X-ray Absorption Fine Structure Spectroscopy Research Articles

Water-induced Surface Ordering Facilitating the Microcutting of Ductile Metals

Metal cutting is a crucial process in modern manufacturing. Enhancing the machinability of metals can significantly improve their production efficiency and surface integrity. Coating surface-active media (SAM) on the free surface of the metals before cutting is an easy method to improve machinability, which usually pertains to the category of the renowned Rehbinder effect. However, the existing SAM are usually hazardous and complex materials. Besides, the effect of the SAM on the local structure of the metal surface remains unclear. In this study, water is employed as a simple yet easily overlooked SAM in the microcutting of copper. Using water as SAM also allows the employment of X-ray absorption fine structure spectroscopy (XAFS) to study the local structure of copper with and without water coating. Results show that water coating on the free surface of copper can significantly reduce the cutting force and chip thickness, and improve the surface finish. Interestingly, removing the water coating enables the recovery of the cutting force, showing a reversible effect. Based on the XAFS results and molecular dynamics simulation, a water-induced surface ordering mechanism is proposed to explain the findings from the microcutting experiments. This mechanism suggests that water molecules can lead to copper surface ordering, resulting in an adequate reduction in the surface energy and fracture toughness of copper, thus enhancing the machinability. This work provides valuable insights into the comprehension of the Rehbinder effect and shows that picometer-scale modifications of the surface atom arrangement can considerably alter the deformation mode of metals, paving the way for the development of new manufacturing processes.

Insight into the complexation of uranium with Bacillus sp. dwc-2 by multi-spectroscopic approaches: FT-IR, TRLF and XAFS spectroscopies

The micromechanisms of the interactions between uranium and microorganisms, especially chemical bonds and bonding numbers between uranium and microbe are not yet clear. In this work, uranium coordination with functional groups in/on Bacillus sp. dwc-2 has been rationally explored by X-ray absorption fine structure (XAFS), Fourier transform infrared (FT-IR), time-resolved laser-induced fluorescence (TRLF) spectroscopies. The results indicate that under acidic condition, 66.8 % of O atoms in coordination shell of U(VI) equatorial plane are provided by organic phosphoryl groups via monodentate coordination, 18.8 % and 15.5 % are provided by water molecules and carboxyl groups via monodentate and bidentate coordination, respectively. While under alkaline condition, these proportions change to 53.1 %, 34.4 % and 22.0 %, respectively. Under neutral condition, U(VI) is mainly deposited by complexing with inorganic phosphates released by microbial cells. Under anaerobic condition, partial U(VI) can be reduced to U(IV) which primarily complex with phosphorus containing groups via monodentate and bidentate coordination, existing as amorphous solids or coordination polymers. This is the first exploration of the binding mechanism between uranium and microorganisms at a semi-quantitative level under different conditions. Our studies will further enhance the contribute to the understanding of coordination mechanism of uranium with microorganism, and demonstrate the potential bioremediation value of this bacterium.

Advanced Characterization Techniques and Theoretical Calculation for Single Atom Catalysts in Fenton-like Chemistry.

Single-atom catalysts (SACs) have attracted extensive attention due to their unique catalytic properties and wide range of applications. Advanced characterization techniques, such as energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy, and X-ray absorption fine-structure spectroscopy, have been used to investigate the elemental compositions, structural morphologies, and chemical bonding states of SACs in detail, aiming at unraveling the catalytic mechanism. Meanwhile, theoretical calculations, such as quantum chemical calculations and kinetic simulations, were used to predict the catalytic reaction pathways, active sites, and reaction kinetic behaviors of SACs, providing theoretical guidance for the design and optimization of SACs. This review overviews advanced characterization techniques and theoretical calculations for SACs in Fenton-like chemistry. Moreover, this work highlights the importance of advanced characterization techniques and theoretical calculations in the study of SACs and provides perspectives on the potential applications of SACs in the field of environmental remediation and the challenges of practical engineering.

