MIL-100(V) derived porous vanadium oxide/carbon microspheres with oxygen defects and intercalated water molecules as high-performance cathode for aqueous zinc ion battery

The development of aqueous zinc ion battery cathode materials with high capacity and high magnification is still a challenge.Herein,porous vanadium oxide/carbon(p-VO_(x)@C,mainly VO_(2) with a small amount of V_(2)O_(3)) core/shell microspheres with oxygen vacancies are facilely fabricated by using a vanadium-based metal-organic framework(MIL-100(V)) as a sacrificial template.This unique structure can improve the conductivity of the VO_(x),accelerate electrolyte diffusion,and suppress structural collapse during circulation.Subsequently,H_(2)O molecules are introduced into the interlayer of VO_(x) through a highly efficient in-situ electrochemical activation process,facilitating the intercalation and diffusion of zinc ions.After the activation,an optimal sample exhibits a high specific capacity of 464.3 mA h g^(-1) at0.2 A g^(-1) and 395.2 mA h g^(-1) at 10 A g^(-1),indicating excellent rate performance.Moreover,the optimal sample maintains a capacity retention of about 89.3% after 2500 cycles at 10 A g^(-1).Density functional theory calculation demonstrates that the presence of oxygen vacancies and intercalated water molecules can significantly reduce the diffusion barrier for zinc ions.In addition,it is proved that the storage of zinc ions in the cathode is achieved by reversible intercalation/extraction during the charge and discharge process through various ex-situ analysis technologies.This work demonstrates that the p-VO_(x)@C has great potential for applications in aqueous ZIBs after electrochemical activation.

Mo Doping and Electrochemical Activation Co-Induced Vanadium Composite as High-Rate and Long-Life Anode for Ca-Ion Batteries

Calcium-ion batteries have been considered attractive candidates for large-scale energy storage applications due to their natural abundance and low redox potential of Ca^(2+)/Ca.However,current calcium ion technology is still hampered by the lack of high-capacity and long-life electrode materials to accommodate the large Ca^(2+)(1.00Å).Herein,an amorphous vanadium structure induced by Mo doping and in-situ electrochemical activation is reported as a high-rate anode material for calcium ion batteries.The doping of Mo could destroy the lattice stability of VS4 material,enhancing the flexibility of the structure.The following electrochemical activation further converted the material into sulfide and oxides co-dominated composite(defined as MoVSO),which serves as an active material for the storage of Ca^(2+)during cycling.Consequently,this amorphous vanadium structure exhibits excellent rate capability,achieving discharge capacities of 306.7 and 149.2 mAh g^(-1)at 5 and 50 A g^(-1)and an ultra-long cycle life of 2000 cycles with 91.2%capacity retention.These values represent the highest level to date reported for calcium ion batteries.The mechanism studies show that the material undergoes a partial phase transition process to derive MoVSO.This work unveiled the calcium storage mechanism of vanadium sulfide in aqueous electrolytes and accelerated the development of high-performance aqueous calcium ion batteries.

Thermodynamics and mechanism of vanadium(IV) extraction from sulphate medium with D2EHPA,EHEHPA and CYANEX 272 in kerosene

Extraction of vanadium（IV） from sulphate acid solution was studied using organophosphorous-based extractants D2EHPA, EHEHPA and CYANEX 272 in kerosene. The different parameters affecting the extraction of vanadium（IV） under equilibrium conditions were separately investigated to elucidate the stoichiometry of the extracted species. The distribution ratio of vanadium increased with increasing equilibrium pH of the aqueous phase, concentration of the extractants and temperature. D2EHPA was found to be a stronger extractant, having greater pH functionality than EHEHPA and CYANEX 272. Extraction of vanadium（IV） by these organophosphorous-based extractants involved cation exchange mechanism, and the extracted species appear to be VOR2（HR）2 in the low equilibrium pH and VOR2 in the higher equilibrium pH, where HR refers to the three acidic extractants.

