Synchrotron-based X-ray Absorption Near-edge Structure Research Articles

Construction of an Axial Charge Transfer Channel Between Single-Atom Fe Sites and Nitrogen-Doped Carbon Supports for Boosting Oxygen Reduction.

The introduction of axial-coordinated heteroatoms in Fe─N─C single-atom catalysts enables the significant enhancement of their oxygen reduction reaction (ORR) performance. However, the interaction relationship between the axial-coordinated heteroatoms and their carbon supports is still unclear. In this work, a gas phase surface treatment method is proposed to prepare a series of X─Fe─N─C (X = O, P, and S) single-atom catalysts with axial X-coordination on graphitic-N-rich carbon supports. Synchrotron-based X-ray absorption near-edge structure spectra and X-ray photoelectron spectroscopy indicate the formation of an axial charge transfer channel between the graphitic-N-rich carbon supports and single-atom Fe sites by axial O atoms in O─Fe─N─C. As a result, the O─Fe─N─C exhibits excellent ORR performance with a half-wave potential of 0.905V versus RHE and a high specific capacity of 884 mAh g-1 for zinc-air battery, which is superior to other X─Fe─N─C catalysts without axial charge transfer and the commercial Pt/C catalyst. This work not only demonstrates a general synthesis strategy for the preparation of single-atom catalysts with axial-coordinated heteroatoms, but also presents insights into the interaction between single-atom active sites and doped carbon supports.

Effect of Li6.4La3Zr1.4Ta0.6O12 Fillers on the Interfacial Properties between Composite PEO-LiTFSI Electrolytes with Li Metal during Cycling.

PEO-LiX solid polymer electrolyte (SPE) with the addition of Li6.4La3Zr1.4Ta0.6O12 (LLZTO) fillers is considered as a promising solid-state electrolyte for solid-state Li-ion batteries. However, the developments of the SPE have caused additional challenges, such as poor contact interface and SPE/Li interface stability during cycling, which always lead to potentially catastrophic battery failure. The main problem is that the real impact of LLZTO fillers on the interfacial properties between SPE and Li metal is still unclear. Herein, we combined the electrochemical measurement and in situ synchrotron-based X-ray absorption near-edge structure (XANES) imaging technology to study the role of LLZTO fillers in directing SPE/Li interface electrochemical performance. In situ XRF-XANES mapping during cycling showed that addition of an appropriate amount of LLZTO fillers (50 wt %) can improve the interfacial contact and stability between SPE and Li metal without reacting with the PEO and Li salts. Additionally, it also demonstrated the beneficial effect of LLZTO particles for suppressing the interface reactions between the Li metal and PEO-LiTFSI SPE and further inhibiting Li-metal dendrite growth. The Li|LiFePO4 batteries deliver long cycling for over 700 cycles with a low-capacity fade rate of 0.08% per cycle at a rate of 0.3C, revealing tremendous potential in promoting the large-scale application of future solid-state Li-ion batteries.

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.

Vanadium Speciation in Ancient Shales Revealed through Synchrotron-Based X-ray Spectroscopy

Redox-sensitive trace elements, such as vanadium, are frequently used as paleoredox proxies to infer the redox status of ancient marine depositional environments. When applied to vanadium, this approach relies on an accurate understanding of vanadium geochemistry in marine sediments. This, in turn, requires the application of analytical techniques capable of providing reliable chemical information on vanadium host phases of vanadium and thus the ability to distinguish authigenic from detrital phases. The increasing availability of synchrotron-based X-ray spectroscopic techniques capable of providing chemical speciation information at both the bulk and micro-scale presents an opportunity to refine our understanding of vanadium geochemistry in ancient marine sediments. Here, we show the utility of synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy and scanning X-ray fluorescence microscopy (SXFM) for investigating vanadium host phases in ancient marine sediments. The studied samples from the 1400 Ma Xiamaling Formation came from strongly contrasting depositional settings (ranging from oxic to euxinic) with a wide range of vanadium enrichments (enrichment factors from 0.7 to 9.6), yet vanadium speciation determined by XANES was consistently found to be phyllosilicate-hosted vanadium (III). High-resolution elemental imaging by SXFM coupled with global statistical colocalization analyses revealed strong associations between vanadium and potassium, consistent with vanadium hosted by potassium-rich clay minerals. These findings, while demonstrating the power of synchrotron-based X-ray methods, imply that differentiating authigenic and detrital vanadium in ancient marine sediments is unlikely to be possible given that post-depositional processes result in similar chemical speciation for both fractions. This will also limit the reliability of vanadium isotope system studies that depend on differentiating authigenic and detrital fractions using selective extraction procedures.

