XANES Research Articles

Uranium oxidation states in zircon and other accessory phases

Zircon and other U-bearing accessory phases are important time-capsules for studying the evolution of Earth and other planetary bodies as these minerals can record both temporal and compositional information regarding their host rocks. In silicate melts, uranium can occur in either the UIV, UV, or UVI valence state and its redox sensitive nature could, in principle, allow for information on magma oxygen fugacity (ƒO2) to be gleaned from U-bearing phases provided they can incorporate multivalent U during crystallization. Currently, however, little is known regarding the details of how U is speciated in these minerals.In this study, we conducted conventional X-ray absorption near-edge structure (XANES) spectroscopy at the U M4-edge on a set of natural zircon (n = 140), titanite (n = 9), apatite (n = 7), baddeleyite (n = 7), and garnet (n = 2) samples to determine the oxidation state of U in these crystals. We also collected U L3-edge spectra for select zircon samples to investigate the bonding environment of U using extended X-ray absorption fine structure (EXAFS) analysis. The effects of crystallographic orientation and radiation damage on zircon U M4-edge spectra are found to be minimal compared to the magnitude of the peak shifts associated with U oxidation state. We find that titanite and garnet contain only tetravalent U, while zircon, apatite, and baddeleyite can contain U of variable valence. Of these phases, zircon shows the greatest variability, with white-line energy, Ewl (i.e., peak absorbance) covering a range of >2.0 eV between grains: i.e., the entire energy range expected between pure UIV and pure UVI species. Moreover, a correlation is observed between the Ewl of zircon U M4-edge spectra (i.e., relative proportions of UIV, UV, UVI) and the ƒO2 of their host rocks. Our results thus establish U oxidation states in zircon as a powerful new tracer of magma redox. Since XANES is non-destructive and can be performed in situ, this technique can be utilized alongside other microanalytical methods (e.g., LA-ICPMS, SIMS) to further expand the breadth of information that can be extracted from single mineral grains.

Reuse potential of municipal solid waste incinerator bottom ash as secondary aggregate: Material characteristics, persistent organic pollutant content and effects of pH and selected environmental lixiviants on leaching behaviour

Increasing municipal solid waste (MSW) production poses challenges for sustainable urban development. Modern energy-from-waste (EfW) facilities incinerate MSW, reducing mass and recovering energy. In the UK, MSW incineration bottom ash (MSW IBA) is primarily reused in civil engineering applications. This study characterizes UK-produced MSW IBA, examining its pH-dependent leaching behaviour and response to environmental lixiviants. Results show predominant components include a melt phase, primary glass and fine ash aggregations, and a chemical composition dominated by SiO2 (30–50 %), CaO (∼15 %), Fe2O3 (∼10 %), and Al2O3 (∼8%). X-ray absorption near edge structure (XANES) analysis shows that Zn and Cu are most likely oxygen-bound (adsorbed to oxy-hydroxides and as oxides) with some sulphur bound. Polychlorinated biphenyls (PCBs) and polychlorinated dibenzodioxins/furans (PCDD/Fs) are well below regulatory limits, and polycyclic aromatic hydrocarbons (PAHs) were undetectable. Leaching tests indicate trace elements mobilize at pHs ≤ 6. With a natural pH of 11.3 and high buffering capacity, significant acid inputs to the MSW IBA are required to reach this pH, which are improbable in the environment. Wood chip additions increase leachate’s dissolved organic carbon (DOC) and reduce pH, but had minimal impact on metal-leaching behaviour. Synthetic plant exudate solutions minimally affect metal leaching at realistic concentrations, only enhancing leaching at ≥ 1500 mg l−1 DOC. This work supports MSW IBA’s low-risk in specified civil engineering applications.

