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1.
Proc Natl Acad Sci U S A ; 121(14): e2318978121, 2024 Apr 02.
Article in English | MEDLINE | ID: mdl-38536755

ABSTRACT

Pressure-induced transformations in an archetypal chalcogenide glass (GeSe2) have been investigated up to 157 GPa by X-ray absorption spectroscopy (XAS) and molecular dynamics (MD) simulations. Ge and Se K-edge XAS data allowed simultaneous tracking of the correlated local structural and electronic changes at both Ge and Se sites. Thanks to the simultaneous analysis of extended X-ray absorption fine structure (EXAFS) signals of both edges, reliable quantitative information about the evolution of the first neighbor Ge-Se distribution could be obtained. It also allowed to account for contributions of the Ge-Ge and Se-Se bond distributions (chemical disorder). The low-density to high-density amorphous-amorphous transformation was found to occur within 10 to 30 GPa pressure range, but the conversion from tetrahedral to octahedral coordination of the Ge sites is completed above [Formula: see text] 80 GPa. No convincing evidence of another high-density amorphous state with coordination number larger than six was found within the investigated pressure range. The number of short Ge-Ge and Se-Se "wrong" bonds was found to increase upon pressurization. Experimental XAS results are confirmed by MD simulations, indicating the increase of chemical disorder under high pressure.

2.
Chem Sci ; 14(41): 11521-11531, 2023 Oct 25.
Article in English | MEDLINE | ID: mdl-37886093

ABSTRACT

The application of Cu-CHA catalysts for the selective catalytic reduction of NOx by ammonia (NH3-SCR) in exhaust systems of diesel vehicles requires the use of fuel with low sulfur content, because the Cu-CHA catalysts are poisoned by higher concentrations of SO2. Understanding the mechanism of the interaction between the Cu-CHA catalyst and SO2 is crucial for elucidating the SO2 poisoning and development of efficient catalysts for SCR reactions. Earlier we have shown that SO2 reacts with the [Cu2II(NH3)4O2]2+ complex that is formed in the pores of Cu-CHA upon activation of O2 in the NH3-SCR cycle. In order to determine the products of this reaction, we use X-ray absorption spectroscopy (XAS) at the Cu K-edge and S K-edge, and X-ray emission spectroscopy (XES) for Cu-CHA catalysts with 0.8 wt% Cu and 3.2 wt% Cu loadings. We find that the mechanism for SO2 uptake is similar for catalysts with low and high Cu content. We show that the SO2 uptake proceeds via an oxidation of SO2 by the [Cu2II(NH3)4O2]2+ complex, resulting in the formation of different CuI species, which do not react with SO2, and a sulfated CuII complex that is accumulated in the pores of the zeolite. The increase of the SO2 uptake upon addition of oxygen to the SO2-containing feed, evidenced by X-ray adsorbate quantification (XAQ) and temperature-programmed desorption of SO2, is explained by the re-oxidation of the CuI species into the [Cu2II(NH3)4O2]2+ complexes, which makes them available for reaction with SO2.

3.
Biotechnol J ; 18(10): e2300173, 2023 Oct.
Article in English | MEDLINE | ID: mdl-37337924

ABSTRACT

Magnetosomes are magnetite nanoparticles biosynthesized by magnetotactic bacteria. Given their potential clinical applications for the diagnosis and treatment of cancer, it is essential to understand what becomes of them once they are within the body. With this aim, here we have followed the intracellular long-term fate of magnetosomes in two cell types: cancer cells (A549 cell line), because they are the actual target for the therapeutic activity of the magnetosomes, and macrophages (RAW 264.7 cell line), because of their role at capturing foreign agents. It is shown that cells dispose of magnetosomes using three mechanisms: splitting them into daughter cells, excreting them to the surrounding environment, and degrading them yielding less or non-magnetic iron products. A deeper insight into the degradation mechanisms by means of time-resolved X-ray absorption near-edge structure (XANES) spectroscopy has allowed us to follow the intracellular biotransformation of magnetosomes by identifying and quantifying the iron species occurring during the process. In both cell types there is a first oxidation of magnetite to maghemite and then, earlier in macrophages than in cancer cells, ferrihydrite starts to appear. Given that ferrihydrite is the iron mineral phase stored in the cores of ferritin proteins, this suggests that cells use the iron released from the degradation of magnetosomes to load ferritin. Comparison of both cellular types evidences that macrophages are more efficient at disposing of magnetosomes than cancer cells, attributed to their role in degrading external debris and in iron homeostasis.


