Pt-WOx/C Catalysts for α, β-Unsaturated Aldehydes Hydrogenation: An NMR Study of the Effect of the Reactant Adsorption on Activity and Selectivity

The selective hydrogenation of alpha,beta-unsaturated aldehydes is an ideal case for studying the structure-activity relationships in heterogeneous catalysis. In particular, cinnamaldehyde can be used as probe molecule for revealing the competition between hydrogenation of C=C and C=O bond. Here, we investigated the effect of the modification of some Pt supported on carbon catalysts by WOx species in cinnamaldehyde hydrogenation, as WOx species are reported to increase the adsorption and activation of the C=O group of alpha, beta-unsaturated aldehydes. Classical techniques used for correlating the catalyst activity and the selectivity to the characteristic of the materials (XRD, HAADF-STEM, XEDS mapping and XPS) have been coupled with NMR relaxometry, as innovative application, to disclose how the molecule approaches the catalyst surface. This indeed constitutes a crucial aspect that rule the catalytic activity. Therefore, an innovative, holistic approach has been used to consider the whole catalytic system

In-Depth Structural and Optical Analysis of Ce-modified ZnO Nanopowders with Enhanced Photocatalytic Activity Prepared by Microwave-Assisted Hydrothermal Method

Pure and Ce-modified ZnO nanosheet-like polycrystalline samples were successfully synthesized by a simple and fast microwave-based process and tested as photocatalytic materials in environmental remediation processes. In an attempt to clarify the actual relationships between functionality and atomic scale structure, an in-depth characterization study of these materials using a battery of complementary techniques was performed. X-ray diffraction (XRD), field emission-scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), energy-dispersive X-Ray spectroscopy-scanning transmission electron microscopy (STEM-XEDS), photoluminescence spectroscopy (PL) and UV-Visible absorption spectroscopy were used to evaluate the effect of Ce ions on the structural, morphological, optical and photocatalytic properties of the prepared ZnO nanostructures. The XRD results showed that the obtained photocatalysts were composed of hexagonal, wurtzite type crystallites in the 34-44 nm size range. The SEM and TEM showed nanosheet-shaped crystallites, a significant fraction of them in contact with bundles of randomly oriented and much smaller nanoparticles of a mixed cerium-zinc phase with a composition close to Ce0.68Zn0.32Ox. Importantly, in clear contrast to the prevailing proposals regarding this type of materials, the STEM-XEDS characterization of the photocatalyst samples revealed that Ce did not incorporate into the ZnO crystal lattice as a dopant but that a heterojunction formed between the ZnO nanosheets and the Ce-Zn mixed oxide phase nanoparticles instead. These two relevant compositional features could in fact be established thanks to the particular morphology obtained by the use of the microwave-assisted hydrothermal synthesis. The optical study revealed that in the ZnO:Ce samples optical band gap was found to decrease to 3.17 eV in the samples with the highest Ce content. It was also found that the ZnO:Ce (2 at.%) sample exhibited the highest photocatalytic activity for the degradation of methylene blue (MB), when compared to both the pure ZnO and commercial TiO2-P25 under simulated sunlight irradiation. The kinetics of MB photodegradation in the presence of the different photocatalysts could be properly described using a Langmuir-Hinshelwood (LH) model, for which the ZnO:Ce (2 at.%) sample exhibited the highest value of effective kinetic constant

Biomass into chemicals: One-pot two- and three-step synthesis of quinoxalines from biomass-derived glycols and 1,2-dinitrobenzene derivatives using supported gold nanoparticles as catalysts

