X-ray induced persistent photoconductivity in Si-doped Al0.35_{0.35}Ga0.65_{0.65}As

We demonstrate that X-ray irradiation can be used to induce an insulator-metal transition in Si-doped Al$_{0.35}$Ga$_{0.65}$As, a semiconductor with {\it DX} centers. The excitation mechanism of the {\it DX} centers into their shallow donor state was revealed by studying the photoconductance along with fluorescence. The photoconductance as a function of incident X-ray energy exhibits an edge both at the Ga and As K-edge, implying that core-hole excitation of Ga and As are efficient primary steps for the excitation of {\it DX} centers. A high quantum yield ($\gg 1$) suggests that the excitation is indirect and nonlocal, due to secondary electrons, holes, and fluorescence photons.Comment: 3 pages of text, 6 figures. An error in Fig.5 was detected, so we corrected i

Dynamics of CrO3–Fe2O3 catalysts during the high-temperature water-gas shift reaction: molecular structures and reactivity

A series of supported CrO3/Fe2O3 catalysts were investigated for the high-temperature water-gas shift (WGS) and reverse-WGS reactions and extensively characterized using in situ and operando IR, Raman, and XAS spectroscopy during the high-temperature WGS/RWGS reactions. The in situ spectroscopy examinations reveal that the initial oxidized catalysts contain surface dioxo (O═)2Cr6+O2 species and a bulk Fe2O3 phase containing some Cr3+ substituted into the iron oxide bulk lattice. Operando spectroscopy studies during the high-temperature WGS/RWGS reactions show that the catalyst transforms during the reaction. The crystalline Fe2O3 bulk phase becomes Fe3O4 ,and surface dioxo (O═)2Cr6+O2 species are reduced and mostly dissolve into the iron oxide bulk lattice. Consequently, the chromium–iron oxide catalyst surface is dominated by FeOx sites, but some minor reduced surface chromia sites are also retained. The Fe3–-xCrxO4 solid solution stabilizes the iron oxide phase from reducing to metallic Fe0 and imparts an enhanced surface area to the catalyst. Isotopic exchange studies with C16O2/H2 → C18O2/H2 isotopic switch directly show that the RWGS reaction proceeds via the redox mechanism and only O* sites from the surface region of the chromium–iron oxide catalysts are involved in the RWGS reaction. The number of redox O* sites was quantitatively determined with the isotope exchange measurements under appropriate WGS conditions and demonstrated that previous methods have undercounted the number of sites by nearly 1 order of magnitude. The TOF values suggest that only the redox O* sites affiliated with iron oxide are catalytic active sites for WGS/RWGS, though a carbonate oxygen exchange mechanism was demonstrated to exist, and that chromia is only a textural promoter that increases the number of catalytic active sites without any chemical promotion effect

Neural Network Approach for Characterizing Structural Transformations by X-Ray Absorption Fine Structure Spectroscopy

AIF acknowledge support by the US Department of Energy, Office of Basic Energy Sciences under Grant No. DE-FG02 03ER15476. AIF acknowledges support by the Laboratory Directed Research and Development Program through LDRD 18-047 of Brookhaven National Laboratory under U.S. Department of Energy Contract No. DE-SC0012704 for initiating his research in machine learning methods. The help of the beamline staff at ELETTRA (project 20160412) synchrotron radiation facility is acknowledged. RMC-EXAFS and MD-EXAFS simulations were performed on the LASC cluster-type computer at Institute of Solid State Physics of the University of Latvia.The knowledge of the coordination environment around various atomic species in many functional materials provides a key for explaining their properties and working mechanisms. Many structural motifs and their transformations are difficult to detect and quantify in the process of work (operando conditions), due to their local nature, small changes, low dimensionality of the material, and/or extreme conditions. Here we use an artificial neural network approach to extract the information on the local structure and its in situ changes directly from the x-ray absorption fine structure spectra. We illustrate this capability by extracting the radial distribution function (RDF) of atoms in ferritic and austenitic phases of bulk iron across the temperature-induced transition. Integration of RDFs allows us to quantify the changes in the iron coordination and material density, and to observe the transition from a body-centered to a face-centered cubic arrangement of iron atoms. This method is attractive for a broad range of materials and experimental conditions.Laboratory Directed Research and Development LDRD 18-047; U.S. Department of Energy DE-FG02 03ER15476; Brookhaven National Laboratory DE-SC0012704; Institute of Solid State Physics, University of Latvia as the Center of Excellence has received funding from the European Union’s Horizon 2020 Framework Programme H2020-WIDESPREAD-01-2016-2017-TeamingPhase2 under grant agreement No. 739508, project CAMART

