Synchrotron Radiation X-ray Absorption Research Articles

Metal-organic framework-derived carbon-supported high-entropy alloy nanoparticles applied in ammonia borane hydrolytic dehydrogenation

While high-entropy alloy nanoparticle (HEA NP) catalysts from a sacrificial high-entropy-MOF (HE-MOF) have been attractive, their conventional characterizations may be misleading. Here, we report HEA NPs on HE-MOF-derived carbon (HE-MDC) via direct pyrolysis of MnFeCoNiCu HE-MOF in Ar and H2 at different temperatures and durations with a fast-ramping rate. With the profound investigations of the metal NPs on HE-MDCs by synchrotron radiation X-ray diffraction and absorption, we revealed that the Ar-treated HE-MDCs had either Cu-dominant solid solution or phase-segregated metal NPs, whereas H2 pyrolysis yielded well-dispersed HEA NPs on HE-MDCs. For ammonia borane hydrolysis, although the metal NP size in H2-treated HE-MDC was not the smallest, it showed the fastest dehydrogenation rate (TOF=5.76 molH₂∙min−1∙molcat-1), 2 ∼ 4 times faster than the Ar-treated HE-MDCs. It emphasized the crucial role of elemental uniformity in the HEA NPs over the catalyst size traditionally reported.

Gram-scale synthesis of Ni-Zn diatomic sites catalyst for efficient electrochemical CO2 reduction

Diatomic catalysts inherit the advantages of single atom catalysts and use the adjacent metal-N sites for functional complementary and synergistic effects in electrochemical CO2 reduction (ECR). However, preparation of diatomic catalysts with high yield, Faradaic efficiency and stability together with low overpotential still remains challenging. In this work, we develop a nitrogen-doped carbon supported Ni-Zn diatomic catalyst, whose CO Faradaic efficiency of is higher than 92.0 % in the wide potential range of −0.57 ∼ −1.07 V vs RHE, and the maximum CO Faradaic efficiency is 97.5 % at −0.77 V vs RHE. And also, CN-NiZn performs an extraordinary stability for 30 h in the long-time durability test. More importantly, large-quantities (around 1.66 g) of Ni-Zn diatomic catalysts with remarkable catalytic performance can be prepared by this method. Synchrotron radiation X-ray absorption spectroscopy was tested to reflect the coordination environment and valence states around Ni and Zn atoms. Theoretical calculations further reveal that the synergistic effect between Ni and Zn binary metal sites largely reduces the energy barrier of the reaction to produce the intermediate *COOH, thus effectively increasing the selectivity of ECR. This work indicates that the introduction of another coordination metal can significantly affect the electronic structure of monatomic catalysts, thus improving the electrocatalytic activity and selectivity of ECR.

Insights into the Phase Purity and Storage Mechanism of Nonstoichiometric Na3.4 Fe2.4 (PO4 )1.4 P2 O7 Cathode for High-Mass-Loading and High-Power-Density Sodium-Ion Batteries.

Mixed-anion-group Fe-based phosphate materials, such as Na4 Fe3 (PO4 )2 P2 O7 , have emerged as promising cathode materials for sodium-ion batteries (SIBs). However, the synthesis of pure-phase material has remained a challenge, and the phase evolution during sodium (de)intercalation is debating as well. Herein, a solid-solution strategy is proposed to partition Na4 Fe3 (PO4 )2 P2 O7 into 2NaFePO4 ⋅ Na2 FeP2 O7 from the angle of molecular composition. Via regulating the starting ratio of NaFePO4 and Na2 FeP2 O7 during the synthesis process, the nonstoichiometric pure-phase material could be successfully synthesized within a narrow NaFePO4 content between 1.6 and 1.2. Furthermore, the proposed synthesis strategy demonstrates strong applicability that helps to address the impurity issue of Na4 Co3 (PO4 )2 P2 O7 and nonstoichiometric Na3.4 Co2.4 (PO4 )1.4 P2 O7 are evidenced to be the pure phase. The model Na3.4 Fe2.4 (PO4 )1.4 P2 O7 cathode (the content of NaFePO4 equals 1.4) demonstrates exceptional sodium storage performances, including ultrahigh rate capability under 100 C and ultralong cycle life over 14000 cycles. Furthermore, combined measurements of ex situ nuclear magnetic resonance, in situ synchrotron radiation diffraction and X-ray absorption spectroscopy clearly reveal a two-phase transition during Na+ extraction/insertion, which provides a new insight into the ionic storage process for such kind of mixed-anion-group Fe-based phosphate materials and pave the way for the development of high-power sodium-ion batteries.