Effect of Cu incorporation in silicate and modified borate bioglass materials for health applications: insights from synchrotron-based x-ray absorption spectroscopy

This contribution investigates the effect of variable copper incorporation (x = 0.2, 1.0, 2.0, and 4.0) in silicate (45 SiO2, 24.5 CaO, 24.5 Na2O, 6P2O5wt%) and modified borate (45 B2O3, 24.5 CaO, 24.5 Na2O, 6P2O5wt%) bioglass materials to be used for bone bonding applications. X-ray absorption fine structure spectroscopy (XAFS) has been used to determine the oxidation states and local coordination structure of Cu atoms in silicate-based and borate-based glasses at the Cu K-edge (~ 8979 eV). The oxidation states of Cu atoms have been determined by near-edge XAFS (XANES) fingerprinting employing reference standard compounds of Cu. Cu (I) and Cu (II) XANES spectra of the standard reference compounds were linearly combined to fit the normalized μ(E) data of the collected XANES spectra using linear combination fitting (LCF approach). The obtained results prove that most of the silicate glass samples contain Cu2O almost exclusively, while modified borate glass samples contain a significant mixture of Cu2O and CuO phases. According to the literature, the remarkable coexistence of Cu2O and CuO phases within the borate sample, particularly when x = 4, promotes the conversion process to allow the more facile formation of hydroxy carbonate apatite (HCA). The best fit structural parameters derived from extended-XAFS (EXAFS) fitting show that the ratio between Cu (I) and Cu (II) in borate glass agreed well with that extracted from XANES analysis. XANES and EXAFS conclude that borate glass with x = 4 is the most suitable composition for bone bonding applications.

Low-coordinated Mn–N2 sites in graphene oxide induce peroxydisulfate activation for tetracycline degradation: Process optimization and theoretical calculation

Atom-dispersed low-coordinated transition metal-Nx catalysts exhibit excellent efficiency in activating peroxydisulfate (PDS) for environmental remediation. However, their catalytic performance is limited due to metal-N coordination number and single-atom loading amount. In this study, low-coordinated nitrogen-doped graphene oxide (GO) confined single-atom Mn catalyst (Mn-SA/NGO) was synthesized by molten salt-assisted pyrolysis and coupled to PDS for degradation of tetracycline (TC) in water. Aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (AC-HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) analysis showed the successful doping of single-atom Mn (weight percentage 1.6%) onto GO and the formation of low-coordinated Mn–N2 sites. The optimized parameters obtained by Box-Behnken Design achieved 100% TC removal in both prediction and experimental results. The Mn-SA/NGO + PDS system had strong anti-interference ability for TC removal in the presence of anions. Besides, Mn-SA/NGO possessed good reusability and stability. O2•−, •OH, and 1O2 were the main active species for TC degradation, and the TC mineralization reached 85.1%. Density functional theory (DFT) calculations confirmed that the introduction of single atoms Mn could effectively enhance adsorption and activation of PDS. The findings provide a reference for the synthesis of high-performance single-atom catalysts for effective removal of antibiotics.

Pt single-atom electrocatalysts at Cu2O nanowires for boosting electrochemical sensing toward glucose

In electrochemical biosensors, rational design and synthesis of high-performance electrochemical glucose sensors based on emerging single-atom catalysts (SACs) are paramount. Herein, a facile approach is proposed for dispersing single-atom doping of cuprous oxide (Cu2O) nanowires with Pt on a copper foam substrate (Pt1/Cu2O@CF) via the electrochemical deposition process. The specific nanostructure of the single-atom catalyst has been elaborately revealed with the aid of atomic resolution scanning transmission electron microscopy (STEM) and X-ray absorption fine structure spectroscopy (XAS). The as-fabricated Pt1/Cu2O@CF biosensor with satisfactory scalability exhibits a low limit of detection (1 μM), ultrahigh sensitivity (31.55 mA mM−1 cm−2), excellent selectivity, and robust reliability toward glucose. The first principles simulations reveal that Pt SAC is beneficial to the adsorption of glucose on the surface and further facilitates the electron transfer for the deprotonation process, resulting in high glucose sensing performance. This work sheds light on the applications of SACs for designing ultrasensitive electrochemical biosensors.

