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FeCo2O4 and CoFe2O4 nanoparticles have been studied as oxygen carriers for the Chemical Loop Reforming (CLR) of ethanol. By using in operando X-ray absorption spectroscopy we have followed in real time the chemical and structural changes that take place on the materials as a function of temperature and reactive atmosphere (i.e. ethanol/water streams). During the first step of CLR for both oxides the most active chemical species are the cations in the tetrahedral sites, irrespective of their chemical nature. Quite rapidly the spinel structure is transformed into a mix of wüstite-type oxide and metal alloys, but the formation of a metal phase is easier in the case of cobalt, while iron shows a marked preference to form wüstite type oxide. Despite the good reducibility of FeCo2O4 imparted by the high amount of cobalt, its performance in the production of hydrogen is quite poor due to an inefficient oxidation by water steam, which is able to oxidize only the outer shell of the nanoparticles. In contrast, CoFe2O4 due to the residual presence of a reducible wüstite phase shows a higher hydrogen yield. Moreover, by combining the structural information provided by X-ray absorption spectroscopy with the analysis of the byproducts of ethanol decomposition we could infer that FeCo2O4 is more selective than CoFe2O4 for the selective dehydrogenation of ethanol to acetaldehyde because of the higher amount of Fe(iii) ions in tetrahedral sites. [ABSTRACT FROM AUTHOR]

TiO2-supported molybdenum oxide has been studied through a combination of X-ray absorption near edge structure (XANES) and Raman operando spectroscopy. XANES gives insights on the electronic structure of the molybdenum embedded in the active phase, while Raman spectroscopy probes the structure of the oxomolybdate phase at the molecular level. These paired experiments have also been complemented by density functional theory calculations to better refine the resulting structure and make it possible to further understand the structure-activity correlations. In line with the approach, we show that the reactivity of the supported oxomolybdate phase is strongly dependent on the molybdenum loading of the catalyst. Indeed, low molybdenum content catalysts exhibit isolated tetrahedrally coordinated molybdenum centers that are not reducible and show a very low activity in methanol conversion. On the other hand, high molybdenum loading catalysts present reducible molybdenum centers that are rather active in methanol conversion. This change in the behavior of the supported phase is found to be related to a change in the oxygen coordination spheres: high loading induces molybdenum oxide clusters of higher nuclearity where the molybdenum atoms are surrounded by five or six oxygen atoms. [ABSTRACT FROM AUTHOR]

A Li-rich lamellar oxide was cycled at high potential and the relevance of using a constant voltage step (CVS) at the end of the charge, needed for industrial application, was investigated by electrochemical performance, X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Electrochemical studies at 4.7 and 4.5 V with and without CVS showed that capacity and voltage fading occurred mostly when cells operated at high potential. After cycling, 3D-type defects involving transition metals trapped in lithium layer were observed by HRTEM into the electrode bulk. These defects are responsible for the voltage fading. XRD microstrain parameter was used to evaluate defects rate in aged materials subjected to a CVS, showing more 3D-type defects when cycled at 4.7 V than at 4.5 V. The time spent at high potential at the end of the charge as well as the value of the upper potential limit, are both relevant parameters to voltage decay. The use of a CVS at the end of the charge needs at the same time, a reduced upper potential window in order to minimize 3D-type defects occurrence. Unfortunately, this approach is still not sufficient to prevent voltage fading. [ABSTRACT FROM AUTHOR]

We provide here a comprehensive investigation spectroscopic of the controlled hydration of Re 2 O 7 using Raman, Fourier-Transform Infrared (FTIR) and X-Rays Absorption (XAS) techniques in complement with ab initio modelling for confirming the spectral assignments. Hence, the Raman signature of Re 2 O 7 .2H 2 O was obtained, and the evolution kinetics was investigated to provide a detailed description of the hydration process., (© 2024 The Author(s). ChemPhysChem published by Wiley-VCH GmbH.)

