Abstract  Vanadium is a polyvalent metallic element. The fact that V-O bears a much larger bond energy than the V-V metal bond challenges the preparation of pure vanadium clusters and the observation of their reactions with oxygen-containing chemicals. Utilizing a customized reflection time-of-flight mass spectrometer (Re-TOFMS), here we have prepared well-resolved small and large cationic vanadium clusters Vn+ (n < 30), and we conducted a comprehensive study on their reactivity with oxygen. It is illustrated that cationic Vn+ clusters readily react with oxygen leading to the production of both etched building blocks and oxygen-rich VnOm+ (n < m) species profiting from the ion-molecule attraction and hence increased collisional cross section. Furthermore, DFT-based energy calculations reveal that the oxygen-addition reactions are thermodynamically and kinetically favorable pathways. Also the generalized charge decomposition analysis (GCDA) illustrates that the ion-molecule charge-transfer interactions initiate the incorporation of vanadium oxides. This finding of synchronous channels of both etching and growth of vanadium clusters clarifies the reactivity of Vn+ clusters with oxygen, interprets the readily formed VnOm+ clusters within the classification of the CxAyBz series (A = VO2, B = VO3, C = VO), and enriches the understanding of the industrial chemistry of vanadium.

Abstract  This study was aimed at examining the possible utilization of iron-rich groundwater treatment sludge in the synthesis of zerovalent iron (ZVI) as a conjugate with kaolin clay (Slu-KZVI), and its application for vanadium adsorption from aqueous solutions. Iron was extracted from the sludge using 1 M HCl and was used in ZVI synthesis by the sodium borohydride reduction method. The characteristics and performance of Slu-KZVI were compared to a kaolin modified with synthetic iron (FeCl3·6H2O) (Syn-KZVI). Adsorption results showed a competitive performance by both classes of KZVI, with Syn-KZVI slightly outperforming Slu-KZVI. X-ray photoelectron spectroscopy, X-ray diffraction and transmission electron microscopy confirmed the formation of Fe0 on the core-shell structure of both modified adsorbents. In addition, the surface analysis of Slu-KZVI indicated the presence of P and Ca to a small extent, originating from the sludge. Both classes of sorbents performed better in solutions with acidic and neutral pH values (3-7). Surface complexation was thought to be the primary mechanism whereas simultaneous V(V) reduction and Fe oxidation (redox) reactions may also have taken place to some extent. A sorption test with groundwater confirmed that adsorbents were able to reduce vanadium to a very low concentration.

Abstract  Oxide nanoparticles in the size range of a few nanometers are typically synthesized in solution or via laser ablation techniques, which open numerous channels for structural change via chemical reactions or fragmentation processes. In this work, neutral vanadium oxide nanoparticles are instead synthesized by sublimation from bulk in combination with a pickup by superfluid helium droplets. Mass spectroscopy measurements clearly demonstrate the preservation of the bulk stoichiometric ratio of vanadium to oxygen in He-grown nanoparticles, indicating a tendency towards tetrahedral coordination of the vanadium centers in finite geometries. This unexpected finding opens up new possibilities for a combined on-the-fly synthesis of nanoparticles consisting of metal and metal-oxide layers. In comparison to mass spectra obtained via direct ionization of vanadium oxide in an effusive beam, where strong fragmentation occurred, we observe a clear preference for (V2O5) n oligomers with even n inside the He nanodroplets, which is further investigated and explained using the electronic structure theory.

Abstract  Transmetallation studies with the phosphaethynolate ion, [OCP]-, have largely resulted in coordination according to classical Lewis acid-base theory. That is, for harder early transition metal ions, O-bound coordination has been observed, whereas in the case of softer late transition metal ions, P-bound coordination predominates. Herein, we report the use of a V(iii) complex, namely [(nacnac)VCl(OAr)] (1) (nacnac- = [ArNC(CH3)]2CH; Ar = 2,6-iPr2C6H3), to transmetallate [OCP]- and bind via the P-atom as [(nacnac)V(OAr)(PCO)] (2), the first example of a 3d early transition metal that binds [OCP]-via the P-atom. Full characterization studies of this molecule including HFEPR spectroscopy, SQuID measurements, and theoretical studies are presented.