Aerosol iron speciation and seasonal variation of iron oxidation state over the western Antarctic Peninsula

The iron (Fe) speciation and oxidation state have been considered critical factors affecting Fe solubility in the atmosphere and bioavailability in the surface ocean. In this study, elemental composition and Fe speciation in aerosol samples collected at the Palmer Station in the West Antarctic Peninsula were determined using synchrotron-based X-ray fluorescence (XRF) and X-ray Absorption Near-Edge Structure (XANES) spectroscopy. The elemental composition of coarse-mode (>1 μm) Fe-containing particles suggests that the region's crustal emission is the primary source of aerosol Fe. The Fe minerals in these aerosol particles were predominantly hematite and biotite, but minor fractions of pyrite and ilmenite were observed as well. The Fe oxidation state showed an evident seasonal variation. The Fe(II) content accounted for 71% of the total Fe in the austral summer, while this fraction dropped to 60% in the austral winter. Multivariate linear models involving meteorological parameters suggested that the wind speed, relative humidity, and solar irradiance were the factors that significantly controlled the percentage of Fe(II) in the austral summer. On the contrary, no relationship was found between these factors and the Fe(II) percentage in the austral winter, suggesting that atmospheric photoreduction and regional dust emission were limited. Moreover, the snow depth was significantly (p < 0.05) correlated with the aerosol Fe concentration, confirming the limiting effect of snow/ice cover on the regional dust emission. Given that the Antarctic Peninsula has experienced rapid warming during recent decades, the ice-free areas in the Antarctic Peninsula may act as potential dust sources.

Controlled high-density interface engineering of Fe3O4-FeS nanoarray for efficient hydrogen evolution

The rational design of double active sites system is vital for constructing high-efficiency iron sulfides electrocatalysts towards hydrogen evolution reaction (HER) in alkaline media. However, it remains a challenge to controllably create the high-density interface of double sites for optimal synergistic effect. Herein, we reported a simple chemical oxidation-induced surface reconfiguration strategy to obtain the interface-rich Fe3O4-FeS nanoarray supported on iron foam (Fe3O4-FeS/IF) using FeS nanosheets as precursors. The abundant Fe3O4-FeS interfaces could improve the dispersion of active sites and facilitate the electron transfer, leading to enhanced hydrogen evolution efficiency. And meanwhile, by altering the oxidation temperature, the content of S and O could be effectively controlled, further achieving the ratio optimization of Fe3O4 to FeS. Synchrotron-based X-ray absorption near-edge structure, X-ray photoelectron spectroscopy and ultraviolet photoemission spectroscopy consistently confirm the changes of electronic structure and d-band center of Fe3O4-FeS after chemical oxidation. Consequently, Fe3O4-FeS/IF exhibits excellent alkaline HER activity with a low overpotential of 120.8 mV to reach 20 mA cm−2, and remains stable ranging from 10, 20 to 50 mA cm−2 for each 20 h, respectively. Therefore, the facile and controllable chemical oxidation may be an effective strategy for designing high-density interfaces of transition metal-based sulfides towards alkaline HER.

Key Cr species controlling Cr stability in contaminated soils before and chemical stabilization at a remediation engineering site