The migration and transformation mechanism of vanadium in a soil-pore water-maize system

The migration mechanism of vanadium (V) in the soil-pore water-maize system has not been revealed. This study conducted pot experiments under artificial control conditions to reveal V's distribution and transport mechanism under different growth stages and V content gradient stress. The V content in the soil pore water gradually increased by an order of magnitude. The V content of pore water in the no-plant group was higher than that in the plant group, indicating that the maize roots absorbed V. The V exists in the form of pentavalent oxygen anions, in which H2VO4− occupies the most significant proportion. With increasing V content, the root area, root number, root length, and tip number decreased significantly. The malondialdehyde content in maize leaves showed an increasing trend, indicating the degree of lipid peroxidation was gradually enhanced. The V content was in the order of root > leaf > stem > fruit and maturity stage > flowering stage > jointing stage, respectively. The transfer coefficient reached a maximum under natural conditions, and increased gradually with the growth. The results of synchrotron radiation X-ray absorption near edge structure (XANES) analysis showed that Fe in maize roots mainly comprised of Fe2O3 and Fe3O4. The Fe in the soil is primarily existed in lepidocrocite and Fe2O3. The μ-XRF analysis showed that V and Fe enriched in the roots with a positive relationship, indicating the synergistic absorption of V and Fe by roots. Part of the Fe2+ reduced V5+ to V4+ or V3+ in the forms of VO2+, V(OH)2+, or V(OH)3 (s), and fixed V at the root. Soil weak acid-soluble fraction V and soil total V were vital factors to maize extraction. This study provides new insights into V biogeochemical behavior and a scientific basis for correctly evaluating its ecological and human health risks.

X-Ray Absorption Spectroscopy Studies of Ti-Mn Redox Flow Battery to Clarify the Redox Reaction

Redox flow battery (RFB) is a promising candidate of large-scale stationary energy storage which is necessary to utilize renewable energy. For RFBs, the capability to easily increase the capacity by enlarging the electrolyte tank, high charge-discharge cycle performance, and wide flexibility to high- and low-frequency fluctuations are highly advantageous.Nowadays vanadium RFBs are used for practical use, but the material cost of vanadium is problematic to further spread them. An alternative candidate for commercial use is titanium-manganese (Ti-Mn) RFBs [1] whose material cost should be lower. On the other hand, the stability of the electrolyte for positive electrode (catholyte) need to be improved, because precipitates are created by a charge disproportionation reaction of Mn ions in the charged catholyte [2]. The formation of precipitates decreases the energy density and degrades the cyclability. To improve the characteristics, the chemical state and redox reaction of the electrolytes of Ti-Mn RFBs should be clarified by precise analyses.We performed synchrotron radiation X-ray absorption spectroscopy (XAS) for the electrolytes of a Ti-Mn RFB to directly observe the redox reaction [3]. In this study, the same Ti-Mn RFB electrolyte was used for both positive and negative electrodes. The Ti K-edge XAS of the electrolyte for negative electrode (anolyte) revealed gradual reduction reaction of Ti from Ti4+ on the charge process. The Ti L 2,3-edge XAS spectrum for the anolyte at state of charge (SOC) of 80% was mostly attributed to Ti3+ state. The results for Ti are consistent with electrochemical views in previous reports [2]. The Mn K-edge XAS of the catholyte gradually shifted to higher energy-side up to SOC of 50%, indicating a slight oxidation reaction of Mn from Mn2+. However, the Mn L 2,3-edge XAS spectrum for the catholyte solution at SOC of 80% was of Mn2+ state that was not changed from the initial state. Instead, scanning transmission X-ray microscopy (STXM; XAS mapping with a high spatial resolution) at the Mn L 3-edge unveiled that the precipitates mostly consist of Mn4+. Thus, the charge disproportionation reaction of 2Mn3+ -> Mn2+ (solution) + Mn4+ (precipitates) in the charged catholyte was confirmed. In the presentation, the electronic-structure change of the Ti and Mn ions in both catholyte and anolyte will be discussed in detail.

