X-ray Absorption Near-edge Structure Analysis Research Articles

Invariant nature of substituted element in metal-hexacyanoferrate

The chemical substitution of a transition metal (M) is an effective method to improve the functionality of materials. In order to design the highly functional materials, we first have to know the local structure and electronic state around the substituted element. Here, we systematically investigated the local structure and electronic state of the host (Mh) and guest (Mg) transition metals in metal-hexacyanoferrate (M-HCF), Nax(Mh, Mg)[Fe(CN)6]y (1.40 < x < 1.60 and 0.85 < y < 0.90), by means of extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) analyses. The EXAFS and XANES analyses revealed that the local structure and electronic state around Mg are essentially the same as those in the pure compound, i.e, Mg-HCF. Such an invariant nature of Mg in M-HCF is in sharp contrast with that in layered oxide, in which the Mg valence changes so that local Mg-O distance (dM-Og) approaches the Mh-O distance (dM-Oh).

Supervised Machine-Learning-Based Determination of Three-Dimensional Structure of Metallic Nanoparticles.

Tracking the structure of heterogeneous catalysts under operando conditions remains a challenge due to the paucity of experimental techniques that can provide atomic-level information for catalytic metal species. Here we report on the use of X-ray absorption near-edge structure (XANES) spectroscopy and supervised machine learning (SML) for refining the 3D geometry of metal catalysts. SML is used to unravel the hidden relationship between the XANES features and catalyst geometry. To train our SML method, we rely on ab initio XANES simulations. Our approach allows one to solve the structure of a metal catalyst from its experimental XANES, as demonstrated here by reconstructing the average size, shape, and morphology of well-defined platinum nanoparticles. This method is applicable to the determination of the nanoparticle structure in operando studies and can be generalized to other nanoscale systems. It also allows on-the-fly XANES analysis and is a promising approach for high-throughput and time-dependent studies.

Phosphate Speciation and Citrate-Induced Mobilization of P in an Acric Oxisol

ABSTRACTBillions of dollars are spent annually in Brazil on imported phosphorus (P) fertilizers for agricultural crops produced on Oxisols. Phosphate fixation by Oxisols is a main limitation to crop productivity because these highly weathered soils have a high phosphate adsorption capacity. The objective was to determine whether reaction of an Acric Oxisol with citrate increases P availability. Columns of P-amended subsoil material were leached with 1 mM citrate solution, and effluent was monitored. Solid-phase speciation was measured for different stages of leaching using X-ray absorption near edge structure (XANES) spectroscopy at the P K-edge. When soil columns were leached with up to 56 column pore volumes of 1 mM citrate solutions, no P was detected in column effluent samples, whereas aluminum (Al) and iron (Fe) increased up to 30 and 1.4 µmol L−1, respectively. The XANES analysis suggested that with increased leaching, a minor proportion of phosphate adsorbed on Fe-oxides increased as phosphate adsorbed on Al-oxides decreased. The results indicated that citrate tends to induce minor species redistribution of phosphate between Al- and Fe-oxide bound forms, but P mobilization was trivial compared with complexometric mobilization of Fe and Al.

Emission properties of Ce-doped alkaline earth borate glasses for scintillator applications

We investigate the photoluminescence (PL) and X-ray-induced luminescence properties of 0.1 mol% Ce-doped MO-B2O3 (M = Ca, Sr, and Ba) glasses. We also determine the Ce3+/(Ce3++Ce4+) ratio by X-ray absorption near-edge structure analyses. The emission intensities of PL, X-ray scintillation, and thermally stimulated luminescence (TSL) depend on the host glass composition. The order of the PL intensity from highest to lowest is as follows: Ca-substituted glass, Ba-substituted glass, and Sr-substituted glass. Our results suggest that the optical absorption edge and quantum yield (QY) are influenced by the local coordination state of Ce3+, which, in turn, is likely to be affected by the optical basicity. The order of the X-ray scintillation intensity from highest to lowest is reverse of that of the PL intensity. This is probably because the interaction probability of X-rays with matter depends on the effective atomic number of the material and the effective atomic number has a stronger influence on the scintillation intensity than does the QY. Though the TSL glow curves reveal that the density and energy depth of the trap sites depend on the substituted alkaline earth oxides, we are unable to correlate the electron spin resonance (ESR) spectra with the TSL results. Therefore, it is considered that the ESR active sites are not responsible for the TSL in these systems.

