ni/Al2O3) and sulfur impurities from the HMF feedstock led to catalyst deactivation by coke deposition and Ni poisoning, respectively.Publicación Continuous Catalytic Condensation of Ethanol into 1‑Butanol: The Role of Metallic Oxides (M = MgO, BaO, ZnO, and MnO) in Cu-M/ Graphite Catalysts(ACS Publications, 2020) López Olmos, Cristina; Morales, María V.; Rodríguez Ramos, Inmaculada; Guerrero Ruiz, Antonio R; https://orcid.org/0000-0003-2834-0296; https://orcid.org/0000-0003-1848-5985; https://orcid.org/0000-0003-4622-6008Bifunctional catalysts supported over high-surface-area graphite comprising copper and a series of metallic oxides (MgO, BaO, ZnO, or MnO) that exhibit different acid/base properties were studied in the ethanol condensation reaction to 1- butanol in a continuous flow reactor. This condensation reaction goes through the Guerbet mechanism, consisting of a multistep process based on hydrogenation/dehydrogenation reactions as well as base-catalyzed aldol condensation and acid-catalyzed dehydration reactions. The catalytic tests were performed in a fixed-bed reactor working in the gas phase at 50 bar and 503 K. The catalyst 5Cu-Mn/G exhibited the highest yield toward 1-butanol followed closely by 5Cu-Mg/G, unlike their counterparts with BaO and ZnO as the metal oxide. The cooperative action between the metal function as the hydrogenating/dehydrogenating agent and the suitable quantity of medium-high-strength basic sites and medium-weak-strength acid sites is responsible for the highest 1- butanol yields.Publicación Cu and Pd nanoparticles supported on a graphitic carbon material as bifunctional HER/ORR electrocatalysts(ELSEVIER, 2020-11-01) Nunes, Marta S.; Fernandes, Diana M.; Morales, M. V.; Rodríguez Ramos, Inmaculada; Freire, Cristina; Guerrero Ruiz, Antonio R; https://orcid.org/0000-0002-0460-451X; https://orcid.org/0000-0001-5263-2737; https://orcid.org/0000-0003-2834-0296; https://orcid.org/0000-0003-4622-6008; https://orcid.org/0000-0003-1848-5985The development of efficient, available and robust substitutes for the Pt-based electrocatalysts is very important for a sustainable energetic future. Herein, we report a series of composites based on Cu, Pd and Cu-Pd nanoparticles (NPs) supported on high surface area graphite (HSAG), as electrocatalysts for the energy-related reduction reactions – oxygen reduction (ORR) and hydrogen evolution (HER) reactions. All the composites showed interesting ORR electrocatalytic activities in alkaline medium. The Pd/HSAG and Cu-Pd/HSAG composites exhibited the most promising performances, with onset potentials of 0.84 and 0.91 V and current densities of jL, 0.3 V, 1600 rpm=−3.5 and −4.2 mA cm−2, respectively. All the composites showed selectivity for the 4-electron process and Tafel slopes in the range 48–77 mV dec−1. The metal/HSAG composites revealed a great tolerance to methanol and moderate electrochemical stability. In highly acidic medium (0.5 mol dm−3 H2SO4, pH=0.3) only the Cu-Pd/HSAG and Pd/HSAG electrocatalysts presented electrocatalytic activity toward HER, with relative low overpotentials (η10=0.145 and 0.063 V, respectively), small Tafel slopes (75 and 42 mV dec−1) and similar exchange current densities (0.43 and 0.57 mA cm−2). These electrocatalysts also showed moderate electrochemical stability, in particular Cu-Pd/ HSAG for which overpotential only changed between 0.033 and 0.038 V for j=40mAcm−2. The results showed that only small loading of Pd NPs (1 wt.% Pd) was able to improve significantly the ORR/ HER electrocatalytic activity, which is a very important outcome to rationalize the design of efficient and costeffective electrocatalysts in future.Publicación Evaluation of graphenic and graphitic materials on the adsorption of Triton X-100 from aqueous solution(ELSEVIER, 2021-09-01) Esteban Arranz, Adrián; Pérez Cadenas, María; Muñoz Andrés, Vicenta; Guerrero Ruiz, Antonio R; https://orcid.org/0000-0003-4953-8066; https://orcid.org/0000-0003-1848-5985Presently, graphenic nanomaterials are being studied as candidates for wastewater pollutant removal. In this study, two graphite oxides produced from natural graphite with different grain sizes (325 and 10 mesh), their respective reduced graphene oxides and one reduced graphene oxide with nitrogen functional groups were synthesized and tested to remove a surfactant model substrate, Triton X-100, from an aqueous solution. Kinetic experiments were carried out and adjusted to pseudo-first order equation, pseudo-second order equation, Elovich, Chain-Clayton and intra-particle diffusion models. Reduced graphene oxides displayed an instantaneous adsorption due to their accessible and hydrophobic surfaces, while graphite oxides hindered the TX100 adsorption rate due to their highly superficial oxygen content. Results from the adsorption isotherms showed that the Sips model perfectly described the TX100 adsorption