X-ray Absorption Near-edge Spectroscopy Research Articles

Ultraviolet-B and Near-Infrared Dual-Band Luminescence in Bi3+/Bi2+ Codoped Persistent Phosphor for Optical Storage Application.

Discovering multifunctional luminescent materials to meet the demands of modern spectroscopy is of great significance. However, it is a standing challenge to enable multiple luminescence properties in a single material system via single metal ion doping. Here, we report the inherently Bi3+/Bi2+ codoped Ca3Ga2Ge3O12 persistent phosphor where Bi3+ is in situ reduced to Bi2+. This phosphor can act as an efficient multimodal luminescence material, which simultaneously exhibits long-lasting (>12 h) ultraviolet-B (UVB) and near-infrared (NIR) dual-band persistent luminescence after irradiation by 254 nm ultraviolet (UV) light. UVB and NIR afterglow are ascribed to the distinct Bi3+ and Bi2+ emitters, respectively, proven by comprehensive spectroscopic investigations including X-ray absorption near-edge structure spectra and X-ray photoelectron spectroscopy. Besides, this phosphor also exhibits exceptional photochromic features, accompanied by a rapid body color transformation from white to brown in response to 254 nm UV light within 60 s and excellent recovery capacity upon thermal or blue/white light stimulation. The combination of UVB persistent luminescence of Bi3+ and NIR afterglow of Bi2+ coupled with reversible white-to-brown photochromism phenomenon offers one type of promising multifunctional luminescence material, showing potential to be used for optical storage and anti-counterfeiting applications.

Protaetia brevitarsis larvae produce frass that can be used as an additive to immobilize Cd and improve fertility in alkaline soils

Bioconversion of agricultural waste by Protaetia brevitarsis larvae (PBL) holds significant promise for producing high-quality frass organic amendments. However, the effects and mechanisms of PBL frass on Cd immobilization in an alkaline environment remain poorly understood. In this study, three types of frass, namely maize straw frass (MF), rice straw frass (RF), and sawdust frass (SF), were produced by feeding PBL. The Cd immobilization efficiencies of three frass in alkaline solutions and soils were investigated through batch sorption and incubation experiments, and spectroscopic techniques were employed to elucidate the sorption mechanisms of Cd onto different frass at the molecular level. The results showed that MF proved to be an efficient sorbent for Cd in alkaline solutions (176.67–227.27 mg g−1). X-ray absorption near-edge structure (XANES) spectroscopy indicated that Cd immobilization in frass is primarily attributed to the association with organic matter (OM-Cd, 78–90%). And MF had more oxygen-containing functional groups than the other frass. In weakly alkaline soils, MF application (0.5–1.5%) significantly decreased Cd bioavailability (5.65–18.48%) and concurrently improved soil nutrients (2.21–56.79%). Redundancy analysis (RDA) unveiled that pH, CEC, and available P were important factors controlling Cd fractions. Path analysis demonstrated that MF application affected Cd bioavailability directly and indirectly by influencing soil chemical properties and nutrients. In summary, MF, the product of PBL-mediated conversion maize straw, demonstrated promise as an effective organic amendment for Cd immobilization and fertility improvement in alkaline soils.

High valency of charge compensator (Mo6+) to substitute Ti site in REE doped zirconolite (REE=Nd, Sm, Gd, Ho and Yb): Solid solubility, phase evolution and structural analysis