Subject(s)
Magnetosomes , Neoplasms , Magnetosomes/chemistry , Iron/metabolism , Ferritins/analysis , Ferritins/metabolism , Macrophages/metabolism , Neoplasms/metabolism
4.
J Phys Condens Matter ; 35(26)2023 Apr 06.
Article in English | MEDLINE | ID: mdl-36990102

ABSTRACT

Pressure-induced transformations in glassy GeSe2have been studied using the x-ray absorption spectroscopy. Experiments have been carried out at the scanning-energy beamline BM23 (European Synchrotron Radiation Facility) providing a micrometric x-ray focal spot up to pressures of about 45 GPa in a diamond anvil cell. Both Se and Ge K-edge experiments were performed under different hydrostatic conditions identifying the metallization onsets by accurate determinations of the edge shifts. The semiconductor-metal transition was observed to be completed around 20 GPa when neon was used as a pressure transmitting medium (PTM), while this transition was slightly shifted to lower pressures when no PTM was used. Accurate double-edge extended x-ray absorption fine structure (EXAFS) refinements were carried out using advanced data-analysis methods. EXAFS data-analysis confirmed the trend shown by the edge shifts for this disordered material, showing that the transition from tetrahedral to octahedral coordination for Ge sites is not fully achieved at 45 GPa. Results of present high pressure EXAFS experiments have shown the absence of significant neon incorporation into the glass within the pressure range up to 45 GPa.

5.
J Phys Chem C Nanomater Interfaces ; 126(11): 5175-5179, 2022 Mar 24.
Article in English | MEDLINE | ID: mdl-36157514

ABSTRACT

Hard X-ray absorption spectroscopy (XAS) is frequently applied in catalysis and gas sorption studies to monitor changes in oxidation states, coordination numbers, and interatomic distances of active sites under in situ and operando conditions. However, transmission XAS data can reveal also the change in the total amount of guest species adsorbed on the whole sample. Surprisingly, to the best of our knowledge, the latter property has never been exploited. Here, we present a simple method to quantify the amount of adsorbates from XAS data collected during the interaction of the sample with gases or liquids. The method relies on monitoring the change of the total absorption level below the measured absorption edge and does not require any additional instrumentation or modification of the XAS data collection procedure. Essentially, it is a way to obtain the information analogous to the one delivered by temperature-programmed reduction (TPR), temperature-programmed desorption (TPD), or thermogravimetric analysis (TGA) directly from XAS at no extra cost.

6.
JACS Au ; 2(4): 787-792, 2022 Apr 25.
Article in English | MEDLINE | ID: mdl-35557768

ABSTRACT

Cu-exchanged chabazite zeolites (Cu-CHA) are effective catalysts for the NH3-assisted selective catalytic reduction of NO (NH3-SCR) for the abatement of NO x emission from diesel vehicles. However, the presence of a small amount of SO2 in diesel exhaust gases leads to a severe reduction in the low-temperature activity of these catalysts. To shed light on the nature of such deactivation, we characterized a Cu-CHA catalyst under well-defined exposures to SO2 using in situ X-ray absorption spectroscopy. By varying the pretreatment procedure prior to the SO2 exposure, we have selectively prepared CuI and CuII species with different ligations, which are relevant for the NH3-SCR reaction. The highest reactivity toward SO2 was observed for CuII species coordinated to both NH3 and extraframework oxygen, in particular for [CuII 2(NH3)4O2]2+ complexes. Cu species without either ammonia or extraframework oxygen ligands were much less reactive, and the associated SO2 uptake was significantly lower. These results explain why SO2 mostly affects the low-temperature activity of Cu-CHA catalysts, since the dimeric complex [CuII 2(NH3)4O2]2+ is a crucial intermediate in the low-temperature NH3-SCR catalytic cycle.