Linking chromium (Cr) speciation with its stability in soils is vital because insoluble Cr(VI) and chemically adsorbed Cr(VI) could hinder the remediation efficiency and release Cr(VI) for a prolonged period of time. In this study, we investigated key Cr species to probe the mechanisms controlling the release of insoluble Cr(VI) at Cr-contaminated sites using synchrotron-based X-ray absorption near-edge structure (XANES) for the first time. Chromite, stichtite and Cr-silicate were predominant forms of Cr(III). Insoluble Cr(VI) was hosted by layered double hydroxides (LDHs) such as brownmilerite and hydrotalcite. Anion competition tests documented a substitution of absorbed Cr(VI) by SO42- and NO3-. Acid extraction released 6.7–25.7% more Cr(VI) than anion extraction, possibly attributing to the erosion of LDH and CaCrO4 in calcite rather than Cr-bearing minerals. Brown and red soils released maximally 62% and 44% of total Cr(VI) by 10 mol/(kg soil) and 2 mol/(kg soil) of H+, respectively. SO42-, H2O and H+ contributed to more release of total Cr(VI) in brown soils (22%, 33% and 7%) than red soils (25%, 17% and 2%). More crystalline Cr structures were found after chemical stabilization, indicating a higher Cr stability in chemically stabilized soils. Cr and Mn exhibited an overlapped distribution pattern in both contaminated and chemically stabilized soils, hinting at the re-oxidation of Cr(III). Insoluble Cr(VI) could be released by acidic rainfalls and soil organic matters, posing potential threats to Cr long-term stability in field-scale remediation.

Sulfur speciation in a tropical soil amended with lime and phosphogypsum under long-term no-tillage system

Sulfur (S) is present mainly in organic forms in the most superficial layers of well-drained soils, despite sulfate (SO42−) being the main S-species absorbed by plants. Coupled broadcast application of lime and phosphogypsum (PG) is widely deployed as an agricultural practice to improve soil chemical properties and increase crop yields in highly weathered tropical soil areas under no-tillage system (NTS). However, the effects of large-scale application of these soil amendments to S-species distribution in soil in NTS are largely unknown. We combined S wet-chemical analysis with Synchrotron-based X-ray Absorption Near-Edge Structure Spectroscopy (XANES) to evaluate the effects of lime and PG application to S-species distribution along the soil profile (up to 150 cm). Soil samples were collected from a field-scale experiment under NTS for over 15 years. Soil was amended with lime and PG, either individually or in combination, four times during the experiment. Soil sampling was conducted 16 months after the last amendments’ application, and treatments (lime, PG and lime + PG) were compared to a control (under NTS without amendments’ application) and with soil samples from a native forest (reference for an undisturbed site). Broadcast PG application increased the contents of Ca-phosphate extractable S and pseudo-total S (microwave assisted acid digestion) contents in the deeper layers. Two peaks representing reduced and oxidized S species were detected in S K-edge XANES spectra of all treatments and NF soil. The oxidized S peak gets sharper with increase in depth, as reduced S peak intensity decreases, and fingerprint analysis suggested a greater contribution of reduced organic S species in the most superficial soil layer followed by an increase in highly oxidized S species as depth increased. Linear combination fitting analysis confirmed a greater contribution of highly oxidized S species to the total S-species as depth increased, especially in soil samples that received PG application.

Efficient electrocatalytic water splitting by bimetallic cobalt iron boride nanoparticles with controlled electronic structure

Developing an efficient bifunctional catalyst for Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) in water splitting technology is very attractive for clean energy. Here, a new Co-Fe-B ternary catalyst with improved crystallinity is successfully synthesized by combining the chemical reduction and subsequent solid-state reaction method. Synchrotron-based X-ray absorption near-edge structure (XANES) and X-ray photoelectron spectroscopy (XPS) indicate the electronic structure redistribution is favor for the improved performance. The overpotential is only 129 mV and 280 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline condition, the corresponding Tafel slope is 67.3 mV dec−1 and 38.9 mV dec−1. Density functional theory calculations distinguish that the ternary crystalline Co-Fe-B catalysts are thermodynamically favorable for HER and OER. The actual active species of the ternary catalyst in OER is the CoOOH and FeOOH as indicated in ex situ Raman spectra. The present work may introduce promising crystallinity borides material for the anode and cathode of water splitting device.