In situ characterization of mesoporous Co/CeO2 catalysts for the high-temperature water-gas shift

Mesoporous Co/CeO2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTS analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.Peer ReviewedPostprint (author's final draft

Metal Core Bonding Motifs of Monodisperse Icosahedral Au13 and Larger Au Monolayer-Protected Clusters As Revealed by X-ray Absorption Spectroscopy and Transmission Electron Microscopy

The atomic metal core structures of the subnanometer clusters Au13[PPh3]4[S(CH2)11CH3]2Cl2 (1) and Au13[PPh3]4[S(CH2)11CH3]4 (2) were characterized using advanced methods of electron microscopy and X-ray absorption spectroscopy. The number of gold atoms in the cores of these two clusters was determined quantitatively using high-angle annular dark field scanning transmission electron microscopy. Multiple-scattering-path analyses of extended X-ray absorption fine structure (EXAFS) spectra suggest that the Au metal cores of each of these complexes adopt an icosahedral structure with a relaxation of the icosahedral strain. Data from microscopy and spectroscopy studies extended to larger thiolate-protected gold clusters showing a broader distribution in nanoparticle core sizes (183 ± 116 Au atoms) reveal a bulklike fcc structure. These results further support a model for the monolayer-protected clusters (MPCs) in which the thiolate ligands bond preferentially at 3-fold atomic sites on the nanoparticle surface, establishing an average composition for the MPC of Au180[S(CH2)11CH3]40. Results from EXAFS measurements of a gold(I) dodecanethiolate polymer are presented that offer an alternative explanation for observations in previous reports that were interpreted as indicating Au MPC structures consisting of a Au core, Au2S shell, and thiolate monolayer

Decoding reactive structures in dilute alloy catalysts

Rational catalyst design is crucial toward achieving more energy-efficient and sustainable catalytic processes. Understanding and modeling catalytic reaction pathways and kinetics require atomic level knowledge of the active sites. These structures often change dynamically during reactions and are difficult to decipher. A prototypical example is the hydrogen-deuterium exchange reaction catalyzed by dilute Pd-in-Au alloy nanoparticles. From a combination of catalytic activity measurements, machine learning-enabled spectroscopic analysis, and first-principles based kinetic modeling, we demonstrate that the active species are surface Pd ensembles containing only a few (from 1 to 3) Pd atoms. These species simultaneously explain the observed X-ray spectra and equate the experimental and theoretical values of the apparent activation energy. Remarkably, we find that the catalytic activity can be tuned on demand by controlling the size of the Pd ensembles through catalyst pretreatment. Our data-driven multimodal approach enables decoding of reactive structures in complex and dynamic alloy catalysts

Solving the structure of nanoparticles by multiple-scattering EXAFS analysis

The particle size effect on the coordination number in nanoparticles is much stronger for more distant coordination shells than for the first nearest neighbor shell. We show, using the EXAFS analysis of carbon-supported Pt and Pt-Ru nanoparticles, that it is possible to analyze the structure of mono- and heteroatomie particles through the 4 ~ shell by taking into account multiple scatterings, and by using multiple edge refinement in the case of Pt-Ru alloy. Combined with the transmission electron microscopy and electron diffraction results, our procedure enabled us to obtain the particle shape and size in both types of the nanoelusters, and non-statistical distribution of Pt and Ru atoms in the alloy