Crystal structure,phase transitions,and thermodynamic properties of magnesium metavanadate(MgV_(2)O_(6))

As a promising anode material for magnesium ion rechargeable batteries,magnesium metavanadate(MgV_(2)O_(6))has attracted considerable research interest in recent years.A MgV_(2)O_(6)sample was synthesized via a facile solid-state reaction by multistep-firing stoichiometric mixtures of MgO and V2O5 powder under an air atmosphere.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)occurred at 841 K and the enthalpy change was 4.37±0.04 kJ/mol.The endothermic effect at 1014 K and the enthalpy change was 26.54±0.26 kJ/mol,which is related to the incongruent melting ofβ-MgV_(2)O_(6).In situ XRD was performed to investigate phase transition of the as-prepared MgV_(2)O_(6)at high temperatures.The cell parameters obtained by Rietveld refinement indicated that it crystallizes in a monoclinic system with the C2/m space group,and the lattice parameters of a=9.280 A°,b=3.501 A°,c=6.731 A°,β=111.76°.The solid-state phase transition fromα-MgV_(2)O_(6)toβ-MgV_(2)O_(6)was further studied by thermal kinetics,indicating that this process is controlled first by a fibril-like mechanism and then by a spherulitic-type mechanism with an increasing heating rate.Additionally,the enthalpy change of MgV_(2)O_(6)at high temperatures was measured utilizing the drop calorimetry,heat capacity was calculated and given as:Cp=208.3+0.03583T-4809000T^(−2)(298-923 K)(J mol^(−1)K^(−1)),the high-temperature heat capacity can be used to calculate Gibbs free energy of MgV_(2)O_(6)at high temperatures.

Phase2接触单元在岩土工程接触分析中的应用

接触分析是工程中岩土体与结构、岩体内部的节理裂隙相互作用时面对的关键问题之一。文章基于Phase2软件接触单元模型,介绍了接触单元的滑移准则,提出了法向刚度和切向刚度这两个参数的估算方法。结果表明:接触单元可以较好地模拟接触面之间的黏接、脱开、相对滑动这三种状态,强度折减安全系数法的计算结果与Goodman-Bray法计算结果基本一致;接触单元对不同材料之间的接触面模拟有较好的效果,同时接触单元也可选择是否考虑接触面内的孔隙水压力。

Optimal parameter space for stabilizing the ferroelectric phase of Hf_(0.5)Zr_(0.5)O_(2) thin films under strain and electric fields

Hafnia-based ferroelectric materials, like Hf_(0.5)Zr_(0.5)O_(2)(HZO), have received tremendous attention owing to their potentials for building ultra-thin ferroelectric devices. The orthorhombic(O)-phase of HZO is ferroelectric but metastable in its bulk form under ambient conditions, which poses a considerable challenge to maintaining the operation performance of HZO-based ferroelectric devices. Here, we theoretically addressed this issue that provides parameter spaces for stabilizing the O-phase of HZO thin-films under various conditions. Three mechanisms were found to be capable of lowering the relative energy of the O-phase, namely, more significant surface-bulk portion of(111) surfaces, compressive c-axis strain,and positive electric fields. Considering these mechanisms, we plotted two ternary phase diagrams for HZO thin-films where the strain was applied along the in-plane uniaxial and biaxial, respectively. These diagrams indicate the O-phase could be stabilized by solely shrinking the film-thickness below 12.26 nm, ascribed to its lower surface energies. All these results shed considerable light on designing more robust and higher-performance ferroelectric devices.

采用PHASE2软件的隧洞一次支护数值模拟与分析

处于V类围岩的隧洞施工时,通常要采取一次支护以保证围岩稳定。采用PHASE2岩土工程弹塑性有限元分析软件,对某引调水工程中处于V类围岩的隧洞围岩位移与塑性区分布进行模拟分析。结果表明:在不采取支护措施情况下,隧洞施工时将发生坍塌破坏,具有极大的安全隐患;在采取拟定措施后,围岩总位移满足规范要求,且未发生塑性破坏,因此支护后隧洞达到稳定且安全的状态,验证支护措施的有效性。但为保证工程安全,建议施工期间做好排水措施,并缩短施工开挖、一次支护措施之间的施工间隔,使支护尽早发挥作用。