Relative proportions of organic carbon functional groups in biochars as influenced by spectral data collection and processing

Solid-state 13C Nuclear Magnetic Resonance (NMR) and synchrotron-based X-ray Absorption Near-Edge Structure (XANES) have applications for determining the relative proportions of organic C functional groups in materials. Spectral data obtained by NMR is typically processed using integration (INTEG) whereas XANES spectral data is typically processed using deconvolution (DECONV). The objective of this study was to examine the impact of spectral data collection and processing on the estimated relative proportions of organic C functional groups in biochars. Biochars showed large variations in aromatic C (45–97%), alkyl C (0–23%), O-alkyl C (1–41%), phenolic C (0–20%) and carboxylic C (0–20%). NMR had a better ability than XANES to differentiate % aromatic C across biochars, and the mean % aromatic C was always greater for NMR-INTEG and NMR-DECONV than for XANES-INTEG or XANES-DECONV. NMR-INTEG showed significant associations with NMR-DECONV and XANES-INTEG for % aromatic C and alkyl C, but there were no significant associations between NMR and XANES for % O-alkyl C, phenolic C and carboxylic C. As well, there was no association between NMR-INTEG and XANES-DECONV for any organic C functional group, and in some cases, spectral data collection and processing influenced the quantification of organic C functional groups in a given biochar to the extent that the differences observed were as large as differences observed between biochars when analyzed using the same spectral data collection and processing technique. We conclude that great caution must be taken when comparing studies that determined organic C functional groups in materials using NMR-INTEG versus XANES-DECONV.

Differential transformation mechanisms of exotic Cr(VI) in agricultural soils with contrasting physio-chemical and biological properties

The transformation mechanisms of Cr(VI) in agricultural soils at the molecular level remain largely unknown due to the multitude of abiotic and biotic factors. In this study, the different speciation and distribution of Cr in two types of agricultural soil (Ultisol and Fluvo-aquic soils) after two weeks of aging was investigated using synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy, microfocused X-ray fluorescence (μ-XRF) and X-ray transmission microscopy (STXM). The microbial community structure of the two soils was also analyzed via high-throughput sequencing of 16S rRNA. Cr(VI) availability was relatively lower in the Ultisol than in the Fluvo-aquic soil after aging. Cr K-edge bulk XANES and STXM analysis indicated that Cr(VI) was reduced to Cr(III) in both soils. μ-XRF analysis and STXM analysis indicated the predominant association of Cr with Mn/Fe oxides and/or organo-Fe oxides in both soils. Additionally, STXM-coupled imaging and multiedge XANES analyses demonstrated that carboxylic groups were involved in the reduction of Cr(VI) and subsequent retention of Cr(III). 16S rRNA analysis showed considerably different bacterial communities across the two soils. Redundancy analysis (RDA) suggested that soil properties, including the total carbon content, Fe oxide component and pH, were closely linked to Cr(VI)-reducing functional bacteria in the Ultisol, including chromium-reducing bacteria (CRB) (e.g., Bacillus sp.) and dissimilatory iron-reducing (DIRB) (e.g., Shewanella sp.) bacteria, which possibly promoted Cr(VI) reduction. These findings shed light on the molecular-level transformation mechanisms of Cr(VI) in agricultural soils, which facilitates the effective management of Cr-enriched farmland.

Long-term changes in land use influence phosphorus concentrations, speciation, and cycling within subtropical soils

While land conversion from native vegetation to agriculture influences the concentration, speciation, and cycling of soil phosphorus (P), the nature of these changes remain poorly understood. We collected surface soils (0–10 cm) from paired sites at three locations, comparing soil from native vegetation with adjacent soils converted for cropping, pasture, and plantation for up to 115 y. The extent of organic P loss upon land use change differed between the three soils, with conversion to cropping causing the largest decreased in soil organic P as well as phosphatase activity. Using solution 31P nuclear magnetic resonance (NMR), it was found that cropping caused a pronounced decrease in organic P – both orthophosphate monoesters and orthophosphate diesters. Furthermore, cropping soils had a substantial reduction in the diester-P/monoester-P ratio, indicating the preferential degradation of the more labile orthophosphate diester-P upon conversion to cropping. Importantly, by subsequently converting cropping land to pasture or plantation, these adverse P-related changes could be reversed or at least halted. Synchrotron-based X-ray absorption near-edge structure (XANES) demonstrated that land use change had no pronounced impact on inorganic P, with sorbed P dominating in all treatments. Changes in land use also influenced bacterial diversity, with land use change effects being specific to the three soils. This study provides information on how land use changes alters P behaviour and cycling in soils, with this being important for ensuring the sustainable use of soils for food production.