Toward mending the marine mass balance model for nickel: Experimentally determined isotope fractionation during Ni sorption to birnessite

In fewer than fifteen years, the study of Ni stable isotopes has advanced from early method development to application of a powerful tool for resolving a long-standing question: why does it appear that output fluxes of Ni from the global oceans far exceed input fluxes? The seawater concentration of Ni, a bioessential trace metal, is almost certainly at steady state on timescales comparable to its residence time of ∼20 kyr, so some of the current flux estimates must be inaccurate. Just as the input and output fluxes should balance, so should the flux-weighted isotopic compositions of the inputs and outputs. Thus, isotopic characterization of inputs and outputs provide an additional constraint on a balanced model of the marine Ni budget. Here, we report on experiments designed to elucidate fractionation mechanisms and magnitudes for sorption of Ni to Mn oxyhydroxide (birnessite), because Mn-rich sediments accumulating on abyssal plains represent the largest sink flux of Ni from seawater to marine sediments. Our results show remarkably large fractionations at low ionic strength (average Δ60/58Nidissolved-sorbed = +1.38 ‰). Neither closed-system equilibrium trends nor Rayleigh curves fit the data well. Fractionations are even larger at high ionic strength (Δ60/58Nidissolved-sorbed ranging from +2.0 to +4.0 ‰), and they decrease with experimental duration from 2 d (49 h) to 27 d. The high ionic strength data fit Rayleigh trends well. Here, we use X-ray absorption fine-structure spectroscopy (EXAFS) and results from previous studies to support interpretation of our data as combinations of kinetic and equilibrium isotope effects that vary in their proportional contributions to the total fractionation with time and with surface loading. One important consequence of this study is that none of the experimental results reported thus far, including ours, are directly applicable to building steady-state models of the Ni cycle. Even our longest duration experiments did not achieve equilibrium, which is likely to be manifest in the very slowly accumulating sediments on abyssal plains. Our work constrains further the mechanisms of Ni sorption to birnessite and clearly indicates that determination of equilibrium fractionation in this system, although challenging, will be a crucial step toward resolving the apparent marine Ni imbalance.

Low-Temperature Methane Activation Reaction Pathways over Mechanochemically-Generated Ce4+/Cu+ Interfacial Sites.

Methane is a valuable resource and its valorization is an important challenge in heterogeneous catalysis. Here it is shown that CeO2/CuO composite prepared by ball milling activates methane at a temperature as low as 250°C. In contrast to conventionally prepared catalysts, the formation of partial oxidation products such as methanol and formaldehyde is also observed. Through an in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and operando Near Edge X-Ray Absorption Fine Structure Spectroscopy (NEXAFS) approach, it can be established that this unusual reactivity can be attributed to the presence of Ce4+/Cu+ interfaces generated through a redox exchange between Ce3+ and Cu2+ atoms facilitated by the mechanical energy supplied during milling. DFT modeling of the electronic properties confirms the existence of a charge transfer mechanism. These results demonstrate the effectiveness and distinctiveness of the mechanical approach in creating unique and resilient interfaces thereby enabling the optimization and refining of CeO2/CuO catalysts in methane activation reactions.

Modification of Visible-Light-Responsive Pb2Ti2O5.4F1.2 with Metal Oxide Cocatalysts to Improve Photocatalytic O2 Evolution toward Z-Scheme Overall Water Splitting.

The development of a highly active photocatalyst for visible-light water splitting requires a high-quality semiconductor material and a cocatalyst, which promote both the migration of photogenerated charge carriers and surface redox reactions. In this work, a cocatalyst was loaded onto an oxyfluoride photocatalyst, Pb2Ti2O5.4F1.2, to improve the water oxidation activity. Among the metal oxides examined as cocatalysts, RuO2 was found to be the most suitable, and the O2 evolution activity depended on the preparation conditions for Ru/Pb2Ti2O5.4F1.2. The highest activity was obtained with RuCl3-impregnated Pb2Ti2O5.4F1.2 heated under a flow of H2 at 523 K. The H2-treated Ru/Pb2Ti2O5.4F1.2 showed an O2 evolution rate an order of magnitude higher than those for the analogues without the H2 treatment (e. g., RuO2/Pb2Ti2O5.4F1.2). Physicochemical analyses by X-ray absorption fine-structure spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and time-resolved microwave conductivity measurements indicated that the optimized photocatalyst contained partially reduced RuO2 species with a particle size of ~5 nm. These partially reduced species effectively trapped the photogenerated charge carriers and promoted the oxidation of water into O2. The optimized Ru/Pb2Ti2O5.4F1.2 could function as an O2-evolving photocatalyst in Z-scheme overall water splitting, in combination with an Ru-loaded, Rh-doped SrTiO3 photocatalyst.

