X-ray Adsorption Near-edge Spectroscopy Research Articles

Construction of Synergistic Co and Cu Diatomic Sites for Enhanced Higher Alcohol Synthesis

Construction of Synergistic Co and Cu Diatomic Sites for Enhanced Higher Alcohol Synthesis

Understanding the role of water-soluble guar gum binder in reducing capacity fading and voltage decay of Li-rich cathode for Li-ion batteries

The practical application of high-capacity Li-rich cathode materials is hindered by capacity fading and voltage decay. The capacity fading and voltage decay could be effectively overcome by using water-soluble guar gum (GG) binder instead of traditional polyvinylidene fluoride (PVDF). However, the specific role of the GG binder is not clear yet, though the GG binder can significantly improve the electrochemical performance of Li-rich cathode. To understand the effect of GG binder on the morphology, microstructure of electrode and electrode/electrolyte interfaces, ex-situ scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray adsorption near edge spectroscopy (XANES), in-situ electrochemical impedance spectroscopy (EIS) were applied to comparatively study the charge-discharge processes of Li-rich Li1.2Ni0.2Mn0.6O2 cathode when using GG and PVDF as binders. The results indicate that the GG binder can prevent electrode crack and active material loss, ascribing to the strong mechanical adhesion of GG binder with active material particles and current collector. It has found that the GG binder can also induce the formation of a uniform layer on Li1.2Ni0.2Mn0.6O2 particles’ surface. As a consequence, both the electrolyte decomposition and the electrode corrosion were significantly inhibited. The strong chelation between Mn2+ and polar OH group restrain Mn ion dissolution, which contributes to surface structural transformation mitigation. The present study reveals the role of water-soluble GG binder in reducing capacity fading and voltage decay of Li-rich material and is of great importance in design functional binders for high-performance Li-rich electrodes.

Disrupting the Double Layer during Electrocatalysis By Applying a Pulsed Potential to Tune Product Selectivity for CO2 Reduction

The ability to control reaction kinetics and double layer species during an electrocatalytic process is highly desirable, especially for electrochemical CO2 reduction (CO2R) — a complex process in which multiple reaction steps are competing on the electrode surface. Here we show evidence suggesting the double layer can be disrupted with the application of a pulsed potential during CO2R.Pulsing the potential during CO2R using copper has been shown to influence product selectivity (i.e., to suppress the undesired hydrogen evolution reaction (HER)) and to improve electrocatalyst stability compared to constant applied potential.1 However, the underlying mechanism and contribution of interfacial/surface phenomena behind the pulsed potential application remain largely unknown. To uncover this unknown we investigated the state of the copper surface during the pulsed potential electrochemical CO2R using in-situ X-ray Adsorption Near Edge Spectroscopy (XANES). We probed the surface valence of the metallic electrode and found that the Cu electrode remains metallic over a broad pulsed potential range and only oxidizes to form Cu(OH)2 in the bulk when the pulsed potential reaches a highly oxidative limit (> 0.6 V vs. reversible hydrogen electrode (RHE)). Our results suggest that the pulsed anodic potential influences the double layer on the electrode surface, i.e., the dynamic competition between protons and hydroxide adsorbates instead of bulk copper oxidation. We attribute the suppressed HER to the electro-adsorption of hydroxides, which outcompetes protons for surface sites. As shown in a recent in-situ infrared study2, adsorbed hydroxides promote CO adsorption, a crucial CO2 reduction intermediate, by preventing CO from becoming inert through a near neighbor effect. We corroborate this interpretation by demonstrating that the pulsed potential application can suppress the HER during the CO reduction just as the CO2R. Our results suggest that the pulsed potential mechanism favors CO2R over the HER due to two effects: 1) proton desorption/displacement during the anodic potential and 2) the accumulation of OHads creating a higher surface-pH environment, promoting CO adsorption. We can describe this pulsed potential dynamic double layer mechanism in a competing quaternary Langmuir isotherm model.We conclude that the active disruption of the double layer can be leveraged to tune the surface reaction environment during CO2R. Furthermore, the insights from this investigation have wide-ranging implications for applying pulsed potential profiles to improve electrocatalytic processes in general by dynamically disrupting double layer species.[1] Kimura, K. W.; Fritz, K. E.; Kim, J.; Suntivich, J.; Abruña, H. D.; Hanrath, T. Controlled Selectivity of CO2 Reduction on Copper by Pulsing the Electrochemical Potential. ChemSusChem 2018, 11 (11), 1781–1786. https://doi.org/10.1002/cssc.201800318.[2] Iijima, G.; Inomata, T.; Yamaguchi, H.; Ito, M.; Masuda, H. Role of a Hydroxide Layer on Cu Electrodes in Electrochemical CO2 Reduction. ACS Catal. 2019, 9 (7), 6305–6319. https://doi.org/10.1021/acscatal.9b00896.

