羟基自由基在菱镁矿界面的吸附特性模拟

为明确水中脉冲放电产生的羟基自由基(·OH)在菱镁矿解离面的吸附特性,本文采用Materials Studio软件对菱镁矿(211)解离面进行态密度分析,选择菱镁矿(211)解离面中Mg原子的顶位,建立·OH吸附模型。模拟结果表明,菱镁矿与·OH之间的吸附能为-4.381eV,·OH可吸附在菱镁矿(211)解离面上。

Electrolyte engineering for optimizing anode/electrolyte interface towards superior aqueous zinc-ion batteries:A review

Aqueous zinc-ion batteries(AZIBs) are promising candidates for the large-scale energy storage systems due to their high intrinsic safety,cost-effectiveness and environmental friendliness.However,issues such as dendrite growth,hydrogen evolution reaction,and interfacial passivation occurring at the anode/electrolyte interface(AEI) have hindered their practical application.Constructing a stable AEI plays a key role in regulating zinc deposition and improving the cycle life of AZIBs.The fundamentals of AEI and the challenges faced by the Zn anode due to unstable interfaces are discussed.A comprehensive summary of electrolyte regulation strategies by electrolyte engineering to achieve a stable Zn anode is provided.The effectiveness evaluation techniques for stable AEI are also analyzed,including the interfacial chemistry and surface morphology evolution of the Zn anode.Finally,suggestions and perspectives for future research are offered about enabling a durable and stable AEI via electrolyte engineering,which may pave the way for developing high-performance AZIBs.

十九种矿物药的检索鉴别

根据晶体形状、解离面和条痕特征,以检索表形式区别十九种常见矿物药。笔者认为该方法简单实用,可供基层单位鉴别矿物药时参考。

溴乙烯在外电场中的解离性质研究

溴乙烯具有极高的毒性,它不仅会污染环境,还会损害人类的身心健康.因此,研究它的分子结构及其解离方式,不仅具有重要的科学意义,而且也具有极高的社会意义.本文采用密度泛函理论(DFT),以B3LYP/6-31G++(d,p)基组,深入探索溴乙烯分子在0 V·nm^(-1)~80 V·nm^(-1)外电场的影响下,其分子结构和解离特性.通过计算,随着外电场的增强:分子总能量和碳碳双键(C=C)的键长减小,碳溴键(C-Br)的键长和偶极矩增大.能隙E_(G)先增大后减小,分子结构稳定性降低.红外光谱主要产生了6个特征吸收峰,且普遍存在红移现象.分子解离特性表现为:当外部电场强度升高时,势垒会显著减弱,直至达到154.26 V·nm^(-1)时,势垒就会完全消除,溴乙烯分子的解离能相应减弱,这表明,当外部电场强度升高时,溴乙烯分子会发生逐步的分解.因此,这一结论可以为进一步探讨溴乙烯分子和其相关的化合物的解离研究提供依据.

Recent developments in visible-light photocatalytic degradation of antibiotics

With the significant discharge of antibiotic wastewater into the aquatic and terrestrial ecosystems, antibiotic pollution has become a serious problem and presents a hazardous risk to the environment. To address such issues, various investigations on the removal of antibiotics have been undertaken. Photocatalysis has received tremendous attention owing to its great potential in removing antibiotics from aqueous solutions via a green, economic, and effective process. However, such a technology employing traditional photocatalysts suffers from major drawbacks such as light absorption being restricted to the UV spectrum only and fast charge recombination. To overcome these issues, considerable effort has been directed towards the development of advanced visible light-driven photocatalysts. This mini review summarises recent research progress in the state-of-the-art design and fabrication of photocatalysts with visible-light response for photocatalytic degradation of antibiotic wastewater. Such design strategies involve the doping of metal and non-metal into ultraviolet light-driven photocatalysts, development of new semiconductor photocatalysts, construction of heterojunction photocatalysts, and fabrication of surface plasmon resonance-enhanced photocatalytic systems. Additionally, some perspectives on the challenges and future developments in the area of photocatalytic degradation of antibiotics are provided.

Competition Between Two Excitation-dissociation Channels for Molecular Ions

When the molecular ions XYZ＋ （XY2＋） are excited simultaneously from an electronic state E0 into two higher electronic states Ea and EZ with supervened dissociation or predisso- ciation, competition between the α and β excitation-dissociation channels occurs. A the- oretical model is provided to deal with the competition of the two excitation-dissociation channels with more than two kinds of ionic products for XYZ＋ （XY2＋）. Supposing that the photo-excitation rates of two states Eα and Eβ are much less than their dissociation or pre-dissociation rates, a theoretical equation can be deduced to fit the measured data, which reflects the dependence of the product branching ratios on the intensity ratios of two excitation lasers. From the fitted parameters the excitation cross section ratios are obtained. In experiment, we studied the competition between two excitation-dissociation channels of CO^2＋. By measuring the dependence of the product branching ratio on the intensity ratio of two dissociation lasers and fitting the experiment data with the theoretical equation, excitation cross section ratios were deduced.