Investigation of hydrothermally-produced ZnO nanorods and the mechanisms of Li incorporation as a possible dopant

Zinc oxide (ZnO) has emerged as one of the most promising candidates for mass-producing cost-efficient optoelectronic devices. This is primarily because it can be synthesized in high-quality nanostructures on a wide range of substrates through relatively simple chemical methods. However, producing p-type ZnO, regardless of the chosen method, remains an open and controversial issue. In this work, Li-doped ZnO nanostructures of varying Li-cocnentration were produced via a two-step hydrothermal growth synthesis and an in-depth analysis based on with Field Emission Scanning Electron Microscopy (FE-SEM), X-ray diffraction (XRD), Raman Spectroscopy, Extended X-Ray Absorption Fine Structure (EXAFS) Spectroscopy, and temperature-dependent Photoluminescence (PL) was carried out in an effort to gain insights into the Li-incorporation mechanisms. The findings indicated a strong interplay between the native defects responsible for the inherent n-type character of the material and Li incorporation. It is suggested that this interplay hinders the successful conversion of the Li-doped nanorods into p-type nanostructures and that when employing the hydrothermal approach it is essential to identify the precise conditions necessary for genuine Li incorporation as a Zn substitutional.

Local structure and phase composition of Neodymium-Zircon solid solution (NdxZr1-xSiO4-x/2)

To address the structural stability of host materials for immobilizing radioactive actinides in nuclear waste management applications, the present study is focused on the effect of various concentrations of Nd substitution on structural properties of synthetic zircon (NdxZr1-xSiO4-x/2). To achieve this, both pure and Nd-substituted zircon powders were prepared using the solid-state synthesis route. Rietveld refinement of X-ray Diffraction (XRD) data was employed to investigate the impact of various Nd substitutions on the phase composition of the zircon (ZrSiO4) crystal structure. This refined data was then utilized as input for the analysis of X-ray absorption spectroscopy (XAS) data. The results were further supported by observations from Raman spectroscopy, which indicated the substitution of Zr by Nd. In this work, we present an analysis of both regimes of XAS i.e. X-ray Absorption Near Edge Structure (XANES) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. Qualitative analysis of XANES data suggests that disorder in the samples increases with higher levels of Nd doping. Additionally, EXAFS analysis around Zr absorption edge also confirms an increased disorder in the system with higher Nd doping levels. However, EXAFS fitting around Nd edge indicated that disorder induced changes are more prominent and Nd–O bond is elongated as compared to Zr–O bond. This disorder in the system escalates at a Nd concentration of 10 atomic % (at %). An important finding of this study is the phase composition analysis using Rietveld refinement of XRD data. While XAS provided an insight into the changes in the local structure, the overall crystal structure remained unaffected even at a high doping of 10 at %. This work provides a comprehensive local structure analysis on this system. Such analysis would help in understanding the structural stability of the system and to determining the maximum loading of actinides in the host zircon for potential nuclear waste management applications.

Tuning the metal-insulator transition temperature by the controlled generation of oxygen vacancies on La0.7Ca0.3MnO3-x epitaxial thin films

This report presents a study on the effect of the controlled generation of oxygen vacancies on the electronic transport properties of La0.7Ca0.3MnO3-x epitaxial thin films. Oxygen defects cause significant changes in the crystalline structure of mixed-valence manganites and lower the Mn valence, resulting in a shift of the metal-insulator transition to lower temperatures due to modifications in the angles and lengths of Mn-O bonds. Experiments using Polarized Extended X-Ray Absorption Fine Structure Spectroscopy have provided strong evidence that oxygen vacancies are mainly formed in the basal plane of the MnO6 octahedra. The accurate control of oxygen vacancies generation opens possibilities for managing and enhancing the magneto-electronic properties of epitaxial manganite thin films with potential in industrial applications.