7.
J Synchrotron Radiat ; 29(Pt 1): 167-179, 2022 Jan 01.
Article in English | MEDLINE | ID: mdl-34985434

ABSTRACT

Results of the 2018 commissioning and experimental campaigns of the new High Power Laser Facility on the Energy-dispersive X-ray Absorption Spectroscopy (ED-XAS) beamline ID24 at the ESRF are presented. The front-end of the future laser, delivering 15 J in 10 ns, was interfaced to the beamline. Laser-driven dynamic compression experiments were performed on iron oxides, iron alloys and bismuth probed by online time-resolved XAS.

8.
Phys Chem Chem Phys ; 22(42): 24299-24309, 2020 Nov 14.
Article in English | MEDLINE | ID: mdl-33094300

ABSTRACT

The electronic and local structural properties of CuO under pressure have been investigated by means of X-ray absorption spectroscopy (XAS) at Cu K edge and ab initio calculations, up to 17 GPa. The crystal structure of CuO consists of Cu motifs within CuO4 square planar units and two elongated apical Cu-O bonds. The CuO4 square planar units are stable in the studied pressure range, with Cu-O distances that are approximately constant up to 5 GPa, and then decrease slightly up to 17 GPa. In contrast, the elongated Cu-O apical distances decrease continuously with pressure in the studied range. An anomalous increase of the mean square relative displacement (EXAFS Debye-Waller, σ2) of the elongated Cu-O path is observed from 5 GPa up to 13 GPa, when a drastic reduction takes place in σ2. This is interpreted in terms of local dynamic disorder along the apical Cu-O path. At higher pressures (P > 13 GPa), the local structure of Cu2+ changes from a 4-fold square planar to a 4+2 Jahn-Teller distorted octahedral ion. We interpret these results in terms of the tendency of the Cu2+ ion to form favorable interactions with the apical O atoms. Also, the decrease in Cu-O apical distance caused by compression softens the normal mode associated with the out-of-plane Cu movement. CuO is predicted to have an anomalous rise in permittivity with pressure as well as modest piezoelectricity in the 5-13 GPa pressure range. In addition, the near edge features in our XAS experiment show a discontinuity and a change of tendency at 5 GPa. For P < 5 GPa the evolution of the edge shoulder is ascribed to purely electronic effects which also affect the charge transfer integral. This is linked to a charge migration from the Cu to O, but also to an increase of the energy band gap, which show a change of tendency occurring also at 5 GPa.

9.
Nanoscale ; 12(26): 14011-14020, 2020 Jul 14.
Article in English | MEDLINE | ID: mdl-32579650

ABSTRACT

Pulsed laser ablation in liquids is a hierarchical multi-step process to produce pure inorganic nanoparticle colloids. Controlling this process is hampered by the partial understanding of individual steps and structure formation. In situ X-ray methods are employed to resolve macroscopic dynamics of nanosecond PLAL as well to analyse the distribution and speciation of ablated species with a microsecond time resolution. High time resolution can be achieved by synchrotron-based methods that are capable of 'single-shot' acquisition. X-ray multicontrast imaging by a Shack-Hartmann setup (XHI) and small angle X-ray scattering (SAXS) resolve evolving nanoparticles inside the transient cavitation bubble, while X-ray absorption spectroscopy in dispersive mode opens access to the total material yield and the chemical state of the ejecta. It is confirmed that during ablation nanoparticles are produced directly as well as reactive material is detected, which is identified in the early stage as Zn atoms. Nanoparticles within the cavitation bubble show a metal signature, which prevails for milliseconds, before gradual oxidation sets in. Ablation is described by a phase explosion of the target coexisting with full evaporation. Oxidation occurs only as a later step to already formed nanoparticles.