Abstract  Non-heme iron, vanadium, and copper complexes bearing hemicryptophane cavities were evaluated in the oxidation of methane in water by hydrogen peroxide. According to 1H nuclear magnetic resonance studies, a hydrophobic hemicryptophane cage accommodates a methane molecule in the proximity of the oxidizing site, leading to an improvement in the efficiency and selectivity for CH3OH and CH3OOH compared to those of the analogous complexes devoid of a hemicryptophane cage. While copper complexes showed low catalytic efficiency, their vanadium and iron counterparts exhibited higher turnover numbers, ≤13.2 and ≤9.2, respectively, providing target primary oxidation products (CH3OH and CH3OOH) as well as over-oxidation products (HCHO and HCOOH). In the case of caged vanadium complexes, the confinement effect was found to improve either the selectivity for CH3OH and CH3OOH (≤15%) or the catalytic efficiency. The confined space of the hydrophobic pocket of iron-based supramolecular complexes plays a significant role in the improvement of both the selectivity (≤27% for CH3OH and CH3OOH) and the turnover number of methane oxidation. These results indicate that the supramolecular approach is a promising strategy for the development of efficient and selective bioinspired catalysts for the mild oxidation of methane to methanol.

Abstract  Aqueous zinc-ion batteries (ZIBs) are considered promising energy storage devices for large-scale energy storage systems as a consequence of their safety benefits and low cost. In recent years, various vanadium-based compounds have been widely developed to serve as the cathodes of aqueous ZIBs because of their low cost and high theoretical capacity. Furthermore, different energy storage mechanisms are observed in ZIBs based on vanadium-based cathodes. In this Minireview, we present a comprehensive overview of the energy storage mechanisms and structural features of various vanadium-based cathodes in ZIBs. Furthermore, we discuss strategies for improving the electrochemical performance of vanadium-based cathodes; including, insertion of metal ions, adjustment of structural water, selection of conductive additives, and optimization of electrolytes. Finally, this Minireview offers insight into potential future directions in the design of innovative vanadium-based electrode materials.

Abstract  OBJECTIVES: Serum uric acid (SUA) is both a strong antioxidant and one of the key risk factors of cardiovascular diseases (CVDs). We aimed to investigate the associations of urinary metal profile with SUA in traffic policemen in Wuhan, China.

DESIGN: A cross-sectional study was carried out in traffic policemen.

SETTING: A seriously polluted Chinese city.

PARTICIPANTS: A total of 186 traffic policemen were recruited in this study. About 56 of them worked in the logistics department and the other 130 maintained traffic order or dealt with traffic accidents on the roads. All these subjects had worked as a policeman for at least 1 year.

MAIN OUTCOME MEASURES: SUA.

RESULTS: The significantly negative association of lead with SUA was consistent between single-metal and multiple-metal models (p=0.004 and p=0.020, respectively). Vanadium, chromium and tin were reversely associated with SUA levels in the single-metal models after false discovery rate (FDR) adjustment (all P_FDR < 0.05). One IQR increase in vanadium, chromium, tin and lead was associated with 26.9 µmol/L (95% CI -44.6 to -9.2; p=0.003), 27.4 µmol/L (95% CI -46.1 to -8.8; p=0.004), 11.2 µmol/L (95% CI -18.9 to -3.4; p=0.005) and 16.4 µmol/L (95% CI -27.6 to -5.2; p=0.004) decrease in SUA, respectively. Significant interaction between smoking and vanadium on decreased SUV was found (pfor interaction = 0.007 and p_FDR = 0.028).

CONCLUSIONS: Urinary vanadium, chromium, tin and lead were negatively associated with SUA. Vanadium and cigarette smoking jointly affected SUA levels. Further studies are needed to replicate these findings and to investigate the potential mechanisms.