Hydrothermally synthesized Ag2Te on metallic 2D templates

Silver telluride, Ag2Te, was synthesized on various 2D templates of carbon nanotubes (CNT) and transition-metal dichalcogenides (WTe2 and VTe2) via hydrothermal synthesis. X-ray diffraction (XRD) and Raman spectroscopy revealed that Ag2Te was synthesized on the 2D templates under optimal synthesis conditions. Differential scanning calorimetry (DSC) confirmed that the structural phase transition of Ag2Te underwent endothermic and exothermic reactions at approximately 410 and 425 K, respectively. Among various metallic templates, a large amount of Ag2Te has been synthesized on strongly acidic CNT. X-ray absorption near-edge structure (XANES) revealed that the chemical state of the metallic support influenced the electronic structure of the as-grown Ag2Te on the metallic supports. Our findings demonstrated that the hybrid 2D catalysts with an appropriate 2D metallic template can be a promising strategy for achieving efficient catalysis.

The Configuration Identification of Guanine Molecules Adsorbed on the Si(100) Surface by Using XPS Shake-up Satellites and NEXAFS.

Bioelectronic devices can be manufactured by organic-inorganic hybrid systems based on biomolecules and silicon semiconductors. The performance of the hybrid systems is largely determined by the adsorption manners of biomolecules on the silicon surface. In this paper, we demonstrated that the X-ray photoelectron spectroscopy (XPS) shake-up satellites and near-edge X-ray absorption fine-structure (NEXAFS) spectra at the carbon K-edges can be used to distinguish the interface of guanine molecules anchored on Si(100) surface. There are only 9 possible stable guanine@Si(100) hybrid systems that have been found based on the density functional theory. According to the characteristic peaks, it is confirmed that NEXAFS spectra are more sensitive to the identification of adsorption configurations. While the first characteristic peak in the low energy region of NEXAFS spectra are capable of distinguishing chemical bonds at the interface of the adsorption configurations. These results may facilitate a better understanding of the interface formations between biomolecules and silicon surfaces, which could be further utilized for the new bioelectronic device design.

Temporary change in NEXAFS spectra of amorphous carbon nitride films with photoinduced deformation by visible light irradiation

Amorphous carbon nitride (a-CNx) films, prepared by reactive radio frequency magnetron sputtering, exhibit unique characteristics under visible light irradiation, referred to as photoinduced deformation. This phenomenon represents an energy conversion system wherein photon energy transforms into kinetic energy. The chemical bonding structure of a-CNx films was analyzed using near-edge x-ray absorption fine structure (NEXAFS) at the NewSUBARU synchrotron facility of the University of Hyogo, Japan. This analysis aimed to elucidate the mechanisms behind the photoinduced deformation observed in a-CNx films. Three variants of a-CNx films, displaying varying degrees of photoinduced deformation, were deposited using a graphite target and nitrogen gas under different deposition temperatures. The NEXAFS spectra of the a-CNx films with substantial photoinduced deformation showed changes under light irradiation from a Xe lamp (directed through an optical window within the NEXAFS chamber). Specifically, the peaks corresponding to the 1s to π* transition related to C—C and 1s to σ* transition related to C—N bonds exhibited high sensitivity to visible light irradiation. Simultaneously, the N K-edge spectra associated with the 1s to π* transition, attributed to the N—C bond, exhibited a slight intensity decrease. Conversely, the C K-edge spectrum in the a-CNx films displaying minimal photoinduced deformation remained unchanged under visible light irradiation. The N K-edge spectra maintained a consistent shape under both visible light and dark conditions.

X‐ray standing wave assisted XANES for depth dependent chemical state analysis of Cr in Cr2O3/Cr bilayer structure

We report the detailed depth‐dependent structural and chemical analysis of the Cr2O3/Cr bilayer structure deposited on Si ˂100˃ substrate. The non‐destructive simultaneous X‐ray reflectivity and grazing incidence X‐ray fluorescence measurements were used for this purpose. Corresponding variation in the chemical state of Cr atoms as a function of depth has been studied using X‐ray standing wave (XSW) assisted X‐ray absorption near edge structure (XANES) measurements. Various oxidation states of Cr atoms present in the Cr2O3/Cr bilayer structure were determined using X‐ray photoelectron spectroscopy (XPS). Depth‐resolved XANES measurements confirmed the presence of chromium oxide (Cr2O3) and hydroxide (Cr (OH)3) at the top surface of the Cr2O3/Cr bilayer structure. The results also reveal the presence of metallic Cr along with its compounds Cr2O3 and Cr (OH)3 at the interface medium, showing significant mixing between the Cr2O3 and Cr layers. Our results clearly demonstrate that the XSW assisted XANES technique is extremely efficient for determining the variation of chemical states at the surface, interface, and different depths of a thin film structure. Such types of analysis are particularly useful for differentiating the presence of a metal from its own oxides, even at higher depths inside a thin film medium.