Electrochemically primed functional redox mediator generator from the decomposition of solid state electrolyte

Recent works into sulfide-type solid electrolyte materials have attracted much attention among the battery community. Specifically, the oxidative decomposition of phosphorus and sulfur based solid state electrolyte has been considered one of the main hurdles towards practical application. Here we demonstrate that this phenomenon can be leveraged when lithium thiophosphate is applied as an electrochemically “switched-on” functional redox mediator-generator for the activation of commercial bulk lithium sulfide at up to 70 wt.% lithium sulfide electrode content. X-ray adsorption near-edge spectroscopy coupled with electrochemical impedance spectroscopy and Raman indicate a catalytic effect of generated redox mediators on the first charge of lithium sulfide. In contrast to pre-solvated redox mediator species, this design decouples the lithium sulfide activation process from the constraints of low electrolyte content cell operation stemming from pre-solvated redox mediators. Reasonable performance is demonstrated at strict testing conditions.

Phosphorus speciation and release kinetics of swine manure biochar under various pyrolysis temperatures.

Converting swine manure to biochar is an effective way to recycle valuable nutrients, but there are few reports on its feasibility as a phosphorus (P) source. The objective of this study was to clarify the unique nature, including P speciation, of manure biochar products under various pyrolysis temperatures. We used solution 31P nuclear magnetic resonance and P K-edge X-ray adsorption near-edge spectroscopy (P XANES) to characterize P species in swine manure biochar. For every 100°C increment starting from 300°C, the P content in manure biochar increased by 2.16 to 3.37gkg-1. However, above 400°C, organic P species did not appear anymore, and only inorganic P, including orthophosphate and pyrophosphate, existed. P K-edge XANES spectra further showed all biochar samples had higher percentages of Ca3 (PO4)2 and NaP2O7, and lower percentages of FePO4, AlPO4, and inositol hexaphosphate compared to manure. Interestingly, percentages of Ca3(PO4)2, FePO4, and AlPO4 in MB400 (indicating manure pyrolysed at 400°C) were comparable with those in MB700 while the percentage of NaP2O7 was higher in MB400. Phosphorus release from MB400 maintained a relatively high level at 0.33gkg-1 during the whole 300-h observation period. These results suggest that with a suitable pyrolysis temperature, it was feasible for manure biochar to be a P source alternative. Graphical abstract ᅟ.

Revealing mechanism responsible for structural reversibility of single-crystal VO2 nanorods upon lithiation/delithiation

A pure phase of VO2(B) nanorods have been synthesized through an energy-efficient microwave hydrothermal reaction and used as cathode materials of lithium ion batteries, which exhibit promising specific capacity (e.g., 130mAhg−1 even after 100 charge/discharge cycles) and rate capacity (e.g., ~130mAhg−1 at a high current of 400mAg−1). The excellent cyclability originates from the structural reversibility of VO2(B) upon lithiation/delithiation that is confirmed by the in situ high-energy synchrotron X-ray diffraction (HEXRD) and in situ x-ray adsorption near-edge spectroscopy (XANES) of the VO2 nanorods in operating battery cells. The real-time results reveal that discharge forces lithium ions to insert firstly into the tunnels with the largest size along b direction followed by the second largest tunnels along c direction, which is completely reversible in the charge process.

Interactions between natural organic matter, sulfur, arsenic and iron oxides in re-oxidation compounds within riparian wetlands: NanoSIMS and X-ray adsorption spectroscopy evidences

Arsenic (As) is a toxic and ubiquitous element which can be responsible for severe health problems. Recently, Nano-scale Secondary Ions Mass Spectrometry (nanoSIMS) analysis has been used to map organomineral assemblages. Here, we present a method adapted from Belzile et al. (1989) to collect freshly precipitated compounds of the re-oxidation period in a natural wetland environment using a polytetrafluoroethylene (PTFE) sheet scavenger. This method provides information on the bulk samples and on the specific interactions between metals (i.e. As) and the natural organic matter (NOM). Our method allows producing nanoSIMS imaging on natural colloid precipitates, including 75As−, 56Fe16O−, sulfur (32S−) and organic matter (12C14N) and to measure X-ray adsorption of sulfur (S) K-edge. A first statistical treatment on the nanoSIMS images highlights two main colocalizations: (1) 12C14N−, 32S−, 56Fe16O− and 75As−, and (2) 12C14N−, 32S− and 75As−. Principal component analyses (PCAs) support the importance of sulfur in the two main colocalizations firstly evidenced. The first component explains 70% of the variance in the distribution of the elements and is highly correlated with the presence of 32S−. The second component explains 20% of the variance and is highly correlated with the presence of 12C14N−. The X-ray adsorption near edge spectroscopy (XANES) on sulfur speciation provides a quantification of the organic (55%) and inorganic (45%) sulfur compositions. The co-existence of reduced and oxidized S forms might be attributed to a slow NOM kinetic oxidation process. Thus, a direct interaction between As and NOM through sulfur groups might be possible.

