CO-PrOx over nano-Au/TiO2: Monolithic catalyst performance and empirical kinetic model fitting

In this work, the performance of ceramic monoliths washcoated with Au/TiO2 is studied on CO preferential oxidation (CO-PrOx) reaction in H2-rich environments under a wide range of operating conditions of practical interest. The parameter estimation of a nonlinear kinetic empirical model representing this system is made via genetic algorithms by fitting the model predictions against our laboratory observations. Parameter uncertainty leading to inaccurate predictions is often present when kinetic models with nonlinear rate equations are considered. Here, after the fitting was concluded, a statistical study was conducted to determine the accuracy of the parameter estimation. Activation energies of ca. 30 kJ/mol and 55 kJ/mol were adjusted for CO and H2 oxidations, respectively. The catalyst showed appropriate activity and selectivity values on the CO oxidation on a H2-rich environment. After ca. 45 h on stream the catalyst showed no deactivation. Results show that the model is suitable for reproducing the behavior of the CO-PrOx reactions and it can be used in the design of reactors for hydrogen purification.Peer ReviewedPostprint (author's final draft

In situ photoelectron spectroscopy study of ethanol steam reforming over RhPd nanoparticles and RhPd/CeO2

In situ X-ray photoelectron spectroscopy (XPS) was carried out over model Rh0.5Pd0.5 nanoparticles and Rh0.5Pd0.5 nanoparticles supported on CeO2 following exposure to oxygen at 573-823 K, to hydrogen at 573 K (activation of the catalyst), to a mixture of ethanol and water at 823 K simulating ethanol steam reforming (ESR) conditions, and to hydrogen at 823 K. The presence of the CeO2 support had a strong influence on the atomic rearrangement and on the oxidation state of Rh0.5Pd0.5 nanoparticles. CeO2 exerted a quenching effect on the metal nanoparticles and limited atomic rearrangement under the different atmospheres tested except for ESR, where a partial segregation of Rh toward the surface of the nanoparticles was observed. When supported on CeO2, Rh0.5Pd0.5 nanoparticles were significantly more oxidized due to metal-support interaction. By comparing these in situ XPS results with a previous operando near ambient pressure XPS study conducted in a synchrotron facility at 0.05 mbar over the same samples, it is concluded that the information obtained for the unsupported Rh0.5Pd0.5 nanoparticles is similar in both cases, whereas Rh0.5Pd0.5 nanoparticles supported on CeO2 are clearly more oxidized and enriched in Pd in the volume sampled under operando ESR conditions compared to that obtained in the in situ experiments. The study of catalytic systems under operando conditions appears essential to identify the active species at work during ESR, as the restructuring driven by the reforming environment induces strong changes in their architecture. (C) 2015 Elsevier B.V. All rights reserved.Postprint (author's final draft

Finding a suitable catalyst for on-board ethanol reforming using exhaust heat from an internal combustion engine

Ethanol steam reforming with pure ethanol and commercial bioethanol (S/C = 3) was carried out inside the housing of the exhaust gas pipe of a gasoline internal combustion engine (ICE) by using exhaust heat (610–620 °C). Various catalytic honeycombs loaded with potassium-promoted cobalt hydrotalcite and with ceria-based rhodium–palladium catalysts were tested under different reactant loads. The hydrogen yield obtained over the cobalt-based catalytic honeycomb at low load (F/W 200 h) at high load (F/W = 150 mLliq·gcat-1·h-1, GHSV = 2.4·103 h-1) showed that promotion of the ceria-supported noble metal catalyst with alumina and zirconia is a key element for practical application using commercial bioethanol. HRTEM analysis of post mortem honeycombs loaded with RhPd/Ce0.5Zr0.5O2–Al2O3 showed no carbon formation and no metal agglomeration.Postprint (author's final draft

Study of Cu-Zn and Au/TiO2 Catalysts on Anodized Aluminum Monoliths for Hydrogen Generation and Purification