A 27 GHz,simple 2-bit 1×8 phased array

This study demonstrates a simple 2-bit phased array operating at 27 GHz that supports one-dimensional beam scanning with left-handed circular polarization(LHCP).The antenna is constructed using a compact four-layer printed circuit board(PCB)structure,consisting of a 90°phase shifter layer with microstrip structures,a ground(GND)layer,a direct current(DC)control layer,and a circularly polarized annular radiation patch layer with 1-bit phase shifting.Based on the proposed unit structure,a 1×8 array with half-wavelength inter-element spacing was designed and validated.Experimental results show that the array achieves a peak gain of 10.23 dBi and is capable of beam scanning within±50°.

Durable hierarchical phosphorus‐doped biphase MoS_(2)electrocatalysts with enhanced H^(*)adsorption

Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.

Regulating crystal phase of TiO_(2) to enhance catalytic activity of Ni/TiO_(2) for solar-driven dry reforming of methane

Ni/TiO_(2) catalyst is widely employed for photo-driven DRM reaction while the influence of crystal structure of TiO_(2) remains unclear.In this work,the rutile/anatase ratio in supports was successfully controlled by varying the calcination temperature of anatase-TiO_(2).Structural characterizations revealed that a distinct TiO_(x) coating on the Ni nanoparticles(NPs)was evident for Ni/TiO_(2)-700 catalyst due to strong metal-support interaction.It is observed that the TiOx overlayer gradually disappeared as the ratio of rutile/anatase increased,thereby enhancing the exposure of Ni active sites.The exposed Ni sites enhanced visible light absorption and boosted the dissociation capability of CH4,which led to the much elevated catalytic activity for Ni/TiO_(2)-950 in which rutile dominated.Therefore,the catalytic activity of solar-driven DRM reaction was significantly influenced by the rutile/anatase ratio.Ni/TiO_(2)-950,characterized by a predominant rutile phase,exhibited the highest DRM reactivity,with remarkable H_(2) and CO production rates reaching as high as 87.4 and 220.2 mmol/(g·h),respectively.These rates were approximately 257 and 130 times higher,respectively,compared to those obtained on Ni/TiO_(2)-700 with anatase.This study suggests that the optimization of crystal structure of TiO_(2) support can effectively enhance the performance of photothermal DRM reaction.

Calculating the number of radial cracks around a wellbore fractured by liquid CO2 phase transition blasting technology

Integrating liquid CO_(2)phase transition blasting(LCPTB)technology with hydraulic fracturing(HF)methods can help reduce wellbore damage,create multiple radial fractures,and establish a complex fracture network.This approach significantly increases the recovery efficiency of low-permeability oil and gas fields.Accurately calculating the number of fractures caused by LCPTB is necessary to predict production enhancement effects and optimize subsequent HF designs.However,few studies are reported on large-scale physical model experiments in terms of a method for calculating the fracture number.This study analyzed the initiation and propagation of cracks under LCPTB,derived a calculation formula for crack propagation radius under stress waves,and then proposed a new,fast,and accurate method for calculating the fracture number using the principle of mass conservation.Through ten rock-breaking tests using LCPTB,the study confirmed the effectiveness of the proposed calculation approach and elucidated the variation rule of explosion pressure,rock-breaking scenario,and the impact of varying parameters on fracture number.The results show that the new calculation method is suitable for fracturing technologies with high pressure rates.Recommendations include enlarging the diameter of the fracturing tube and increasing the liquid CO2 mass in the tube to enhance fracture effectiveness.Moreover,the method can be applied to other fracturing technologies,such as explosive fracturing(EF)within HF formations,indicating its broader applicability and potential impact on optimizing unconventional resource extraction technologies.

