金属硼化物的制备、性质与应用研究进展

金属原子与硼原子间电荷转移量决定了金属硼化物中化学键的成键方式、成键强弱和功能特性。金属硼化物的制备、晶体结构和应用一直是化学和材料领域的研究热点。基于金属硼化物广泛的应用前景以及其在国内外多数基础无机化学教材中的介绍非常有限,本文结合史实文献和最新研究成果,重点介绍了碱金属/碱土金属硼化物、过渡金属硼化物和稀土金属硼化物的结构、性质、制备和应用研究进展。拓展了金属硼化物在教学中的深入介绍,有助于提升学生的知识视野,体现科学研究对本科教学内容改革的推进作用。

Exceptional thermal stability and enhanced hardness in a nanostructured Mg-Gd-Y-Zn-Zr alloy processed by high pressure torsion

A Mg-8.2Gd-3.8Y-1.0Zn-0.4Zr(wt.%) alloy is processed by solution treatment and high pressure torsion(HPT) at room temperature to produce a nanostructured light material with high hardness. The stability of this alloy is subsequently tested through isochronal annealing for 0.5 h at 373 K to 673 K. The results reveal a thermal stability that is vastly superior to that of conventional Mg-based alloys processed by severe plastic deformation: the grain size remains at around 50 nm on heating to 573 K, and as the temperature is increased to 673 K,grain growth is restricted to within 500 nm. The stability of grain refinement of the present alloy/processing combination allowing grain size to be limited to 55 nm after exposure at 573 K, appears to be nearly one order of magnitude better than for the other SPD processed Mg-RE type alloys, and 2 orders of magnitude better than those of SPD processed RE-free Mg alloys. This superior thermal stability is attributed to formation of co-clusters near and segregation at grain boundaries, which cause a thermodynamic stabilization of grain size, as well as formation of β-Mg_(5)RE equilibrium phase at grain boundaries, which impede grain growth by the Zener pinning effect. The hardness of the nanostructured Mg-Gd-Y-Zn-Zr alloy increases with increasing annealing temperature up to 573 K, which is quite different from the other SPD-processed Mg-based alloys. The high hardness of 136 HV after annealing at 573 K is mainly due to solute segregation and solute clustering at or near grain boundaries.

Observing single cells in whole organs with optical imaging

Cells are the basic unit of human organs that are not fully understood.The revolutionary advancements of optical imaging alowed us to observe single cells in whole organs,revealing the complicated composition of cells with spatial information.Therefore,in this review,we revisit the principles of optical contrast related to those biomolecules and the optical techniques that transform optical contrast into detectable optical signals.Then,we describe optical imaging to achieve threedimensional spatial discrimination for biological tisutes.Due to the milky appearance of tissues,the spatial information burred deep in the whole organ.Fortunately,strategies developed in the last decade could circumvent this issue and lead us into a new era of investigation of the cells with their original spatial information.

Diagnostic Value and Safety of CT and US-Guided PTNB for Peripheral Pulmonary Lesions: A Meta-Analysis and Clinical Study

Objective: To evaluate the diagnostic value and safety of CT and ultrasound-guided PTNB for peripheral type of occupying lung lesions by meta-analysis and clinical study. Methods: 1) The target data of randomized controlled trials of CT and ultrasound-guided PTNB for peripheral type of occupying lung lesions were extracted by computer search of foreign PubMed, Embase, the Cochrane Library, Web of Science databases, since the establishment of the database. Cochrane quality assessment criteria were used for evaluation. Statistical analysis was performed using Review Manager 5.3 software. 2) To retrospectively study the diagnosis rate and complication rate of patients, undergoing CT or ultrasound-guided PTNB in the First Affiliated Hospital of Dali University from January 2015 to December 2020. Results: Meta-analysis included 7 papers with a total of 1177 patients including 502 patients in the ultrasound group and 675 patients in the CT group. Meta-analysis results showed that there was no difference in the diagnosis rate of PTNB guided by ultrasound and CT. The incidence of postoperative complications was higher in the CT group than in the ultrasound group. The incidence of postoperative pneumothorax was higher in the CT group than in the ultrasound group, and there was no difference in the incidence of postoperative bleeding. 3) Clinical study results show that the puncture success rate was 100% in both of the ultrasound and CT groups, the pathological diagnosis rate was 85.48% in the ultrasound group and 91.67% in the CT group, and there was no difference in the overall complication rate between the two puncture groups. Conclusion: Either ultrasound or CT-guided PTNB is a safe and effective clinical diagnostic method for the diagnosis of peripheral pulmonary occupations.