Volcanic Eruption in the Nanoworld: Efficient Oxygen Exchange at the Si/SnO2 Interface.

Here, a phenomenon of efficient oxygen exchange between a silicon surface and a thin layer of tin dioxide during chemical vapor deposition is presented, which leads to a unique Sn:SiO2 layer. Under thermodynamic conditions in the temperature range of 725-735°C, the formation of nanostructures with volcano-like shapes in "active" and "dormant" states are observed. Extensive characterization techniques, such as electron microscopy, X-ray diffraction, synchrotron radiation-based X-ray photoelectron, and X-ray absorption near-edge structure spectroscopy, are applied to study the formation. The mechanism is related to the oxygen retraction between tin(IV) oxide and silicon surface, leading to the thermodynamically unstable tin(II)oxide, which is immediately disproportionate to metallic Sn and SnO2 localized in the SiO2 matrix. The diffusion of metallic tin in the amorphous silicon oxide matrix leads to larger agglomerates of nanoparticles, which is similar to the formation of a magma chamber during the natural volcanic processes followed by magma eruption, which here is associated with the formation of depressions on the surface filled with metallic tin particles. This new effect contributes a new approach to the formation of functional composites but also inspires the development of unique Sn:SiO2 nanostructures for diverse application scenarios, such as thermal energy storage.

Electroluminescent white quantum dot light-emitting diodes based on high pressure synthesis of graphitic C3N4 semiconductor

Graphitic carbon nitride (g-C3N4) has shown promising potentials for quantum dot light-emitting diodes (QLEDs), which might be an effective alternative of the mostly used Cd(Se,S)/Zn(S,Se) emitting layers and can achieve both low toxicity and high stability, meeting the goal of sustainable development. Herein, we for the first report a white electroluminescent QLED device with blue and orange dual-color emissions, which were attributed to the σ*-LP, π*- π, and π*-LP transitions, respectively, from a single-compound g-C3N4 quantum dots (QDs) by synthesizing the precursor at 0.8 Mpa high-pressure N2. By selectively exciting the δ and π bonds with X-ray, the luminescence mechanism was approved with the synchrotron radiation techniques of X-ray absorption near edge structure (XANES) and the X-ray excited optical luminescence (XEOL).The chromaticity coordinate changes from cayan color space with CIE (0.2034, 0.1939) to white color space with CIE (0.3009, 0.2697) as pressure increases from 0.06 to 0.8 Mpa, with the increased overlap of the δ* and π* orbital upon the contraction of crystal lattice. The breakthrough achieved in this work will promisingly promote the development of future white light sources as thin as paper for human home and office lighting by using direct current-driven electroluminescence of QDs, instead of photoluminescence of phosphors.

Arsenic speciation in picromerite K2Mg(SO4)2•6H2O: Electron paramagnetic resonance and synchrotron X-ray absorption spectroscopic characterizations and implications for organic fertilizers