10.
J Synchrotron Radiat ; 26(Pt 3): 801-810, 2019 May 01.
Article in English | MEDLINE | ID: mdl-31074445

ABSTRACT

A new cell for in situ combined X-ray absorption, diffuse reflectance IR Fourier transform and mass spectroscopies (XAS-DRIFTS-MS) is presented. The cell stands out among others for its achievements and flexibility. It is possible to perform XAS measurements in transmission or fluorescence modes, and the cell is compatible with external devices like UV-light and Raman probes. It includes different sample holders compatible with the different XAS detection modes, different sample forms (free powder or self-supporting pellet) and different sample loading/total absorption. Additionally, it has a small dead volume and can operate over a wide range of temperature (up to 600°C) and pressure (up to 5 bar). Three research examples will be shown to illustrate the versatility of the cell. This cell covers a wider range of applications than any other cell currently known for this type of study.

11.
Sci Rep ; 7(1): 16453, 2017 11 28.
Article in English | MEDLINE | ID: mdl-29184091

ABSTRACT

X-ray spectroscopic techniques have proven to be particularly useful in elucidating the molecular and electronic structural information of chemically heterogeneous and complex micro- and nano-structured materials. However, spatially resolved chemical characterization at the micrometre scale remains a challenge. Here, we report the novel hyperspectral technique of micro Energy Dispersive X-ray Absorption Spectroscopy (µED-XAS) tomography which can resolve in both 2D and 3D the spatial distribution of chemical species through the reconstruction of XANES spectra. To document the capability of the technique in resolving chemical species, we first analyse a sample containing 2-30 µm grains of various ferrous- and ferric-iron containing minerals, including hypersthene, magnetite and hematite, distributed in a light matrix of a resin. We accurately obtain the XANES spectra at the Fe K-edge of these four standards, with spatial resolution of 3 µm. Subsequently, a sample of ~1.9 billion-year-old microfossil from the Gunflint Formation in Canada is investigated, and for the first time ever, we are able to locally identify the oxidation state of iron compounds encrusting the 5 to 10 µm microfossils. Our results highlight the potential for attaining new insights into Precambrian ecosystems and the composition of Earth's earliest life forms.

12.
Angew Chem Int Ed Engl ; 56(45): 14031-14035, 2017 11 06.
Article in English | MEDLINE | ID: mdl-28981203

ABSTRACT

Fluid catalytic cracking is a chemical conversion process of industrial scale. This process, utilizing porous catalysts composed of clay and zeolite, converts heavy crude-oil fractions into transportation fuel and petrochemical feedstocks. Among other factors iron-rich reactor and feedstream impurities cause these catalyst particles to permanently deactivate. Herein, we report tomographic X-ray absorption spectroscopy measurements that reveal the presence of dissimilar iron impurities of specific localization within a single deactivated particle. Whereas the iron natural to clay in the composite seems to be unaffected by operation, exterior-facing and feedstream-introduced iron was found in two forms. Those being minute quantities of ferrous oxide, located near regions of increased porosity, and impurities rich in Fe3+ , preferentially located in the outer dense part of the particle and suggested to contribute to the formation of an isolating amorphous silica alumina envelope.

13.
Nat Chem ; 8(8): 784-90, 2016 08.
Article in English | MEDLINE | ID: mdl-27442284

ABSTRACT

The noble gases are the most inert group of the periodic table, but their reactivity increases with pressure. Diamond-anvil-cell experiments and ab initio modelling have been used to investigate a possible direct reaction between xenon and oxygen at high pressures. We have now synthesized two oxides below 100 GPa (Xe2O5 under oxygen-rich conditions, and Xe3O2 under oxygen-poor conditions), which shows that xenon is more reactive under pressure than predicted previously. Xe2O5 was observed using X-ray diffraction methods, its structure identified through ab initio random structure searching and confirmed using X-ray absorption and Raman spectroscopies. The experiments confirm the recent prediction of Xe3O2 as a stable xenon oxide under high pressure. Xenon atoms adopt mixed oxidation states of 0 and +4 in Xe3O2 and +4 and +6 in Xe2O5. Xe3O2 and Xe2O5 form extended networks that incorporate oxygen-sharing XeO4 squares, and Xe2O5 additionally incorporates oxygen-sharing XeO5 pyramids. Other xenon oxides (XeO2, XeO3) are expected to form at higher pressures.