Zirconolite ceramics have been proven to be a promising matrix for high-level waste immobilization, especially for minor actinides. In this study, a series of CaZr1-2xREE2xTi2-xMoxO7 (REE = Nd, Sm, Gd, Ho, Yb) samples were prepared to investigate the formation of zirconolite REE as surrogates of minor actinides and Mo6+ as charge compensator. Synchrotron and in-house powder X-ray diffraction (XRD), X-ray absorption near edge spectroscopy (XANES), and scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX) were used to study their solid solubility, phase evolution, and structural details. XRD results show that the formation of zirconolite-2M can be up to x = 0.15 in the CaZr1-2xNd2xTi2-xMoxO7 samples when co-existence of 2 M and 4 M was observed at x = 0.20 and 0.25. The “yellow phase” appears when x exceeds 0.4. The phase evolutions of CaZr1-2xSm2xTi2-xMoxO7, CaZr1-2xGd2xTi2-xMoxO7, CaZr1-2xHo2xTi2-xMoxO7 and CaZr1-2xYb2xTi2-xMoxO7 solid solutions are similar to each other: (1) zirconolite-2M in x = 0.05 and 0.10; (2) co-existence of 2 M and 4 M and then formation of 4 M phase from x = 0.15 to 0.25; (3) formation of “yellow phase” and pyrochlore when x ≥ 0.30. Interestingly, perovskite exits in all the ceramic samples, and its lattice parameters slightly change when increasing the dopants. Rietveld refinement results reveal that Sm/Ho mainly incorporates into 8f (Wyckoff position) Zr-sites while Mo replaces the 8f (Wyckoff position) Ti-sites. XANES results further confirm the occupation of Mo in TiO5 coordination environments. Furthermore, there is a considerable amount of Sm/Ho incorporated into 8f Ca-sites, demonstrating a different substitution mechanism from the preliminary design.

Saltwater intrusion increases phosphorus abundance and alters availability in coastal soils with implications for future sea level rise

Sea level rise (SLR) promotes saltwater intrusion (SWI) into coastal soils globally at an increasing rate, impacting phosphorus (P) dynamics and adjacent water quality. However, how SWI influences P molecular speciation and availability in coastal soils remains poorly understood. By using a space-for-time substitution strategy, we evaluated the SWI impacts on P transformation along a SWI gradient at the Rehoboth Inland Bay, which consists of five sampling locations along a transect representing different SWI degrees. Soils were analyzed at the macro- and micro-scale using X-ray absorption near edge spectroscopy (XANES) and the modified Hedley fractionation. With increasing distance from the Bay, soil salinity (29.3–0.07 mmhos cm−1), the proportion of Fe3+ to total Fe, and P concentrations decreased. The fractionation showed that recalcitrant P was dominant (86.9–89.5% of total P). With increasing SWI, labile P increased gradually, reached a plateau, and then decreased sharply. Bulk XANES spectroscopy showed that soil P was likely dominated by iron and aluminum-associated P (Fe/Al-P), regardless of the SWI degree. Hence, with increasing SWI, P increasingly accumulated in a recalcitrant pool, mainly as Fe/Al-P. μ-XANES spectroscopy revealed that calcium-associated P (Ca-P) existed in P-rich spots of the greatest SWI soil while Al-P occurred in P-rich spots of the low SWI soil, consistent with the greater HCl-P (presumably Ca-P) in the former soil. Overall, results demonstrate that SWI impacts P availability and environmental risk in coastal soils depending on the degree of SWI. These findings have important implications for understanding soil P cycling and availability in SLR-impacted coastal areas.

In situ arsenic immobilization by natural iron (oxyhydr)oxide precipitates in As–contaminated groundwater irrigation canals

Arsenic-contaminated groundwater is widely used in agriculture. To meet the increasing demand for safe water in agriculture, an efficient and cost-effective method for As removal from groundwater is urgently needed. We hypothesized that Fe (oxyhydr)oxide (FeOOH) minerals precipitated in situ from indigenous Fe in groundwater may immobilize As, providing a solution for safely using As-contaminated groundwater in irrigation. To confirm this hypothesis and identify the controlling mechanisms, we comprehensively evaluated the transport, speciation changes, and immobilization of As and Fe in agricultural canals irrigated using As-contaminated groundwater. The efficiently removed As and Fe in the canals accumulated in shallow sediment rather than subsurface sediment. Linear combination fitting (LCF) analysis of X–ray absorption near edge spectroscopy (XANES) indicated that As(V) was the dominant As species, followed by As(III), and there was no FeAsO4 precipitate. Sequential extraction revealed higher contents of amorphous FeOOH and associated As in shallower sediment than in the subsurface layer. Stoichiometric molar ratio calculations, SEM‒EDS, FTIR, and fluorescence spectroscopy collectively demonstrated that the microbial reductive dissolution of amorphous FeOOH proceeded via reactive dissolved organic matter (DOM) consumption in subsurface anoxic porewater environment facilitating high labile As, whereas in surface sediment, the in situ-generated amorphous FeOOH was stable and strongly inhibited As release via adsorption. In summary, groundwater Fe2+ can efficiently precipitate in benthic surface sediment as abundant amorphous FeOOH, which immobilizes most of the dissolved As, protecting agricultural soil from contamination. This field research supports the critical roles of the phase and reactivity of in situ-generated FeOOH in As immobilization and provides new insight into the sustainable use of contaminated water.