N-Induced Electron Transfer Effect on Low-Temperature Activation of Nitrogen for Ammonia Synthesis over Co-Based Catalysts

The industrial synthesis of ammonia (NH₃) using Fe-based derived catalysts requires harsh reaction conditions (400–600 °C, 20–40 MPa). It is desirable to develop catalysts that perform well at low temperature and pressure (<400 °C, <2 MPa). The main challenge of low-temperature NH₃ synthesis is the dissociation of the extremely stable N≡N triple bond (945 kJ/mol). Herein, the N-doped C-supported Co catalyst was demonstrated to be active and efficient for NH₃ synthesis under mild conditions, resulting from the hybridization of the d orbitals of Co with p orbitals of nitrogen for Co–N coordination. The doping of N has three relevant effects. The first is the size decrease in Co nanoparticles. It is proven by in situ X-ray photoelectron spectroscopy and synchrotron-based X-ray absorption near-edge structure and extended X-ray absorption fine structure analyses coupled with density functional theory calculation that there is strong electron transfer from the doped N to Co. Hence, the second effect of N doping is the increase in electronic state of Co d orbitals which promotes the donation of 3d electrons from Co to the π* orbital of N₂, leading to a decrease in activation energy for the N₂ molecule. The third is the involvement of nitrogen vacancies. The pyridine N weakly coordinated with highly dispersed Co reacts with adsorbed H₂ to form NH₃, simultaneously generating N vacancies; then, the consumed N species can be replenished via N₂ adsorption on vacancy sites. These factors contribute to the superiority of the N-doped carbon-supported Co-based catalyst, which achieves an NH₃ production rate of 1.59 mmolNH₃·gcₐₜ–¹·h–¹ at even 250 °C and 1 MPa.

The fate of calcium in temperate forest soils: a Ca K-edge XANES study

Calcium (Ca) plays a crucial role for plant nutrition, soil aggregation, and soil organic matter (SOM) stabilization. Turnover and ecological functions of Ca in soils depend on soil Ca speciation. For the first time, we used synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the Ca K-edge (4038 eV) to investigate Ca speciation in soils. We present Ca K-edge XANES spectra of standard compounds with relevance in soils (e.g. calcite, dolomite, hydroxyapatite, anorthite, clay mineral-adsorbed Ca; Ca oxalate, formate, acetate, citrate, pectate, phytate). Calcium XANES spectra with good signal-to-noise ratios were acquired in fluorescence mode for Ca concentrations between 1 and 10 mg g−1. Most standard spectra differed markedly among each other, allowing the identification of different Ca species in soils and other environmental samples as well as Ca speciation by linear combination fitting. Calcium XANES spectra obtained for samples from different horizons of twelve temperate forest soils revealed a change from dominating lithogenic Ca to clay mineral-bound and/or organically bound Ca with advancing pedogenesis. O layer Ca was almost exclusively organically bound. With increasing SOM decomposition, shares of oxalate-bound Ca decreased. Oxalate-bound Ca was absent in calcareous, but not in silicate subsoil horizons, which can be explained by microbial decomposition in the former vs. stabilization by association to pedogenic minerals in the latter soils. Synchrotron-based Ca XANES spectroscopy is a promising novel tool to investigate the fate of Ca during pedogenesis and—when performed with high spatial resolution (µ-XANES), to study aggregation and SOM stabilization mechanisms produced by Ca.

Molecular Mechanisms of Chromium(III) Immobilization by Organo-Ferrihydrite Co-precipitates: The Significant Roles of Ferrihydrite and Carboxyl.