14.
J Phys Condens Matter ; 28(35): 355401, 2016 09 07.
Article in English | MEDLINE | ID: mdl-27385480

ABSTRACT

The local structure and dynamics of α-iron have been investigated by extended x-ray absorption fine structure (EXAFS) spectroscopy and x-ray diffraction (XRD) in order to shed light on some thermal and magnetic anomalies observed in the last decades. The quantitative EXAFS analysis of the first two coordination shells reveals a peculiar local vibrational dynamics of α-iron: the second neighbor distance exhibits anharmonicity and vibrational anisotropy larger than the first neighbor distance. We search for possible distortions of the bcc structure to justify the unexplained magnetostriction anomalies of α-iron and provide a value for the maximum dislocation of the central Fe atom. No thermal anomalies have been detected from the current XRD data. On the contrary, an intriguing thermal anomaly at about 150 K, ascribed to a stiffening of the Fe-Fe bonds, was found by EXAFS.

15.
Sci Rep ; 6: 27317, 2016 06 07.
Article in English | MEDLINE | ID: mdl-27273197

ABSTRACT

Pressure induced structural modifications in vitreous GexSe100-x (where 10 ≤ x ≤ 25) are investigated using X-ray absorption spectroscopy (XAS) along with supplementary X-ray diffraction (XRD) experiments and ab initio molecular dynamics (AIMD) simulations. Universal changes in distances and angle distributions are observed when scaled to reduced densities. All compositions are observed to remain amorphous under pressure values up to 42 GPa. The Ge-Se interatomic distances extracted from XAS data show a two-step response to the applied pressure; a gradual decrease followed by an increase at around 15-20 GPa, depending on the composition. This increase is attributed to the metallization event that can be traced with the red shift in Ge K edge energy which is also identified by the principal peak position of the structure factor. The densification mechanisms are studied in details by means of AIMD simulations and compared to the experimental results. The evolution of bond angle distributions, interatomic distances and coordination numbers are examined and lead to similar pressure-induced structural changes for any composition.

16.
Sci Rep ; 6: 26402, 2016 06 01.
Article in English | MEDLINE | ID: mdl-27246145

ABSTRACT

Understanding Warm Dense Matter (WDM), the state of planetary interiors, is a new frontier in scientific research. There exists very little experimental data probing WDM states at the atomic level to test current models and those performed up to now are limited in quality. Here, we report a proof-of-principle experiment that makes microscopic investigations of materials under dynamic compression easily accessible to users and with data quality close to that achievable at ambient. Using a single 100 ps synchrotron x-ray pulse, we have measured, by K-edge absorption spectroscopy, ns-lived equilibrium states of WDM Fe. Structural and electronic changes in Fe are clearly observed for the first time at such extreme conditions. The amplitude of the EXAFS oscillations persists up to 500 GPa and 17000 K, suggesting an enduring local order. Moreover, a discrepancy exists with respect to theoretical calculations in the value of the energy shift of the absorption onset and so this comparison should help to refine the approximations used in models.

17.
Environ Sci Technol ; 49(24): 14065-75, 2015 Dec 15.
Article in English | MEDLINE | ID: mdl-26544528

ABSTRACT

U(VI) sorption to iron oxyhydroxides, precipitation of phosphate minerals, as well as biosorption on bacterial biomass are among the most reported processes able to scavenge U(VI) under oxidizing conditions. Although phosphates significantly influence bacterially mediated as well as iron oxyhydroxide mediated scavenging of uranium, the sorption or coprecipitation of U(VI) with poorly crystalline nanosized iron phosphates has been scarcely documented, especially in the presence of microorganisms. Here we show that dissolved U(VI) can be bound to amorphous iron phosphate during their deposition on Sphaerotilus natans filamentous bacteria. Uranium LIII-edge EXAFS analysis reveals that the adsorbed uranyl ions share an equatorial oxygen atom with a phosphate tetrahedron of the amorphous iron phosphate, with a characteristic U-P distance of 3.6 Å. In addition, the uranyl ions are connected to FeO6 octahedra with U-Fe distances at ~3.4 Å and at ~4.0 Å. The shortest U-Fe distance corresponds to a bidentate edge-sharing complex often reported for uranyl adsorption onto iron oxyhydroxides, whereas the longest U-Fe and U-P distances can be interpreted as a bidentate corner-sharing complex, in which two adjacent equatorial oxygen atoms are shared with the vertices of a FeO6 octahedron and of a phosphate tetrahedron. Furthermore, based on these sorption reactions, we demonstrate the ability of an attached S. natans biofilm to remove uranium from solution without any filtration step.