Highly active CoP-CO_(2)N confined in nanocarbon enabling efficient electrocatalytic immobilizing-conversion of polysulfide targeting high-rate lithium-sulfur batteries

Lithium-sulfur batteries suffer from poor cycling stability because of the intrinsic shuttling effect of intermediate polysulfides and sluggish reaction kinetics,especially at high rates and high sulfur loading.Herein,we report the construction of a CoP-CO_(2)N@N-doped carbon polyhedron uniformly anchored on three-dimensional carbon nanotubes/graphene(CoP-CO_(2)N@NC/CG)scaffold as a sulfur reservoir to achieve the trapping-diffusion-conversion of polysulfides.Highly active CoP-CO_(2)N shows marvelous catalytic effects by effectively accelerating the reduction of sulfur and the oxidation of Li_(2)S during the discharging and charging process,respectively,while the conductive NC/CG network with massive mesoporous channels ensures fast and continuous long-distance electron/ion transportation.DFT calculations demonstrate that the CoP-CO_(2)N with excellent intrinsic conductivity serves as job-synergistic immobilizing-conversion sites for polysulfides through the formation of P…Li/N…Li and Co…S bonds.As a result,the S@CoP-CO_(2)N@NC/CG cathode(sulfur content 1.7 mg cm^(-2))exhibits a high capacity of988 mAh g^(-1)at 2 C after 500 cycles,which is superior to most of the electrochemical performance reported.Even under high sulfur content(4.3 mg cm^(-2)),it also shows excellent cyclability with high capacity at 1 C.

Construction and Application of High Temperature Heat Damage Index for River Crab Culture in Hongze Lake Beach

Agrometeorology and agricultural statistics methods were used to analyze the cases of high temperature heat damage to crab breeding since 2008 in Hongze Lake Beach, finding that the high temperature heat damage was mainly under the comprehensive effects of the highest temperature, duration of high temperature weather, amount of precipitation and sunshine hours. Based on the function relation between the high temperature heat damage index and the influence factors, the linear model was used to describe the weight coefficient of each heat damage factor by using the synthesis correlation of multiple factors. The historical values of the influencing factors were used to make statistical calculation of the heat damage index model of crab culture in Hongze Lake Beach, which achieved good effects when applied in the meteorological operation of river crab culture.

Laboratory creep tests for time-dependent properties of a marble in Jinping Ⅱ hydropower station

In order to investigate the time-dependent behaviors of deep hard rocks in the diversion tunnel of Jinping II hydropower station, uniaxial creep tests were carried out by using the triaxial testing machine RC-2000. The axial compressive load was applied step by step and each creep stage was kept for over several days. Test results show that： （1） The lateral deformation of rock specimens is 2-3 times the axial compressive deformation and accelerates drastically before damage, which may be employed as an indicator to predict the excavation-induced instability of rocks. （2） The resultant deformation changes from compression to expansion when the Poisson＇s ratio is larger than 0.5, indicating the starting point of damage. （3） In the step-loading stages, the Poisson＇s ratio approximately remains constant; under constantly imposed load, the Poisson＇s ratio changes with elapsed time, growing continuously before the specimen is damaged. （4） When the applied load reaches a certain threshold value, the rock deteriorates with time, and the strength of rocks approximately has a negative exponent relation with time. （5） The failure modes of the deep marble are different in long- and short-term loading conditions. Under the condition of short-term loading, the specimen presents a mode of tensile failure; while under the condition of long-term loading, the specimen presents a mode of shear failure, followed by tensile failure.