behavior of these materials. Higher adsorption capacities were developed with reduced graphene oxides, being maximum for the material produced from the lower graphite grain size (qe = 3.55·10−6 mol/m2), which could be explained by a higher surface area (600 m2/g), a lower amount of superficial oxygen (O/C = 0.04) and a more defected structure (ID/IG = 0.85). Additionally, three commercial high surface area graphites in the range of 100–500 m2/g were evaluated for comparison purposes. In this case, better adsorption results were obtained with a more graphitic material, HSAG100 (qe = 1.72·10−6 mol/m2). However, the best experimental results of this study were obtained using synthesized graphenic materials.Publicación Effect of surface, structural and textural properties of graphenic materials over cooperative and synergetic adsorptions of two chloroaromatic compounds from aqueous solution(ELSEVIER, 2018) Esteban Arranz, Adrián; Tordesillas, Compte; Muñoz Andrés, Vicenta; Pérez Cadenas, María; Guerrero Ruiz, Antonio R; https://orcid.org/0000-0003-4953-8066; https://orcid.org/0000-0003-1848-5985Graphenic materials have been recently applied for adsorption processes due to their high efficiency and their easy capability of surface modification. In the present study two different graphene oxides, two reduced graphene oxides under inert atmosphere and one reduced graphene oxide under ammonia atmosphere were used as adsorbents for removing two chloroaromatic compounds from water: 2,4-dichlorophenol and 2,4-dichlorophenoxyacetic acid. Hydrogen bonds and πsingle bondπ interactions have been detected by Attenuated Total Reflectance infrared spectroscopy in the solids with adsorbed species. Besides, two direct relationships between their adsorption capacities and graphenic surface, textural and structural properties were found. In order to obtain real adsorption information, some experiments with the presence of both pollutants at the same time were performed. From these mixture experiments, when graphene oxide was used as adsorbent some cooperative effects between pollutants were detected. Based on XRD results and an innovative comparison between different infrared techniques, the importance of interlayer spaces during adsorption was demonstrated. Otherwise, synergetic interactions between pollutants were revealed as the main adsorption forces when reduced graphene oxides were used, being their aromatic structures a decisive factor in their final adsorption capacity.Publicación Comparative study of Cu, Ag and Ag-Cu catalysts over graphite in the ethanol dehydrogenation reaction: Catalytic activity, deactivation and regeneration(ELSEVIER, 2019) Conesa, J.M.; Morales, María V.; López-Olmos, Cristina; Rodríguez Ramos, Inmaculada; Guerrero Ruiz, Antonio R; https://orcid.org/0000-0003-2834-0296; https://orcid.org/0000-0003-4622-6008; https://orcid.org/0000-0003-1848-5985The physicochemical and catalytic properties of bimetallic AgCu catalysts and their monometallic counterparts supported on a high surface area graphite have been comparatively evaluated in the ethanol dehydrogenation reaction, performed in a continuous-flow reactor. While Cu was incorporated by the incipient wetness impregnation technique, for Ag catalysts two synthesis procedures were explored: incipient wetness impregnation and adsorption of Tollens’ reagent. The catalysts prepared by wetness impregnation exhibited higher metal dispersion, being improved for the bimetallic catalysts in comparison with the monometallic counterparts. The results obtained in the catalytic tests revealed that Cu catalysts is nearly two orders of magnitude more active than Ag catalyst in the dehydrogenation reaction of ethanol on either a turnover frequency or a weight basis, but at the same time both catalysts were 100% selective to acetaldehyde. Whereas selectivity was not affected by the bimetallic composition, there was a substantial decrease in the reaction rate among the bimetallic catalysts as the Cu/Ag ratio diminished, due to blockage of copper surface active sites by silver. Both silver and copper, and the bimetallic catalysts, suffered from deactivation at 523 K, caused by blocking of active sites by adsorbed hydrocarbons on the catalyst surface (fouling). Carbonaceous deposits were removed through a thermal treatment under H2 flow, which allowed the total recovery of the initial catalytic activity.Publicación Selective hydrogenation reactions of 5-hydroxymethylfurfural over Cu and Ni catalysts in water: Effect of Cu and Ni combination and the reagent purity(ELSEVIER, 2023) Morales, María V.; Conesa, José M.; Galvin, Antonio J.; Rodríguez Ramos, Inmaculada; Guerrero Ruiz, Antonio R; https://orcid.org/0000-0003-2834-0296; https://orcid.org/0000-0003-1848-5985; https://orcid.org/0000-0003-4622-6008This work studies the catalytic properties of Cu and Ni catalysts, as well as the