The Structural Evolution of V2O5 Nanocystals during Electrochemical Cycling Studied Using In operando Synchrotron Techniques

The structural evolution of vanadium oxide (V2O5) nanocrystals was studied during Li+ ion intercalation and deintercalation (i.e. electrochemical discharge/charge) processes using in operando high-energy x-ray diffraction (HEXRD) and in operando x-ray adsorption near edge spectroscopy (XANES). The HEXRD results clearly show that V2O5 undergoes phase transformations during the first Li+ ion intercalation (i.e. discharge) process. The analysis of the XANES data suggests that the average oxidation state of vanadium in fully charged V2O5 nanocrystals decreases to less than +5 after the first four cycles. The combined results of the unchanged crystal structure (HEXRD) and the decreased oxidation state (XANES) lead to the conclusion that some of the Li+ ions are trapped within the V2O5 framework and the V2O5 exists as Li0.18V2O5 instead of pure V2O5 after the first four cycles, while the trapped Li+ ion may increase the stability of V2O5 framework.

Elucidating the mechanism of Cr(VI) formation upon the interaction with metal oxides during coal oxy-fuel combustion

The thermodynamics underpinning the interaction of Cr-bearing species with basic metal oxides, i.e. K2O, Fe2O3, MgO and CaO, during the air and oxy-fuel combustion of coal have been examined. The synchrotron-based X-ray adsorption near-edge spectroscopy (XANES) was used for Cr speciation. For the oxides tested, Cr(VI) formation is dominated by the reduction potential of the metals. The oxides of Ca2+ with high reduction potential favored the oxidation of Cr(III), same for K+. The other two basic metals, Fe2O3 and MgO with lower reduction potentials reacted with Cr(III) to form the corresponding chromites at the temperatures above 600°C. Coal combustion experiments in drop-tube furnace have confirmed the rapid capture of Cr vapors, either trivalent or hexavalent, by CaO into solid ash. The existence of HCl in flue gas favored the vaporization of Cr as CrO2Cl2, which was in turn captured by CaO into chromate. Both Fe2O3 and MgO exhibited less capability on scavenging the Cr(VI) vapor. Particularly, MgO alone exhibited a low capability for capturing the vaporized Cr(III) vapors. However, its co-existence with CaO in the furnace inhibited the Cr(VI) formation. This is beneficial for minimizing the toxicity of Cr in the coal combustion-derived fly ash.

Effect of Synthesis Parameters on the Chromium Content and Catalytic Activities of Mesoporous Cr−MSU-x Prepared under Acidic Conditions

A series of chromium-incorporated MSU-x mesoporous molecular sieves were synthesized under different templates, initial Si/Cr molar ratios, aging times, and temperatures in acid solution. The synthesis was performed by using sodium silicate, chromium nitrate, and nonionic poly(ethylene oxide) surfactant as the source of silicone, metal, and the template, respectively. The Cr-MSU-x products were analyzed by inductively couple plasma-optical emission spectrometry to determine the actual Cr content and were characterized by X-ray diffraction, N(2) adsorption-desorption, scanning electron microscopy, high-resolution transmission electron microscopy, diffuse reflectance UV-visible, X-ray adsorption near-edge spectroscopy, and temperature-programmed reduction techniques. The Cr species were mostly formed as Cr(VI) in tetrahedral coordination. Two kinds of Cr(VI) species with different reduction abilities were distinguished. The catalytic activities of Cr-MSU-x in the dehydrogenation of ethane to ethylene with CO(2) were investigated at the same time. The synthesis parameters explored strongly influence the chromium content in Cr-MSU-x and, subsequently, the catalytic activities. The Cr-MSU-x synthesized with Si/Cr = 20, aging at 25 degrees C for 22 h, and templating by fatty alcohol polyoxyethylene ether gave the best activities, resulting in 58.0% ethane conversion and 92.1% ethylene selectivity. The Cr species in Cr-MSU-x are more efficient in activating and converting ethane molecules than are conventional catalysts.