Unraveling the coordination behavior and transformation mechanism of Cr^(3+) in Fe–Cr redox flow battery electrolytes

Currently,the iron chromium redox flow battery(ICRFB)has become a research hotspot in the energy storage field owing to its low cost and easily-scaled-up.However,the activity of electrolyte is still ambiguous due to its complicated solution environment.Herein,we performed a pioneering investigation on the coordination behavior and transformation mechanism of Cr^(3+)in electrolyte and prediction of impurity ions impact through quantum chemistry computations.Based on the structure and symmetry of electrostatic potential distribution,the activity of different Cr^(3+)complex ions is confirmed as[Cr(H2O)5Cl]^(2+)>[Cr(H2O)4Cl2]+>[Cr(H2O)6]^(3+).The transformation mechanism between[Cr(H2O)6]^(3+)and[Cr(H2O)5Cl]^(2+)is revealed.We find the metal impurity ions(especially Mg^(2+))can exacerbate the electrolyte deactivation by reducing the transformation energy barrier from[Cr(H2O)5Cl]^(2+)(24.38 kcal mol^(−1))to[Cr(H2O)6]^(3+)(16.23 kcal mol^(−1)).The solvent radial distribution and mean square displacement in different solvent environments are discussed and we conclude that the coordination configuration limits the diffusivity of Cr^(3+).This work provides new insights into the activity of electrolyte,laying a fundamental sense for the electrolyte in ICRFB.

Preparation and properties of CMAS resistant bixbyite structured high-entropy oxides RE_(2)O_(3)(RE=Sm,Eu,Er,Lu,Y,and Yb):Promising environmental barrier coating materials for Al_(2)O_(3)f/Al_(2)O_(3) composites

Y_(2)O_(3) is regarded as one of the potential environmental barrier coating(EBC)materials for Al_(2)O_(3)f/Al_(2)O_(3)ceramic matrix composites owing to its high melting point and close thermal expansion coefficient to Al_(2)O_(3).However,the relatively high thermal conductivity and unsatisfactory calcium-magnesium-aluminosilicate(CMAS)resistance are the main obstacles for the practical application of Y_(2)O_(3).In order to reduce the thermal conductivity and increase the CMAS resistance,four cubic bixbyite structured high-entropy oxides RE_(2)O_(3),including(Eu_(0.2)Er_(0.2)Lu_(0.2)Y_(0.2)Yb_(0.2))2O_(3),(Sm_(0.2)Er_(0.2)Lu_(0.2)Y_(0.2)Yb_(0.2))2O_(3),(Sm_(0.2)Eu_(0.2)Er_(0.2)Y_(0.2)Yb_(0.2))2O_(3),and(Sm_(0.2)Eu_(0.2)Lu_(0.2)Y_(0.2)Yb_(0.2))2O_(3)were designed and synthesized,among which(Eu_(0.2)Er_(0.2)Lu_(0.2)Y_(0.2)Yb_(0.2))2O_(3)and(Sm_(0.2)Er_(0.2)Lu_(0.2)Y_(0.2)Yb_(0.2))2O_(3)bulks were prepared by spark plasma sintering(SPS)to investigate their mechanical and thermal properties as well as CMAS resistance.The mechanical properties of(Eu_(0.2)Er_(0.2)Lu_(0.2)Y_(0.2)Yb_(0.2))2O_(3)and(Sm_(0.2)Er_(0.2)Lu_(0.2)Y_(0.2)Yb_(0.2))2O_(3) are close to those of Y_(2)O_(3) but become more brittle than Y_(2)O_(3).The thermal conductivities of(Eu_(0.2)Er_(0.2)Lu_(0.2)Y_(0.2)Yb_(0.2))2O_(3) and(Sm_(0.2)Er_(0.2)Lu_(0.2)Y_(0.2)Yb02)2O_(3)(5.1 and 4.6 W·m^(-1)·K^(-1))are only 23.8%and 21.5%respectively of that of Y_(2)O_(3)(21.4 W·m^(-1)·K^(-1)),while their thermal expansion coefficients are close to those of Y_(2)O_(3) and A12O_(3).Most importantly,HE RE_(2)O_(3) ceramics exhibit good CMAS resistance.After being attacked by CMAS at 1350℃for 4 h,the HE RE_(2)O_(3) ceramics maintain their original morphologies without forming pores or cracks,making them promising as EBC materials for Al_(2)O_(3)f/Al_(2)O_(3) composites.