An efficient and selective one-pot two-step method, for the synthesis of quinoxalines by oxidative coupling of vicinal diols with 1,2-phenylenediamine derivatives, has been developed by using gold nanoparticles supported on nanoparticulated ceria (Au/CeO2) or hydrotalcite (Au/HT) as catalysts and air as oxidant, in the absence of any homogeneous base. Reaction kinetics shows that the reaction controlling step is the oxidation of the diol to a-hydroxycarbonyl compound. Furthermore, a one-pot three-step synthesis of 2-methylquinoxaline starting from 1,2-dinitrobenzene and 1,2-propanediol has been success fully carried out with 98% conversion and 83% global yield to the final product.The authors wish to acknowledge the Spanish Ministry of Education and Science for the financial support in the projects Consolider-Ingenio 2010 and CTQ-2011-27550. Generalitat Valenciana is also thanked for funding through the Prometeo program. S.M.S thanks Spanish Ministry of Education and Science for FPI fellowships.Climent Olmedo, MJ.; Corma Canós, A.; Hernández, JC.; Hungría, AB.; Iborra Chornet, S.; Martínez Silvestre, S. (2012). Biomass into chemicals: One-pot two- and three-step synthesis of quinoxalines from biomass-derived glycols and 1,2-dinitrobenzene derivatives using supported gold nanoparticles as catalysts. Journal of Catalysis. 292:118-129. https://doi.org/10.1016/j.jcat.2012.05.002S11812929

Determining the Role of Fe-Doping on Promoting the Thermochemical Energy Storage Performance of (Mn1-xFex)(3)O-4 Spinels

Mn oxides are promising materials for thermochemical heat store, but slow reoxidation of Mn3O4 to Mn2O3 limits efficiency. In contrast, (Mn1-xFex)(3)O-4 oxides show an enhanced transformation rate, but fundamental understanding of the role played by Fe cations is lacking. Here, nanoscale characterization of Fe-doped Mn oxides is performed to elucidate how Fe incorporation influences solid-state transformations. X-ray diffraction reveals the presence of two distinct spinel phases, cubic jacobsite and tetragonal hausmannite for samples with more than 10% of Fe. Chemical mapping exposes wide variation of Fe content between grains, but an even distribution within crystallites. Due to the similarities of spinels structures, high-resolution scanning transmission electron microscopy cannot discriminate unambiguously between them, but Fe-enriched crystallites likely correspond to jacobsite. In situ X-ray absorption spectroscopy confirms that increasing Fe content up to 20% boosts the reoxidation rate, leading to the transformation of Mn2+ in the spinel phase to Mn3+ in bixbyite. Extended X-ray absorption fine structure shows that Fe-O length is larger than Mn-O, but both electron energy loss spectroscopy and X-ray absorption near edge structure indicate that iron is always present as Fe3+ in octahedral sites. These structural modifications may facilitate ionic diffusion during bixbyite formation.The authors thank the financial support from "Ramon Areces" Foundation (project SOLARKITE), Comunidad de Madrid and European Structural Funds (project ACES2030 P2018/EMT-4319), and University of Cadiz and European Structural Funds (project FEDER-UCA18-107139). A.J.C. thanks the financial support by Juan de la Cierva Formacion Program (MICINN), grant FJCI-2017-33967. The authors acknowledge ALBA-CELLS Synchrotron facility for granting beamtime at CLAESS (experiment 2016021666-2) and Electron Microscopy division located in the Servicios Centrales de Investigacion Cientifica y Tecnologica (SC-ICYT) of the University of Cadiz. Assistance of Dr. Laura Simonelli during the XAS measurements in ALBA is fully appreciated

Quantitative Evaluation of Supported Catalysts Key Properties from Electron Tomography Studies: Assessing Accuracy Using Material-Realistic 3D-Models