Demonstration of Sensitivity of the Total-Electron-Yield Extended X-ray Absorption Fine Structure Method on Plastic Deformation of the Surface Layer

X-ray Absorption Fine Structure Spectroscopy (XAFS) has proven instrumental for the study of atomic-scale structures across diverse materials. This study conducts a meticulous comparative analysis between total electron yield (TEY) and absorption coefficients at the K absorption edge of polycrystalline Fe and Zr60Cu20Fe20 alloy. Our findings not only highlight differences between TEY and transmission XAFS measurements but also demonstrate the capabilities and limitations inherent in these measurement modes within the context of XAFS. This article provides an experimental exploration of widely used X-ray absorption spectroscopy methods, shedding light on the nuances of TEY and transmission XAFS. Through presenting experimental results, we aim to offer insights crucial to the material science community, guiding experimentalists in optimizing measurements while raising awareness about potential misinterpretations.

Compressed sensing for rapid tabletop X-ray absorption spectroscopy

X-ray Absorption Fine Structure (XAFS) spectroscopy is an analytical technique of chemical insight. Improvements to this technique are continuously carried out for reduction of the acquisition time and increasing the resolution, especially for studying operando processes. The accurate reconstruction of XAFS signals requires that the collected data are noise-free to extract elemental structure information in post-processing. A novel approach to rapid sampling (encoded measurement) is validated conceptually. The technique relies on sparse signal recovery, i.e. using compressed sensing to reconstruct under-sampled signals. The proof of concept is demonstrated by using a python code to reconstruct under-sampled XAFS spectra. A case study of transition metal samples and their oxides is considered for this purpose. The results demonstrate a robust recovery of chemical information from a 30% sampled signal for the near-edge region analysis and from a 45% sampled signal for extended-edge region analysis. The application of this procedure is important for demonstrating the feasibility of tabletop operation using laboratory X-ray sources which are not continuously tunable.

Structural analysis of pharmaceutical tablets using two-dimensional X-ray absorption fine-structure spectroscopy and its combination with X-ray computed tomography

The pharmaceutical properties of a solid formulations depend on their structure. To obtain structural information, such as the density, porosity, crystal forms of drugs, and the three-dimensional distribution of the drug and excipient particles within the formulations, is useful for formulation design and development. In this research, two-dimensional X-ray absorption fine-structure spectroscopy (2D-XAFS) and its combination with X-ray computed tomography (CT) were used for internal-structure analysis of tablets. Tablets containing form-II crystals and/or an amorphous solid dispersion (ASD) of bromhexine hydrochloride (BRH) were prepared and measured at a synchrotron radiation facility. The XAFS spectra of form-II crystals and the ASD of BRH were obtained after properly calibrating the irradiated X-ray energies. Their XAFS spectra showed small but marked differences. Form-II crystals and the ASD could be distinguished and visualized in the 2D-XAFS transmission and CT-XAFS slice images. Both 2D-XAFS and CT-XAFS provided detailed structural information and may be a useful alternative method in the development stage of solid dosage formulations.

Unveiling the significant promoting effect of SO2 on Ir/SiO2 catalyst for the CO-SCR of NOx in the presence of O2

Selective catalytic reduction of NOx by CO (CO-SCR) in the presence of O2 is challenging because in this process CO is prone to being oxidized by O2, thus inhibiting NOx reduction by CO. Furthermore, SO2 typically leads to the deactivation of the CO-SCR catalyst. Herein, a significant promoting effect of SO2 on Ir/SiO2 catalyst for the CO-SCR of NOx in the presence of O2 is reported. In-situ X-ray Absorption Fine Structure (XAFS) and X-ray photoelectron spectroscopy (XPS) analysis showed that SO2 does not affect the chemical nature of Ir0 under reaction conditions. However, SO2 can be oxidized to sulfate and deposit on the catalyst surface. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis demonstrated that the presence of SO2 can inhibit the CO + O2 reaction, thus leaving more CO available to reduce NOx over the active Ir0 sites. As a result, the reduction of NOx is remarkably promoted even in the presence of O2 and SO2.