The interaction mechanisms of heavy metals with organo-Fe hydroxides co-precipitates (OFC) remain unclear due to the structural complexity of the OFC. In this study, batch experiments were conducted to investigate the immobilization mechanisms of Cr(III) by the OFC, which was prepared by co-precipitating Fe3+ with rice/rape straw-derived dissolved organic carbon, through sorption and co-precipitation using synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy and scanning transmission X-ray microscopy (STXM). At an Fe/C molar ratio ≥ 0.3, both the sorption and co-precipitation immobilized the majority of Cr(III), but the co-precipitation desorbed less Cr(III) than the sorption regardless of DOC loadings and sources. In contrast, Cr(III) immobilization was significantly reduced at an Fe/C molar ratio of 0.1 for both reactions. Linear combination fitting of Cr K-edge XANES spectra revealed the predominance of ferrihydrite-bound Cr(III), but enhanced organic Cr(III) occurred with increased organic carbon (OC) loading for both the sorption and co-precipitation. STXM coupled with multi-edge XANES analysis confirmed the primary association of Cr(III) with ferrihydrite and directly probed carboxyl as the binding site for Cr(III) retention on the OC constituents of the OFC. These results provided new molecular-level insights into the Cr(III) retention mechanisms on the OFC, particularly for the interactions of Cr(III) and OC constituents of the OFC, which could benefit the management of Cr-contaminated soils with straw returning.

A Novel Approach for the Quantification of Different Inorganic and Organic Phosphorus Compounds in Environmental Samples by P L2,3-Edge X-ray Absorption Near-Edge Structure (XANES) Spectroscopy.

Phosphorus (P) is an essential element for life on Earth, with an important and oftentimes unaccounted organic biogeochemical component. Current methods for the quantification of different organic P compounds in environmental samples (e.g., soils, sediments) are based on extraction techniques and often associated with incomplete P recovery or sample changes. In this study, we present a protocol for the quantification of different organic and inorganic P species in soils using synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy at the P L2,3-edge. Its accuracy and precision was evaluated by analyzing 40 standard mixtures composed of seven different inorganic and organic P compounds (with a mean of R2 = 0.85). In addition, we quantified the P species of two soils and two agro-industrial byproducts using P L2,3-edge XANES spectroscopy and the results were compared with those obtained by P K-edge XANES or 31P NMR spectroscopy. Using the P L2,3-edge, we identified different organic Pspecies, including those not identified by the common P K-edge XANES. However, there is a consistent underestimation of organic polyphosphates. Overall, the application of P L2,3-edge XANES provides a higher level of information than by P K-edge XANES, although the ubiquitous use of this novel methodology is still limited to samples with a phosphorus content above 3 mg g-1.

Transformation of Calcium Phosphates in Alkaline Vertisols by Acidified Incubation

Acid-soluble soil phosphorus (P) is a potential resource in P-limited agricultural systems that may become critical as global P sources decrease in the future. The fate of P in three alkaline Vertisols, a major agricultural soil type, after acidic incubation was investigated using synchrotron-based K-edge X-ray absorption near-edge structure (XANES) spectroscopy, geochemical modeling, wet chemistry soil extraction, and a P sorption index. Increases in labile P generally coincided with decreased stability and dissolution of calcium phosphate (CaP) minerals. However, only a minor proportion of the CaP dissolved in each soil was labile. In two moderate-P soils (800 mg P kg-1), XANES indicated that approximately 160 mg kg-1 was repartitioned to sorbed phases at pH 5.1 of one soil and at pH 4.4 of the second; however, only 40 and 28% were labile, respectively. In a high-P soil (8900 mg P kg-1), XANES indicated a decrease in P of 1170 mg kg-1 from CaP minerals at pH 3.8, of which approximately only 33% was labile. Phosphorus mobilized by agricultural practices without concurrent uptake by plants may be repartitioned to sorbed forms that are not as plant-available as prior to acidification.

Highly efficient and stable p-type ZnO nanowires with piezotronic effect for photoelectrochemical water splitting

Unremitting efforts have been made to develop high-performance photoelectrochemical (PEC) water-splitting system to produce clean hydrogen fuel using sunlight. In this work, a novel way, combining highly-ordered nanowires (NWs) structure and piezotronic effect of p-type ZnO has been demonstrated to dramatically enhance PEC hydrogen evolution performance. Systematic characterizations indicate that the Sb atoms uniformly dope into ZnO NWs and substitute Zn sites with the introduction of two zinc vacancies to form the shallow acceptor SbZn–2VZn complex. Detailed synchrotron-based X-ray absorption near-edge structure (XANES) experiments in O K-edge and Zn L-edge further confirm the formation of the complex, and theoretical calculation verifies the Sb5+ state dominating the complex. The optimal photocurrent density of the 0.2Sb/ZnO-anneal NWs can reach −0.85 mA/cm2 (0 VRHE) which is 17.2 times larger than that of the n-ZnO NWs under sunlight illumination (100 mW/cm2). Furthermore, the piezotronic effect can be introduced to regulate the charge separation and transfer in the ZnO NWs through modulating the band structure near the interface. The photocurrent density can further increase to −1.08 mA/cm2 (0 VRHE) under a 0.6% tensile strain, which is 27.4% enhancement with respect to the ZnO sample without strain. These results provide an efficient way to design and develop high-performance photoelectrodes toward PEC hydrogen evolution.