Picromerite K2Mg(SO4)2•6H2O (also known as schoenite, schönite, or sulfate of potash) formed from alkaline lakes by evaporation is an increasingly important chlorine-free fertilizer and has been used to produce other organic fertilizers such as arcanite K2SO4 and boussingaultite (NH4)2Mg(SO4)2•6H2O. Picromerite and boussingaultite, two Tutton’s salts, are also common secondary solid phases in diverse types of mine tailings and play important roles in controlling the mobility and bioavailability of various heavy metal(loid)s, including arsenic. In this study, picromerite crystals containing 64 ppm As have been synthesized at ambient conditions from aqueous solutions by slow evaporation. Arsenic K-edge X-ray absorption near-edge-structure (XANES) and extended X-ray absorption fine structure (EXAFS) data show that the dominant oxidation state is +5 and that As5+ occupies the S site in picromerite. Single-crystal and powder electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated picromerite reveal three arsenic-associated oxyradicals: AsO42−, AsO32−, and AsO22−. The orientations of the principal 75As hyperfine directions of the AsO32− and AsO22− radicals match the bonding directions of the SO42− groups in the picromerite structure, further supporting substitutions of their respective diamagnetic precursors AsO43- and AsO33- for the sulfate group. These AsO42−, AsO32−, and AsO22− radicals in picromerite are similar but not identical to their counterparts in boussingaultite and gypsum, suggesting that sulfate minerals are capable of sequestrating both arsenate and arsenite, with important implications for understanding the fate and bioavailability of arsenic associated with agricultural applications of organic fertilizers.

Actinyl Electronic Structure Probed by XAS: The Role of Many-Body Effects.

A detailed analysis of the wave functions for the M5 to 5f excitations in the linear actinyls, UO22+, NpO22+, and PuO22+, and the theoretical X-ray absorption spectra obtained with these wave functions in comparison with experimental M5-edge high-resolution X-ray absorption near-edge structure (HR-XANES) spectra is presented. The wave functions include full treatment of scalar and spin-orbit relativistic effects through the use of a Dirac-Coulomb Hamiltonian; many-body effects are included in determining the wave functions. The character of the excited states and of the active spaces to describe the wave functions for these states are investigated and analyzed. It is shown that the excited states cannot, in general, be described with a single configuration but have an essential multiconfiguration character. The characterization of the properties of the excited states and the X-ray absorption spectra was achieved through the use of novel methods.

Photon-Modulated Bond Covalency of [Sm(II)(η9-C9H9)2

Lanthanides are widely assumed not to form covalent bonds due to the localized nature of their 4f valence electrons. This work demonstrates that the ionic bond of Sm(II) with cyclononatetraenyl (η9-C9H9-) in [Sm(η9-C9H9)2] can be modulated and becomes more covalent by photon-induced transfer of Sm 4f electrons to Sm 5d orbitals. This photon-induced change in bonding properties facilitates a subsequent reconfiguration of [Sm(η9-C9H9)2]. As a result, Sm-C bond length contraction is detected and the local Sm coordination environment exhibits more extensive disorder. Both Sm 4f and 5d electrons have increased participation in covalent Sm-ligand interactions. The Sm L3-edge valence band resonant inelastic X-ray scattering (VB-RIXS), high-resolution X-ray absorption near-edge structure (HR-XANES), and quantum chemical computations showcase a spectroscopic methodology for in-depth studies of bond covalency of lanthanide atoms.

Influence of the 4f5d-1S0 energy gap on the decay times of Pr3+-doped fluoride scintillating glasses

A comparative analysis of praseodymium (Pr3+)-doped fluoride glasses, APLF [20Al(PO3)3–80LiF–PrF3], BCAYF (19BaF2–33.25CaF2–42.75AlF3–5YF3–PrF3), and BCAPLF (19BaF2–33.25CaF2–42.75AlF3–15P2O5–20LiF–PrF3), reveals the effect of the host matrix on the optical properties, particularly the luminescence behavior of Pr3+ ions. X-ray absorption near edge structure (XANES) spectroscopy verifies the presence of Pr ions in the glasses with a +3 oxidation state. Absorption spectra results suggest that the lowest energy level of the Pr3+ 4f5d configuration is influenced by the oxide/fluoride ratio of the glasses. As both interconfigurational 4f5d and intraconfigurational 4f2 transitions are observed, the energy gap between the lowest level of the 4f5d configuration and the overlapping 1S0 level of the 4f2 configuration is found to influence the predominance of UV emissions from the 4f5d and 1S0 levels as well as their decay times. Consequently, a larger 4f5d-1S0 energy gap of ∼5000 cm−1 leads to a more intense UV emission from the 4f5d level with a faster decay time. These results underscore the significance of minimizing the energy of the 4f5d level and increasing the gap between 4f5d-1S0 levels to be able to obtain fast UV emissions from Pr3+-doped fluoride glasses.