Fe-nanocluster embedded biomass-derived carbon for efficient photo-Fenton-like activity in water purification

Single-atom catalysts (SACs) as photo-Fenton-like catalysts have attracted widespread attention in water purification. However, the development of SACs with renewability, cleanliness, high mass loading, and raw material abundance is a formidable challenge to achieve efficient pollutant removal. In this study, we fabricated high-performance Fe-nanocluster embedded biomass-derived carbon (Fe/Bio-C) from Ficus altissima wastes for quinolone antibiotics degradation. The high-angle annular dark-field scanning transmission electron microscopy with aberration correction (AC-HAADF-STEM) and X-ray absorption fine structure spectroscopy (XAFS) revealed that the Fe/Bio-C exhibited a porous structure with abundant Fe-N4 active sites. The Fe/Bio-C catalysts achieved an exceptional efficiency of 98.6 % for the removal of the representative quinolone antibiotic, namely lomefloxacin (LOM), within 30 min. Furthermore, an in-depth exploration was conducted to assess the influence of reaction parameters on degradation performance, kinetics, toxicity, and mechanism. The free radical quenching experiments and electron paramagnetic resonance (EPR) spectra demonstrated the existence of ·O2−, 1O2, ·OH, SO4·− in the reaction system and the ·O2− radicals played a relatively important role in the degradation progress. This work broaden the avenue for constructing metal-nanocluster photocatalysts with the high reactivity, low metal leaching, and universality to various pollutants.

Beagle: a near-edge X-ray absorption fine-structure spectroscopy data processing solution for beamline experiments at Pohang Accelerator Laboratory.

Near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy is a powerful tool for identifying chemical bonding states at synchrotron radiation facilities. Advances in new materials require researchers in both academia and industry to measure tens to hundreds of samples during the available beam time on a synchrotron beamline, which is typically allocated to users. Automated measurement methods, along with analysis software, have been developed for beamlines. Automated measurements facilitate high-throughput experiments and accumulate vast amounts of measured spectral data. The analysis software supports various functions for analyzing the experimental data; however, these analysis methods are complicated, and learning them can be time-consuming. To process large amounts of spectral data, a new analysis software, dedicated to NEXAFS spectroscopy, that is easy to use and can provide results in a short time is desired. Herein, the development of Beagle is described, software calculating molecular orientation from NEXAFS spectroscopy data that can report results in a short time comparable with that required to measure one sample at the beamline. It was designed to progress in a single sequence from data loading to the printing of the results with a `click of a button'. The functions of the software include recognizing the dataset, correcting the background, normalizing the plot, calculating the electron yield and determining the molecular orientation. The analysis results can be saved as {\tt{.txt}} files (spectral data), {\tt{.pdf}} files (graphic images) and Origin files (spectral data and graphic images).

Accelerating nano-XANES imaging via feature selection

We utilize feature selection to reduce experimental time by ∼80% of a nanoscale X-ray Absorption Fine Structure (XANES) spectroscopy imaging study of a sample with Fe-bearing mineral phases.

Formation of uranium disulfide from a uranium thioamidate single-source precursor.

A single-source-precursor approach was developed to synthesize uranium-based materials outside of the typically-studied oxides. This approach allows for shorter reaction times, milder reaction conditions, and control over the chemicals present in synthesis. To this end, the first homoleptic uranium thioamidate complex was synthesized as a precursor for US2 materials. Pyrolysis of the thioamidate results in decomposition via an alkene elimination pathway and formation of γ-US2, which has historically been hard to access without the need for a secondary sulfur source. Despite the oxophilicity of uranium, the method successfully forms US2 without the inclusion of oxygen in the bulk final product. These findings are supported by simultaneous thermal analysis, elemental analysis, powder X-ray diffraction, and uranium L3-edge X-ray absorption fine-structure spectroscopy. This work represents the first example of a single-source precursor approach to target and synthesize actinide materials other than the oxides.