Different partitioning behaviors of molybdenum and tungsten in a sediment–water system under various redox conditions

Molybdenum (Mo) and tungsten (W) are redox-sensitive elements that exhibit contrasting geochemical behaviors under different redox and/or sulfidic conditions despite belonging to the same group in the periodic table. In this study, the geochemistry of Mo and W in a sediment–porewater system was investigated using a core sample collected from sediment containing hydrothermal minerals (Izena Hole, Okinawa, Japan). The Mo contents in the sediment and the porewater were quantified to calculate the partition coefficient Kd (concentration ratio of the solid phase to the aqueous phase) for Mo. However, the W concentration in the porewater was exceedingly low to be detected. Thus, we also conducted laboratory experiments simulating the sediment–porewater system to clarify the partitioning behaviors of Mo and W under redox conditions. X-ray absorption near-edge structure (XANES) spectra were obtained to determine the chemical species of Mo and W in sediment at different depths to understand the chemical processes of Mo and W. In particular, high-sensitivity XANES spectroscopy using wavelength-dispersive fluorescence mode was applied to W L3 edge XANES spectra to reduce the interference signals from coexistent elements (Zn and Ni). This step thereby facilitating the identification of oxygen- and sulfur-coordinated species for W in the sediments.The collected core sample covered a broad range of redox conditions under various hydrogen sulfide (H2S) concentrations depending on the depth. The presence of iron oxides in the upper layer suggested an oxic condition above within 4cm depth below the seafloor (cmbsf). Iron and Zn sulfide minerals were found in deeper layers (16–24 cmbsf) and indicated the reductive conditions formed in such layer. Hydrogen sulfide was also observed in the porewater of the deeper layer. Analyses for Mo in the natural sediments, as well as XANES analyses, revealed that the Kd was higher in the deeper layer, with high pyrite and H2S contents, than in the upper layer. These results implied that Mo was removed from the porewater under reductive and/or sulfidic conditions. The chemical species of Mo was also an oxygen-coordinated species in the upper layer (0–8 cmbsf). Meanwhile, the detection of sulfide in the deeper layer suggests that Mo sulfidation is an important reaction in Mo enrichment in sediments.On the other hand, at all the depths, W formed oxygen-coordinated species in the sediment. The subtle change of Kd for W with depth suggested that H2S did not affect the W adsorption in our samples. Hence, the Mo/W ratio in the sediments increased with the development of reducing conditions and vice versa in the coexistent porewater. Speciation analysis revealed that the high stability of oxygen-coordinated species of W was responsible for the variations of the Mo/W ratio under various redox conditions.

Mechanistic Origin of Enhanced CO Catalytic Oxidation over Co3O4/LaCoO3 at Lower Temperature

AbstractCO catalytic oxidation on the perovskite oxide LaCoO3, which can be ascribed to a decoration of Co3O4 nanoparticles on the surface, was achieved with 90 % conversion rate at 202 °C. The obtained dual‐phase catalyst was successfully synthesized through a non‐stoichiometric Ce‐induced exsolution‐like process, after an electrospinning treatment with subsequent annealing. The enhanced activity originates from the surface oxygen of LaCoO3/Co3O4 and Co3+ in the Co3O4 nanoparticles, as confirmed by X‐ray photoelectron spectroscopy (XPS) and X‐ray absorption near‐edge structure analysis (XANES). The synergic effect of the surfaced Co3O4 and parent LaCoO3 may open a path to unlocking the activity of perovskite oxides for enhanced low‐temperature CO oxidation.