负压封闭引流联合保留臀上动脉浅支的臀大肌肌皮瓣修复骶尾部IV期压疮的临床效果

目的:探讨负压封闭引流联合保留臀上动脉浅支的臀大肌旋转肌皮瓣修复骶尾部压疮的临床效果。方法:选取2019年6月—2023年10月温州医科大学附属第一医院收治的12例骶尾部压疮患者,其中男7例,女5例,年龄31~86岁。入院后I期予行负压封闭引流术,4~7 d后行保留臀上动脉浅支的臀大肌肌皮瓣修复创面。观察术后皮瓣成活情况、并发症发生情况,随访观察皮瓣外形、压疮复发情况。结果:本组12例患者,均因长期卧床致骶尾部受压出现IV期压疮,压疮病因:截瘫患者5例,各种原因所致的长期卧床患者7例,其中脑梗死后遗症患者2例,帕金森病患者3例,老年痴呆症患者1例,股骨颈骨折患者1例。病程2周至8年,清创后创面面积为5.0 cm×5.0 cm~10.0 cm×12.0 cm。12例患者术后皮瓣均完全成活,无皮瓣坏死、静脉淤血、创缘开裂等发生。术后随访2~6个月,皮瓣外形较佳、骶尾部软组织饱满、压疮无复发。结论:保留臀上动脉浅支的臀大肌旋转肌皮瓣血运可靠,设计、操作简单,皮瓣可修复面积大,切取不需要离断臀上动脉浅支,供瓣区一般能直接缝合,修复骶尾部压疮效果较佳。

Impact of Vanadium on Enzyme Activity and Microbial Biomass in Soils

[Objective] This study aimed to investigate the impact of vanadium at dif- ferent concentration on enzyme activity and microbial biomass in soils. [Method] Us- ing pot experiments in the growth cabinet, we would like to investigate the changes of the soil enzyme activity and microbial biomass at different growing stages of rape （Brassica juncea L.） at different soil vanadium concentrations （soil background value was 147 mg/kg, spiked with 0, 50, 100, 150, 250 and 500 mg/kg of exogenous vanadium）. [Result] Among all enzymes examined, polyphenol oxidase was most sensitive to soil vanadium. Addition of 50 mg/kg vanadium decreased its activity up to 56% of the control probably due to the vanadium toxicity. In comparison, the ac- tivities of sucrase, urease and catalase was less affected by soil vanadium. Surpris- ingly, the activity of sucrase, urease and catalase at the rape seedling stage differed significantly from at the maturity stage, highlighting the potential impact of plant growth on the vanadium-soil enzyme interaction. Different soil vanadium concentra- tions led to increases of microbial biomass to different extents. However, the corre- lation between soil microbial biomass carbon and phosphorus with vanadium con- centrations was insignificant. This revealed that the presence of additional factors （eg. plant） affected soil microbial biomass carbon and phosphorus aside from soil vanadium. [Conclusion] Polyphenol oxidase may be considered as an indicator of soil vanadium contamination. Due to the highly complicated interaction between vanadium and soil biological activities during plant growth, more investigations are required to reveal the mechanisms beyond our findings here.

Extraction of vanadium from vanadium slag by high pressure oxidative acid leaching

To extract vanadium in an environment friendly manner, this study focuses on the process of leaching vanadium from vanadium slag by high pressure oxidative acid leaching. Characterizations of the raw slag, mineralogy transformation, and the form of leach residues were made by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The result shows that the vana-dium slag is composed of major phases of fayalite, titanomagnetite, and spinel. During the high pressure oxidative acid leaching process, the fayalite and spinel phases are gradually decomposed by sulfuric acid, causing the release of vanadium and iron in the solution. Meanwhile, unreacted silicon and titanium are enriched in the leach residues. With the initial concentration of sulfuric acid at 250 g·L^-1, a leaching tem-perature of 140℃, a leaching time of 50 min, a liquid-solid ratio of 10：1 mL·g^-1, and oxygen pressure at 0.2 MPa, the leaching rate of vana-dium reaches 97.69%.