In-situ structure reconstitution of NiCo2Px for enhanced electrochemical water oxidation

Gaining insight into the structure evolution of transition-metal phosphides during anodic oxidation is significant to understand their oxygen evolution reaction(OER) mechanism, and then design highefficiency transition metal-based catalysts. Herein, NiCo_2P_x nanowires(NWs) vertically grown on Ni foam were adopted as the target to explore the in-situ morphology and chemical component reconstitution during the anodic oxidation. The major factors causing the transformation from NiCo_2P_x into the hierarchical NiCo_2P_x@CoNi(OOH)_x NWs are two competing reactions: the dissolution of NiCo_2P_x NWs and the oxidative re-deposition of dissolved Co^(2+) and Ni^(2+) ions, which is based primarily on the anodic bias applied on NiCo2 Px NWs. The well balance of above competing reactions, and local pH on the surface of NiCo_2P_x NW modulated by the anodic oxidation can serve to control the anodic electrodeposition and rearrangement of metal ions on the surface of NiCo_2P_x NWs, and the immediate conversion into CoNi(OOH)_x. Consequently, the regular hexagonal CoNi(OOH)_x nanosheets grew around NiCo_2P_x NWs.Benefiting from the active catalytic sites on the surface and the sufficient conductivity, the resultant NiCo_2P_x@CoNi(OOH)_x arrays also display good OER activity, in terms of the fast kinetics process, the high energy conversion efficiency, especially the excellent durability. The strategy of in-situ structure reconstitution by electrochemical reaction described here offers a reliable and valid way to construct the highly active systems for various electrocatalytic applications.

Reduced graphene oxide-supported CoP nanocrystals confined in porous nitrogen-doped carbon nanowire for highly enhanced lithium/sodium storage and hydrogen evolution reaction

Rational synthesis of a hierarchical porous architecture with highly active and consecutive conductive network is very critical to achieve the high-performance of nanomaterials in electrochemical energy conversion and storage.We propose here a hierarchical micro-/nanostructured hybrids constructed by the dual carbon shell nanowire host containing CoP nanocrystals of several nanometers,which generates Co-based metal-organic framework on graphene oxide nanosheets in situ and followed a direct phosphorization(CoP@NC/rGO).The dual carbon shell,consisting of Co-based metal-organic framework derived porous doped carbon(NC)and reduced graphene oxide(rGO),can not only impedes CoP nanocrystals from coalescing,and renders highly exposed the electrochemically accessible active sites,but also provides the multidimensional pathways for rapid electron and ion transportation.More importantly,the covered dual carbon shell on CoP nanocrystals plays a role as a protective layer to impede the nanocrystals’corrosion.By virtue of compositional and structural advantages,the micro-/nanostructured CoP@NC/rGO hybrids manifest outstanding energy storage properties when evaluated as anodes for lithium/sodium ion batteries.Remarkably,it also reveals highly efficient electrocatalytic performance for hydrogen evolution reaction in acid media with low Tafel slope,overpotential and robust durability.

Preparation of a tantalum-based MoSi_(2)–Mo coating resistant to ultra-high-temperature thermal shock by a new two-step process

To develop an ultra-high-temperature resistant coating for a reusable thermal protection system,the preparation of a tantalum-based MoSi_(2)-Mo coating by a new two-step process of multi-arc ion plating and halide activated pack cementation is presented.The coating has a dense structure and is well compatible with the tantalum substrate,which can be thermally shocked from room temperature to 1750℃ for 360 cycles without failure.The mechanism of the coating’s excellent resistance to high-temperature thermal shocks is that a strong-binding gradient interface and a dense SiO_(2) oxide scale with good oxygen resistance are formed by the high-temperature self-diffusion of Si.

Ultrathin MoS2 with expanded interlayers supported on hierarchical polypyrrole-derived amorphous N-doped carbon tubular structures for high-performance Li/Na-ion