An XPS and XANES Study on the Bioleaching of Arsenopyrite with or without Pyrite

In the present study, we investigated the bioleaching of arsenopyrite with or without pyrite by moderate thermophiles. In both chemical leaching and bioleaching, the addition of pyrite decreased the leaching rate of arsenopyrite. The arsenic speciation and minerology changes in the residues were analysed by X-ray Absorption Near Edge Structure (XANES) Spectroscopy, X-ray Photoelectron Spectroscopy (XPS) and powder X-ray Diffraction (XRD). The XANES analysis showed no detectable arsenopyrite in the final residues from the experiments without pyrite. However, there was still 21.7% of arsenic species presented as arsenopyrite after bioleaching, when the initial arsenopyrite/pyrite ratio was 1:5. The XPS analysis revealed there was only As(V) on the surface of most of the residues, except on one chemically leached sample where As(III) was found.

High-Performance Cathode Based on Microporous Mo-V-Bi Oxide for Li Battery and Investigation by Operando X-ray Absorption Fine Structure.

The development of cathode-active material of Li battery is important for the current emerging energy transferring and saving problems. A stable crystalline microporous complex metal oxide based on Mo, V, and Bi is an active and suitable material for Li battery. High capacity (380 Ah/kg) and stable cycle performance are achieved. X-ray absorption near-edge structure analyses demonstrate that the original Mo6+ and V4+ ions are reduced to Mo4+ and V3+ in the discharging process, respectively, which results in a 70-electron reduction per formula. The reduced metal ions can be reoxidized reversibly in the next charging process. Furthermore, extended X-ray absorption fine structure analyses reveal that the Mo-O bonds in the material are lengthened in the discharging process probably due to interaction with Li+ without change of the basic structure.

Speciation of magnesium in monohydrocalcite: XANES, ab initio and geochemical modeling

Monohydrocalcite (MHC: CaCO3·H2O), a rare carbonate mineral formed under surface conditions, is usually observed in nature as containing a variable amount of Mg, with a 0.007–0.45Mg/Ca mole ratio. The variable Mg composition in MHC is anticipated as a promising proxy to assess paleo-hydrochemistry especially in saline lakes. Although the roles of Mg on the formation and stability of MHC have been studied intensively, the Mg speciation in MHC has remained unclear and controversial. This study examined Mg speciation in MHC using X-ray absorption near edge structure (XANES), ab initio molecular simulation, and geochemical modeling. Mg-XANES spectra of MHC with different Mg/Ca ratios prepared from mixing solutions of Na2CO3, CaCl2 and MgCl2 revealed that the Mg in MHC is a mixture of amorphous Mg carbonate (AMC) and other Mg containing phase. The contribution of AMC to total Mg is negatively correlated to the crystallinity of MHC. Results show that AMC might play a protective role in the crystallization and the transformation to stable calcium carbonates. Ab initio calculation of Mg2+ substitution into MHC showed that a limited amount of Mg2+ can be incorporated into the MHC structure. Six-fold coordination of Mg2+ is substituted for eight-fold coordination of Ca2+ in the MHC structure. The other type of Mg in MHC revealed from the XANES analyses most likely corresponds to the structural Mg in MHC. The contribution of the structural Mg is almost constant at 0.06 in Mg/Ca, representing the limit of solid solubility of Mg in MHC. The solubility products of the MHC with the limit of solid solubility of Mg and the AMC associated with MHC were estimated from the reacted solution compositions. Prediction of the Mg/Ca ratio as a function of the initial solution conditions using solubility reasonably reproduces the observed apparent Mg/Ca ratios in MHC from the present study and earlier studies. The apparent Mg/Ca ratio of MHC is useful to elucidate water chemistry, especially for CO3/Ca and Mg concentrations during MHC formation.

Achieving high capacity and rate capability in layered lithium transition metal oxide cathodes for lithium-ion batteries

In this study, we target to find a new composition for a layered mixed metal oxide, which has a high structural stability and a good electrochemical performance. Our strategy is to alter the transition metal composition focusing on the relative amounts of redox active Ni and Co to the inactive Mn, based on highly-stabilized LiNi1/3Co1/3Mn1/3O2. X-ray absorption near-edge structure and X-ray diffraction analyses show that the degree of cation disorder decreases on increasing the ratio of Ni and Co to Mn, by the presence of Ni3+, suggesting that slightly higher Ni and Co contents lead to improved structural stability. Electrochemical studies demonstrate that LiNi0.4Co0.4Mn0.2O2 cathodes exhibit considerable improvements in both the reversible capacity and the rate capabilities at a voltage range of 2.5–4.6 V. In situ XRD measurements reveal that LiNi0.4Co0.4Mn0.2O2 maintains a single-phase and undergoes lesser structural variations compared to controlled compositions during a delithiation process up to 4.6 V, while achieving a high reversible capacity over 200 mAh g−1. As a result, LiNi0.4Co0.4Mn0.2O2 experiences fewer structural degradations during electrochemical cycling, which explains the excellent long-term cycling performance.