基于MIMIC-IV构建及评估脓毒症患者近期和远期死亡风险预测模型

目的:鉴于脓毒症的高发病率和高病死率,早期识别高风险患者并及时干预至关重要,而现有死亡风险预测模型在操作、适用性和预测长期预后等方面均存在不足。本研究旨在探讨脓毒症患者死亡的危险因素,构建近期和远期死亡风险预测模型。方法:从美国重症监护医学信息数据库IV(Medical Information Mart for Intensive Care-IV,MIMIC-IV)中选取符合脓毒症3.0诊断标准的人群,按7?3的比例随机分为建模组和验证组,分析患者的基线资料。采用单因素Cox回归分析和全子集回归确定脓毒症患者死亡的危险因素并筛选出构建预测模型的变量。分别用时间依赖性曲线下面积(area under the curve,AUC)、校准曲线和决策曲线评估模型的区分度、校准度和临床实用性。结果:共纳入14240例脓毒症患者,28 d和1年病死率分别为21.45%(3054例)和36.50%(5198例)。高龄、女性、高感染相关器官衰竭评分(sepsis-related organ failure assessment,SOFA)、高简明急性生理学评分(simplified acute physiology score II,SAPS II)、心率快、呼吸频率快、脓毒症休克、充血性心力衰竭、慢性阻塞性肺疾病、肝脏疾病、肾脏疾病、糖尿病、恶性肿瘤、高白细胞计数(white blood cell count,WBC)、长凝血酶原时间(prothrombin time,PT)、高血肌酐(serum creatinine,SCr)水平均为脓毒症死亡的危险因素(均P<0.05)。由PT、呼吸频率、体温、合并恶性肿瘤、合并肝脏疾病、脓毒症休克、SAPS II及年龄8个变量构建的模型,其28 d和1年生存的AUC分别为0.717(95%CI 0.710~0.724)和0.716(95%CI 0.707~0.725)。校准曲线和决策曲线表明该模型具有良好的校准度及较好的临床应用价值。结论:基于MIMIC-IV建立的脓毒症患者近期和远期死亡风险预测模型有较好的识别能力,对患者预后风险评估及干预治疗具有一定的临床参考意义。

Study on stabilities and electrochemical behavior of V(V) electrolyte with acid additives for vanadium redox flow battery

Several acid compounds have been employed as additives of the V(V) electrolyte for vanadium redox flow battery(VRB) to improve its stability and electrochemical activity. Stability of the V(V) electrolyte with and without additives was investigated with ex-situ heating/cooling treatment at a wide temperature range of-5 ?C to 60 ?C. It was observed that methanesulfonic acid, boric acid, hydrochloric acid, trifluoroacetic acid,polyacrylic acid, oxalic acid, methacrylic acid and phosphotungstic acid could improve the stability of the V(V) electrolyte at a certain range of temperature. Their electrochemical behaviors in the V(V) electrolyte were further studied by cyclic voltammetry(CV), steady state polarization and electrochemical impedance spectroscopy(EIS). The results showed that the electrochemical activity, including the reversibility of electrode reaction, the diffusivity of V(V) species, the polarization resistance and the flexibility of charge transfer for the V(V) electrolyte with these additives were all improved compared with the pristine solution.

A Novel Hierarchical Porous 3D Structured Vanadium Nitride/Carbon Membranes for High-performance Supercapacitor Negative Electrodes

Transition-metal nitrides exhibit wide potential windows and good electrochemical performance, but usually experience imbalanced practical applications in the energy storage field due to aggregation, poor circulation stability, and complicated syntheses. In this study, a novel and simple multiphase polymeric strategy was developed to fabricate hybrid vanadium nitride/carbon(VN/C) membranes for supercapacitor negative electrodes, in which VN nanoparticles were uniformly distributed in the hierarchical porous carbon 3D networks. The supercapacitor negative electrode based on VN/C membranes exhibited a high specific capacitance of 392.0 F g^(-1) at 0.5 A g^(-1) and an excellent rate capability with capacitance retention of 50.5% at 30 A g^(-1). For the asymmetric device fabricated using Ni(OH)_2//VN/C membranes, a high energy density of 43.0 Wh kg^(-1) at a power density of800 W kg^(-1) was observed. Moreover, the device also showed good cycling stability of 82.9% at a current density of 1.0 A g^(-1) after 8000 cycles. This work may throw a light on simply the fabrication of other high-performance transition-metal nitridebased supercapacitor or other energy storage devices.