Catalytic Water Electrolysis by Co-Cu-W Mixed Metal Oxides: Insights from X-ray Absorption Spectroelectrochemistry.

Mixed metal oxides (MMOs) are a promising class of electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Despite their importance for sustainable energy schemes, our understanding of relevant reaction pathways, catalytically active sites, and synergistic effects is rather limited. Here, we applied synchrotron-based X-ray absorption spectroscopy (XAS) to explore the evolution of the amorphous Co-Cu-W MMO electrocatalyst, shown previously to be an efficient bifunctional OER and HER catalyst for water splitting. Ex situ XAS measurements provided structural environments and the oxidation state of the metals involved, revealing Co2+ (octahedral), Cu+/2+ (tetrahedral/square-planar), and W6+ (octahedral) centers. Operando XAS investigations, including X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS), elucidated the dynamic structural transformations of Co, Cu, and W metal centers during the OER and HER. The experimental results indicate that Co3+ and Cu0 are the active catalytic sites involved in the OER and HER, respectively, while Cu2+ and W6+ play crucial roles as structure stabilizers, suggesting strong synergistic interactions within the Co-Cu-W MMO system. These results, combined with the Tafel slope analysis, revealed that the bottleneck intermediate during the OER is Co3+ hydroperoxide, whose formation is accompanied by changes in the Cu-O bond lengths, pointing to a possible synergistic effect between Co and Cu ions. Our study reveals important structural effects taking place during MMO-driven OER/HER electrocatalysis and provides essential experimental insights into the complex catalytic mechanism of emerging noble-metal-free MMO electrocatalysts for full water splitting.

Simultaneous removal of tetracycline hydrochloride and hexavalent chromium by heterogeneous Fenton in a photocatalytic fuel cell system

In this work, a novel double-chamber system (PFC-Fenton), combined photocatalytic fuel cell (PFC) with Fenton, was constructed for tetracycline hydrochloride (TCH) and hexavalent chromium (Cr(VI)) removal and electricity production. Therein, Zn5(OH)6(CO3)2/Fe2O3/BiVO4/fluorine-doped SnO2 (ZIO/BiVO4/FTO) and carboxylated carbon nanotubes/polypyrrole/graphite felt (CCNTs/Ppy/GF) were served as photoanode and cathode, respectively. Under light irradiation, the removal efficiencies of TCH and Cr(VI) with the addition of H2O2 (2 mL) could reach 93.1% and 80.4%, respectively. Moreover, the first-order kinetic constants (7.37 × 10−3 min−1 of TCH and 3.94 × 10−3 min−1 of Cr(VI)) were 5.26 and 5.57 times as much as the absence of H2O2. Simultaneously, the maximum power density could be obtained 0.022 mW/cm2 at a current density of 0.353 mA/cm2. Therein, the main contribution of TCH degradation was ·OH and holes in anode chamber. The synergistic effect of photoelectrons, generated ·O2−, and H2O2 played a crucial role in the reduction of Cr(VI) in cathode chamber. The high-performance liquid chromatography-mass spectrometry indicated that TCH could be partially mineralized into CO2 and H2O. X-ray photoelectron spectroscope and X-ray absorption near-edge structure spectra showed that Cr(VI) could be reduced to Cr(III). After 5 times of cycling, the removal efficiencies of TCH and Cr(VI) were still greater than 70%, indicating the remarkable stability of the PFC-Fenton system. Overall, this system could remove TCH/Cr(VI) and generate power simultaneously without iron sludge formation, demonstrating a promising method to further develop PFC-Fenton technology.

L3-edge X-ray spectroscopy of rhodium and palladium compounds.

