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KF post-deposition treatment of industrial Cu(In, Ga)(S, Se) 2 thin-film surfaces: Modifying the chemical and electronic structure
The chemical and electronic structures of industrial chalcopyrite photovoltaic absorbers after KF post-deposition treatment (KF-PDT) are investigated using electron spectroscopies to probe the occupied and unoccupied electronic states. In contrast to a variety of recent publications on the impact of KF-PDT, this study focuses on industrial Cu(In,Ga)(S,Se) 2 absorbers that also contain sulfur at the surface. We find that the KF-PDT removes surface adsorbates and oxides and also observe a change in the S/Se ratio. Furthermore, the KF-PDT leads to a Cu reduction at the surface but to a much lower degree than the strongly Cu-depleted or even Cu-free surfaces reported for (non-industrial) sulfur-free Cu(In,Ga)Se 2 absorbers. Furthermore, the valence band maximum at the surface is found at a lower energy compared to the untreated absorber, and the conduction band minimum is found at a higher energy, overall revealing a widening of the bandgap in the surface region.
Chemical compositions, methods of making the chemical compositions, and structures made from the chemical compositions
Embodiments of the present disclosure include chemical compositions, structures, anodes, cathodes, electrolytes for solid oxide fuel cells, solid oxide fuel cells, fuel cells, fuel cell membranes, separation membranes, catalytic membranes, sensors, coatings for electrolytes, electrodes, membranes, and catalysts, and the like, are disclosed.
Enhanced CO 2 Methanation Activity of Sm 0.25 Ce 0.75 O 2-δ –Ni by Modulating the Chelating Agents-to-Metal Cation Ratio and Tuning Metal–Support Interactions
Highly active and selective CO 2 methanation catalysts are critical to CO 2 upgrading, synthetic natural gas production, and CO 2 emission reduction. Wet impregnation is widely used to synthesize oxide-supported metallic nanoparticles as the catalyst for CO 2 methanation. However, as the reagents cannot be homogeneously mixed at an atomic level, it is challenging to modulate the microstructure, crystal structure, chemical composition, and electronic structure of catalysts via wet impregnation. In this work, a scalable and straightforward catalyst fabrication approach has been designed and validated to produce Sm 0.25 Ce 0.75 O 2-δ -supported Ni (SDC–Ni) as the CO 2 methanation catalyst. By varying the chelating agents-to-total metal cations ratio (C/I ratio) during the catalyst synthesis, we can readily and simultaneously modulate the microstructure, metallic surface area, crystal structure, chemical composition, and electronic structure of SDC–Ni, consequently fine-tuning the oxide–support interactions and CO 2 methanation activity. The optimal C/I ratio (0.1) leads to an SDC–Ni catalyst that facilitates C–O bond cleavage and significantly improves CO 2 conversion at 250 °C. A CO 2 -to-CH 4 yield of >73% has been achieved at 250 °C. Furthermore, a stable operation of >1500 hours has been demonstrated, and no degradation is observed. Extensive characterizations were performed to fundamentally understand how to tune and enhance CO 2 methanation activity of SDC–Ni by modulating the C/I ratio. The correlation of physical, chemical, and catalytic properties of SDC–Ni with the C/I ratio is established and thoroughly elaborated in this work. This study could be applied to tune the oxide–support interactions of various catalysts for enhancing the catalytic activity.
Heating induced structural and chemical behavior of KD{sub 2}PO{sub 4} in the 25 °C–215 °C temperature range
We have used powder x-ray diffraction (XRD) to investigate the structural and chemical modifications undergone by KD{sub 2}PO{sub 4} (DKDP) upon heating from room temperature to 215 °C. Full-profile (Le Bail) analysis of our temperature-resolved data shows no evidence of polymorphic structural transitions or deuterium–hydrogen isotope exchange occurring below T{sub s} = 185 °C. The lattice parameters of DKDP vary smoothly upon heating to T{sub s} and are 0.2% to 0.6% greater than those of its isostructural hydrogenated counterpart KH{sub 2}PO{sub 4} (KDP). In addition, XRD isotherms collected at T{sub s} demonstrate the structural and chemical stability of the title compound at this temperature over a 10.5 h time period. Upon further heating, however, the tetragonal DKDP phase becomes unstable, as evidenced by its transition to a monoclinic DKDP modification and eventual chemical decomposition via dehydration. - Highlights: • Structural and chemical behavior of KD{sub 2}PO{sub 4} is investigated upon heating to 215 °C • No polymorphic transitions or deuterium-hydrogen isotope exchange below T{sub s} = 185 °C • KD{sub 2}PO{sub 4} is structurally and chemically stable at T{sub s} over a 10.5 h time period • KD{sub 2}PO{sub 4} chemically decomposes via dehydration upon heating above T{sub d} = 195 °C.