Preparation and characterization of vanadium(IV) oxide supported on SBA-15 and its catalytic performance in benzene hydroxylation to phenol using molecular oxygen

Preparation of dispersed transition metal oxides catalyst with low oxidation state still remains a challenging task in heterogeneous catalysis.In this study,vanadium oxides supported on zeolite SBA-15 have been prepared under hydrothermal condition using V 2 O 5 and oxalic acid as sources of vanadium and reductant,respectively.The structures of samples,especially the oxidation state of vanadium,and the surface distribution of vanadium oxide species,have been thoroughly characterized using various techniques,including N 2-physisorption,X-ray diffraction（XRD）,transmission electron microscopy（TEM）,X-ray photoelectron spectroscopy（XPS）,UV-visible spectra（UV-Vis） and UV-visible-near infrared spectra（UV-Vis-NIR）.It is found that the majority of supported vanadium was in the form of vanadium（IV） oxide species with the low valence of vanadium.By adjusting hydrothermal treatment time,the surface distribution of vanadium（IV） oxide species can be tuned from vanadium（IV） oxide cluster to crystallites.These materials have been tested in the hydroxylation of benzene to phenol in liquid-phase with molecular oxygen in the absence of reductant.The catalyst exhibits high selectivity for phenol（61%） at benzene conversion of 4.6%,which is a relatively good result in comparison with other studies employing molecular oxygen as the oxidant.

A review of electrolyte additives and impurities in vanadium redox flow batteries

As one of the most important components of the vanadium redox flow battery （VRFB）, the electrolyte can impose a significant impact on cell properties, performance and capital cost. In particular, the electrolyte composition will influence energy density, operating temperature range and the practical applications of the VRFB. Various approaches to increase the energy density and operating temperature range have been proposed. The presence of electrolyte impurities, or the addition of a small amount of other chemical species into the vanadium solution can alter the stability of the electrolyte and influence cell perfor- mance, operating temperature range, energy density, electrochemical kinetics and cost effectiveness. This review provides a detailed overview of research on electrolyte additives including stabilizing agents, im- mobilizing agents, kinetic enhancers, as well as electrolyte impurities and chemical reductants that can be used for different purposes in the VRFBs.

KHCO_3 activated carbon microsphere as excellent electrocatalyst for VO^(2+)/VO_2^+ redox couple for vanadium redox flow battery

In this paper,carbon microsphere prepared by hydrothermal treatment was activated by KHCO_3 at high temperature,and employed as the catalyst for VO^(2+)/VO_2^+redox reaction for vanadium redox flow battery(VRFB).Carbon microsphere can be etched by KHCO_3 due to the reaction between the pyrolysis products of KHCO_3 and carbon atoms.Moreover,KHCO_3 activation can bring many oxygen functional groups on carbon microsphere,further improving the wettability of catalyst and increasing the active sites.The electrocatalytic properties of carbon microsphere from hydrothermal treatment are improved by high temperature carbonization,and can further be enhanced by KHCO_3 activation.Among carbon microsphere samples,the VO^(2+)/VO_2^+redox reaction exhibits the highest electrochemical kinetics on KHCO_3 activated sample.The cell using KHCO_3 activated carbon microsphere as the positive catalyst demonstrates higher energy efficiency and larger discharge capacity,especially at high current density.The results reveal that KHCO_3 activated carbon microsphere is an efficient,low-cost carbon-based catalyst for VO^(2+)/VO_2^+redox reaction for VRFB system.

Modified carbon cloth as positive electrode with high electrochemical performance for vanadium redox flow batteries

Carbon cloth modified by hydrothermal treatment in ammonia water is developed as the positive electrode with high electrochemical performance for vanadium redox flow batteries. The SEM shows that the treatment has no obvious influence on the morphology of carbon cloth. XPS measurements indicate that the nitrogenous functional groups can be introduced on the surface of carbon cloth successfully. The electrochemical performance of V(IV)/V(V) redox couple on the prepared electrode is evaluated with cyclic voltammetry and linear sweep voltammetry measurements. The N-doped carbon cloth exhibits outstanding electrochemical activity and reversibility toward V(IV)/V(V) redox couple. The rate constant of V(IV)/V(V) redox reaction on carbon cloth can increase to 2.27 x 10(-4) cm/s from 1.47 x 10(-4) cm/s after nitrogen doping. The cell using N-doped carbon cloth as positive electrode has larger discharge capacity and higher energy efficiency compared with the cell using pristine carbon cloth. The average energy efficiency of the cell using N-doped carbon cloth for 50 cycles at 30 mA/cm(2) is 87.8%, 4.3% larger than that of the cell using pristine carbon cloth. It indicates that the N-doped carbon cloth has a promise application prospect in vanadium redox flow batteries. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