Local electronic structures of annealing induced phases in cobalt doped TiO2 nanoparticles: a combined study of transmission electron microscopy and x-ray absorption fine structure spectroscopy

The evolution of the nanostructures and electronic properties of 5% cobalt-doped TiO2 nanoparticles (NPs) annealed at 400 °C, 600 °C, and 800 °C have been investigated to understand the structural phase transformations through chemical co-precipitation synthesis. A detailed analysis of the X-ray Diffractogram confirms that the sample annealed at 400 °C is anatase, at 600 °C, the mixed phase of anatase and rutile evolves, and at 800 °C, the sample is of rutile structure. A detailed morphological study by scanning transmission electron microscope provides the particle size, lattice spacing, and variation in polycrystalline grain growth at different phases. Electron Energy Loss Spectroscopy analysis indicates from the O K, Co, and Ti L 2,3-edges that Ti4+ ions are primarily in an octahedral symmetry with the oxygen ligands changing their structural phases from anatase to mixed phase and then stable rutile phase with increasing temperature of annealing. X-ray Absorption Near Edge Spectroscopy (XANES) extracts information about the varying oxidation states and 3-dimensional geometry of Ti-ions. The unresolved issues of the structural details at the atomic-scale picture with the local environment of the cation with a few nearest neighbour shells are derived from Extended X-ray Absorption Fine Structure (EXAFS) and pre-edge parts of the absorption spectra. The limits of EXAFS in this situation of asymmetric bond length disorder, which is typical for mixed-valence oxides, are generated to reconcile the two data and highlight the value of pre-edge XANES analysis for identifying local heterogeneities in structural and compositional motifs. TiO2 possesses unique properties depending upon its structural phase. The Ti L 2,3-edge spectrum indicates that there is an octahedron connectivity of the Oxygen atoms at the anatase state which transforms to a higher energetic tetrahedral correspondence as it proceeds towards the rutile phase. The driving force behind such interest is to modulate the properties of TiO2 NPs to better photocatalytic material and to integrate its application as a versatile energy storage device.

Phosphorus fractions and speciation in an alkaline, manured soil amended with alum, gypsum, and Epsom salt.

Snowmelt runoff is a dominant pathway of phosphorus (P) losses from agricultural lands in cold climatic regions. Soil amendments effectively reduce P losses from soils by converting P to less soluble forms; however, changes in P speciation in cold climatic regions with fall-applied amendments have not been investigated. This study evaluated P composition in soils from a manured field with fall-amended alum (Al2(SO4)3·18H2O), gypsum (CaSO4·2H2O), or Epsom salt (MgSO4·7H2O) using three complementary methods: sequential P fractionation, scanning electron microscopy with energy-dispersive X-rays (SEM-EDX) spectroscopy, and P K-edge X-ray absorption near-edge structure spectroscopy (XANES). Plots were established in an annual crop field in southern Manitoba, Canada, with unamended and amended (2.5 Mg ha-1) treatments having four replicates in 2020 fall. Soil samples (0-10cm) taken from each plot soon after spring snowmelt in 2021 were subjected to P fractionation. A composite soil sample for each treatment was analyzed using SEM-EDX and XANES. Alum- and Epsom salt-treated soils had significantly greater residual P fraction with a higher proportion of apatite-like P and a correspondingly lower proportion of P sorbed to calcite (CaCO3) than unamended and gypsum-amended soils. Backscattered electron imaging of SEM-EDX revealed that alum- and Epsom salt-amended treatments had P-enriched microsites frequently associated with aluminum (Al), iron (Fe), magnesium (Mg), and calcium (Ca), which was not observed in other treatments. Induced precipitation of apatite-like species may have been responsible for reduced P loss to snowmelt previously reported with fall application of amendments.