Full-field transmission X-ray microscopy has been recently implemented at the hard X-ray ROCK-SOLEIL quick-EXAFS beamline, adding micrometre spatial resolution to the second time resolution characterizing the beamline. Benefiting from a beam size versatility due to the beamline focusing optics, full-field hyperspectral XANES imaging has been successfully used at the Fe K-edge for monitoring the pressure-induced spin transition of a 150 µm × 150 µm Fe(o-phen) 2 (NCS) 2 single crystal and the charge of millimetre-sized LiFePO 4 battery electrodes. Hyperspectral imaging over 2000 eV has been reported for the simultaneous monitoring of Fe and Cu speciation changes during activation of a FeCu bimetallic catalyst along a millimetre-sized catalyst bed. Strategies of data acquisition and post-data analysis using Jupyter notebooks and multivariate data analysis are presented, and the gain obtained using full-field hyperspectral quick-EXAFS imaging for studies of functional materials under process conditions in comparison with macroscopic information obtained by non-spatially resolved quick-EXAFS techniques is discussed., (open access.)

Despite the great commercial relevance of zinc-promoted copper catalysts for methanol synthesis, the nature of the Cu-ZnO x synergy and the nature of the active Zn-based promoter species under industrially relevant conditions are still a topic of vivid debate. Detailed characterization of the chemical speciation of any promoter under high-pressure working conditions is challenging but specifically hampered by the large fraction of Zn spectator species bound to the oxidic catalyst support. We present the use of weakly interacting graphitic carbon supports as a tool to study the active speciation of the Zn promoter phase that is in close contact with the Cu nanoparticles using time-resolved X-ray absorption spectroscopy under working conditions. Without an oxidic support, much fewer Zn species need to be added for maximum catalyst activity. A 5-15 min exposure to 1 bar H 2 at 543 K only slightly reduces the Zn(II), but exposure for several hours to 20 bar H 2 /CO and/or H 2 /CO/CO 2 leads to an average Zn oxidation number of +(0.5-0.6), only slightly increasing to +0.8 in a 20 bar H 2 /CO 2 feed. This means that most of the added Zn is in a zerovalent oxidation state during methanol synthesis conditions. The Zn average coordination number is 8, showing that this phase is not at the surface but surrounded by other metal atoms (whether Zn or Cu), and indicating that the Zn diffuses into the Cu nanoparticles under reaction conditions. The time scale of this process corresponds to that of the generally observed activation period for these catalysts. These results reveal the speciation of the relevant Zn promoter species under methanol synthesis conditions and, more generally, present the use of weakly interacting graphitic supports as an important strategy to avoid excessive spectator species, thereby allowing us to study the nature of relevant promoter species., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Thermal decomposition of (NH4)3[IrCl6]·H2O, (NH4)2[IrCl6] and (NH4)2[IrBr6] in reductive and inert atmospheres has been investigated in situ using quick-EXAFS and temperature-resolved powder X-ray diffraction. For the first time, (NH4)2[Ir(NH3)Cl5] and (NH4)2[Ir(NH3)Br5] have been proven as intermediates of thermal decomposition of (NH4)3[IrCl6]·H2O, (NH4)2[IrCl6] and (NH4)2[IrBr6]. Thermal degradation of (NH4)2[IrCl6] and (NH4)2[IrBr6] is a more complex process as suggested previously and includes simultaneous formation of (NH4)2[Ir(NH3)Cl5] and (NH4)2[Ir(NH3)Br5] intermediates mixed with metallic iridium. In the inert atmosphere, complexes (NH4)[Ir(NH3)2Cl4] and (NH4)[Ir(NH3)2Br4] as well as [Ir(NH3)3Br3] were proposed as possible intermediates before formation of metallic iridium particles.