Strategic differences in phosphorus stabilization by alum and dolomite amendments in calcareous and red soils.

Surplus phosphorus (P) above agronomic requirements can negatively affect the water status of connected surface and subsurface water bodies. The in situ stabilization of soil P through soil amendment has been recognized as an efficient way to reduce this environmental pressure. However, the mechanism of how P is stabilized during this process and how plant available P is affected are unknown. This can be achieved by sequential chemical extraction and synchrotron-based X-ray absorption near-edge structure (XANES) spectroscopy investigations. Therefore, in the present study, P-enriched calcareous and red soils were amended with alum, dolomite, and a 1:1 mixture of alum and dolomite (MAD) at a 20g/kg soil rate, and soil properties and P fractions were measured after a 45-day period. Results showed that alum amendment significantly decreased CaCl2-P and Olsen-P contents in calcareous and red soils when compared with dolomite. However, dolomite incorporation maintained relatively high P availability and even increased CaCl2-P and Olsen-P contents by 1.32% and 40.5% in red soil, respectively, compared to control. Amendment with MAD was not as effectively as the alum in P stabilization. Sequential inorganic P extraction indicated that alum dominantly contributed labile P transformed to Al-P in both soils. P K-edge XANES spectroscopy measurements further explained that alum adsorbed phosphate in calcareous soil and precipitated phosphate as AlPO4 in red soil. Results of P fractionation and Mehlich-3-extracted Ca showed that dolomite mainly adsorbed loosely bound P in calcareous soil and red soil. However, dolomite incorporation in red soil led to Al-P and Fe-P release. The P sorption isotherms showed that dolomite and alum increased soil P sorption maxima and decreased the degree of P saturation (DPS) in both soils, while dolomite declined the Langmuir bonding energy in red soil. Differences in P stabilization by alum and dolomite addition across soil types were closely related to their characteristics, and soil properties changed, especially soil pH.

Electronic structure and d-band center control engineering over M-doped CoP (M = Ni, Mn, Fe) hollow polyhedron frames for boosting hydrogen production

The practical application of hydrogen evolution reaction (HER) through water splitting depends on the development of low cost and efficient non-noble-metal catalysts. As a potential electrocatalyst, the improvement of HER performance catalyzed by nanostructured transition metal phosphides still remains a great challenge. Tuning the novel nanostructure, morphology, and electronic state from nanoscale is of great important to achieve highly efficient HER electrocatalysts. Herein, we first developed an electronic structure and d-band center control engineering for accelerating the HER process in both acid and alkaline media over M-doped CoP (M = Ni, Mn, Fe) hollow polyhedron frames (HPFs), which were synthesized by a self-templating transformation (STT) strategy. Impressively, the HER electrocatalytic activity can be maximumly promoted and maintained at least 21 h for Ni-CoP/HPFs catalyst. Synchrotron-based X-ray absorption near-edge structure, X-ray photoelectron spectroscopy, auger electron spectroscopy, ultraviolet photoemission spectroscopy and density functional theory calculations consistently reveal the improved performance is attributed to the changes of the electronic structure and the downshift of d-band center after metal doping. The Ni-CoP/HPFs catalyst also indicates excellent activity with a cell voltage of 1.43 V to achieve the current density of 10 mA cm−2 and superior stability when it was employed as a cathode for HER and an anode for urea oxidation in 1 M KOH with 0.5 M urea. The success modulation of HER performance in current STT strategy will provide a promising pathway for designing various transition metal-doped compounds for energy-related catalysis processes.