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This study investigates the structural evolution and redox characteristics of the double perovskite Sr2FeMo0.6Ni0.4O6-d (SFMN) during hydrogen (H2) and carbon dioxide (CO2) redox cycles and explores the material performance in the Reverse Water-Gas Shift Chemical Looping (RWGS-CL) reaction. In-situ and ex-situ X-Ray Diffraction (XRD) and High-Resolution Transmission Electron Microscopy (HRTEM) studies reveal that H2 reduction at temperatures above 800 °C leads to the exsolution of bimetallic Ni-Fe alloy particles and the formation of a Ruddlesden-Popper (RP) phase. A core–shell structure with Ni-Fe core and a perovskite oxide shell is formed with subsequent redox cycles, and the resulting material exhibits better performance and high stability in the RWGS-CL process. Thermogravimetric (TGA) and Temperature Programmed Reduction (TPR) and Oxidation (TPO) analyses show that the optimal reduction and oxidation temperatures for maximizing the CO yield are around 850 °C and 750 °C respectively, and that the cycled material is able to work steadily under isothermal conditions at 850 °C., Peer Reviewed, Postprint (published version)

Mechanochemical synthesis for the preparation of bimetallic catalysts is gaining increasing interest, and in recent years, some important milestones have been reached. However, the complexity of mechanochemically prepared bimetallic supported catalysts still leaves many open questions that need a systematic approach to be solved. In this work, we summarize our experience of mechanochemically milling bimetallic catalysts, introducing some key parameters that should be taken into account, particularly the thermal stability and hydrophilicity of precursor salts, and the effect of the milling order, highlighting the differences with wet synthesis methods. Finally, we will provide some suggestions on the application of the design of experiments approach to the rationalization of the milling procedure for the preparation of supported bimetallic catalysts., Peer Reviewed, Postprint (published version)

In this review, we report on recent advances in the use of mechanochemistry to synthesize new catalytic materials. We report recent results obtained by our groups where a rational design of the milling parameters led to the synthesis of advanced materials with novel properties such as unconventional arrangements of metals on the surface of oxide support materials, highly dispersed metals or the stabilization of species in particular oxidation states. These properties resulted in superior catalytic performances of the mechanochemically-synthesized catalysts compared to their counterparts prepared by traditional impregnation methods. To illustrate these advances, we review the progress made in two important fields of catalysis where noble metals are used: (i) emission-control catalysis using Pd-based materials, and (ii) the development of photocatalysts to produce hydrogen based on Au and Pd materials., Peer Reviewed, Postprint (author's final draft)

In addition of a key catecholamine neurotransmitter, dopamine is is the metabolite predominantly produced by specific types of tumors (e.g. paragangliomas and neuroblastomas), which cannot be diagnosed using conventional sensitive tests. Within this context, development of flexible electrochemical sensors to monitor dopamine levels in physiological fluids for the early diagnosis and control of diseases related to abnormal levels of such compound, is necessary. In this work, a flexible self-supported membrane, which acts directly as electrode, has been developed to detect dopamine. The membrane consists of three nanoperforated polylactic acid (PLA) layers, which provide flexibility and mechanical integrity, separated by two layers of an electroactive copolymer, which are obtained by electrochemical copolymerization of 3,4-ethylenedioxythiophene and aniline. The sensitivity and detection limit provided by the electroactive copolymer, which is accessible to dopamine molecules through the nanoperforations of the PLA outer layers, is 1.846 µA/(cm2·µM) and 1.7 µM, respectively, in a urea-rich environments that mimics urine. These values allow us to propose the self-standing flexible electrodes developed in this study for the detection of dopamine in patients affected by paragangliomas and neuroblastomas tumors, which typically present dopamine concentrations between 2 and 7 µM., Peer Reviewed, Postprint (author's final draft)

The selective oxidation of primary alcohols into their corresponding carbonyl compounds is challenging because of the easy over oxidization to acids and esters. The traditional reaction requires large amounts of solvent and oxidant, causing serious environmental issues. Recently, several efforts have been made to transform the reaction into a more sustainable process. Here, we investigated the solvent-free oxidation of benzyl alcohol using air as a green oxidant in the presence of ruthenium supported on alumina and zirconia, thereby meeting atom economy and environmental requirements. The materials were extensively characterized and, in addition to their activity, selectivity, and reusability, the environmental sustainability of the process was assessed according to green chemistry metrics. XRD, TEM, and XPS analyses suggest that the formation of metallic Ru on the support plays a key role in the catalytic activity. Ru supported on alumina, after a reduction treatment, achieves good activity (62% conversion) and a complete selectivity in a very sustainable process (without a solvent and with air as oxidant), as indicated by the very low E-factor value. The formulation is very stable and maintains high activity after recycling., Peer Reviewed, Postprint (published version)

The optimization of the supported Pd phase for CH4 activation on Pd/CeO2 catalysts has been a matter of great interest in the recent literature, aiming at the design of efficient methane abatement catalysts for Natural Gas fueled Vehicles (NGVs). Under lean conditions, a mixed Pd0/PdO combination has been indicated as exhibiting the best performance, while controversial results have been reported under stoichiometric conditions depending on the support oxide, where either Al2O3 or zeolite-based supports are usually considered. Here, by means of synchrotron-based in situ NAP-XPS and XRD measurements, we follow the evolution of Pd species on Pd/CeO2 samples prepared by dry mechanochemical synthesis (M) under stoichiometric CH4 oxidation feed, unravelling a stable Pd0/Pd2+ arrangement in a close to 1[thin space (1/6-em)]:[thin space (1/6-em)]1 ratio as the most active palladium state for CH4 activation when excess oxygen is not available, in contrast to what was reported for Pd/alumina materials, where metallic Pd0 nanoparticles showed the highest activity. The combination of NAP-XPS analysis and activity test results highlights the promotional effect of the Pd–Ce interaction, resulting in enhanced oxygen transfer and improved activity and stability of the Pd/CeO2 catalyst prepared by a novel mechanochemical approach even under low O2 content, large excess of water vapor (10 vol%) and high temperature exposure (>700 °C)., Peer Reviewed, Objectius de Desenvolupament Sostenible::13 - Acció per al Clima, Objectius de Desenvolupament Sostenible::7 - Energia Assequible i No Contaminant, Postprint (published version)

The methane dry reforming (DRM) reaction mechanism was explored via mechanochemically prepared Pd/CeO2 catalysts (PdAcCeO2M), which yield unique Pd–Ce interfaces, where PdAcCeO2M has a distinct reaction mechanism and higher reactivity for DRM relative to traditionally synthesized impregnated Pd/CeO2 (PdCeO2IW). In situ characterization and density functional theory calculations revealed that the enhanced chemistry of PdAcCeO2M can be attributed to the presence of a carbon-modified Pd0 and Ce4+/3+ surface arrangement, where distinct Pd–CO intermediate species and strong Pd–CeO2 interactions are activated and sustained exclusively under reaction conditions. This unique arrangement leads to highly selective and distinct surface reaction pathways that prefer the direct oxidation of CHx to CO, identified on PdAcCeO2M using isotope labeled diffuse reflectance infrared Fourier transform spectroscopy and highlighting linear Pd–CO species bound on metallic and C-modified Pd, leading to adsorbed HCOO [1595 cm–1] species as key DRM intermediates, stemming from associative CO2 reduction. The milled materials contrast strikingly with surface processes observed on IW samples (PdCeO2IW) where the competing reverse water gas shift reaction predominates., Peer Reviewed, Postprint (published version)