effect of Cu and Ni combination on the activity and selectivity during the aqueous phase hydrogenation of 5-hydroxymethylfurfural (HMF) in a batch reactor, at 60 °C under 30 bar H2. Catalysts with different Ni/Cu ratios (10 wt%) were synthesized over a high surface area graphite (HSAG). While Ni provides the bimetallic catalyst the capacity for hydrogenation of Cdouble bondO and Cdouble bondC groups, Cu contributes to suppress the hydrogenation of the furan ring, reaching a 99% of selectivity to the partial hydrogenated product, 2,5-di-hydroxymethylfuran (DHMF), over 5Cu5Ni/HSAG. The increase of reaction temperature (180 °C) conduced to the hydrolytic ring-opening and rearrangement of HMF. Under such reaction conditions, monometallic Ni afforded the highest yield towards the hydrogenative rearrangement product, 3-hydroxymethylcyclopentanone (81%). However, Cu and CuNi bimetallic catalysts were less reactive to the ring-rearrangement reaction and showed higher tendency to deactivation, especially when the HMF supplier contain sulfur impurities.Publicación Graphite supported heteropolyacid as a regenerable catalyst in the dehydration of 1-butanol to butenes(ELSEVIER, 2023) Conesa, José M.; Morales, María V.; García-Bosch, N.; Rodríguez Ramos, Inmaculada; Guerrero Ruiz, Antonio R; https://orcid.org/0000-0003-2834-0296; https://orcid.org/0000-0003-1848-59851-butanol dehydration reaction has recently emerged as a sustainable route to produce butenes which can be further oligomerized to be applied as jet fuel. However, the high catalyst deactivation rates observed during this reaction due to coke deposition is still a pending matter. As promising catalysts for this reaction, we have supported two heteropolyacids (HPA), i.e. H4SiW12O40 (STA) and H3PW12O40 (TPA), on two commercial carbon materials: an activated carbon (AC) and a high surface area graphite (HSAG). Aiming to evaluate the role of HPA-support interactions, the STA was also dispersed over metallic oxides of different acidic nature, namely SiO2, Al2O3 and ZrO2. An exhaustive physicochemical characterization revealed that after the HPA dispersion thorough the support, the Keggin structure was maintained and an increase in the amount and strength of acid sites was provoked, but in different degree according to the HPA type and support’s nature. While the TPA-based catalysts developed less quantity of total acid sites, but higher strength than their STA-carbon counterparts, the STA/AC and TPA/AC samples exhibited a slight major amount of acid sites than STA/HSAG and TPA/HSAG. The HPA-support interactions have ultimately modulated to some extent the activity, selectivity, stability and regeneration ability of the synthesized catalysts, when applied in the gas phase butanol dehydration reaction at 275 °C. The higher STA decomposition temperature prompted by the graphitic support, among other factors, allowed the total regeneration of the highly active (39 mmolBuOH∙min−1∙ga.p) and n-butenes selective (>98 %) STA/HSAG catalyst by means of combustion of carbon deposits at 400 °C.Publicación Tunable selectivity of Ni catalysts in the hydrogenation reaction of 5-hydroxymethylfurfural in aqueous media: Role of the carbon supports(ELSEVIER, 2021) Morales, María V.; Conesa, José M.; Rodríguez Ramos, Inmaculada; Guerrero Ruiz, Antonio R; https://orcid.org/0000-0003-2834-0296; https://orcid.org/0000-0001-5470-7958; https://orcid.org/0000-0003-1848-5985; https://orcid.org/0000-0003-4622-6008In addition to the nature of the solvent, the intrinsic metal properties and degree of dispersion, the selective hydrogenation of 5-hydroxymethylfurfural (HMF) has been reported to be greatly affected by the nature of the support. In this work, four Ni catalysts were prepared starting from different carbonaceous supports ─with diverse graphitic and porous structure─ and comparatively evaluated in the hydrogenation reaction of HMF. The reaction was conducted in a batch stirred reactor under 30 bar H2 pressure at 60 °C in aqueous media. Ni supported on a commercial silica and Raney Ni were also tested for reference purposes. We found that carbon supports limit in some extent the reactivity of Ni towards Cdouble bondC hydrogenation, offering higher selectivity to the carbonyl hydrogenated compound, 2,5-di-hydroxymethylfuran (DHMF), in detrimental to the total hydrogenated derivative, 2,5-di-hydroxymethyl-tetrahydrofuran (DHMTHF). However, the latter was the major product over Raney Ni and Ni/SiO2. The unusual catalytic performance of our Ni/carbon catalysts was related to the composition, structural and surface properties. Among all tested Ni/carbon catalysts, Ni over the commercial high surface area graphite (HSAG) exhibited the best catalytic behaviour in terms of DHMF selectivity (90%) and intrinsic catalytic activity. Furthermore, Ni/HSAG displayed satisfactory stability after three consecutive runs.