Engineering Phase Transition from 2H to 1T in MoSe2 by W Cluster Doping toward Lithium-Ion Battery.

Phase engineering synthesis strategy is extremely challenging to achieve stable metallic phase molybdenum diselenide for a better physicochemical property than the thermodynamically stable semiconducting phase. Herein, we introduce tungsten atom clusters into the MoSe2 layered structure, realizing the phase transition from the 2H semiconductor to 1T metallic phase at a high temperature. The combination of synchrotron radiation X-ray absorption spectroscopy, Cs-corrected transmission electron microscopy, and theoretical calculation demonstrates that the aggregation doping of W atoms is the factor of MoSe2 structure transformation. When utilizing this distinct structure as an anode component, it demonstrates outstanding rate capability and durability. After 500 cycles, this results in a specific capacity of 1007.4 mAh g-1 at 500 mA g-1. These discoveries could open the door for the future development of high-performance anodes for ion battery applications.

Construction of High-Density Binuclear Site Catalysts from Double Framework Interfaces at the Cooling Stage.

Low-nuclear site catalysts with dual atoms have the potential for applications in energy and catalysis chemistry. Understanding the formation mechanism of dual metal sites is crucial for optimizing local structures and designing desired binuclear sites catalysts. In this study, we demonstrate for the first time the formation process of dual atoms through the pyrolysis of the interface of a double framework using Zn atoms in metal-organic frameworks and Co atoms in covalent organic frameworks. We unambiguously revealed that the cooling stage is the key point to form the binuclear sites by employing the in situ synchrotron radiation X-ray absorption spectrum technique. The binuclear site catalysts show higher activity and selectivity than single dispersed atom catalysts for electrocatalytic oxygen reduction. This work guides us to synthesize and optimize the various binuclear sites for extensive catalytic applications.

Optical, surface, and structural studies of InN thin films grown on sapphire by molecular beam epitaxy

A series of indium nitride (InN) thin films have been grown on sapphire substrates by molecular beam epitaxy (MBE) technology under different growth conditions of temperature and plasma power. Their structural, surface, and optical properties are studied by a variety of techniques of scanning electron microscopy, Hall effect, x-ray diffraction, photoluminescence (PL), Raman scattering, x-ray photoelectron spectroscopy (XPS), synchrotron radiation x-ray absorption near edge structure (XANES), and so on. The lower carrier concentration in InN can be obtained with a higher MBE growth temperature and a lower plasma power. As the plasma power increases, the PL peak energy is observed to shift toward the higher energy side and the Raman E2 (high) and A1 (LO) modes are shifted to the lower frequency. The residual compressive strain in epitaxial InN is relaxed. The lower plasma power and the higher growth temperature are preferred for the MBE growth of high-quality InN films. The influencing factors on the InN PL peak and band gap Eg have been revealed. It is evidenced that the InN PL peak and Eg can be shifted from high down to ∼0.65 eV with the carrier concentration down to low E19 cm−3 and the plasma power down to ∼80 W. Both the XPS and N K-edge XANES revealed the antisite defect of N on the In site, NIn. The XANES In L-edge measurements on the In L3-edge of InN films with various carrier concentrations has indicated the fourfold InN intermediate crystal structures. These obtained results are significant and useful to deepen the understanding and promote further investigation in InN and III-N materials.

Toward Complete Transformation of Sodium Polysulfides by Regulating the Second-Shell Coordinating Environment of Atomically Dispersed Fe.

Room temperature sodium-sulfur (RT Na-S) batteries are highly competitive as potential energy storage devices. Nevertheless, their actually achieved reversible capacities are far below the theoretical value due to incomplete transformation of polysulfides. Herein, atomically dispersed Fe-N/S active center by regulating the second-shell coordinating environment of Fe single atom is proposed. The Fe-N4S2 coordination structure with enhanced local electronic concentration around the Fermi level is revealed via synchrotron radiation X-ray absorption spectroscopy (XAS) and theoretical calculations, which can not only significantly promote the transformation kinetics of polysulfides, but induce uniform Na deposition for dendrite-free Na anode. As a result, the obtained S cathode delivers a high initial reversible capacity of 1590 mAh g-1, nearly the theoretical value. This work opens up a new avenue to facilitate the complete transformation of polysulfides for RT Na-S batteries.