L3-edge high-energy-resolution fluorescence-detection X-ray absorption near-edge structure (XANES) spectra for palladium and rhodium compounds are presented, with focus on their electronic structures. The data are compared with transmission XANES spectra recorded at the K-edge. A correlation between the absorption edge energy and the metal ion oxidation state is not observed. Despite the different filling of the 4d orbitals and different local coordination, the Rh and Pd compounds show remarkably similar spectral shapes. Calculation of the density of states and of the L3-XANES data reproduce the experimental results.

Influence of snowpack on soil organic carbon decomposition in a northern peatland

Peatlands play a significant role in maintaining the carbon balance and regulating the climate. The turnover of soil organic carbon (SOC) in peatlands is mediated by snowpack, which affects microbial decomposition through its regulation of hydrothermal conditions. However, the impact of snowpack on carbon dynamics in peatlands is not fully understood, particularly in the context of decline in snowpack due to climate warming. To address this issue, an on-site experiment was conducted involving snowpack manipulation (undisturbed and snow removal) to investigate the effects of snowpack on SOC decomposition at depths of 0–30 cm (topsoil) and 30–60 cm (subsoil). Various techniques such as X-ray absorption near-edge structure, synchrotron radiation micro computed tomography technology and microbial metagenomics were utilized to measure SOC content and fractions, pore structure and bacterial community’s structure and function. Results showed that snow removal delayed the start of soil freezing date by 27 days and advanced the start of thawing date by 39 days, increased maximum freezing depth by 27.9 cm and frequency of freeze–thaw cycles, and decreased average temperature of topsoil and subsoil by 1.48 °C and 1.34 °C, respectively. Additionally, snow removal increased SOC content by 8.27 % and 3.19 % and its stability by 53 % and 13.92 % in the topsoil and subsoil, respectively, and decreased microbial decomposition potential functioning by 55.89 % and 5.75 % in both soil layers. The three-dimensional spatial distribution of SOC and soil pores at the micro-scale indicated that snow removal significantly influenced pore structure and microbe feedback loops, thereby affecting SOC decomposition. Notably, snow removal led to an increase in the proportion of micropores by 3.44 % and 4.41 % in the topsoil and subsoil, respectively, suggesting enhanced protection of pore structure and preservation of SOC during decomposition processes. Overall, the findings suggest that snow removal may intensify the response of carbon pools to climate change in peatlands.

An electrochemical flow cell for operando XPS and NEXAFS investigation of solid–liquid interfaces

Suitable reaction cells are critical for operando near ambient pressure (NAP) soft x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) studies. They enable tracking the chemical state and structural properties of catalytically active materials under realistic reaction conditions, and thus allow a better understanding of charge transfer at the liquid–solid interface, activation of reactant molecules, and surface intermediate species. In order to facilitate such studies, we have developed a top-side illuminated operando spectro-electrochemical flow cell for synchrotron-based NAP-XPS/-NEXAFS studies. Our modular design uses a non-metal (PEEK) body, and replaceable membranes which can be either of x-ray transparent silicon nitride (SiN x ) or of water permeable polymer membrane materials (e.g. NafionTM). The design allows rapid sample exchange and simultaneous measurements of total electron yield, Auger electron yield and fluorescence-yield. The developed system is highly modular and can be used in the laboratory or directly at the beamline for operando XPS/ x-ray absorption spectroscopy investigations of surfaces and interfaces. We present examples to demonstrate the capabilities of the flow cell. These include an operando NEXAFS study of the Cu-redox chemistry using a SiN x /Ti-Au/Cu working electrode assembly (WEA) and a NAP-XPS/-NEXAFS study of water adsorption on a NafionTM polymer membrane based WEA (NafionTM/C/IrO x catalyst). More importantly, the spectro-electrochemical flow cell is available for user community of B07 beamlines at Diamond Light Source.