Local structural and sensing properties of TiO2 thin film using the PVD method

This paper studied the structural, morphological, optical, and X-ray absorption near-edge spectroscopy (XANES) and sensing properties of titanium dioxide (TiO2) thin film. The TiO2 thin film is prepared in the thin film laboratory on a clean glass plate using a physical vapor deposition (PVD) method. The structural, morphological, Optical, and electronic properties of the fabricated samples are presented by X-ray diffraction (XRD), atomic force microscope (AFM), UV-visible, and XANES. It is found from XRD the crystallite size was ∼25.66 nm with microstrain ∼0.0064 using the Williamson-Hall (W-H) plot. The fractal terms such as grain size, roughness, kurtosis, and skewness were estimated using AFM. The grain size lies in the nanometric range and found that ∼77.21 nm. The band gap of the fabricated film is ∼3.23 eV. The XANES analysis is well supported by XRD measurement and the result found that the fabricated TiO2 thin film was anatase phase. The sensing properties of TiO2 are studied for the detection of Liquified Petroleum Gas (LPG) concentration (0-5000 ppm) at room temperature. Results found that the TiO2 film is highly sensitive and is the fast response for LPG gas sensors with a maximum sensitivity of ∼198 %.

Trace Element Distribution and Arsenic Speciation in Toenails as Affected by External Contamination and Evaluation of a Cleaning Protocol.

Trace element concentrations in toenail clippings have increasingly been used to measure trace element exposure in epidemeological research. Conventional methods such as inductively coupled plasma mass spectrometry (ICP-MS) and high-performance liquid chromatography ICP-MS (HPLC-ICP-MS) are commonly used to measure trace elements and their speciation in toenails. However, the impact of the removal of external contamination on trace element quantification has not been thoroughly studied. In this work, the microdistribution of trace elements (As, Ca, Co, Cu, Fe, K, Mn, Ni, Rb, S, Sr, Ti, and Zn) in dirty and washed toenails and the speciation of As in situ in toenails were investigated using synchrotron X-ray fluorescence microscopy (XFM) and laterally resolved X-ray absorption near edge spectroscopy (XANES). XFM showed different distribution patterns for each trace element, consistent with their binding properties and nail structure. External (terrestrial) contamination was identified and distinguished from the endogenous accumulation of trace elements in toenails─contaminated areas were characterized by the co-occurrence of Co, Fe, and Mn with elements such as Ti and Rb (i.e., indicators of terrestrial contamination). The XANES spectra showed the presence of one As species in washed toenails, corresponding to As bound to sulfhydryl groups. In dirty specimens, a mixed speciation was found in localized areas, containing AsIII-S species and AsV species. ArsenicV is thought to be associated with surface contamination and exogenous As. These findings provide new insights into the speciation of arsenic in toenails, the microdistribution of trace elements, and the effectiveness of a cleaning protocol in removing external contamination.

The Effect of Water Co-Feeding on the Catalytic Performance of Zn/HZSM-5 in Ethylene Aromatization Reactions.

During the methanol-to-aromatics (MTA) process, a large amount of water is generated, while the influence and mechanism of water on the activity and selectivity of the light olefin aromatization reaction are still unclear. Therefore, a study was conducted to systematically investigate the effects of water on the reactivity and the product distribution in ethylene aromatization using infrared spectroscopy (IR), intelligent gravitation analyzer (IGA), and X-ray absorption fine structure (XAFS) characterizations. The results demonstrated that the presence of water reduced ethylene conversion and aromatic selectivity while increasing hydrogen selectivity at the same contact time. This indicated that water had an effect on the reaction pathway by promoting the dehydrogenation reaction and suppressing the hydrogen transfer reaction. A detailed analysis using linear combination fitting (LCF) of Zn K-edge X-ray absorption near-edge spectroscopy (XANES) on Zn/HZSM-5 catalysts showed significant variations in the state of existence and the distribution of Zn species on the deactivated catalysts, depending on different reaction atmospheres and water contents. The presence of water strongly hindered the conversion of ZnOH+ species, which served as the active centers for the dehydrogenation reaction, to ZnO on the catalyst. As a result, the dehydrogenation activity remained high in the presence of water. This study using IR and IGA techniques revealed that water on the Zn/HZSM-5 catalyst inhibited the adsorption of ethylene on the zeolite, resulting in a noticeable decrease in ethylene conversion and a decrease in aromatic selectivity. These findings contribute to a deeper understanding of the aromatization reaction process and provide data support for the design of efficient aromatization catalysts.