Ultra-fast surface reconstruction enabled by the built-in electric field in heterostructured CoS2/CuS for water electrolysis

Transition-metal chalcogenides (TMCs) show great potential as highly efficient and cost-effective electrocatalysts for oxygen evolution reaction (OER). Yet the electrochemical conversion into oxides/hydroxides remains poorly understood. In this work, we develop a built-in, electric-field-induced surface reconstruction strategy for ultra-fast self-activation of transition metal sites in self-supporting CoS 2 /CuS heterostructures. The activated CoS 2 /CuS grown on carbon cloth with oxygenated surface species displays an outstanding OER electrocatalytic activity with ultra-low overpotentials of only 136 mV at the current density of 10 mA cm −2 and 266 mV at 100 mA cm −2 in 1.0 M KOH. Comparative studies via synchrotron radiation X-ray absorption spectroscopy and theoretical calculations are employed to elucidate that the built-in electric field within heterointerfaces significantly promotes the reconstruction efficiency by decreasing the formation energy of (oxy)hydroxide species. We believe this work provides new perspectives to conceive catalysts with ultra-low overpotentials and complements the fundamental comprehension of TMCs’ self-reconstruction mechanism. • The nature of metallic site reconstruction upon OER is revealed via combined XAS and DFT • A simplified reconstruction process enabled by the built-in electric field of CoS 2 /CuS • The self-standing electrode shows practical potential for overall water electrolysis A comprehensive perception of the structural transformation and reconstruction of metallic surface sites upon the OER process is essential for the rational design of high-performance OER catalysts. To simplify the energy-consuming activation process and achieve rapid reconstruction, Man et al. report a built-in electric field strategy for modulating surface dynamics of heterostructured CoS 2 /CuS.

Bifunctional OER/NRR Catalysts Based on a Thin-Layered Co3O4-x/GO Sandwich Structure.

Due to ample low-coordinated surface atoms, a distorted lattice endows thin-layered transition metal oxides with a flexible electronic structure, making them the ideal candidates for overall ammonia synthesis. This work proposes a novel and facile method for the controllable synthesis of thin-layered Co3O4 catalysts with graphene as a conductive matrix to further enhance the overall N2 fixation performance. X-ray photoelectron spectroscopy (XPS) and synchrotron radiation X-ray absorption spectroscopy (XAS) demonstrate that the sandwiched Co3O4-x/GO catalysts enable exposure of more coordination unsaturated active sites, resulting in numerous oxygen vacancies. With a higher conductivity and distorted crystalline structure, excellent electrochemical NRR activity is realized with a NH3 production rate of 5.19 mmol g-1 h-1 and a Faradaic efficiency of 10.68% at -0.4 V vs reversible hydrogen electrode (RHE). The density functional theory (DFT) calculation demonstrates that introducing oxygen vacancies in thin-layered cobalt oxides could result in an increased density of states (DOS) near the Fermi level, which would accelerate the NRR rate-determining step. Charge transfer could be accelerated through a weak Co 3d-N 2p σ hybrid bond with a lower energy level. No obvious performance decay could be found after six cycles. Furthermore, the sandwiched Co3O4-x/GO catalyst exhibits a low overpotential of 280 mV@10 mA cm-2 and an outstanding durability for the anode OER, even better than those of the benchmark RuO2. Such an inexpensive sandwiched transition metal oxide catalyst shows great potential in the field of overall N2 fixation.

Tuning the electronic structure of bimetallic CoCu clusters for efficient hydrolysis of ammonia borane

Efficient and low cost catalysts for the hydrogen production from ammonia borane (AB) are highly required to build up the upcoming hydrogen economy. Here we demonstrated that the non-active material could be directly transformed to highly active catalyst for the hydrolysis of AB when the surface parts were stripped to form tiny clusters on graphene oxide (GO), with the presence of strong cluster-support interaction. Moreover, the catalytic activity can be greatly enhanced by further tuning the electronic structure of clusters with various compositions. As a result, the final bimetallic CoCu catalyst on GO can achieve a high total turnover frequency (TOF) value of 72.4 (H2) mol/(Cat-metal) mol·min with an activation energy of 47.8 kJ/mol, which is over 3 times higher than the monometallic clusters on GO. The cluster-support interaction has been clearly identified by synchrotron radiation X-ray absorption spectroscopy. An internal charge transfer from Cu to Co in the clusters can also be identified, which will weaken the B-N bond in AB and then effectively accelerate the hydrolysis of AB to achieve the high performance.