The understanding of phase transformation upon activation, reaction and deactivation of catalysts is of prime importance for tailoring catalysts with better performances. Herein we combined Quick-EXAFS and Raman spectroscopies in operando conditions through the monitoring of reaction products by mass spectrometry in order to study in depth active species and deactivating ones for Ethanol Steam Reforming reaction. Quick-EXAFS data analyzed by multivariate analysis allows one to determine the nickel and copper species involved during the activation of a Ni-Cu hydrotalcite-like precursors. Upon reaction and regeneration monitoring, Raman spectroscopy combined with mass spectrometry highlights the side products formed upon ESR leading to the formation of amorphous coke species encapsulating active metallic species and inducing catalyst deactivation. The coke encapsulation of active species was demonstrated by the simultaneous observation of oxidation of nickel and copper as soon as the amorphous coke was burnt by the oxidative regeneration treatment. Formation of filamentous coke species is also confirmed as causing little impact in catalyst deactivation.

Operando EPR, XANES/EXAFS, UV-Vis and ATR-IR spectroscopic methods have been coupled for the first time in the same experimental setup for investigation of unclear mechanistic aspects of selective aerobic oxidation of benzyl alcohol by a Cu/TEMPO catalytic system (TEMPO=2,2,6,6-tetramethylpiperidinyloxyl). By multivariate curve resolution with alternating least-squares fitting (MCR-ALS) of simultaneously recorded XAS and UV-Vis data sets, it was found that an initially formed (bpy)(NMI)Cu I - complex (bpy=2,2'-bipyridine, NMI=N-methylimidazole ) is converted to two different Cu II species, a mononuclear (bpy)(NMI)(CH 3 CN)Cu II -OOH species detectable by EPR and ESI-MS, and an EPR-silent dinuclear (CH 3 CN)(bpy)(NMI)Cu II (μ-OH) 2 ⋅Cu II  (bpy)(NMI) complex. The latter is cleaved in the further course of reaction into (bpy)(NMI)(HOO)Cu II -TEMPO monomers that are also EPR-silent due to dipolar interaction with bound TEMPO. Both Cu monomers and the Cu dimer are catalytically active in the initial phase of the reaction, yet the dimer is definitely not a major active species nor a resting state since it is irreversibly cleaved in the course of the reaction while catalytic activity is maintained. Gradual formation of non-reducible Cu II leads to slight deactivation at extended reaction times., (© 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.)

The catalytic performance and optical properties of bimetallic nanoparticles critically depend on the atomic distribution of the two metals in the nanoparticles. However, at elevated temperatures, during light-induced heating, or during catalysis, atomic redistribution can occur. Measuring such metal redistribution in situ is challenging, and a single experimental technique does not suffice. Furthermore, the availability of a well-defined nanoparticle system has been an obstacle for a systematic investigation of the key factors governing the atomic redistribution. In this study, we follow metal redistribution in precisely tunable, single-crystalline Au-core, Ag-shell nanorods in situ, both at a single particle and an ensemble-averaged level, by combining in situ transmission electron spectroscopy with in situ extended X-ray absorption fine structure validated by ex situ measurements. We show that the kinetics of atomic redistribution in Au-Ag nanoparticles depend on the metal composition and particle volume, such that a higher Ag content or a larger particle size led to significantly slower metal redistribution. We developed a simple theoretical model based on Fick's first law that can correctly predict the composition- and size-dependent alloying behavior in Au-Ag nanoparticles, as observed experimentally.

Heterogeneous Re/SiO(2) catalysts prepared using a one pot sol-gel synthesis were found to display high activity in the direct, selective methanol conversion to methylal, which is correlated to an unprecedented rhenium oxide structure.

Digestive tract cancers are infrequent during pregnancy. Prognosis is usually dismal both because diagnosis is delayed as a result of symptoms being ascribed to the pregnancy and because saving both the mother and fetus is difficult. A review of the relevant literature, focused on colorectal and gastric cancers which are the most common forms, emphasizes the need for early diagnosis and for adjusting treatment to gestational age at diagnosis.