Electron Tomography (ET) reconstructions can be analysed, via segmentation techniques, to obtain quantitative, 3D-information about individual nanoparticles in supported catalysts. This includes values of parameters out of reach for any other technique, like their volume and surface, which are required to determine the dispersion of the supported particle system or the specific surface area of the support; two figures that play a major role in the performance of this type of catalysts. However, both the experimental conditions during the acquisition of the tilt series and the limited fidelity of the reconstruction and segmentation algorithms, restrict the quality of the ET results and introduce an undefined amount of error both in the qualitative features of the reconstructions and in all the quantitative parameters measured from them. Here, a method based on the use of well-defined 3D geometrical models (phantoms), with morphological features closely resembling those observed in experimental images of an Au/CeO2 catalyst, has been devised to provide a precise estimation of the accuracy of the reconstructions. Using this approach, the influence of noise and the number of projections on the errors of reconstructions obtained using a Total Variation Minimization in 3D (TVM-3D) algorithm have been determined. Likewise, the benefits of using smart denoising techniques based on Undecimated Wavelet Transforms (UWT) have been also evaluated. The results clearly reveal a large impact of usual noise levels on both the quality of the reconstructions and nanometrological measurement errors. Quantitative clues about the key role of UWT to largely compensate them are also provided.This work has received support from Projects: PID2020-113006-RB-I00, PID2019-110018GA-I00, PID2020-114594GB-C22, funded by MCIN/AEI/https://doi.org/10.13039/501100011033.This work has also been co-financed by Project ref: MAT2017-87579-R and by the 2014 -2020 ERDF Operational Programme and by the Department of Economy, Knowledge, Business and University of the Regional Government of Andalusia, Project references: FEDER-UCA18-107139, FEDERUCA18-106895 and P18-FR-1422. STEM ET experiments were recorded at the DME-UCA Node of the Spanish Singular Infrastructure for Electron Microscopy of Materials (ICTS ELECMI)

NO Oxidation on Lanthanum-Doped Ceria Nanoparticles with Controlled Morphology

The present work aims to assess the impact of morphology and reducibility on lanthanum-doped ceria nanocatalysts with controlled morphology on the NO oxidation reaction. Specifically, samples were prepared using a hydrothermal method incorporating lanthanum at varying molar concentrations (0, 5, 10, and 15 mol.%) into ceria with a controlled morphology (nanocubes and nanorods). The structural, compositional, and redox characterization of these catalysts has been performed via scanning transmission electron microscopy (STEM), X-ray diffraction (XRD), X-ray energy dispersive spectroscopy (X-EDS), inductively coupled plasma (ICP), hydrogen temperature-programmed reduction (H2-TPR), and oxygen storage capacity (OSC). NO oxidation catalytic tests were conducted, and the results were compared with estimated curves (obtained by considering the proportions of the corresponding components), which revealed the presence of a synergistic effect between lanthanum and ceria. The degree of enhancement was found to depend on both the morphology and the amount of lanthanum incorporated into CeO2. These findings may facilitate the optimization of features concerning ceria-based nanocatalysts for the removal of NOx emissions from exhaust gases.This research was funded by Generalitat Valenciana (CIPROM/2021/070 project), the Spanish Ministry of Science and Innovation/Research Spanish Agency (PID2019-105542RB-I00/AEI/10.13039/501100011033, PID2020-113006RB-I00/AEI/10.13039/501100011033 and PID2020-113809RB-C33 projects), and UE-FEDER funding

Enhanced Artificial Enzyme Activities on the Reconstructed Sawtoothlike Nanofacets of Pure and Pr-Doped Ceria Nanocubes

In this work, a simple one-step thermal oxidation process was established to achieve a significant surface increase in {110} and {111} nanofacets on well-defined, pure and Pr-doped, ceria nanocubes. More importantly, without changing most of the bulk properties, this treatment leads to a remarkable boost of their enzymatic activities: from the oxidant (oxidase-like) to antioxidant (hydroxyl radical scavenging) as well as the paraoxon degradation (phosphatase-like) activities. Such performance improvement might be due to the thermally generated sawtoothlike {111} nanofacets and defects, which facilitate the oxygen mobility and the formation of oxygen vacancies on the surface. Finally, possible mechanisms of nanoceria as artificial enzymes have been proposed in this manuscript. Considering the potential application of ceria as artificial enzymes, this thermal treatment may enable the future design of highly efficient nanozymes without changing the bulk composition.This work has been supported by the Ministry of Science, Innovation and Universities of Spain with Reference Numbers of ENE2017-82451-C3-2-R, MAT2016-81118-P and MAT2017-87579-R. The research projects funded by the Natural Science Foundation of Shandong Province (Grant ZR2017LB028), Key R&D Program of Shandong Province (Grant 2018GSF118032), and Fundamental Research Funds for the Central Universities (Grant 18CX02125A) in China are also acknowledged. TEM/STEM data were obtained at DMEUCA node of the Spanish Unique Scientific and Technological Infrastructure (ICTS) of Electron Microscopy of Materials ELECMIM. M. Tinoco thanks the FPU Scholarship Program (Grant AP2010-3737) from Ministry of Education of Spain. H. Pan is grateful for financial support (Grant 201406140130) from the Chinese Scholarship Council to accomplish her Ph.D. study at the University of Cadiz (Spain). J. M. Gonzalez, G. Blanco, and X. Chen are also grateful for the financial support from the joint project (Proyectos Integradores, Grant PI20201) in IMEYMAT of the University of Cadiz