Layered molybdenum disulfide （MoS2） has received much attention as one of the most promising energy-storage and conversion materials for Li/Na ion batteries. Here, a simple and effective approach is proposed for the rational design and preparation of hierarchical three-d imensional （3D） amorphous N-doped carbon nanotube@MoS2 nanosheets （3D-ANCNT@MoS2） via a simple hydrothermal method, followed by an annealing process. With such a unique nanoarchitecture, ultrathin MoS2 nanosheets grown on the external surfaces of polypyrrole-derived ANCNTs are assembled to form a hierarchical 3D nanoarchitecture, where the adopted ANCNTs serve not only as the template and continuous conductive matrix, but can also prevent MoS2 from aggregating and restacking, and help to buffer the volumetric expansion of MoS2 during cycling. More importantly, when evaluated as an anode material for lithium-ion batteries, the 3D-ANCNT@MoS2 composite exhibits excellent cycling stability, superior rate performance, and reversible specific capacity as high as 893.4 mAh·g^-1 at 0.2 A·g^-1 after 200 cycles in a half battery, and 669.4 mAh·g^-1 at 0.2 A·g^-1 after 100 cycles in the 3D-ANCNT@Mo2//LiCoO2 full battery. With respect to sodium-ion batteries, the outstanding reversible capacity, excellent rate behavior, and good cycling performance of 3D-ANCNT@MoS2 composites are also achieved.

Fabrication of micro/nano-structures by electrohydrodynamic jet technique

Electrohydrodynamicjet （E-Jet） is an approach to the fabrication of micro/nano-structures by the use of electrical forces. In this process, the liquid is subjected to electrical and mechanical forces to form a liquid jet, which is further disintegrated into droplets. The major advantage of the E-Jet technique is that the sizes of the jet formed can be at the nanoscale far smaller than the nozzle size, which can realize high printing resolution with less risk of nozzle blockage. The E-Jet technique, which mainly includes E-Jet deposition and E-Jet printing, has a wide range of applications in the fabrication ofmicro/nano-structures for micro/nano-electromechanical system devices. This tech- nique is also considered a micro/nano-fabrication method with a great potential for commercial use. This study mainly reviews the E-Jet deposition/printing fundamentals, fabrication process, and applications.

Balance control of grid currents for UPQC under unbalanced loads based on matching-ratio compensation algorithm

In three-phase four-wire systems, unbalanced loads can cause grid currents to be unbalanced, and this may cause the neutral point potential on the grid side to shift. The neutral point potential shift will worsen the control precision as well as the performance of the threephase four-wire unified power quality conditioner(UPQC),and it also leads to unbalanced three-phase output voltage,even causing damage to electric equipment. To deal with unbalanced loads, this paper proposes a matching-ratio compensation algorithm(MCA) for the fundamental active component of load currents, and by employing this MCA,balanced three-phase grid currents can be realized under 100% unbalanced loads. The steady-state fluctuation and the transient drop of the DC bus voltage can also be restrained. This paper establishes the mathematical model of the UPQC, analyzes the mechanism of the DC bus voltage fluctuations, and elaborates the interaction between unbalanced grid currents and DC bus voltage fluctuations;two control strategies of UPQC under three-phase stationary coordinate based on the MCA are given, and finally, the feasibility and effectiveness of the proposed control strategy are verified by experiment results.

A superior strength-ductility synergy of Al_(0.1)CrFeCoNi high-entropy alloy with fully recrystallized ultrafine grains and annealing twins

Grain refinement usually makes the materials stronger,while ductility has a dramatic loss.Here,a superior tensile strength–ductility synergy in a fully recrystallized ultrafine-grained(UFG)Al_(0.1)CrFeCoNi with abundant annealing twins was achieved by cold rolling at room temperature and short-time annealing.The microstructure characterization using electron backscattered scattering diffraction demonstrates that abundant geometrically necessary dislocations(GNDs)gather around the grain boundaries and twin boundaries after tensile deformation.Although coarse-grained(CG)samples undergo a larger plastic deformation than UFG samples,the GND density decreases with grain size ranging from UFG to CG.Transmission electron microscopy results reveal that the annealing twin boundary,which effectively hinders the dislocation slip and stores dislocation in grain interior,and the activation of multiple deformation twins are responsible for the superior strength–ductility synergy and work hardening ability.In addition,the yield strength of fully recrystallized Al_(0.1)CrFeCoNi follows a Hall–Petch relationship(σ_y=24+676d^(–1/2)),where d takes into account both grain boundaries and annealing twin boundaries.The strengthening effects of grain boundaries and annealing twin boundaries were also evaluated separately.