High-Performance Zinc Tin Oxide Semiconductor Grown by Atmospheric-Pressure Mist-CVD and the Associated Thin-Film Transistor Properties.

Zinc tin oxide (Zn-Sn-O, or ZTO) semiconductor layers were synthesized based on solution processes, of which one type involves the conventional spin coating method and the other is grown by mist chemical vapor deposition (mist-CVD). Liquid precursor solutions are used in each case, with tin chloride and zinc chloride (1:1) as solutes in solvent mixtures of acetone and deionized water. Mist-CVD ZTO films are mostly polycrystalline, while those synthesized by spin-coating are amorphous. Thin-film transistors based on mist-CVD ZTO active layers exhibit excellent electron transport properties with a saturation mobility of 14.6 cm2/(V s), which is superior to that of their spin-coated counterparts (6.88 cm2/(V s)). X-ray photoelectron spectroscopy (XPS) analyses suggest that the mist-CVD ZTO films contain relatively small amounts of oxygen vacancies and, hence, lower free-carrier concentrations. The enhanced electron mobility of mist-CVD ZTO is therefore anticipated to be associated with the electronic band structure, which is examined by X-ray absorption near-edge structure (XANES) analyses, rather than the density of electron carriers.

Effects of Potassium and Manganese Promoters on Nitrogen-Doped Carbon Nanotube-Supported Iron Catalysts for CO2 Hydrogenation

Nitrogen-doped carbon nanotubes (NCNTs) were used as a support for iron (Fe) nanoparticles applied in carbon dioxide (CO2) hydrogenation at 633 K and 25 bar (1 bar = 105 Pa). The Fe/NCNT catalyst promoted with both potassium (K) and manganese (Mn) showed high performance in CO2 hydrogenation, reaching 34.9% conversion with a gas hourly space velocity (GHSV) of 3.1 L·(g·h)−1. Product selectivities were high for olefin products and low for short-chain alkanes for the K-promoted catalysts. When Fe/NCNT catalyst was promoted with both K and Mn, the catalytic activity was stable for 60 h of reaction time. The structural effect of the Mn promoter was demonstrated by X-ray diffraction (XRD), temperature-programmed reduction (TPR) with molecular hydrogen (H2), and in situ X-ray absorption near-edge structure (XANES) analysis. The Mn promoter stabilized wüstite (FeO) as an intermediate and lowered the TPR onset temperature. Catalytic ammonia (NH3) decomposition was used as an additional probe reaction for characterizing the promoter effects. The Fe/NCNT catalyst promoted with both K and Mn had the highest catalytic activity, and the Mn-promoted Fe/NCNT catalysts had the highest thermal stability under reducing conditions.

A Study of Ziegler-Natta Propylene Polymerization Catalysts by Spectroscopic Methods.

Ziegler–Natta polymerization catalysts were characterized by a complex of surface- and bulk-sensitive methods (DRIFTS, XPS, ESR, and XAS = XANES + EXAFS). A diffuse-reflectance Fourier-transform IR spectroscopy (DRIFTS) study showed the presence of strong Lewis acid sites in different concentrations and absence of strong basic sites in the polymerization catalysts. X-ray photoelectron spectroscopy (XPS), electron-spin resonance (ESR), and (X-ray absorption near-edge structure (XANES) analysis revealed the presence of Ti4+, Ti3+, Ti2+, and Ti1+ species in the surface layers and in the bulk of catalysts. The samples under study differ drastically in terms of the number of ESR-visible paramagnetic sites. The EXAFS study shows the presence of a Cl atom as a nearest neighbor of the absorbing Ti atom.