Confocal μ-XANES as a tool to analyze Fe oxidation state in heterogeneous samples: the case of melt inclusions in olivine from the Hekla volcano

Abstract. Here we present a confocal Fe K-edge μ-XANES method (where XANES stands for X-ray absorption near-edge spectroscopy) for the analysis of Fe oxidation state in heterogeneous and one-side-polished samples. The new technique allows for an analysis of small volumes with high spatial 3D resolution of <100 µm3. The probed volume is restricted to that just beneath the surface of the exposed object. This protocol avoids contamination of the signal by the host material and minimizes self-absorption effects. This technique has been tested on a set of experimental glasses with a wide range of Fe3+ / ΣFe ratios. The method was applied to the analysis of natural melt inclusions trapped in forsteritic to fayalitic olivine crystals of the Hekla volcano, Iceland. Our measurements reveal changes in Fe3+ / ΣFe from 0.17 in basaltic up to 0.45 in dacitic melts, whereas the magnetite–ilmenite equilibrium shows redox conditions with Fe3+ / ΣFe ≤0.20 (close to FMQ, fayalite–magnetite–quartz redox equilibrium) along the entire range of Hekla melt compositions. This discrepancy indicates that the oxidized nature of glasses in the melt inclusions could be related to the post-entrapment process of diffusive hydrogen loss from inclusions and associated oxidation of Fe in the melt. The Fe3+ / ΣFe ratio in silicic melts is particularly susceptible to this process due to their low FeO content, and it should be critically evaluated before petrological interpretation.

Organic amendments temporarily change arsenic speciation and bioaccessibility in a lead and arsenic co-contaminated urban soil.

Organic amendments often reduce the bioaccessibility of soil lead (Pb) but not that of soil arsenic (As). The effect of Pb on As bioaccessibility is rarely studied in co-contaminated soils. In a field study, we assessed the effect of mushroom compost, leaf compost, noncomposted biosolids, and composted biosolids amendments on As speciation in a co-contaminated (As and Pb) soil at 7, 349, and 642 days after amending soils and the change of As speciation during an in vitro bioaccessibility extraction (gastric solution, pH 2.5) using bulk X-ray absorption near-edge structure spectroscopy. Soil was contaminated by coal combustion and other diffuse sources and had low As bioaccessibility (7%-12%). Unamended soil had As(III) sorbed onto pyrite (As(III)-pyrite; ∼60%) and As(V) adsorbed onto Fe oxy(hydr)oxides (As(V)-Fh; ∼40%). In amended soils, except in composted biosolids-amended soils, at 7 days, As(V)-Fh decreased to 15%-26% and redistributed into As(III)-Fh and/or As(III)-pyrite. This transformation was most pronounced in mushroom compost amended soil resulting in a significant (46%) increase of As bioaccessibility compared to the unamended soil. Composted biosolids-amended soils had relatively stable As(V)-Fh. Lead arsenate formed during the in vitro extraction in amended soils, except in composted biosolids-amended soils. Arsenic speciation and bioaccessibility were similar in 349- and 642-day in all the amended and unamended soils. Reduction of As(V)-Fh to As(III) forms in the short term in three of the amended soils showed the potential to increase As bioaccessibility. The formation of stable lead arsenate during the in vitro extraction would counteract the short-term increase of As bioaccessibility in those amended soils.

Controllable sulfur redox multi-pathway reactions regulated by metal-free electrocatalysts anchored with LiS3* radicals