A phosphotungstic acid coupled silica-Nafion composite membrane with significantly enhanced ion selectivity for vanadium redox flow battery

An ultra-high ion-selective Nafion composite membrane modified by phosphotungstic acid(PWA)coupled silica for vanadium redox flow battery(VRB)was constructed and prepared through solution casting.The composite membrane exhibits excellent proton conductivity and vanadium ions blocking property by incorporating the nanohybrid composed of silica and PWA into the Nafion ionomer.Simple tuning for the filling amount of the nanohybrid endows the obtained membranes preeminent vanadium barrier property including a minimum vanadium permeability of 3.13×10-7cm2min-1and a maximum proton conductivity of 0.081 S cm-1at 25°C.These indicate an ion selectivity of 2.59×105S min cm-3,which is 6.8times higher than that of recast Nafion(0.33×105S min cm-3).As a result,the VRB with the composite membrane shows superior battery performance containing a lower self-discharge rate,higher capacity retention and more robust cyclic stability compared with recast Nafion over a range of current densities from 40 to 100 m A cm-2.

Selective leaching of vanadium from V-Ti magnetite concentrates by pellet calcification roasting-H_(2)SO_(4) leaching process

A novel method of pellet calcification roasting-H_(2)SO_(4) leaching was proposed to efficiently separate and extract vanadium(V)from vanadium-titanium(V-Ti)magnetite concentrates.The leaching rate of V is as high as 88.98%,while the leaching rate of impurity iron is only 1.79%.Moreover,the leached pellets can be used as raw materials for blast furnace ironmaking after secondary roasting.X-ray photoelectron spectroscopy(XPS)and scanning electron microscopy with energy dispersive X-ray spectrometry(SEMEDS)analyses showed that V^(3+)was oxidized to V^(5+)after roasting at 1200℃,and V^(5+)was then leached by H_(2)SO_(4).X-ray diffraction(XRD)analyses and single factor experiment revealed a minimal amount of dissolved Fe_(2)O_(3) during H_(2)SO_(4) leaching.Therefore,a high separation degree of V and iron(Fe)from V-Ti magnetite concentrate was achieved through H_(2)SO_(4) leaching.Compared with the traditional roastingleaching process,this process can achieve a high selectivity of V and Fe,and has excellent prospects for industrial production.

Enhancement in Activity of a Vanadium Catalyst for the Oxidation of Sulfur Dioxide by Radio Frequency Plasma During the Preparation Process

Radio frequency plasma was used to prepare a vanadium catalyst. The resultsshowed that activating time of the catalyst could be shortened quickly and the catalytic activitywas improved to some extent with the use of plasma. Catalyst Ls-9 was prepared under an optimalcondition of 40 W discharge power, 10 min discharge time and 8 Pa gas pressure. The catalyticactivity was up to 54.7% at 410℃, which was 2.2% higher than that of the Ls-8 catalyst. Only 10 minwas needed to activate the catalyst with plasma, which was 1/9 of the traditional calcination time.For Ls-9, both the endothermic as well as the exothermic peaks detected by differential thermalanalysis shifted to higher temperatures obviously, indicating that its crystal phase could melteasily. There existed an apparent endothermic peak at 283℃. SEM photographs showed a uniform sizedistribution. It is inferred that the quadrivalent vanadium compound may exist mainly in the form ofVOSO_4.