JUPITER- CHEMICAL COMPOSITION, STRUCTURE AND ORIGIN OF A GIANT PLANET
Chemical composition and structure of jupiter as test case of origin of giant planets
Atomic-Scale Structure of Chemically Distinct Surface Oxygens in Redox Reactions
During redox reactions, oxide-supported catalytic systems undergo structural and chemical changes. Improving subsequent catalytic properties requires an understanding of the atomic-scale structure with chemical state specificity under reaction conditions. For the case of 1/2 monolayer vanadia on α-TiO 2 (110), we use X-ray standing wave (XSW) excited X-ray photoelectron spectroscopy to follow the redox induced atomic positional and chemical state changes of this interface. Furthermore, while the resulting XSW 3D composite atomic maps include the Ti and O substrate atoms and V surface atoms, our focus in this report is on the previously unseen surface oxygen species with comparison to density functional theory predictions.
Chemical and Structural Stability of Lithium-Ion Battery Electrode Materials under Electron Beam
Our investigation of chemical and structural dynamics in battery materials is essential to elucidation of structure-property relationships for rational design of advanced battery materials. Spatially resolved techniques, such as scanning/transmission electron microscopy (S/TEM), are widely applied to address this challenge. But, battery materials are susceptible to electron beam damage, complicating the data interpretation. In this study, we demonstrate that, under electron beam irradiation, the surface and bulk of battery materials undergo chemical and structural evolution equivalent to that observed during charge-discharge cycling. In a lithiated NiO nanosheet, a Li2CO3-containing surface reaction layer (SRL) was gradually decomposed during electron energy loss spectroscopy (EELS) acquisition. For cycled LiNi 0.4 Mn 0.4 Co 0.18 Ti 0.02 O 2 particles, repeated electron beam irradiation induced a phase transition from an R$\bar{3}$m layered structure to an rock-salt structure, which is attributed to the stoichiometric lithium and oxygen removal from R$\bar{3}$m 3a and 6c sites, respectively. Nevertheless, it is still feasible to preserve pristine chemical environments by minimizing electron beam damage, for example, in using fast electron imaging and spectroscopy. Finally, the present study provides examples of electron beam damage on lithium-ion battery materials and suggests that special attention is necessary to prevent misinterpretation of experimental results.
Hybrid X-ray Spectroscopy-Based Approach To Acquire Chemical and Structural Information of Single-Walled Carbon Nanotubes with Superior Sensitivity
High-resolution nondestructive chemical analysis of both bulk and surface of application-ready carbon nanomaterials is needed to connect the material properties to the observed performance. This is needed to enable application-specific tailoring of carbon nanomaterials. However, detailed studies of effects of oxidizing treatments on the chemical composition and structural integrity of carbon and on the metal seed materials are rare. Here we show a hybrid X-ray-based study retrieving this hard-to-access chemical and structural information of application-ready ferrocene-grown single-walled carbon nanotubes and their nitric acid- and oxygen plasma-treated versions. We have executed photoelectron, absorption, and X-ray emission spectroscopy (XES) measurements in the soft X-ray regime providing chemical and structural information with high energy resolution and throughput. We observed that the nitric acid treatment did not significantly alter the chemical state of the carbon matrix, whereas the oxygen plasma treatment was associated with strong effects and chemical conversions toward oxygen-functionalized groups such as carboxyl. Additionally, an Fe catalyst was present before and after the oxidizing treatments at considerable concentrations as detected by both X-ray absorption spectroscopy and XES, with a near complete conversion of Fe 2+ to Fe 3+ . Additional minor elements (metals <0.1 at. %) were detected only with XES. With this combined approach, we can study the effect of different treatments on application-ready carbon nanomaterials’ physicochemical and structural properties with unmatched precision, which helps understand the nature of these materials.
Chemical and Structural Effects on the Rate of Xylan Hydrolysis during Dilute Acid Pretreatment of Poplar Wood
Economic biofuel production requires high sugar yields during biomass pretreatment, however, the chemical and structural features of biomass can be obstructive toward efficient xylose hydrolysis. Here, we tested the hindrance imposed by the multiscale structure of biomass on the hydrolysis of xylan during dilute acid pretreatment by studying the effects of both the chemical nature of xylan and physical structure of biomass. Dilute acid pretreatment of poplar wood at particle sizes ranging from 10 um to 10 mm was conducted, however, no significant differences in the rates of xylan hydrolysis were observed over more than 2 orders of magnitude in particle size. A significant reduction in the rate of xylan hydrolysis was observed when compared to the intrinsic rate of hydrolysis for isolated xylan. Thus, it appears likely that the chemical structure of xylan and/or the interaction of xylan with other polymers in the cell wall matrix have greater effects on xylan hydrolysis rates than mass transfer limitations.