Abstract  Methane oxidation by methanotrophs is a very important environmental process in the mitigation of methane. Methylobacter (Mtb.) clade 2 members have been reported as dominant methane oxidisers in soils and sediments worldwide. We enriched and purified a methanotroph from a tropical rice field soil sample from India. The highly enriched culture showed the presence of motile, long and thick rods (3-5 µm × 0.9-1.2 µm) and minor presence of short, thin rods. The culture was purified on agarose medium and formed yellow colonies which showed the presence of only thick and long rods, henceforth termed as strain KRF1. Based on 16S rRNA gene sequence analysis, strain KRF1 shows close phylogenetic affiliation to Methylobacter tundripaludum SV96T (98.6% similarity). Due to the taxonomic novelty, and being the first member of Mtb. related to Mtb. tundripaludum from the tropics, the draft genome was sequenced. From the blastx analysis of the contigs, it was clear that the culture still had contamination of another organism, a Methylophilus species. The data binned in two clear bins: Mtb. related contigs and Methylophilus-related contigs. The binned draft genome of KRF1 shows features including the typical pathways for methane metabolism, denitrification and the presence of molybdenum iron and vanadium-iron nitrogenase genes. KRF1 is phylogenetically distinct from the five strains of Mtb. tundripaludum including SV96T, Lake Washington strains and OWC strains, showing ~ 26% DDH and ~ 81% ANIb values and a unique position in a phylogenomic tree. Subsequently, KRF1 has been completely purified from its methylotrophic partner and a pure culture has been established and maintained in a WDCM approved culture collection, the MACS Collection of Microorganisms (as MCM 1471). KRF1 is thus the first cultured member of a putative novel species of Methylobacter clade 2 isolated from the tropics.

Abstract  The chemical composition of biomaterials can drive their biological responses; therefore, this in vitro study aimed to evaluate the proteomic profile of the salivary pellicle formed on titanium (Ti) alloys containing niobium (Nb) and zirconium (Zr). The experimental groups consisted of Ti35NbxZr (x = 5 and 10 wt%) alloys, and commercially pure titanium (cpTi); titanium aluminium vanadium (Ti6Al4V) alloys were used as controls. The physical and chemical characteristics of the Ti materials were analysed. The proteomic profile was evaluated by liquid chromatography coupled with tandem mass spectrometry. Bacterial adhesion (2 h) of mixed species (Streptococcus sanguinis and Actinomyces naeslundii) was investigated as colony-forming units (n = 6). This paper reports the finding that salivary pellicle composition can be modulated by the composition of the Ti material. The Ti35NbxZr group showed a significant ability to adsorb proteins from saliva, which can favour interactions with cells and compatibility with the body.

Abstract  As one of the most promising cathode materials for next-generation energy storage applications, spinel LiNi0.5Mn1.5O4 (LNMO) has been highlighted due to many advantages. However, it is still hindered by poor electrochemical stability derived from the bulk/interface structure degradation and side reactions under high working voltage. In this work, fast ion conductor Li3V2(PO4)3 (LVPO) is adopted to modify the surface of spinel LNMO by a one-step facile method to harvest the maximum benefit of interface properties. It is found that 1 wt % LVPO-LNMO exhibits the most excellent cycling performances, retaining great capacity retention of 87.8% after 500 cycles at room temperature and 82.4% for 150 cycles at 55 °C. Moreover, the rate performance is also significantly improved (90.4 mAh g-1 under 20C). It is revealed that the LVPO-involved layer could effectively suppress the surface side reactions under high working voltage, which mainly contributes to an improved interface with desirable structural stability and excellent kinetics behavior without sacrificing the surface electrochemical activity in an electrochemical environment. Thus, the dissolution of transition-metal ions is effectively mitigated, avoiding further structure degradation of the bulk material. Especially, it is also established that the vanadium (V) ions in LVPO could be to a certain extent migrated into the surface lattice of LNMO to generate a V-involved transition layer (Li-Ni-Mn-V-O surface solid solution), which greatly co-contributes to the enhanced electrochemical performances owing to the prominently depressed charge-transfer resistance.

Abstract  The scarce inventory of cathode materials with reasonable diffusion of Mg ions is the main obstacle in the development of rechargeable magnesium batteries. In this regard, vanadium pentoxide (V2O5) has been reported to be a candidate cathode material for Mg batteries. In this study, via first-principles calculations, we showed that the Mg-ion diffusion energy barrier in α-V2O5 could be substantially decreased through hydrogenation. It is found that the Mg-ion migration energy barrier in HxV2O5 is gradually decreased with an increase in H concentration. When the H concentration x reaches 2, the migration barrier is decreased to 0.56 eV from that in α-V2O5 without hydrogenation (1.28 eV). This indicates that the Mg diffusion kinetics can be substantially improved through hydrogenation, and the resultant energy barrier makes Mg diffusion acceptable even at room temperature. The mechanism of the H-enhanced Mg-diffusion has also been studied, and it has been found that H atoms not only can expand the Mg-diffusion pathway, but also have a screening effect on the interactions between Mg ions and the α-V2O5 lattice.