This work reports the preparation of Cu-Zn and Au/TiO2 catalysts on anodized aluminum monoliths(AAM). The structured catalysts were studied for the generation of H2 by methanol steam reforming (MSR) and its purification by preferential oxidation of CO (CO-PrOx). Initially, it was possible to generate a surface with whiskers and larger surface area by hydrothermal treatment of the AAM. Subsequently, the structured catalysts were synthesized by incipient wetness impregnation (IWI) and ydrothermal synthesis (HS). IWI synthesis allowed for the deposition of a larger amount of catalytic material than HS, with very good adhesion. The TiO2-IWI structured catalyst presented a homogeneous catalytic coating, with the presence of agglomerated particles. On theother hand, Cu-Zn-IWI showed good dispersion of the deposited particles with a homogeneous surface coating. EDX analysis corroborated the presence of Ti, Cu and Zn in all the catalytic surfaces. The incorporation of Au over TiO2-IWI structured catalysts was successfully performed by IWI using a colloidal solution of gold nanoparticles.MSR was studied over the developed metallic monoliths functionalized with Cu-Zn by the IWI method. The samples showed promising results in terms of activity, selectivity, and stability. Both diluted and concentrated methanol + water feeds were assayed. Complete methanol conversion was achieved for the diluted feed. Maximum methanol conversions of 55% with 60% H2 yield were measured when the concentrated feed was selected. Promising results were also achieved for the Au-based structured catalysts in the CO-PrOx in an H2- rich atmosphere. Although CO conversions of approximately 60% were achieved, operating with higher catalyst loadings would be recommended to reach the high CO conversions required for PrOx catalysts.Fil: Adrover, María Esperanza. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Boldrini, Diego Emmanuel. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Jiménez Divins, Nuria. Universidad Politecnica de Catalunya; EspañaFil: Casanovas Hoste, Adria. Universidad Politecnica de Catalunya; EspañaFil: Tonetto, Gabriela Marta. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Lopez, Eduardo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Bahía Blanca. Planta Piloto de Ingeniería Química. Universidad Nacional del Sur. Planta Piloto de Ingeniería Química; ArgentinaFil: Llorca Piqué, Jordi. Universidad Politecnica de Catalunya; Españ

The influence of nano-architectured CeOx supports in RhPd/CeO2 for the catalytic ethanol steam reforming reaction

The ethanol steam reforming (ESR) reaction has been tested over RhPd supported on polycrystalline ceria in comparison to structured supports composed of nanoshaped CeO2 cubes and CeO2 rods tailored toward the production of hydrogen. At 650-700 K the hydrogen yield follows the trend RhPd/CeO(2)cubes >RhPd/CeO2-rods >RhPd/CeO2-polycrystalline, whereas at temperatures higher than 800K the catalytic performance of all samples is similar and close to the thermodynamic equilibrium. The improved performance of RhPd/CeO2-cubes and RhPd/CeO2-rods for ESR at low temperature is mainly ascribed to higher water-gas shift activity and a strong interaction between the bimetallic-oxide support interaction. STEM analysis shows the existence of RhPd alloyed nanoparticles in all samples, with no apparent relationship between ESR performance and RhPd particle size. X-ray diffraction under operating conditions shows metal reorganization on {1 0 0} and {1 1 0} ceria crystallographic planes during catalyst activation and ESR, but not on {1 1 1} ceria crystallographic planes. The RhPd reconstructing and tuned activation over ceria nanocubes and nanorods is considered the main reason for better catalytic activity with respect to conventional catalysts based on polycrystalline ceria. (C) 2015 Elsevier B.V. All rights reserved.Postprint (author's final draft

In Situ Electrochemical Oxidation of Cu2S into CuO Nanowires as a Durable and Efficient Electrocatalyst for Oxygen Evolution Reaction

Development of cost-effective oxygen evolution catalysts is of capital importance for the deployment of large-scale energy-storage systems based on metal-air batteries and reversible fuel cells. In this direction, a wide range of materials have been explored, especially under more favorable alkaline conditions, and several metal chalcogenides have particularly demonstrated excellent performances. However, chalcogenides are thermodynamically less stable than the corresponding oxides and hydroxides under oxidizing potentials in alkaline media. Although this instability in some cases has prevented the application of chalcogenides as oxygen evolution catalysts and it has been disregarded in some others, we propose to use it in our favor to produce high-performance oxygen evolution catalysts. We characterize here the in situ chemical, structural, and morphological transformation during the oxygen evolution reaction (OER) in alkaline media of CuS into CuO nanowires, mediating the intermediate formation of Cu(OH). We also test their OER activity and stability under OER operation in alkaline media and compare them with the OER performance of Cu(OH) and CuO nanostructures directly grown on the surface of a copper mesh. We demonstrate here that CuO produced from in situ electrochemical oxidation of CuS displays an extraordinary electrocatalytic performance toward OER, well above that of CuO and Cu(OH) synthesized without this transformation

Bimetallic NiFe nanoparticles supported on CeO2 as catalysts for methane steam reforming