Electrical, structural, and chemical characterization of silicon sheet materials
Progress on the electrical, structural, and chemical characterization of silicon sheet material is reported. In the study on high temperature deformation of dendritic web ribbon, experimental creep tests were performed in four point bending under constant load conditions, and unusual behavior was observed. Also, measurements of oxygen content in web ribbon were made. Two conclusions reached are creep behavior of web which is very different from any seen for single crystal silicon and oxygen level in web silicon which is near the saturation level at the melting point of silicon.
Analysis of plasma-nitrided steels
The analysis of plasma nitrided steels can be divided to two main categories - structural and chemical. Structural analysis can provide information not only on the hardening mechanisms but also on the fundamental processes involved. Chemical analysis can be used to study the kinetics for the nitriding process and its mechanisms. In this paper preliminary results obtained by several techniques of both categories are presented and the applicability of those techniques to the analysis of plasma-nitrided steels is discussed.
Analysis of plasma nitrided steels
The analysis of plasma nitrided steels can be divided to two main categories - structural and chemical. Structural analysis can provide information not only on the hardening mechanisms but also on the fundamental processes involved. Chemical analysis can be used to study the kinetics for the nitriding process and its mechanisms. In this paper preliminary results obtained by several techniques of both categories are presented and the applicability of those techniques to the analysis of plasma-nitrided steels is discussed.
Enabling Ultralow Volume Analysis with a High-Resolution Ion Mobility Mass Spectrometry Platform
Of all the molecules thought to exist in the universe, it is estimated that researchers only know the chemical structures of 5% of them. Identifying the chemical structures of the remaining 95% has proven extremely challenging because many molecules exhibit low abundance, are contained in small volumes (e.g., <10 nL), do not readily ionize, exhibit similar structures to other molecules, etc. No single analytical technique exists to definitively identify the structure of an unknown molecule, and thus multiple different molecular measurements are typically made (i.e., multi-modal approach). Ion mobility (IMS) and mass spectrometry (MS) are two key tools that researchers use to determine the chemical structures of unknown molecules, and recently high-resolution and ultrahigh resolution IMS-MS instruments have provided greater confidence than ever before. However, HR-IMS-MS instruments typically exhibit low ion utilization efficiency, meaning they require large amounts of sample for an analysis (e.g., >10 µL). Unfortunately, this limitation prohibits the analysis of small volume samples where many unknown molecules exist. Described herein are the efforts made to enable the analysis of ultralow volumes with an HR-IMS-MS platform. A new scanning technique, termed a ‘stuttered traveling wave scan’, was developed as a replacement for the dual-gated scanning technique and works by halting the traveling waves after allowing ions to separate and then repeatedly restarting and stopping the traveling waves to incrementally move ions from the SLIM to the Orbitrap. Ions were stored inside the SLIM while the TWs were stopped, allowing the Orbitrap to perform high-resolution mass analysis. When the Orbitrap was ready, the TWs were restarted for short periods of time (<10 ms) to move ions from the SLIM to the Orbitrap. It was discovered that lower TW amplitudes and speeds than used during IMS separation were required to produce IMS peaks with the highest signal intensities and best resolving powers. The stuttered TW scan was found to produce similar resolutions and signal intensities compared to the dual-gated scanning technique. A new IMS design possessing an intersecting ‘tee’ with a reversible traveling wave was also developed to improve ion utilization efficiency during cyclic operation, which is necessary when only a single IMS spectrum can be acquired, such as when analyzing ultralow volume samples. The new capabilities described in this report lay the groundwork for acquiring HR-IMS-MS spectra of ultralow volume biological samples, such as single cells, where HR-IMS-MS can help elucidate the structures of unknown compounds.
MetILs 3 : A Strategy for High Density Energy Storage Using Redox-Active Ionic Liquids
We present a systematic approach for increasing the concentration of redox-active species in electrolytes for nonaqueous redox flow batteries (RFBs). Starting with an ionic liquid consisting of a metal coordination cation (MetIL), ferrocene-containing ligands and iodide anions are substituted incrementally into the structure. While chemical structures can be drawn for molecules with 10 m redox-active electrons (RAE), practical limitations such as melting point and phase stability constrain the structures to 4.2 m RAE, a 2.3× improvement over the original MetIL. Dubbed “MetILs 3 ,” these ionic liquids possess redox activity in the cation core, ligands, and anions. Throughout all compositions, infrared spectroscopy shows the ethanolamine-based ligands primarily coordinate to the Fe 2+ core via hydroxyl groups. Calorimetry conveys a profound change in thermophysical properties, not only in melting temperature but also in suppression of a cold crystallization only observed in the original MetIL. Square wave voltammetry reveals redox processes characteristic of each molecular location. Testing a laboratory-scale RFB demonstrates Coulombic efficiencies >95% and increased voltage efficiencies due to more facile redox kinetics, effectively increasing capacity 4×. Application of this strategy to other chemistries, optimizing melting point and conductivity, can yield >10 m RAE, making nonaqueous RFB a viable technology for grid scale storage.