Occurrence of yttrium in the Zhijin phosphorus deposit in Guizhou Province, China

Abstract The Zhijin phosphorite (P)-bearing rare earth element (REE) deposit in Guizhou Province (China) hosts vast ore resources (P: 1.348 billion tonnes; REE: 1.44 Mt). Up to date, the Zhijin phosphorite resource has not been exploited because of the uncertain occurrence of the associated REEs, which hampers mineral processing and extraction. In this study, the structure, the valence state, and the coordination position of Y in the REE-yttrium-rich bioclastic samples from Zhijin were revealed by means of synchrotron radiation X-ray absorption fine structure analysis. The results show that the Y occurs as Y(iii) in the samples, and that the form of Y is different from the Y2O3 form in standard xenotime samples. Yttrium in the samples was in a complex coordination position without Y–O–Y bonding, and the Y–O bond lengths range widely without clear patterns. We suggest that Y in the samples is surrounded by organic or macro-molecular compounds, rather than in inorganic ones. Thus, Y in collophanite is unlikely to be in the form of isomorphism.

Positively Charged Pt-Based Nanoreactor for Efficient and Stable Hydrogen Evolution.

Positively charged Pt can work as the active center for hydrogen evolution reaction (HER) but the corresponding design of state‐of‐the‐art electrocatalysts at high current densities has never been realized. Here the application of positively charged Pt in an effective Fe‐PtNiPO nanoreactor for highly efficient and stable HER is demonstrated. Synchrotron radiation X‐ray absorption spectroscopy confirms the formation of internal positively charged Pt and the in situ experiments reveal the quick charge transfer in the nanoreactor. Ni‐based materials around Pt are used to tune the electronic structure and promote the water dissociation to form locally enriched H+, while a porous Fe shell can both prevent the loss of active material and allow the efficient material transport. All the beneficial compositions work together to form an effective nanoreactor for HER. As a result, the Fe‐PtNiPO nanoreactor shows a low overpotential of 19 mV to achieve 10 mA cm−2 and exhibits a high mass activity of 10.93 A mgPt −1 (at 100 mV). Most importantly, it only needs an ultra‐low overpotential of 193 mV to achieve a high current density of 1000 mA cm−2 with an excellent stability over 300 h, which represents one of the best electrocatalysts for alkaline HER and might be used for large‐scale industrial application in the future.

Microwave-assisted synthesis and characterization of undoped and manganese doped zinc sulfide nanoparticles

Undoped and Mn-doped ZnS nanocrystals were produced by the microwave-assisted solvothermal method and characterized by X-ray diffraction, photoluminescence spectroscopy and scanning electron microscopy with energy-dispersive X-ray spectroscopy. All samples have the cubic zinc blende structure with the lattice parameter in the range of a = 5.406–5.411 Å, and the average size of crystallites is in the range of 6–9 nm. These nanoparticles agglomerate and form large grains with an average size of up to 180 nm. The photoluminescence of the undoped ZnS sample shows a broad emission band located at 530 nm, attributed to the defects at the surface of nanoparticles. In all Mn-doped samples, the emission peak at 598 nm was observed assigned to the characteristic forbidden transition between excited (4T1) and ground (6A1) levels of Mn2+. Synchrotron radiation X-ray absorption spectroscopy at the Zn and Mn K-edges combined with reverse Monte Carlo (RMC) simulations based on the evolutionary algorithm confirms that manganese ions substitute zinc ions. However, the difference in the ion sizes (R(Mn2+(IV)) = 0.66 Å and R(Zn2+(IV)) = 0.60 Å) is responsible for the larger interatomic distances Mn–S (2.40(2) Å) compared to Zn–S (2.33(2) Å). The static structural relaxations in ZnS:Mn nanoparticles are responsible for the large values of the mean-square displacements factors for Zn, S and Mn atoms obtained by RMC simulations.

Tracking the Oxygen Dynamics of Solid-Liquid Electrochemical Interfaces by Correlative In Situ Synchrotron Spectroscopies.