β-PbO_2电极中加入纳米级TiO_2的性能研究

通过对传统电沉积β-PbO2工艺技术的改进(在镀液中加入纳米级TiO2),使镀层β-PbO2的脆性大大降低,从而使其可在温度为90℃的H2SO4介质中使用,镀层不会从基材剥落,而是自然损耗。

Influence of nano-CeO_2 on coating structure and properties of electrodeposited Al/α-PbO_2/β-PbO_2

Al/α-PbO2/β-PbO2 composite electrodes doped with rare earth oxide （CeO2） were prepared by anodic oxidation method investigate the influence of nano-CeO2 dopants on the properties of Al/α-PbO2/β-PbO2-CeO2 electrodes and the impact of α-PbO2 as the intermediate layer. The results show that using α-PbO2 as the intermediate layer will benefit the crystallization of β-PbO2 and β-PbO2 is more suitable as the surface layer than α-PbO2. CeO2 dopants change the crystallite size and crystal structure, enhance the catalytic activity, and even change the deposition mechanism of PbO2. The doping of CeO2 in the PbO2 electrodes can enhance the electro-catalytic activity, which is helpful for oxygen evolution, and therefore reduce the cell voltage.

Ti/α-PbO_2/β-PbO_2电极电催化氧化处理苯酚废水

采用电催化氧化法,以自制Ti/α-PbO2/β-PbO2电极为阳极,在室温条件下对苯酚模拟废水进行降解研究,探讨电流密度、电极间距、pH值及苯酚初始质量浓度对苯酚降解效率的影响规律.结果表明,在电流密度为600 A.m-2,电极间距为1.0 cm,pH值为3,苯酚初始质量浓度为100 mg.L-1的条件下,苯酚降解效率达92%以上.紫外光谱等实验结果表明,苯酚在氧化降解过程中会产生苯醌等中间产物,苯酚及其中间产物最终被矿化为CO2和H2O.

β-PbO_2电极的改性制备及其性能

通过对传统电沉积 β PbO2 工艺技术的改进 (在镀液中加入纳米级TiO2 ) ,使镀层 β PbO2 ,的脆性大大降低 ,从而使其在温度为 90℃的H2 SO4 介质中使用 ,镀层不会与基材剥落 ,而是自然损耗。

α-PbO_2型TiO_2电子结构的第一性原理计算

基于密度泛函理论(DFT)的平面波超软赝势方法,从第一性原理计算的角度,应用GGA对Ti O2的高压相α-PbO2型Ti O2的晶格参数和电子结构作了比较系统的计算,得到优化后的晶格参数与实验值十分符合。电子结构计算表明α-PbO2型Ti O2属于间接带隙半导体,其禁带宽度为2.47 eV,大于锐钛矿型Ti O2计算的带隙值Eg=2.12eV,主要原因在于α-PbO2型Ti O2结构具有较低的晶体对称性,并且其Ti—O平均键长更长,Ti与O离子的正负电荷数较少,Ti3d轨道与O2p轨道杂化程度较弱。在理论上确认对称性较低的高压矿物—α-PbO2型Ti O2高压相的光催化效果不及常态相锐钛矿型Ti O2好。

Ti/α-PbO_2/β-PbO_2电极电化学降解2-氯酚（英文）

采用电化学沉积法在Ti基底上制备了复合电极Ti/α-PbO 2/β-PbO 2,扫描电镜结果表明电极呈现由β-PbO 2小晶体组成的菜花状微观形貌.所制电极在电化学降解环境污染物2-氯酚时表现出较高的电催化效率、较好的电极稳定性和较长的电极寿命.用正交实验优化了电化学降解2-氯酚的实验条件.在最优的实验条件(2-氯酚初始浓度50 mg/L,电解质0.1 mol/L Na2SO4,温度35 oC,阳极电流密度20 mA/cm2)下电化学降解180 min后,2-氯酚的去除率达100%.动力学结果表明,Ti/α-PbO 2/β-Pb O2电极上2-氯酚的电化学氧化符合准一级动力学过程.

纳米Ag_2O_2-PbO_2化学修饰电极对大肠杆菌细胞膜壁和DNA损伤的研究

制备了一种新型纳米Ag2O2-PbO2修饰电极,在选定的正电位下,电极表面产生羟基自由基(.OH).通过测定产生的脂质过氧化物和漏出蛋白质的量来研究羟基自由基对大肠杆菌细胞膜壁损伤的情况,并运用电泳和DNA测序的方法对大肠杆菌质粒DNA的损伤及其对序列变化进行了研究.