Variation of mineralogy and organic material during the early stages of aqueous activity recorded in Antarctic micrometeorites

Micrometeorites (MMs) recovered from surface snow near the Dome Fuji Station, Antarctica are almost free from terrestrial weathering and contain very primitive materials, and are suitable for investigation of the evolution and interaction of inorganic and organic materials in the early solar system. We carried out a comprehensive study on seven porous and fluffy MMs [four Chondritic porous (CP) MMs and three fluffy fine-grained (Fluffy Fg) MMs] and one fine-grained type 1 (Fg C1) MM for comparison with scanning electron microscope, transmission electron microscope, X-ray absorption near-edge structure analysis, and secondary ion mass spectrometer.They show a variety of early aqueous activities. Four out of the seven CP MMs contain glass with embedded metal and sulfide (GEMS) and enstatite whiskers/platelets and do not have hydrated minerals. Despite the same mineralogy, organic chemistry of the CP MMs shows diversity. Two of them contain considerable amounts of organic materials with high carboxyl functionality, and one of them contains nitrile (CN) and/or nitrogen heterocyclic groups with D and 15N enrichments, suggesting formation in the molecular cloud or a very low temperature region of the outer solar system. Another two CP MMs are poorer in organic materials than the above-mentioned MMs. Organic material in one of them is richer in aromatic C than the CP MMs mentioned above, being indistinguishable from those of hydrated carbonaceous chondrites. In addition, bulk chemical compositions of GEMS in the latter organic poor CP MMs are more homogeneous and have higher Fe/(Si+Mg+Fe) ratios than those of GEMS in the former organic-rich CP MMs. Functional group of the organic materials and amorphous silicate in GEMS in the organic-poor CP MMs may have transformed in the earliest stage of aqueous alteration, which did not form hydrated minerals.Three Fluffy Fg MMs contain abundant phyllosilicates, showing a clear evidence of aqueous alteration. Phyllosilicates in thee MMs are richer in Fe than those in hydrated IDPs, typical fine-grained hydrated (Fg C1) MMs, and hydrated carbonaceous chondrites. One of the Fluffy Fg MMs contains amorphous silicate, which is richer in Fe than GEMS and contains little or no nanophase Fe metal but contains Fe sulfide. Because the chemical compositions of the amorphous silicate are within the compositional field of GEMS in CP IDPs, the amorphous silicate may be alteration products of GEMS. The entire compositional field of GEMS in the CP MMs and the amorphous silicate in the Fluffy Fg MM matches that of the previously reported total compositional range of GEMS in IDPs.One Fluffy Fg MM contains Mg-rich phyllosilicate along with Fe-rich phyllosilicate and Mg-Fe carbonate. Mg-rich phyllosilicate and Mg-Fe carbonate may have been formed through the reaction of Fe-rich phyllosilicate, Mg-rich olivine and pyroxene, and water with C-bearing chemical species.These data indicate that CP MMs and Fluffy Fg MMs recovered from Antarctic surface snow contain materials that throw a light on the earliest stages of aqueous alteration on very primitive solar system bodies. Because mineralogy and isotopic and structural features of organic materials in D10IB009 are comparable with isotopically primitive IDPs, its parent body could be comets or icy asteroids showing mass ejection (active asteroids). By contrast, organic-poor CP MMs may have experienced the earliest stage of aqueous alteration and Fluffy Fg MMs experienced weak aqueous alteration. The precursor materials of the parent bodies of Fluffy Fg MMs probably contained abundant GEMS or GEMS-like materials like CP IDPs, which is common to fine-grained matrices of very primitive carbonaceous chondrites such as CR3s. However, highly porous nature of organic-poor CP MMs and Fluffy Fg MMs suggests that parent bodies of these MMs must have been much more porous than the parent bodies of primitive carbonaceous chondrites. Given no phyllosilicate among the returned samples of 81P/Wild 2 comet, the MMs may have been derived from porous icy asteroids such as active asteroids as well as P- and D-type asteroids rather than comets.