Correlación estructura/actividad en catalizadores de metales soportados sobre óxidos nanoestructurados de tipo (Ce, M)Ox y (Ce, M)Ox/A12O3

Tesis Doctoral inédita leída en la Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química-Física Aplicada, Fecha de lectura 26-11-200

Influence of {111} nanofaceting on the dynamics of CO adsorption and oxidation over Au supported on CeO2 nanocubes: An operando DRIFT insight

CO adsorption and further reaction with O2 on two Au/CeO2 model systems have been investigated by operando diffuse reflectance infrared Fourier transform spectroscopy (DRIFT) in order to unveil the active sites for CO oxidation. One of the ceria supports was constituted by crystallites depicting a nanocube shape bounded mostly by {100} planes, whilst the second one was consisted of nanocubes whose {110} surfaces were reconstructed into {111}-nanofacets with a zig-zag shape. The deconvolution of the CO adsorption bands and a detailed analysis of the time-evolution of these bands were also carried out. These studies evidenced a fast adsorption of CO over Au° and then Auδ--CO bands appeared during exposure to CO, in parallel with the appearance of Ce3+ features. Such changes suggest that CO adsorption process starts on Au sites on the low coordinated sites of the surface of the Au nanoparticles and their transfer to the interface sites. By comparing the nanostructure of the two catalysts, the Auδ--CO species could be fruitfully related to CO adsorption on sites located at the Au||CeO2 perimeter. The sample containing gold nanoparticles dispersed over the {111}-nanofaceted CeO2 nanocubes, which retained a higher amount of gold nanoparticles, depicts higher contribution of Auδ−−CO bands than the other Au catalyst in the DRIFT spectra. The dynamic DRIFT study clearly revealed that the CO species adsorbed on Auδ- sites were the most reactive ones in both gold supported systems for CO oxidation. This explains much higher TOF values observed on the catalyst prepared on the surface reconstructed support. A detailed analysis on the reactivity was performed by modulation excitation spectroscopy (MES). The presence of peroxide surface species (O2 2-) in nanofaceted {111} could lead to higher catalytic activity than that of gold on the non-reconstructed catalyst..Ministerio de Ciencia InnovaciónNational Agency for the Promotion of Science and Technology of ArgentinaDepto. de Química InorgánicaFac. de Ciencias QuímicasTRUEpu

A Macroscopically Relevant 3D-Metrology Approach for Nanocatalysis Research

A 3D nanometrological approach, which considers as an unbiased validation criterion the quantitative match between values of properties determined by macroscopic characterization techniques and those determined from the nanoscopic results, is developed to unveil the details of complex nanocatalysts. This approach takes into account both the peculiar characteristics of this type of materials and the large influence of noise in the tilt series. It combines, in an optimized way, the latest experimental developments in high angle annular dark field scanning transmission electron microscopy mode (HAADF-STEM) tomography, such as batch tomography, image denoising by undecimated wavelet transforms, improved reconstructions by total variation minimization and a more efficient, user-independent, segmentation scheme. To illustrate the use of this novel approach, the 3D structural characterization of a model nanocatalyst comprising gold nanoparticles dispersed on the surface of CeO2 nanocubes is performed, and the obtained results used to compute the values of different macroscopic chemical and textural properties. Comparison with values obtained by macroscopic characterization techniques match very closely those obtained by 3D nanometrology. Importantly, the new approach described in this work also illustrates a pipeline for nearly fully automated HAADF-STEM tomography studies, guaranteeing reliable correlations between nanoscopic and macroscopic properties.Depto. de Química InorgánicaFac. de Ciencias QuímicasTRUEpu