Ni-Fe nanocatalysts supported on CeO2 have been prepared for the catalysis of methane steam reforming (MSR) aiming for coke-resistant noble metal-free catalysts. The catalysts have been synthesized by traditional incipient wetness impregnation as well as dry ball milling, a green and more sustainable preparation method. The impact of the synthesis method on the catalytic performance and the catalysts’ nanostructure has been investigated. The influence of Fe addition has been addressed as well. The reducibility and the electronic and crystalline structure of Ni and Ni-Fe mono- and bimetallic catalysts have been characterized by temperature programmed reduction (H2-TPR), in situ synchrotron X-ray diffraction (SXRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy. Their catalytic activity was tested between 700 and 950 °C at 108 L gcat-1 h-1 and with the reactant flow varying between 54 and 415 L gcat-1 h-1 at 700 °C. Hydrogen production rates of 67 mol gmet-1 h-1 have been achieved. The performance of the ball-milled Fe0.1Ni0.9/CeO2 catalyst was similar to that of Ni/CeO2 at high temperatures, but Raman spectroscopy revealed a higher amount of highly defective carbon on the surface of Ni-Fe nanocatalysts. The reorganization of the surface under MSR of the ball-milled NiFe/CeO2 has been monitored by in situ near-ambient pressure XPS experiments, where a strong reorganization of the Ni-Fe nanoparticles with segregation of Fe toward the surface has been observed. Despite the catalytic activity being lower in the low-temperature regime, Fe addition for the milled nanocatalyst increased the coke resistance and could be an efficient alternative to industrial Ni/Al2O3 catalysts.Peer ReviewedPostprint (published version

Shape-dependent CO2 hydrogenation to methanol over Cu2O nanocubes supported on ZnO

The hydrogenation of CO2 to methanol over Cu/ZnO-based catalysts is highly sensitive to the surface composition and catalyst structure. Thus, its optimization requires a deep understanding of the influence of the pre-catalyst structure on its evolution under realistic reaction conditions, including the formation and stabilization of the most active sites. Here, the role of the pre-catalyst shape (cubic vs spherical) in the activity and selectivity of ZnO-supported Cu nanoparticles was investigated during methanol synthesis. A combination of ex situ, in situ, and operando microscopy, spectroscopy, and diffraction methods revealed drastic changes in the morphology and composition of the shaped pre-catalysts under reaction conditions. In particular, the rounding of the cubes and partial loss of the (100) facets were observed, although such motifs remained in smaller domains. Nonetheless, the initial pre-catalyst structure was found to strongly affect its subsequent transformation in the course of the CO2 hydrogenation reaction and activity/selectivity trends. In particular, the cubic Cu particles displayed an increased activity for methanol production, although at the cost of a slightly reduced selectivity when compared to similarly sized spherical particles. These findings were rationalized with the help of density functional theory calculations.Peer ReviewedPostprint (published version

Investigation of the evolution of Pd-Pt supported on ceria for dry and wet methane oxidation

Efficiently treating methane emissions in transportation remains a challenge. Here, we investigate palladium and platinum mono- and bimetallic ceria-supported catalysts synthesized by mechanical milling and by traditional impregnation for methane total oxidation under dry and wet conditions, reproducing those present in the exhaust of natural gas vehicles. By applying a toolkit of in situ synchrotron techniques (X-ray diffraction, X-ray absorption and ambient pressure photoelectron spectroscopies), together with transmission electron microscopy, we show that the synthesis method greatly influences the interaction and structure at the nanoscale. Our results reveal that the components of milled catalysts have a higher ability to transform metallic Pd into Pd oxide species strongly interacting with the support, and achieve a modulated PdO/Pd ratio than traditionally-synthesized catalysts. We demonstrate that the unique structures attained by milling are key for the catalytic activity and correlate with higher methane conversion and longer stability in the wet feed.Peer ReviewedPostprint (published version

A general approach to fabricate fe3O4 nanoparticles decorated with Pd, Au, and Rh: Magnetically recoverable and reusable catalysts for Suzuki C-C cross-coupling reactions, hydrogenation, and sequential reactions

A facile strategy has been explored for loading noble metals onto the surface of ferrite nanoparticles with the assistance of phosphine-functionalized linkers. Palladium loading is shown to occur with participation of both the phosphine function and the surface hydroxyl groups. Hybrid nanoparticles containing simultaneously Pd and Au (or Rh) are obtained by successive loading of metals. Similarly, ferrite nanoparticles decorated with Pd, Au, and Rh have also been formed by using the same strategy. The catalytic properties of the new nanoparticles are evidenced in processes such as reduction of 4-nitrophenol or hydrogenation of styrene. Besides, the sequential process involving a cross-coupling reaction followed by reduction of 1-nitrobiphenyl has been successfully achieved by employing Pd/Au decorated nanoferrite particles. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.Postprint (published version