Abstract  Copper (Cu) is an essential metal involved in many physiological processes of living organisms. However, beyond a certain threshold, Cu can become highly toxic. For instance, in the summer sporeling production of the economic kelp Saccharina japonica, the excess Cu accidently released from the low-quality alloys of the refrigerating machine was deadly to the seedlings and led to the failure of hatchery operations. However, the molecular basis underlying high toxicity of Cu remains unclear. In this study, juvenile sporophytes were cultured in seawater containing different concentrations of Cu2+ (10, 100, and 200 μg L-1). Bleaching was observed in the meristem of individuals in the 100 and 200 μg L-1 treatment groups on the third day, indicating that Cu has caused severe harm at these concentrations. RNA-Seq was used to profile transcriptomic changes under different Cu2+ concentrations. Compared with the control, the number of differentially expressed genes (DEGs) was 11,350 (4944 up- and 6406 down-regulated) in the 200 μg L-1 treatment group and 2868 (1075 up- and 1793 down-regulated) in the 100 μg L-1 treatment group, whereas much fewer DEGs were detected in the 10 μg L-1 treatment group. Genes coding for glutathione-S-transferase and vanadium-dependent bromoperoxidase and iodoperoxidase were found to be remarkably regulated, especially in the 200 μg L-1 treatment group. Gene Ontology (GO) and Kyoto Encyclopedia of Genes and Genomes (KEGG) analyses showed that only down-regulated DEGs were enriched. There were 45 enriched GO terms and four enriched KEGG pathways common to the 100 and 200 μg L-1 treatment groups, which were associated with diverse essential biological processes such as photosynthesis, protein synthesis, redox activity, and metabolism and biosynthesis of functional biomolecules, among others. Suppression of these biological processes at the transcriptional level likely contributes to the observed high toxicity of Cu2+ in S. japonica.

Abstract  Mn3O4 is a potential anode for alkali-metal (Li/Na/K)-ion batteries because of the high capacity, abundant resources, and eco-friendliness. However, its ion storage performance is limited by poor electronic conductivity and large volume expansion during the charging/discharging process. In this study, we presented a facile dissolution strategy to fabricate ultrathin nanosheet-assembled hierarchical Mn3O4/graphene microflowers, realizing enhanced alkali-metal-ion storage performance. The synthetic mechanism was proven as the selective dissolution of vanadium via controlled experiments with different reaction times. The as-synthesized composites showed high lithium storage capacity (about 900 mA h g-1) and superior cyclability (∼400 mA h g-1 after 500 cycles). In addition, when evaluated as a Na-ion battery anode, the reversible capacity of about 200 mA h g-1 was attained, which remained at 167 mA h g-1 after 200 cycles. Moreover, to the best of our knowledge, the potassium storage properties of Mn3O4 were evaluated for the first time and a reversible capacity of about 230 mA h g-1 was achieved. We believe that our findings will be instructive for future investigations of high-capacity anode materials for alkali-metal-ion batteries.

Abstract  By combining a newly developed two-color laser pulsed field ionization-photoion (PFI-PI) source and a double-quadrupole-double-octopole (DQDO) mass spectrometer, we investigated the integral cross sections (σs) of the vanadium cation (V+) toward the activation of CO2 in the center-of-mass kinetic energy (Ecm) range from 0.1 to 10.0 eV. Here, V+ was prepared in single spin-orbit levels of its lowest electronic states, a5DJ (J = 0-4), a5FJ (J = 1-5), and a3FJ (J = 2-4), with well-defined kinetic energies. For both product channels VO+ + CO and VCO+ + O identified, V+(a3F2,3) is found to be greatly more reactive than V+(a5D0,2) and V+(a5F1,2), suggesting that the V+ + CO2 reaction system mainly proceeds via a "weak quintet-to-triplet spin-crossing" mechanism favoring the conservation of total electron spins. In addition, no J-state dependence was observed. The distinctive structures of the quantum electronic state selected integral cross sections observed as a function of Ecm and the electronic state of the V+ ion indicate that the difference in the chemical reactivity of the title reaction originated from the quantum-state instead of energy effects. Furthermore, this work suggests that the selection of the quantum electronic states a3FJ (J = 2-4) of the transition metal V+ ion can greatly enhance the efficiency of CO2 activation.