β-PbO_2纳米棒及Pb_3O_4纳米晶的制备与表征

利用 Na Cl O在碱性溶液中与 Pb(Ac) 2 进行氧化反应直接合成出直径为 1 0～ 2 0 nm、长度为 40 0 nm、长径比达 2 0以上的纯相 β-Pb O2 纳米棒 .对所得 β-Pb O2 在 42 0℃下进行热解 ,得到晶粒尺寸为 2 0 nm左右的 Pb3O4 .对液相氧化反应的温度、时间、氧化剂浓度、p H等因素的影响进行了详细研究 ,获得了最佳合成反应条件 .所得产物利用粉末 X射线衍射和透射电子显微镜分析进行了表征 .

Mechanical properties and electronic structures of MgCu_2, Mg_2Ca and MgZn_2 Laves phases by first principles calculations

Mechanical properties and electronic structure of MgCu2, Mg2 Ca and MgZn2 phases were investigated by means of first principles calculations from CASTEP program based on density functional theory（DFT）. The calculated lattice parameters are in good agreement with the experimental and literature values. The calculated heat of formation and cohesive energies showed that MgCu2 has the strongest alloying ability and structural stability. Elastic constants of MgCu2, Mg2 Ca and MgZn2 were calculated, and the bulk moduli, shear moduli, elastic moduli and Poisson ratio were derived. The calculated results show that MgCu2, Mg2 Ca and MgZn2 are all ductile phases. Among the three phases, MgCu2 has the strongest stiffness and the plasticity of MgZn2 phase is the best. Melting points of the three phases were predicted using cohesive energy and elastic constants. Density of states（DOS）, Mulliken population, electron occupation number and charge density difference were discussed. Finally, Debye temperature was calculated and discussed.

Ti/SnO_2+Sb_2O_3/β-PbO_2阳极电化学氧化异噻唑啉酮

采用提拉法和电沉积法制作Ti/SnO2+Sb2O3/β-PbO2阳极,通过SEM扫描、XRD分析和极化曲线测定表征具有良好结构和催化性能.利用该电极氧化异噻唑啉酮水溶液,研究运行参数(电化学氧化时间、电流密度和水溶液pH值)的变化对异噻唑啉酮和化学耗氧量(ChemicalOxygenDemand,CODcr)降解效果的影响,降解过程符合一级动力学方程.在异噻唑啉酮水溶液初始浓度200mg/L、电流密度15mA/cm2、电化学氧化180min时,异噻唑啉酮、CODcr去除率可分别达到98%和43%.通过紫外光谱图分析了异噻唑啉酮氧化过程为先开环,再生成低分子有机酸,最后矿化为CO2和H2O.

表面处理对碳纤维基β-PbO_2电极性能的影响

对碳纤维布进行表面处理,采用电沉积法制备碳纤维基β-PbO_2电极材料,并对碳纤维基β-PbO_2电极材料的导电性能、电化学性能和耐腐蚀性能进行研究。结果表明:通过表面处理,能够显著改善碳纤维的表面粗糙度和化学活性。热空气氧化温度为400℃时,碳纤维表面的化学活性最高;热空气氧化和液相氧化双重氧化发现,碳纤维表面的化学活性进一步提高,表面的沟槽和凹坑更为明显,经此表面处理条件后制备的碳纤维电极界面电阻率最低为6.19×10^(-5)Ω·m,导电性能和电化学性能最好,耐腐蚀性能最强,腐蚀速率仅为1.44×10^(-3)g·cm^(-2)·h^(-1),由此说明,不同表面处理条件能够极大地影响碳纤维电极材料界面结合性能,从而影响碳纤维基β-PbO_2电极材料的导电性能、电化学性能和耐腐蚀性能。

Al/β-PbO_2电极的制备及其性能

利用直流电沉积的方法,在铝基体上电解沉积β-PbO2镀层。通过条件实验分析了电流密度、镀液温度和沉积时间对电解沉积β-PbO2的电流效率、沉积速度、镀层厚度和硬度的影响,并确定了最佳工艺条件:Pb-(NO3)2200～250g/L,HNO310g/L,电流密度3～4A/dm2,镀液温度50～55℃,电沉积时间4h。