Synthesis and Characterization of Alkoxide-Derived Pt Nanoparticles

Identification of the species formed during the in situ reduction of hexachloroplatinic acid by sodium ethoxide, forming a Pt sol, is made. The solution phase is shown to consist of suspended metallic Pt nanoparticles (1-3 nm in diameter), acetaldehyde, and a Pt(II) species, identified by NMR and X-ray adsorption near-edge spectroscopy (XANES) to be NaPtCl3(C2H4), a sodium analogue of Zeise's salt [KPtCl3(C2H4)]. The NaPtCl3(C2H4) product exhibits greater stability in both ethanol and air than the conventional Zeise's salt, providing a means of storing the useful Zeise's anion [PtCl3(C2H4)-]. Electrochemistry, X-ray diffraction (XRD), and transmission electron microscopy (TEM) analyses have shown that the precipitate phase formed during the synthesis is composed solely of Pt particles approximately 6 nm in diameter and NaCl. Thermal gravimetric analysis/differential scanning calorimetry (TGA/DSC) showed that the color of the precipitate is an accurate gauge of the ratio of Pt to NaCl, with the lightest to darkest precipitates containing from 1% to 40% nanoparticulate Pt by mass, respectively. A comprehensive characterization of both phases formed has allowed us to propose a mechanism for the conversion of hexachloroplatinic acid to Pt nanoparticles.

The behavior of mixed-metal oxides: physical and chemical properties of bulk Ce1-xTbxO2 and nanoparticles of Ce1-xTbxOy.

The physical and chemical properties of bulk Ce(1-x)Tb(x)O(2) and Ce(1-x)Tb(x)O(y) nanoparticles (x<or =0.5) were investigated using synchrotron-based x-ray diffraction (XRD), x-ray adsorption near edge spectroscopy (XANES), Raman spectroscopy (RS), and first-principles density-functional (DF) calculations. DF results and Raman spectra point to a small tetragonal distortion after introducing terbium in ceria. The results of XRD show a small contraction (< or = 0.08 A) in the cell dimensions. The presence of Tb generates strain in the lattice through the variation of the ionic radii and creation of crystal imperfections and O vacancies. The strain increases with the content of Tb and affects the chemical reactivity of the Ce(1-x)Tb(x)O(y) nanoparticles towards hydrogen, SO(2), and NO(2). DF calculations for bulk Ce(1-x)Tb(x)O(2) and Ce(8-n)Tb(n)O(16) (n=0, 1, 2, or 4) clusters show oxide systems that are not fully ionic. The theoretical results and XANES spectra indicate that neither a Ce<-->Tb exchange nor the introduction of oxygen vacancies in Ce(1-x)Tb(x)O(y) significantly affect the charge on the Ce cations. In contrast, the O K-edge and Tb L(III)-edge XANES spectra for Ce(1-x)Tb(x)O(y) nanoparticles show substantial changes with respect to the corresponding spectra of Ce and Tb single oxide references. The Ce(0.5)Tb(0.5)O(y) compounds exhibit a much larger Tb(3+)/Tb(4+) ratio than TbO(1.7). A comparison with the properties of Ce(1-x)Zr(x)O(y) and Ce(1-x)Ca(x)O(y) shows important differences in the charge distribution, the magnitude of the dopant induced strain in the oxide lattice, and a superior behavior in the case of the Ce(1-x)Tb(x)O(y) systems. The Tb-containing oxides combine stability at high temperature against phase segregation and a reasonable concentration of O vacancies, making them attractive for chemical and catalytic applications.

Chromate Removal by Dithionite-Reduced Clays: Evidence from Direct X-Ray Adsorption Near Edge Spectroscopy (XANES) of Chromate Reduction at Clay Surfaces

AbstractChromium(VI) in the environment is of particular concern because it is toxic to both plants and animals, even at low concentrations. As a redox-sensitive element, the fate and toxicity of chromium is controlled by soil reduction-oxidation (redox) reactions. In-situ remediation of chromium combines reduction of Cr(VI) to Cr(III) and immobilization of chromium on mineral surfaces. In this study, Fe-rich smectite, montmorillonite, illite, vermiculite, and kaolinite were examined to determine reactivity in sorption-reduction of Cr(VI). The clays were compared to forms that were reduced by sodium dithionite. Clays containing Fe(II) efficiently removed soluble Cr(VI) from solution. Chromium K-edge X-ray absorption near edge structure (XANES) suggested that clays containing Fe(II) reduced Cr(VI) to Cr(III), immobilizing Cr at the clay/water interface. Adsorption of Cr(VI) by the Fe(II)-containing clay was a prerequisite for the coupled sorption-reduction reaction. Sodium dithionite added directly to aqueous suspensions of non-reduced clays reduced Cr(VI) to Cr(III), but did not immobilize Cr on clay surfaces. The capacity of clays to reduce Cr(VI) is correlated with the ferrous iron content of the clays. For dithionite-reduced smectite, the exchangeable cation influenced the sorption reaction, and thus it also influenced the coupled sorption-reduction reaction of Cr(VI). The pH of the aqueous system affected both the amount of Cr(VI) reduced to Cr(III) and the partition of Cr(III) between aqueous and adsorbed species. A plot of pH vs. amount (adsorption envelope) adsorbed for the coupled sorption-reduction reaction of Cr by reduced smectite exhibited a similar pattern to that of typical anion-sorption.