Abstract  In this work, the influence of simple acids in the room temperature sol-gel synthesis of TiO₂ was investigated and the efficiency of prepared photocatalysts was evaluated in the removal of caffeine. To improve the photoactivity of TiO₂, vanadium-doped TiO₂ (VTiO₂) samples were obtained starting from different amount of vanadyl sulphate as a dopant source. The samples were centrifuged, washed and finally dried at room temperature, and no calcination step was carried out. The prepared photocatalysts were characterized by different techniques (X-ray powder diffraction (XRD), specific surface area (SSA), ultraviolet-visible diffuse reflectance spectra (UV-vis DRS) and Raman). VTiO₂ photocatalysts were tested in the photocatalytic removal of aqueous solutions containing caffeine. The photocatalytic tests were carried out in a recirculating batch cylindrical photoreactor irradiated by a UV LEDs strip (nominal power of 12 W and wavelength emission peak at about 365 nm) surrounding the external surface of the reactor. The optimized VTiO₂ photocatalyst was able to reach a caffeine degradation of about 96% after 360 min of UV light irradiation with a total organic carbon (TOC) removal of 72%.

Abstract  Photocatalytic ozonation is an attractive advanced oxidation process for wastewater treatment, but highly active catalysts with strong response to visible light are urgently needed to push forward its practical application. In this study, a hierarchical biomimetic monoclinic bismuth vanadate (BiVO4) with leaves morphology was synthesized by a hydrothermal method, and employed as catalyst for oxalic acid and penicillin degradation in photocatalytic ozonation. The results show that the organics degradation was more efficient using leaves shaped BiVO4 as catalyst than the bulk shaped one in photocatalytic ozonation and the synergy index is ranged from 2.8 to 3.3, indicating a superior positive synergistic effect between photocatalysis and ozonation. The higher activity of the leaves shaped BiVO4 was probably attributed to the distinctive biomimetic morphology and preferable band structure with more negative CB potential. Mechanism studies suggested that the main reactive species were h+ and OH for the degradation of persistent oxalic acid in photocatalytic ozonation. In addition, the effect of ozone concentration and inorganic ions and reusability of the material were also intensively investigated.

Abstract  Inspired by the cascade reactions occurring in micro-organelles of living systems, we have developed a hybrid hydrogel, a nanozyme that mimics three key enzymes including peroxidase, superoxide dismutase, and catalase. The organic/inorganic nanostructured hydrogel constituting VO x incorporated hexacyanoferrate Berlin green analogue complex (VO x BG) is prepared by a simple one-step hydrothermal process, and its composition, structure, and properties are thoroughly investigated. Polyvinylpyrrolidone, a low-cost and biocompatible polymer, was utilized as a scaffold to increase the surface area and dispersion of the highly active catalytic centers of the nanozyme. Compared to the widely used horseradish peroxidase in enzyme-linked immunosorbent assay, our VO x BG analogue hydrogel displays an excellent affinity toward the chromogenic substrate that is used in these peroxidase-based assays. This higher affinity makes it a competent nanozyme for detection and oxidation of biomolecules, including glucose, in a cascade-like system which can be further used for hydrogel photolithography. The VO x BG analogue hydrogel also holds a good ability for the rapid and efficient oxidative degradation of environmentally unfriendly recalcitrant substrates under light irradiation. Detailed mechanistic studies of this multifaceted material suggest that different complex catalytic processes and routes are involved in these photo-Fenton and Fenton reactions that are responsible for the generation as well as consumption of reactive oxygen species, which are effectively activated by a multienzyme mimetic of the VO x BG analogue hydrogel.