Regulating sulfur redox kinetics is an effective strategy for addressing the critical issues in lithium-sulfur batteries and improving their comprehensive performance. However, the sluggish and complex sulfur reduction reaction (SRR) kinetics can seriously deteriorate the electrochemical performance of lithium-sulfur batteries, hindering a clear comprehension of the electrocatalytic mechanism and presenting challenges for targeted design. Hence, it is crucial to elucidate the SRR mechanism and further refine the catalytic principle. In this study, the SRR mechanism and the pivotal role of radicals are comprehensively explored using ultrathin nitrogen-oxygen co-doped carbon nanosheets (UN/O-CNS) as an electrocatalytic model, combining density functional theory calculations with experimental techniques, such as X-ray absorption near-edge structure spectroscopy. The abundant N-O active sites of UN/O-CNS can synergistically anchor LiS3* radicals, facilitating efficient multi-pathway sulfur conversion. Additionally, UN/O-CNS can capture and catalyze polysulfides while also bi-directionally catalyzing Li2S. The S@UN/O-CNS cells ultimately demonstrate ultra-long cycling performance and high load capacity. The successful operation in pouch cells validates the practical effectiveness of UN/O-CNS. Overall, this study offers novel insights into the complexity and potential pathways of sulfur redox reaction, providing new perspectives for exploring the catalytic mechanism of cost-effective metal-free electrocatalysts.

Mechanisms of Uptake and Translocation of Thallium in Brassica Vegetables: An X-ray Fluorescence Microspectroscopic Investigation.

Most nonoccupational human exposure to thallium (Tl) occurs via consumption of contaminated food crops. Brassica cultivars are common crops that can accumulate more than 500 μg Tl g-1. Knowledge of Tl uptake and translocation mechanisms in Brassica cultivars is fundamental to developing methods to inhibit Tl uptake or conversely for potential use in phytoremediation of polluted soils. Brassica cultivars (25 in total) were subjected to Tl dosing to screen for Tl accumulation. Seven high Tl-accumulating varieties were selected for follow-up Tl dosing experiments. The highest Tl accumulating Brassica cultivars were analyzed by synchrotron-based micro-X-ray fluorescence to investigate the Tl distribution and synchrotron-based X-ray absorption near-edge structure spectroscopy (XANES) to unravel Tl chemical speciation. The cultivars exhibited different Tl tolerance and accumulation patterns with some reaching up to 8300 μg Tl g-1. The translocation factors for all the cultivars were >1 with Brassica oleracea var. acephala (kale) having the highest translocation factor of 167. In this cultivar, Tl is preferentially localized in the venules toward the apex and along the foliar margins and in minute hot spots in the leaf blade. This study revealed through scanning electron microscopy and X-ray fluorescence analysis that highly Tl-enriched crystals occur in the stoma openings of the leaves. The finding is further validated by XANES spectra that show that Tl(I) dominates in the aqueous as well as in the solid form. The high accumulation of Tl in these Brassica crops has important implications for food safety and results of this study help to understand the mechanisms of Tl uptake and translocation in these crops.

Understanding phosphorus mobilization mechanisms in acidic soil amended with calcium-silicon-magnesium-potassium fertilizer

Calcium-silicon-magnesium-potassium fertilizer (CSMP) is usually used as an amendment to counteract soil acidification caused by historical excessive nitrogen (N) applications. However, the impact of CSMP addition on phosphorus (P) mobilization in acidic soils and the related mechanisms are not fully understood. Specifically, a knowledge gap exists with regards to changes in soil extracellular enzymes that contribute to P release. Such a knowledge gap was investigated by an incubation study with four treatments: i) initial soil (Control), ii) urea (60 mg kg−1) addition (U); iii) CSMP (1%) addition (CSMP) and iv) urea (60 mg kg−1) and CSMP (1%) additions (U + CSMP). Phosphorus mobilization induced by different processes was distinguished by biologically based P extraction. The Langmuir equation, K edge X-ray absorption near-edge structure spectroscopy, and ecoenzyme vector analysis according to the extracellular enzyme activity stoichiometry were deployed to investigate soil P sorption intensity, precipitation species, and microbial-driven turnover of organophosphorus. Results showed that CaCl2 extractable P (or citric acid extractable P) content increased by 63.4% (or 39.2%) in the soil with CSMP addition, compared with the study control. The accelerated mobilization of aluminum (Al)/iron (Fe)-bound P after CSMP addition, indicated by the reduction of the sum of FePO4·2H2O and AlPO4 proportion, contributed to this increase. The decrease of P sorption capacity can also be responsible for it. The CSMP addition increased enzyme extractable P in the soil nearly 7-fold and mitigated the limitations of carbon (C) and P for soil microorganisms (indicated by the enzyme stoichiometry and ecoenzyme vector analysis), suggesting that microbial turnover processes also contribute to P mobilization in amended acidic soil. These findings indicate that the P mobilization in CSMP amended acidic soil not only attributed to both decreasing P sorption capacity and dissolving phosphate precipitation, but also to the increase of the microbial turnover of the organophosphorus pool.