A XANES and Raman investigation of sulfur speciation and structural order in Murchison and Allende meteorites

AbstractInsoluble organic matter (IOM) and hydrothermally treated IOM extracted from two carbonaceous chondrites, Murchison and Allende, was studied using sulfur K‐edge XANES (X‐ray absorption near edge structure) and μ‐Raman spectroscopy, with the aim to understand their IOM's sulfur speciation and structural order, and how aqueous alteration or thermal metamorphism may have transformed these materials. We found that the sulfur‐functional group chemistry of both the Murchison IOM and hydrothermally treated IOM samples have a large chemical variability ranging from oxidation states of S−2 to S+6, and exhibit a transformation in their oxidation state after the hydrothermal treatment (HT) to produce thiophenes and thiol compounds. Sulfoxide and sulfite peaks are also present in Murchison. Sulfates considered intrinsic to Murchison are most likely preaccretionary in nature, and not a result of reactions with water at high temperatures on the asteroid parent body. We argue that the reduced sulfides may have formed in the CM parent body, while the thiophenes and thiol compounds are a result of the HT. Micro‐Raman spectra show the presence of aliphatic and aromatic moieties in Murchison's material as observed previously, which exhibits no change after HT. Because the Murchison IOM was modified, as seen by XANES analysis, absence of a change observed using micro‐Raman indicated that although the alkyl carbons of IOM were cleaved, the aromatic network was not largely modified after HT. By contrast, Allende IOM contains primarily disulfide and elemental sulfur, no organic sulfur, and shows no transformation after HT. This nontransformation of Allende IOM after HT would indicate that parent body alteration of sulfide to sulfate is not feasible up to temperatures of 300°C. The reduced sulfur products indicate extreme secondary chemical processing from the precursor compounds in its parent body at temperatures as high as 624°C, as estimated from μ‐Raman D band parameters. The Raman parameters in Allende IOM that was interpreted in terms of amorphous carbon with regions of large clusters of benzene rings, was transformed after the HT to those with fewer benzene rings.

Effects of organic ligands on Pb absorption and speciation changes in Arabidopsis as determined bymicro X-ray fluorescence and X-ray absorption near-edge structure analysis.

Pb can pass through the food chain via plants and threaten human health, which has attracted widespread attention. Changes in Pb speciation affect its bioavailability in soils and water. However, whether organic ligands can change the uptake and mobility of Pb in plants and increase or decrease Pb bioavailability remains uncertain. To reveal the roles of organic and inorganic Pb in Pb metabolism in plants, the localization and speciation changes of Pb in Arabidopsis thaliana plants grown in organic and inorganic Pb were characterized by synchrotron radiation micro X-ray fluorescence and X-ray absorption near-edge structure, respectively. These results demonstrated that Arabidopsis absorbed more Pb from Pb(NO3)2 than Pb(CH3COO)2 at the same exposure concentration. A higher percentage of Pb-citrate was found in Arabidopsis exposed to inorganic Pb solution, which suggested that Pb-citrate was the main complex for root-to-shoot transportation in Arabidopsis exposed to inorganic Pb solutions. Pb complexed with the organic ligand CH3COO- significantly inhibited primary root growth and lateral root development, while, at the same time, Pb was blocked by root hairs, which represented another way to reduce Pb absorption and protect the plant from biotoxicity.

Synthesis of ε-Keggin-Type Cobaltomolybdate-Based 3D Framework Material and Characterization Using Atomic-Scale HAADF-STEM and XANES.

We describe the preparation of ε-Keggin-type cobaltomolybdate-based 3D frameworks with sodium cations, NaH9[ε-CoIIMoV8MoVI4O40CoII2], and their characterization by high-resolution high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption fine structure (XAFS) spectroscopy. Atomic-scale HAADF-STEM images of ε-Keggin compounds were obtained for the first time, and positions of Mo and Co were confirmed. Furthermore, clear evidence of the presence of a CoO4 tetrahedron was obtained by X-ray absorption near-edge structure (XANES) analysis. Their characterization clearly revealed that ε-Keggin-type cobaltomolybdate units, [ε-CoMo12O40]n-, constructed by a central CoIIO4 tetrahedron and 12 surrounding MoO6 octahedra, are linked with CoII to form 3D frameworks.