Modeling of conducting bridge evolution in bipolar vanadium oxide-based resistive switching memory

We investigate the resistive switching characteristics of a Cu/VOx/W structure. The VOx film is deposited by radio- frequency magnetron sputtering on the Cu electrode as a dielectric layer. The prepared VOx sample structure shows reproducible bipolar resistive switching characteristics with ultra-low switching voltage and good cycling endurance. A modified physical model is proposed to elucidate the typical switching behavior of the vanadium oxide-based resistive switching memory with a sudden resistance transition, and the self-saturation of reset current as a function of compliance current is observed in the test, which is attributed to the conducting mechanism is discussed in detail. growth pattern of the conducting filaments. Additionally, the related

The effect of phosphate additive on the positive electrolyte stability of vanadium redox flow battery

The electrolyte is one of the most important components of vanadium redox flow battery （VRFB）. and its stability and solubility determines the energy density of a VRFB. The performance of current positive elec- trolyte is limited by the low stability of VO2＋ at a higher temperature. Phosphate is proved to be a very effective additive to improve the stability of VO2＋. Even though, the stabilizing mechanism is still not clear, which hinders the further development of VRFBs. In this paper, to clarify the effect of phosphate additive on the positive electrolyte stability, the hydration structures of VO2＋ cations and the reaction mechanisms of precipitation with or without phosphate in the supporting electrolyte of H_2SO_4 solutions were investigated in detail based on calculations of electronic structure. The stable configurations of com- plexes were optimized at the B3LYP/6-311 ＋ G（d,p） level of theory. The zero-point energies and Gibbs free energies for these complexes were further evaluated at the B3LYP/aug-cc-pVTZ level of theory. It shows that a structure of [VO_2（H_2O）_2]＋ surrounded by water molecules in H2S04 solution can be formed at the room temperature. With the temperature rises, [VO_2（H_2O）_2]＋ will lose a proton and form the interme- diate of VO（OH）_3, and the further dehydration among VO（OH）_3 molecules will create the precipitate of V_2O_5. When H_3PO_4 was added into electrolytes, the V-O-P bond-containing neutral compound could be formed through interaction between VO（OH）_3 and H_3PO_4, and the activation energy of forming the V-O-P bond-containing neutral compound is about 7 kcal tool-1 lower than that of the VO（OH）_3 dehydration, which could avoid the precipitation of V_2O_5 and improve the electrolyte stability.

Sucrose pyrolysis assembling carbon nanotubes on graphite felt using for vanadium redox flow battery positive electrode

In the present paper, multi-walled carbon nanotubes（MWCNTs） are successfully assembled on graphite felt（GF） using sucrose pyrolysis method for the first time. The in situ formed pyrolytic carbon is chosen as the binder because it is essentially carbon materials as well as CNTs and GF which has a natural tendency to achieve high bonding strength and low contact resistance. The MWCNTs/GF electrode is demonstrated to increase surface area, reduce polarization, lower charge transfer resistance and improve energy conversion efficiency comparing with GF. This excellent electrochemical performance is mainly ascribed to the high electro-catalytic activity of MWCNTs and increasing surface area.

Vanadium Haloperoxidases Model Compounds: Synthesis, Structural Characterization and Mimic Catalytic Bromination Activity of [VO(C_2O_4)(2,2′-bipy)(H_2O)]·C_2H_5OH and VO(C_2O_4)(phen)(H_2O)

Two oxo-vanadium（IV） complexes, [VO（C2O4）（2,2′-bipy）（H2O）]·C2H5OH（1） and VO（C2O4）（phen）（H2O） （2）, where 2,2′-bipy=2,2′-bipyridyl, phen=1,10-phenanthroline, were synthesized as potential functional models of vanadium haloperoxidases（VHPOs） in mixed solvent of ethanol and water at room temperature. The complexes were characterized by elemental analysis, infrared（IR）, UV-Vis and X-ray crystallography. Structural analyses showed that vanadium atom was coordinated by a terminal oxygen, one oxygen atom from coordinated water, two oxygen atoms from the carboxylate group of oxalic acid, and two nitrogen atoms（N1 and N2） from 2,2′-bipy/phen. Central vanadium atoms in complexes 1 and 2 were both in a distorted-octahedral environment, and some intermolecular hydrogen bonding linkages were also observed in each complex. Bromination reaction activity of the two complexes was evaluated with phenol red as organic substrate in the presence of H2O2, Br-and phosphate buffer, indicating that they can be considered as a potential functional model of VHPO. In addition, thermal analysis was also performed and discussed in detail.