一步硫/磷热处理制备空心Co_(9)S_(8)/CoP/C纳米复合材料及其储钠性能研究

低成本、高性能的钠离子电池有望成为代替锂离子电池的下一代核心器件.但是开发出高比容量、高倍率的钠离子电池负极材料依然是瓶颈.本文通过水热/溶剂热法制备了Co基前驱体,然后将其一步硫/磷热处理制得具有空心多孔结构的h-Co_(9)S_(8)/CoP/C纳米复合材料.通过X-射线粉末衍射(XRD)、拉曼光谱(Raman)、扫描电镜(SEM)、透射电镜(TEM)和X-射线光电子能谱(XPS)等表征以确定纳米复合物的物相以及形貌特征.当h-Co_(9)S_(8)/CoP/C作为钠离子电池负极材料时,该电极材料展示了高的比容量(561 mAh g^(-1)@0.1 Ag^(-1))、较好的循环性能(可逆比容量200 mAh g^(-1)@2 Ag^(-1))和倍率性能.h-Co_(9)S_(8)/CoP/C之所以显示出良好的储钠性能,主要得益于其空心多孔结构不仅提供更多的空间缓解钠在反复嵌入和脱出过程造成的体积膨胀效应,而且可以缩短离子/电荷扩散途径以加快反应动力学,此外,Co_(9)S_(8)、CoP和C独特的电子结构优势得以共同发挥.

A new thinprep cytologic test of cervical cells and its application

In order to improve the quality of routine cervical smears,we investigated the new Thinprep cytologic test(TCT)for cervical cells.In this study,100 women who were enrolled were randomly divided into two groups.In one group,the TCT for cervical cells was applied(TCT group),and in the other group routine cervical smear was used.In addition,the cells in the TCT group were screened by double sifters,and centrifuged using a separation medium so as to eliminate mucus,inflammatory cells and blood cells.According to the cell distribution and the thickness of the smear,the results were assigned to three groups,including satisfactory smears,less satisfactory smears and unsatisfactory smears.The TCT had a higher satisfactory rate(98%)compared to the routine cervical smear(32%)(P<0.01),indicating the TCT was superior to the routine cervical smear.It is concluded that the TCT is more acceptable.Meanwhile,in comparison to the routine cervical smear,the TCT for cervical cells has 5 advantages which can greatly increase the cytological accuracy.

Revealing the Unusual Efficiency Enhancement of Organic Solar Cells with Polymer-Donor-Treated Cathode Contacts

The metal oxides with low trap density of states as the electron transport layer are crucial for the high performance of the organic solar cells(OSCs).It is universally acknowledged that modifying n-type metal oxide contacts with polymer donors will harm the carrier extraction on account of the mismatched energy level.However,we find that modifying interlayer consisting of the alcohol amines with some polymer donor additive can unusually enhance the performance of the OSCs.Compared with triethanolamine(TEA)passivated ZnO,TEA:polymer donor treated ZnO shows lower trap density and enhances electron mobility resulting in higher current density in OSC devices.Here,we reveal that the enhanced oxygen-defect passivation ability of TEA with polymer additive is attributed to the enhanced negative electrostatic potential of TEA owing to the hydrogen bond formation between the polymer and the hydroxyl group in TEA.This strategy that enhancing the negative electrostatic potential of the passivators for improving oxygen defect passivation can be extended to other types of organic electronic devices.

Sacrificial layer-assisted nanoscale transfer printing

Transfer printing is an emerging assembly technique for flexible and stretchable electronics.Although a variety of transfer printing methods have been developed,transferring patterns with nanometer resolution remains challenging.We report a sacrificial layer-assisted nanoscale transfer printing method.A sacrificial layer is deposited on a donor substrate,and ink is prepared on and transferred with the sacrificial layer.Introducing the sacrificial layer into the transfer printing process eliminates the effect of the contact area on the energy release rate(ERR)and ensures that the ERR for the stamp/ink-sacrificial layer interface is greater than that for the sacrificial layer/donor interface even at a slow peel speed(5mm s−1).Hence,large-area nanoscale patterns can be successfully transferred with a yield of 100%,such as Au nanoline arrays(100 nm thick,4 mm long and 47 nm wide)fabricated by photolithography techniques and PZT nanowires(10mm long and 63nm wide)fabricated by electrohydrodynamic jet printing,using only a blank stamp and without the assistance of any interfacial chemistries.Moreover,the presence of the sacrificial layer also enables the ink to move close to the mechanical neutral plane of the multilayer peel-off sheet,remarkably decreasing the bending stress and obviating cracks or fractures in the ink during transfer printing.