Surface States in Ternary CdSSe Quantum Dot Solar Cells.

Ternary CdSSe quantum dot-sensitized solar cells (QDSCs) have demonstrated advantages such as wide absorption ranges and tunable band structures. However, the oxygen additives absorbed on such multicomponent quantum dot (QD) surfaces induce band bending at the TiO₂/CdSSe interface and prevent charge transport in QDSCs, as determined via X-ray photoelectron spectroscopy (XPS) and synchrotron-based X-ray Absorption Near-Edge Structure (XANES) analysis. Annealing of TiO₂/CdSSe QDs photoanodes was conducted at different temperatures under Ar atmospheres to eliminate oxygen additives and interfacial band bending. The short-circuit current (J(sc))of the annealed ternary CdSSe QDSCs is obviously improved, whereas the TiCl4 treatment and MgO coating of the TiO₂ nanocrystals are assisted by the annealing to compensate for the loss of opencircuit voltage (V(oc)) and fill factor (FF). Ternary CdSSe QDSCs with efficiencies of 4.72% have been achieved using the optimized annealing conditions.

(Invited) Local Environment Analysis of Dilute Rare-Earth Dopants in Phosphor Materials

Doping technique, i.e., incorporation of dilute amount of additional element, has been widely applied to add new functions for various kinds of materials. Appropriate doping can change their specific properties significantly, e.g., electric, magnetic, optical, mechanical and chemical properties, etc. It is, of course, fundamental to know the crystal and electronic structures of such materials. In addition to such studies, it is mandatory to investigate the local environment of dopants on an atomic scale to understand the mechanism of appearance of new properties by doping and to design new materials with desired properties by such doping technique. Although crystal structure analysis has been widely carried out by the X-ray diffraction (XRD) technique, it is very difficult to determine the local environment of dilute dopants only by XRD. There are some experimental methods to investigate such local environment of dilute dopants. Among these methods, X-ray absorption near-edge structure (XANES) analysis by using the synchrotron radiations is one of the most powerful methods, which enables us to determine the local environment of dopant at an ultra-dilute concentration level, such as atomic ppm level of concentration [1]. We have reported quantitative analysis of XANES from many different kinds of functional materials [2, 3] with the aid of the first-principles calculations within the density functional theory (DFT). The fingerprint type analysis is widely accepted for various kinds of analysis, but such strategy requires reliable fingerprints to be compared with the newly observed result. However, in the case of local environment analysis by XANES, observed XANES spectrum from dopant often shows different profile from any of the standard ones, which yields that fingerprint type of analysis does not work for the local environment analysis. From such reason, theoretical fingerprint prepared by using first-principles calculation plays a key role for the local environment analysis of dopant by XANES. In the current study, we focus upon local environment analysis of dilute dopants in phosphor materials. After introduction of our analytical method of the local environment analysis with XANES and first-principles calculation, several results on such dopants, rare-earth ions and 3d-transition metal ions in perovskite structured oxides, will be shown. As an example, Ga XANES analysis of Ga doped SrTiO3:Pr, in which Ga codoping enhances red luminescence of Pr doped SrTiO3 [3], is shown in Fig. 1.

Fabrication of a Dipole-assisted Solid Phase Extraction Microchip for Trace Metal Analysis in Water Samples

This paper describes a fabrication protocol for a dipole-assisted solid phase extraction (SPE) microchip available for trace metal analysis in water samples. A brief overview of the evolution of chip-based SPE techniques is provided. This is followed by an introduction to specific polymeric materials and their role in SPE. To develop an innovative dipole-assisted SPE technique, a chlorine (Cl)-containing SPE functionality was implanted into a poly(methyl methacrylate) (PMMA) microchip. Herein, diverse analytical techniques including contact angle analysis, Raman spectroscopic analysis, and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) analysis were employed to validate the utility of the implantation protocol of the C-Cl moieties on the PMMA. The analytical results of the X-ray absorption near-edge structure (XANES) analysis also demonstrated the feasibility of the Cl-containing PMMA used as an extraction medium by virtue of the dipole-ion interactions between the highly electronegative C-Cl moieties and the positively charged metal ions.