Topologically identical, but geometrically isomeric layers in hydrous α-, β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O and anhydrous Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]
The hydrothermal reaction of uranyl nitrate with rubidium nitrate and arsenic (III) oxide results in the formation of polymorphic α- and β-Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O (α-, β-RbUAs) and the anhydrous phase Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] (RbUAs). These phases were structurally, chemically and spectroscopically characterized. The structures of all three compounds are based upon topologically identical, but geometrically isomeric layers. The layers are linked with each other by means of the Rb cations and hydrogen bonding. Dehydration experiments demonstrate that water deintercalation from hydrous α- and β-RbUAs yields anhydrous RbUAs via topotactic reactions. - Graphical abstract: Three different layer geometries observed in the structures of Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})] and α- and β- Rb[UO{sub 2}(AsO{sub 3}OH)(AsO{sub 2}(OH){sub 2})]·H{sub 2}O. Two different coordination environments of uranium polyhedra (types I and II) are shown schematically on the top of the figure. - Highlights: • Three new uranyl arsenates were synthesized from the hydrothermal reactions. • The phases consist of the topologically identical but geometrically different layers. • Topotactic transitions were observed in the processes of mono-hyrates dehydration.
Structural and Chemical Features Giving Rise to Defect Tolerance of Binary Semiconductors
Defect tolerance, or the resilience of electronic transport properties of a crystalline material to the presence of defects, has emerged as a critical factor in the success of hybrid lead halide perovskites as photovoltaic absorbers. A key aspect of defect tolerance is the shallow character of dominant intrinsic defects. However, while qualitative heuristics to identify other defect-tolerant materials have been proposed, in particular, the presence of a partially oxidized ns 2 cation such as Pb, no compelling comprehensive understanding of how these shallow defects arise has yet emerged. Using modern defect theory and defect calculations, we conduct a detailed investigation of the mechanisms and identify specific features related to the chemical composition and crystal structure that give rise to defect tolerance. We find that an ns 2 cation is necessary but not sufficient to guarantee shallow cation vacancies in an s-p system, and that a compound's crystal structure can ensure shallow anion vacancies in a variety of ways. Specifically, the crystal site symmetry can enforce weak interactions between the orbitals that form the defect states, thus ensuring that those defect states are shallow. We substantiate our findings by computing defect formation energies in several known as well as hypothetical materials and conclude by discussing prospects for identifying semiconductors that satisfy these criteria.
Oxide– and Silicate–Water Interfaces and Their Roles in Technology and the Environment
Interfacial reactions drive all elemental cycling on Earth and play pivotal roles in human activities such as agriculture, water purification, energy production and storage, environmental contaminant remediation, and nuclear waste repository management. The onset of the 21st century marked the beginning of a more detailed understanding of mineral aqueous interfaces enabled by advances in techniques that use tunable high-flux focused ultrafast laser and X-ray sources to provide near-atomic measurement resolution, as well as by nanofabrication approaches that enable transmission electron microscopy in a liquid cell. This leap into atomic- and nanometer-scale measurements has uncovered scale-dependent phenomena whose reaction thermodynamics, kinetics, and pathways deviate from previous observations made on larger systems. A second key advance is new experimental evidence for what scientists hypothesized but could not test previously, namely, interfacial chemical reactions are frequently driven by “anomalies” or “non-idealities” such as defects, nanoconfinement, and other nontypical chemical structures. Third, progress in computational chemistry has yielded new insights that allow a move beyond simple schematics, leading to a molecular model of these complex interfaces. In combination with surface-sensitive measurements, we have gained knowledge of the interfacial structure and dynamics, including the underlying solid surface and the immediately adjacent water and aqueous ions, enabling a better definition of what constitutes the oxide– and silicate–water interfaces. This critical review discusses how science progresses from understanding ideal solid–water interfaces to more realistic systems, focusing on accomplishments in the last 20 years and identifying challenges and future opportunities for the community to address. Further, we anticipate that the next 20 years will focus on understanding and predicting dynamic transient and reactive structures over greater spatial and temporal ranges as well as systems of greater structural and chemical complexity. Closer collaborations of theoretical and experimental experts across disciplines will continue to be critical to achieving this great aspiration.