Abstract  OBJECTIVE: The Ti-6Al-4V (TAV) alloy is commercially used as a dental implant material. This work seeks to elucidates the origins of degradation of Ti-6Al-4V (TAV) implant alloys that result in peri-implant bone loss. 
Methods: In this work, a combination of microstructure, surface, and solution analyses was utilized to study the corrosion mechanism of the TAV alloy in oral environments. The corrosion of TAV alloys in the F--enriched environment of a crevice was evaluated through nanoscale surface analysis. And, the findings were further rationalized via electrochemical means. 
 RESULTS: Our results suggest the bone loss was caused by crevice corrosion and the consequential release of by-products, and the crevice corrosion was potentially induced by the buildup of corrosive species such as fluorides, which are common additives in dental products. In turn, the corrosion properties of the TAV alloy were evaluated in fluoride enriched environments. Nanoscale analysis of corroded surfaces, carried out using vertical scanning interferometry (VSI) showed that the corrosion susceptibility of the constituent phases dictates the corrosion product species. In specific, the aluminum-rich α phase preferentially dissolves under potential-free conditions and promotes the formation of insoluble Al-Ti oxides. Notably, under conditions of applied potential, oxidative dissolution of the vanadium-rich β phase is favored, and the vanadium release is promoted. 
 SIGNIFICANCE: These findings elucidate the origins of degradation of TAV-implants that result in the release of corrosion by-products into the local biological environment. More important, they offer guidelines for materials design and improvement to prevent this nature of degradation of dental implants.

Abstract  Land use change alters the hydrological process, which in turn affects the migration of heavy metals. However, analyses of the watershed-scale distribution of heavy metals from slope to dam fields have seldom been studied. In this study, three land-use types on the slope (cropland, shrubland, grassland) and dam land in the channel on the Loess Plateau were selected to analyze the relationship between the change of slope erosion rate and the migration process of Manganese (Mn), Chromium (Cr), Zinc (Zn), Vanadium (V), Nickel (Ni), Copper (Cu), Arsenic (As) and Cobalt (Co) in soil. Moreover, the sources of heavy metals in sediments and their historical deposition process were revealed. It was found that the concentrations of Cr and As were higher in cropland than that in grassland and shrubland. The soil erosion of cropland was the most serious, and the maximum annual erosion rate was as high as 10,853.56 t km-2. The distribution of heavy metals was related to erosion rate in the cropland. With soil erosion, Cr, V, As, Co and Zn in cropland were prone to runoff migration. Cr and As in dam sediments mainly originated from the agricultural activities in cropland. Cu, Co, Mn, Ni, V and Zn in the dam land were largely affected by soil parent material. Land use and soil erosion were important factors influencing the redistribution of heavy metals. By optimizing land use patterns and reducing soil erosion, it is possible to control the migration and accumulation of heavy metals in the watershed. The findings of this study can serve as important reference for reducing non-point source pollution.

Abstract  The development of a nonprecious and Earth-abundant electrocatalyst with high electrocatalytic activity for the oxygen evolution reaction (OER) is an emerging hot issue and remains a grand challenge. In the present work, we proposed a facile strategy to construct ultrathin NiO nanosheets decorated with Fe-V nanoparticles on nickel foam (Fe-V@NiO/NF) for use as an OER electrocatalyst. Due to the 3D rational configuration, the Fe-V@NiO/NF with a heterostructure shows excellent electrocatalytic activity towards the OER. Interestingly, it is found that in situ oxidation by galvanostatic electrolysis in alkaline solution is beneficial to enhance the OER performance. After 10 h of electrolysis, a current density of 50 mA cm-2 is achieved at a low overpotential of 271.1 mV. This is because during the in situ oxidation process, iron and vanadium ions insert into the NiO lattice and lead to the generation of highly active α-FeOOH and an amorphous (oxy)-hydroxide layer. Additionally, the charge transfer resistance dramatically reduces with the prolonging of oxidation time.

Abstract  The sodium-vanadium fluorophosphate family has been actively investigated recently, but few examples tackle chemical doping or the substitution of vanadium. This work presents a series of iron-doped compounds Na3V2-yO2-yFe y (PO4)2F1+y (y ≤ 0.3) prepared by hydrothermal synthesis with low iron content. The amount of iron in the structure is confirmed by X-ray and neutron powder diffraction, electronic paramagnetic resonance, magnetic susceptibility measurements, and solid-state nuclear magnetic resonance (ssNMR). The degree of vanadium substitution, together with the solubility limit for iron in sodium-vanadium fluorophosphates, has been calculated by ssNMR and magnetic susceptibility measurements to be y = 0.3 based on the synthetic route used here. The introduction of small amounts of Fe3+ to the structure leads to the reduction of a fraction of V4+ to V3+, and the voltage profiles do not change with the introduction of iron to the structure. In situ synchrotron X-ray diffraction demonstrates that the electrochemical-structural changes during charge and discharge are very similar to those observed in the V3+/V4+ mixed-valent Na3V2O1.6(PO4)2F1.4, which could be related to the existence of both iron dopant and V3+ in the phase.