Promoted Overall Water Splitting Catalytic Activity and Durability of Ni3Fe Alloy by Designing N-Doped Carbon Encapsulation.

Combining an electrochemically stable material onto the surface of a catalyst can improve the durability of a transition metal catalyst, and enable the catalyst to operate stably at high current density. Herein, the contribution of the N-doped carbon shell (NCS) to the electrochemical properties is evaluated by comparing the characteristics of the Ni3Fe@NCS catalyst with the N-doped carbon shell, and the Ni3Fe catalyst. The synthesized Ni3Fe@NCS catalyst has a distinct overpotential difference from the Ni3Fe catalyst (ηOER = 468.8mV, ηHER = 462.2mV) at (200 and -200)mAcm-2 in 1m KOH. In stability test at (10 and -10)mAcm-2, the Ni3Fe@NCS catalyst showed a stability of (95.47 and 99.6)%, while the Ni3Fe catalyst showed a stability of (72.4 and 95.9)%, respectively. In addition, the in situ X-ray Absorption Near Edge Spectroscopy (XANES) results show that redox reaction appeared in the Ni3Fe catalyst by applying voltages of (1.7 and -0.48)V. The decomposition of nickel and iron due to the redox reaction is detected as a high ppm concentration in the Ni3Fe catalyst through Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) analysis. This work presents the strategy and design of a next-generation electrochemical catalyst to improve the electrocatalytic properties and stability.

Impacts of atmospheric deposition on the heavy metal mobilization and bioavailability in soils amended by lime

Atmospheric deposition is an important source of heavy metal in agricultural soils, but there is limited research on the mobility of these metals in soil and their impact on soil amendment. Here, we performed a dust incubation experiment in soils in the laboratory and a factorial transplant experiment at three field sites with a gradient of atmospheric deposition to examine the impacts of atmospherically deposited heavy metals (Cu, Cd, and Pb) on the mobility and bioavailability in soils with and without lime applications. Results showed that the atmospherically deposited heavy metals showed high mobility and were primarily presented in the soluble ionic fractions in the wet part and acid-exchangeable and reducible fractions in the dry part of atmospheric deposition. Atmospheric dust addition caused the 2p3/2 and 2p1/2 electrons of Cu atoms in uncontaminated soils to transition the 3d vacant states, resulting in similar copper absorption peaks as atmospheric particles by the observation of X-ray absorption near-edge spectroscopy (XANES). In the field, atmospheric deposition can only increase the mobile fractions in the surface soils, but not in the deeper layers. However, the deposition can increase the soluble and diffusive gradients in thin films (DGT)-measured bioavailable fractions in profile along with the soil depth. Lime applications cannot significantly reduce the mobile fractions of heavy metals in the surface soils exposed to atmospheric deposition, but significantly reduce the heavy metal concentrations in soil solutions and the DGT-measured bioavailable concentrations, particularly in the deeper layer (6–10 cm). The major implication is that atmospherically deposited heavy metals can significantly increase their bioavailable concentrations in the plough horizon of soil and constrain the effects of soil amendments on heavy metal immobilization, thereby increasing the risks of crop uptake.

Dynamic Transformation of Nano-MoS2 in a Soil-Plant System Empowers Its Multifunctionality on Soybean Growth.