Oxygen-involved electrocatalytic processes, including the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR), are central to a series of advanced modern energy and conversion technologies, such as water electrolyzers, fuel cells, and CO2 reduction or N2 fixation devices. A comprehensive and in-depth understanding of the charge transfer and energy conversion process that ubiquitously occurs over solid-liquid electrochemical interfaces during oxygen electrocatalysis is crucial for understanding the key essence of oxygen-related electrochemistry. The huge challenges for dynamic studies over solid-liquid interfaces during oxygen electrocatalysis lie in the all-embracing electrochemical processes of the catalytic reactions, associated with both structural and reactive intermediates evolution on the electrode surface, and in the significant influence of the aqueous environments of electrolytes used. Hence, overcoming these challenges intrinsically calls for a great cooperation of multiple cutting-edge in situ technologies. Synchrotron radiation (SR) X-ray absorption fine structure (SR-XAFS) spectroscopy is highly sensitive to the local atomic structure of nanomaterials, and SR-based Fourier transform infrared (SR-FTIR) spectroscopy features unique molecular fingerprint identification to determine active species on the surface of electrodes. One can imagine that the correlative in situ SR-XAFS/FTIR spectroscopic investigations will potentially provide sufficient, reliable, and complementary information at the atomic/molecular level to depict vivid and comprehensive "dynamic movies" of solid-liquid electrochemical interfaces during oxygen electrocatalysis, which will help effectively promote/simplify the complicated screening process of advanced oxygen electrocatalysts for efficient high-energy-density energy systems.In this Account, starting with some fundamentals of SR-based spectroscopic technologies, tips for obtaining high-quality SR-XAFS and SR-FTIR spectroscopy results during the electrocatalytic process are comprehensively specified. Subsequently, the latest research achievements of dynamic investigations mainly from our group based on in situ SR-XAFS and/or SR-FTIR spectroscopies will be systematically scrutinized and properly emphasized in detail, where the currently attractive metal-organic-framework (MOF) nanomaterials and single-atom catalysts (SACs) are selected as the main object of research. Moreover, the vital contributions of correlative in situ SR-XAFS/FTIR studies on new discoveries of the dynamic evolution of solid-liquid interfaces during oxygen electrocatalysis are highlighted. In particular, our pioneering research found that the potential-dependent dynamically coupled oxygen formed in the precatalytic stage was a very useful promoter in SACs to promote efficient OER kinetics under acidic conditions. In addition, the in situ generated metastable Ni1-N2 centers with more structural degrees of freedom in SACs could potentially facilitate the fast 4e- ORR kinetics. This Account is anticipated to stimulate broad interest in dynamic explorations in various catalytic processes of interest in the material science and electrochemistry communities using correlative SR-based technologies.

Structural Characterization of Titanium-Silica Oxide Using Synchrotron Radiation X-ray Absorption Spectroscopy.

In this study, titania–silica oxides (TixSiy oxides) were successfully prepared via the sol–gel technique. The Ti and Si precursors were titanium (IV), isopropoxide (TTIP), and tetraethylorthosilicate (TEOS), respectively. In this work, the effects of pH and the Ti/Si atomic ratio of titanium–silicon binary oxide (TixSiy) on the structural characteristics of TixSiy oxide are reported. 29Si solid-state NMR and FTIR were used to validate the chemical structure of TixSiy oxide. The structural characteristics of TixSiy oxide were investigated using X-ray diffraction, XRF, Fe-SEM, diffraction particle size analysis, and nitrogen adsorption measurements. By applying X-ray absorption spectroscopy (XAS) obtained from synchrotron light sources, the qualitative characterization of the Ti–O–Si and Ti–O–Ti bonds in Ti–Si oxides was proposed. Some Si atoms in the SiO2 network were replaced by Ti atoms, suggesting that Si–O–Ti bonds were formed as a result of the synthesis accomplished using the sol–gel technique described in this article. Upon increasing the pH to alkaline conditions (pH 9.0 and 10.0), the nanoparticles acquired a more spherical shape, and their size distribution became more uniform, resulting in an acceptable nanostructure. TixSiy oxide nanoparticles were largely spherical in shape, and agglomeration was minimized. However, the Ti50Si50 oxide particles at pH 10.0 become nano-sized and agglomerated. The presence of a significant pre-edge feature in the spectra of Ti50Si50 oxide samples implied that a higher fraction of Ti atoms occupied tetrahedral symmetry locations, as predicted in samples where Ti directly substituted Si. The proportion of Ti atoms in a tetrahedral environment agreed with the value of 1.83 given for the Ti–O bond distance in TixSiy oxides produced at pH 9.0 using extended X-ray absorption fine structure (EXAFS) analysis. Photocatalysis was improved by adding 3% wt TiO2, SiO2, and TixSiy oxide to the PLA film matrix. TiO2 was more effective than Ti50Si50 pH 9.0, Ti50Si50 pH 10.0, Ti50Si50 pH 8.0, and SiO2 in degrading methylene blue (MB). The most effective method to degrade MB was TiO2 > Ti70Si30 > Ti50Si50 > Ti40Si60 > SiO2. Under these conditions, PLA/Ti70Si30 improved the effectiveness of the photocatalytic activity of PLA.