Speciation, phytoavailability, and accumulation of toxic elements and sulfur by humic acid-fertilized lemongrass and common sage in a sandy soil treated with heavy oil fly ash: A trial for management of power stations wastes

Globally, power stations generate huge amounts of the hazardous waste heavy oil fly ash (HOFA), which is rich in Ni, V, Fe, S, and dumped into landfills. Thus, exploring new approaches for a safe recycling and sustainable management of HOFA is needed and of great environmental interest. The potential application of HOFA as an amendment to sandy soils has not been studied yet. This is the first research investigating the potentiality of using HOFA as a soil conditioner. To this end, we conducted a greenhouse experiment in order to investigate the impacts of HOFA addition (1.2, 2.4, 3.6 t ha−1) to sandy soil on the total and available content of nutrients (e.g., S, Fe, Mn, Cu, Zn) and toxic elements (TEs; e.g., Cd, Co, Cr, Ni, Pb, V) in the soil and their phytoextraction and translocation by lemongrass (Cymbopogon citratus) and common sage (Salvia officinalis). We also assessed the impact of humic acid (HA) foliar application (50 and 100 l ha−1) on the growth and elements accumulation by the two plants. The studied HOFA was acidic and highly enriched in S (43,268.0), V (3,527.0), Ni (1774.0), and Fe (15,159.0) (units in mg kg−1). The X-ray absorption near edge structure (XANES) data showed that V in HOFA was composed primarily of V(IV) sorbed onto goethite, V(V) sorbed onto humic substances, in the forms of V2O3, and VCl4. Addition of the lower doses of HOFA (1.2 and 2.4 t ha−1) did not change significantly soil pH, salinity, and the total and available elements content compared to the unamended soil. Although the elements content in the 3.6 t ha−1 HOFA-treated soil was significantly higher than the untreated, the total content of all elements (except for Ni) was lower than the maximum allowable concentrations in soils. HOFA addition, particularly in the highest dose (3.6 t ha−1), decreased significantly the growth and biomass of both plants. Common sage accumulated more elements than lemongrass; however, the elements content in the plants was lower than the critical concentrations for sensitive plants. The foliar application of humic acid enhanced significantly the plant growth and increased their tolerance to the HOFA-induced stress. We conclude that the addition of HOFA up to 2.4 t ha−1 in a single application as amendment to sandy soils is not likely to create any TE toxicity problems to plants, particularly if combined with a foliar application of humic acid; however, repeated additions of HOFA may induce toxicity. These findings should be verified under field conditions.

Highly sensitive 2D X-ray absorption spectroscopy via physics informed machine learning

Improving the spatial and spectral resolution of 2D X-ray near-edge absorption structure (XANES) has been a decade-long pursuit to probe local chemical reactions at the nanoscale. However, the poor signal-to-noise ratio in the measured images poses significant challenges in quantitative analysis, especially when the element of interest is at a low concentration. In this work, we developed a post-imaging processing method using deep neural network to reliably improve the signal-to-noise ratio in the XANES images. The proposed neural network model could be trained to adapt to new datasets by incorporating the physical features inherent in the latent space of the XANES images and self-supervised to detect new features in the images and achieve self-consistency. Two examples are presented in this work to illustrate the model’s robustness in determining the valence states of Ni and Co in the LiNixMnyCo1-x-yO2 systems with high confidence.

Realizing B-site high-entropy air electrode for superior reversible solid oxide cells

The operational efficiency of reversible solid oxide cells (R-SOCs) is hindered by the limited electroactivity and longevity of air electrodes. High-entropy engineering at the B site can reduce the Co content, enhance the compatibility of air electrodes and electrolyte thermal expansion coefficients, and introduce synergistic effects of multi-elements. In this pioneering work, we successfully prepared a single-phase air electrode, PrBa0.8Ca0.2Fe0.4Co0.4Ni0.4Cu0.4Zn0.4O6-δ (HE-PBC-FCNCZ). The cell with HE-PBC-FCNCZ as the air electrode exhibits a peak power density of 1.42 W cm−2 in fuel cell (FC) mode at 700 ℃, demonstrating robust stability. Its remarkable electrochemical performance and stability rank among the top tier of perovskite cathode materials. X-ray absorption near edge structure (XANES) analyses indicated minimal changes in the oxygen content after the stability test compared to PBCC. This study introduces novel B-site high-entropy air electrodes for R-SOCs, featuring both elevated activity and extended durability.