Molybdenum disulfide (nano-MoS2) nanomaterials have shown great potential for biomedical and catalytic applications due to their unique enzyme-mimicking properties. However, their potential agricultural applications have been largely unexplored. A key factor prior to the application of nano-MoS2 in agriculture is understanding its behavior in a complex soil-plant system, particularly in terms of its transformation. Here, we investigate the distribution and transformation of two types of nano-MoS2 (MoS2 nanoparticles and MoS2 nanosheets) in a soil-soybean system through a combination of synchrotron radiation-based X-ray absorption near-edge spectroscopy (XANES) and single-particle inductively coupled plasma mass spectrometry (SP-ICP-MS). We found that MoS2 nanoparticles (NPs) transform dynamically in soil and plant tissues, releasing molybdenum (Mo) and sulfur (S) that can be incorporated gradually into the key enzymes involved in nitrogen metabolism and the antioxidant system, while the rest remain intact and act as nanozymes. Notably, there is 247.9 mg/kg of organic Mo in the nodule, while there is only 49.9 mg/kg of MoS2 NPs. This study demonstrates that it is the transformation that leads to the multifunctionality of MoS2, which can improve the biological nitrogen fixation (BNF) and growth. Therefore, MoS2 NPs enable a 30% increase in yield compared to the traditional molybdenum fertilizer (Na2MoO4). Excessive transformation of MoS2 nanosheets (NS) leads to the overaccumulation of Mo and sulfate in the plant, which damages the nodule function and yield. The study highlights the importance of understanding the transformation of nanomaterials for agricultural applications in future studies.

Bioluminescence-induced photocatalysis on semiconducting oxide nanosheets

ABSTRACT A novel semiconductor photocatalytic reaction system employing a photo-emitting enzyme as an internal light source is pro-posed in the present study. The system completely overturns common sense that conventional photocatalytic reactions must require irradiation from an external light source. A horseradish peroxidase (HRP) catalyzing oxidative bioluminescence reaction of luminol in the presence of H2O2 and manganate nanosheets (MNSs) with a narrow bandgap were utilized for an internal light source and semiconductor photocatalysts, respectively, and both of them coexisted in a same reactant solution. In other words, nano-sized light sources were highly dispersed in the solution, resulting in photo-excitation of MNSs over the entire solution. Photo-activated MNSs simultaneously caused oxidation and reduction, where platinum hexachloride anions (PtCl6 2-) were utilized as a model substance to be reacted photocatalytically. According to X-ray absorption near edge spectroscopy (XANES) of MNSs after the photocatalytic reaction, the anions were mainly transformed into solid phases of PtO2 and/or Pt(OH)4 by reacting with holes in MNSs. In contrast, a control experiment without HRP, i.e. a dark experiment, did not leave any evidence for photocatalytic reaction of PtCl6 2-. The detailed mechanism and the advantages/disadvantages of the proposed unique system are explained.

Inorganic-organic hybrid Cu-dipyridyl semiconducting polymers based on the redox-active cluster [SFe3(CO)9]2-: filling the gap in iron carbonyl chalcogenide polymers.

The construction of sulfur-incorporated cluster-based coordination polymers was limited and underexplored due to the lack of efficient synthetic routes. Herein, we report facile mechanochemical ways toward a new series of SFe3(CO)9-based dipyridyl-Cu polymers by three-component reactions of [Et4N]2[SFe3(CO)9] ([Et4N]2[1]) and [Cu(MeCN)4][BF4] with conjugated or conjugation-interrupted dipyridyl ligands, 1,2-bis(4-pyridyl)ethylene (bpee), 1,2-bis(4-pyridyl)ethane (bpea), 4,4'-dipyridyl (dpy), or 1,3-bis(4-pyridyl)propane (bpp), respectively. X-ray analysis showed that bpee-containing 2D polymers demonstrated unique SFe3(CO)9 cluster-armed and cluster-one-armed coordination modes via the hypervalent μ5-S atom. These S-Fe-Cu polymers could undergo flexible structural transformations with the change of cluster bonding modes by grinding with stoichiometric amounts of dipyridyls or 1/[Cu(MeCN)4]+. They exhibited semiconducting behaviors with low energy gaps of 1.55-1.79 eV and good electrical conductivities of 3.26 × 10-8-1.48 × 10-6 S cm-1, tuned by the SFe3(CO)9 cluster bonding modes accompanied by secondary interactions in the solid state. The electron transport efficiency of these polymers was further elucidated by solid-state packing, X-ray photoelectron spectroscopy (XPS), X-ray absorption near-edge spectroscopy (XANES), density of states (DOS), and crystal orbital Hamilton population (COHP) analysis. Finally, the solid-state electrochemistry of these polymers demonstrated redox-active behaviors with cathodically-shifted patterns compared to that of [Et4N]2[1], showing that their efficient electron communication was effectively enhanced by introducing 1 and dipyridyls as hybrid ligands into Cu+-containing networks.