Quantitative study on Ru local atomic structure in Ni-Al-Ru ternary alloys

The synchrotron radiation X-ray absorption fine structure (XAFS) technique is used to study the local structure of the key atom Ru in a series of Ni-Al-Ru ternary alloys with different Ru contents and heat treatments. All the investigated alloys consist of two phases, γ and γ', and especially Ru exists as an atom coordinated by 12 Ni atoms in the first shell without Ru clusters or intermetallic compounds. In γ phase Ru resides on the Ni lattice site introducing an outward relaxation of the neighboring atoms, while in the γ' phase Ru replaces the Al lattice site causing an inward relaxation. The interatomic distance of Ru–Ni bond and Debye-Waller factor are mainly affected by the composition and increase with the increasing Ru content. While the effect of heat treatment is obvious when the Ru content is higher than 6 at%. The variation of Ru local atomic structure can greatly influence the microstructural evaluation and deformation mechanism by changing the lattice misfit and the vacancy formation energy to control the creep properties of Ni-Ru-Al ternary alloys.

Mercury Reduction, Uptake, and Species Transformation by Freshwater Alga Chlorella vulgaris under Sunlit and Dark Conditions.

As a major entry point of mercury (Hg) to aquatic food webs, algae play an important role in taking up and transforming Hg species in aquatic ecosystems. However, little is known how and to what extent Hg reduction, uptake, and species transformations are mediated by algal cells and their exudates, algal organic matter (AOM), under either sunlit or dark conditions. Here, using Chlorella vulgaris (CV) as one of the most prevalent freshwater model algal species, we show that solar irradiation could enhance the reduction of mercuric Hg(II) to elemental Hg(0) by both CV cells and AOM. AOM reduced more Hg(II) than algal cells themselves due to cell surface adsorption and uptake of Hg(II) inside the cells under solar irradiation. Synchrotron radiation X-ray absorption near-edge spectroscopy (SR-XANES) analyses indicate that sunlight facilitated the transformation of Hg to less bioavailable species, such as β-HgS and Hg-phytochelatins, compared to Hg(Cysteine)2-like species formed in algal cells in the dark. These findings highlight important functional roles and potential mechanisms of algae in Hg reduction and immobilization under varying lighting conditions and how these processes may modulate Hg cycling and bioavailability in the aquatic environment.

Robust ferromagnetic insulating and large exchange bias in LaMnO3:CoO composite thin films

Ferromagnetic insulators (FMIs) have received widespread attention for applications in novel low power consumption spintronic devices. Further optimizing robust ferromagnetic insulation and developing a multifunctional FMI by integrating other magnetic properties can not only ease or pave the way for actual application but also provide an additional degree of freedom for device design. In this work, by introducing antiferromagnetic CoO into the FMI LaMnO3, we constructed (1 − x)LaMnO3:xCoO composite thin films. The films simultaneously show robust FMI characteristics and a large exchange bias (EB). For the x = 0.5 sample, the resistivity is 120 Ω cm at 250 K, the magnetization is 100 emu cm−3, and the EB field is −2200 Oe at 10 K. In particular, the blocking temperature is up to 140 K. Synchrotron radiation x-ray absorption spectroscopy reveals the coexistence of Mn3+, Mn2+, Co2+ and Co3+, arising from interfacial charge transfer and space charge/defect trapping, which should be responsible for the enhanced and integrated multifunctional magnetic properties.