Subject(s)
Ferric Compounds/chemistry , Iron/chemistry , Sphaerotilus/chemistry , Uranium/chemistry , Adsorption , Biofilms , Chemical Precipitation , Least-Squares Analysis , Microscopy, Electron, Scanning , Minerals/chemistry , Phosphates/chemistry , Spectrometry, X-Ray Emission , Uranium/isolation & purification
18.
Chemistry ; 21(43): 15280-9, 2015 Oct 19.
Article in English | MEDLINE | ID: mdl-26471442

ABSTRACT

Co-components are a powerful tool to tune the performance of catalysts, but their nature and their impact on the catalysts is often controversially discussed. In this study X-ray absorption spectroscopy (XAS) was employed to elucidate the nature of co-components and their impact on the catalytic reaction. In anatase-supported Pd-based catalysts for the gas-phase acetoxylation of toluene, less noble co-components (e.g., Mn, Co, and Sb) spread over the support in their oxidic form and changed their valence state on stream. Incorporated atoms such as C or a small part of the Sb affect the electronic structure of Pd. For the noble Au, only a weak interaction with the support and Pd was observed during time on stream. Only XAS at the K-edges together with investigations of the Pd L-edge for a better understanding of the electronic structure, supplemented by STEM for elemental mapping, allow such detailed insights.

19.
Proc Natl Acad Sci U S A ; 112(39): 12042-5, 2015 Sep 29.
Article in English | MEDLINE | ID: mdl-26371317

ABSTRACT

Temperature, thermal history, and dynamics of Earth rely critically on the knowledge of the melting temperature of iron at the pressure conditions of the inner core boundary (ICB) where the geotherm crosses the melting curve. The literature on this subject is overwhelming, and no consensus has been reached, with a very large disagreement of the order of 2,000 K for the ICB temperature. Here we report new data on the melting temperature of iron in a laser-heated diamond anvil cell to 103 GPa obtained by X-ray absorption spectroscopy, a technique rarely used at such conditions. The modifications of the onset of the absorption spectra are used as a reliable melting criterion regardless of the solid phase from which the solid to liquid transition takes place. Our results show a melting temperature of iron in agreement with most previous studies up to 100 GPa, namely of 3,090 K at 103 GPa.

20.
Phys Chem Chem Phys ; 17(4): 2464-74, 2015 Jan 28.
Article in English | MEDLINE | ID: mdl-25491072

ABSTRACT

The structural properties of liquid 1-butyl-3-methylimidazolium iodide [C4mim]I have been investigated using an integrated approach that combines EXAFS spectroscopy and molecular dynamics (MD) simulations. A well defined first coordination shell composed on average of 4.5 I(-) ions around the imidazolium cation has been evidenced, and the structural arrangement of the I(-) ions has been found to be different in the proximity of the most acidic hydrogen atom of the imidazolium ring, as compared to the other two ring protons: in the former case the I(-) ion is not coplanar with the imidazolium ring plane, but it prefers to be above and below the plane itself, while in the latter the anion has the same probability of being or not being coplanar with the plane. A quantitative analysis of the I K-edge EXAFS spectrum of liquid [C4mim]I has been carried out starting from the structural information on the system derived from the MD simulation. This combined approach allows one to reduce the number of correlated model parameters required in the fitting of the experimental data and to increase the reliability of the EXAFS data analysis that represents a non-trivial task when dealing with disordered systems. Moreover, the good agreement between the EXAFS experimental and theoretical spectra of liquid [C4mim]I has proven the reliability of the MD results and force field employed.

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