Abstract  The lattice symmetry of strongly correlated oxide heterostructures determines their exotic physical properties by coupling the degrees of freedom between lattices and electrons, orbitals, and spin states. Systematic studies on VO2, a Mott insulator, have previously revealed that lattice distortion can be manipulated by the interfacial strain and electronic phase separation can emerge. However, typical epitaxial film-substrate interface strain provides a very limited range for exploring such interface-engineered phenomena. Herein, epitaxially grown VO2 thin films on asymmetrically faceted m-plane sapphire substrates with the hill-and-valley type surfaces have been demonstrated. Interestingly, lattice symmetry breaking has been proven based on the large residual strain from the different faceted planes. By this lattice symmetry breaking, electronic phase separation and metal-insulator transition in the VO2 films are modulated, and anisotropy in optical responses is exhibited. These results on asymmetrical interfacial engineering in oxide heterostructures open up new routes for novel functional materials design and functional electro/optic device nanofabrication.

Abstract  Nitrogenases catalyze the ambient reduction of N2 and CO at its cofactor site. Herein we present a biochemical and spectroscopic characterization of an Azotobacter vinelandii V nitrogenase variant expressing a citrate-substituted cofactor. Designated VnfDGKCit , the catalytic component of this V nitrogenase variant has an αβ2 (δ) subunit composition and carries an 8Fe P* cluster and a citrate-substituted V cluster analogue in the αβ dimer, as well as a 4Fe cluster in the "orphaned" β-subunit. Interestingly, when normalized based on the amount of cofactor, VnfDGKCit shows a shift of N2 reduction from H2 evolution toward NH3 formation and an opposite shift of CO reduction from hydrocarbon formation toward H2 evolution. These observations point to a role of the organic ligand in proton delivery during catalysis and imply the use of different reaction sites/mechanisms by nitrogenase for different substrate reductions. Moreover, the increased NH3 /H2 ratio upon citrate substitution suggests the possibility to modify the organic ligand for improved ammonia synthesis in the future.

Abstract  Biology has evolved excellent spatial structures for high-selectivity and high-affinity capture of heavy metals. Inspired by the spatial structure of the superb-uranyl binding protein SUP, we mimic the spatial structure of SUP in metal-organic frameworks (MOFs). The MOF UiO-66-3C4N fabricated by introducing 4-aminoisophthalic acid into UiO-66 shows high uranyl adsorption capacity both in simulated seawater and in natural seawater. In natural seawater, UiO-66-3C4N exhibits 17.03 times higher uranium extraction capacity than that of vanadium, indicating the high selectivity of the adsorbent. The EXAFS analysis and DFT calculation reveal that UiO-66-3C4N forms smaller nano-pocket for uranyl capture than that of SUP protein, which can both restrict the entrance of the other interfering ions with larger size and reinforce the binding by increasing the coordination interaction, and therefore qualify the nano-pocket with high affinity and high selectivity to uranyl.

Abstract  We present a combined experimental and theoretical study of monolayer vanadium ditelluride, VTe2, grown on highly oriented pyrolytic graphite by molecular-beam epitaxy. Using various in situ microscopic and spectroscopic techniques, including scanning tunneling microscopy/spectroscopy, synchrotron X-ray and angle-resolved photoemission, and X-ray absorption, together with theoretical analysis by density functional theory calculations, we demonstrate direct evidence of the metallic 1T phase and 3d1 electronic configuration in monolayer VTe2 that also features a (4 × 4) charge density wave order at low temperatures. In contrast to previous theoretical predictions, our element-specific characterization by X-ray magnetic circular dichroism rules out a ferromagnetic order intrinsic to the monolayer. Our findings provide essential knowledge necessary for understanding this interesting yet less explored metallic monolayer in the emerging family of van der Waals magnets.