Structure of Reconstructed Cu（100） Surface Induced by Dissociative Adsorption of Gaseous Oxygen

The reconstructed structures of Cu（100） surface induced by O2 dissociative adsorption were investigated by low energy electron diffraction and scanning tunneling microscopy. At lower oxygen coverage, it was found that two reconstructed structures, i.e. c（2×2）-O and （√2×2√2）R45°-O are coexistent. The domain size of the c（2×2）-O structure decreased with the increasing of O2 exposure. The reconstructed structure at very small coverage was also investigated and a “zigzag” structure was observed at this stage. The “zigzag” structure was identified as boundaries of local c（2×2） domains. It was found that the strip region shows much stronger molecule-substrate interaction than that of oxygen covered regions, making it a proper template for patterned organic films. The sequence of the thermal stability was found as zigzag structure〉c（2×2）〉（√2×2√2）R45°-O.

Stability of Crystal Growth Face and Dissolution Face in Crystallization from Solution under Microgravity

The stability of the shapes of crystal growth face and dissolution face in a two-dimensional mathematical model of crystal growth from solution under microgravity is studied. It is proved that the stable shapes of crystal growth face and dissolution face do exist, which are suitably shaped curves with their upper parts inclined backward properly.The stable shapes of crystal growth faces and dissolution faces are calculated for various values of parameters, Ra, Pr and Sc. It is shown that the stronger the convection relative to the diffusion in solution is, the more backward the upperparts of the stable crystal growth face and dissolution face are inclined. The orientation and the shape of dissolution face hardly affect the stable shape of crystal growth face and vice versa.

Proton Dissociation from Surfaces of Variable Charge Soil andMnierals

Experiments on proton dissociation from the surfaces of goethite, amorphous Al oxide, kaolinite and latosolwere carried out, showing amphoteric behavior with reactions of proton dissociation-association on the surfaces andbuffering capacity in such a sequence as amorphous Al oxide > latosol > kaolinite > goethite. Dissociation con-stants of surface proton, pK_(sa) are significantly correlated with surface charge density, which has been proved with anelectrochemical model. Tbe intrinsic constants of proton dissociation, K_(sa)(int), gained by extrapolation to zero charconditions of plots of pK_(sa) against σ_o, could be used to estimate the acidity strength of variable charge surfaces. Thevalue of pK_(sa)(int) is 8.08 for goethite, 1 .2 for amorphous Al oxide, 6.62 for kaolinite and 5 .32 for latosol.

Effect of electrolyte on mechanical properties of AZ31B Mg alloy in electrolytic plasma processing

Coatings on Mg alloys were prepared using NaOH + Na2SiO3 as basic electrolyte containing electrolyte of Na2SiF6 or NaF. EPP treatment was carried out on AZ31 Mg alloys matrix under a hybrid voltage of AC of 200 V combined with DC of 260 V for 30 min. Structural and morphological analyses of ceramic coatings were analyzed by XRD and SEM. Wear and hardness of coatings were measured by pin-on disk test and Vickers hardness test. The coatings formed in Na2SiF6 and NaF electrolytes were mainly composed of MgO and Mg2SiO4. The measured micro-hardness of coating formed in Na2SiF6 electrolyte was found to be over HV 1100, while, coating formed in NaF electrolyte possessed micro-hardness of HV ~900. These results show that the mechanical properties of AZ31 B Mg alloys can be enhanced by the proper selection of electrolyte agent.

In situ Investigations of Interfacial Degradation and Ion Migration at CH3NH3PbI3 Perovskite/Ag Interfaces

Interfacial properties between perovskite layers and metal electrodes play a crucial role in the device performance and the long-term stability of perovskite solar cells.Here,we report a comprehensive study of the interfacial degradation and ion migration at the interface between CH3NH3PbI3 perovskite layer and Ag electrode.Using in situ photoemission spectroscopy measurements,we found that the Ag electrode could induce the degradation of perovskite layers,leading to the formation of PbI2 and AgI species and the reduction of Pb^2+ions to metallic Pb species at the interface.The unconventional enhancement of the intensities of I 3d spectra provides direct experimental evidences for the migration of iodide ions from CH3NH3PbI3 subsurface to Ag electrode.Moreover,the contact of Ag electrode and perovskite layers induces an interfacial dipole of 0.3 eV at CH3NH3PbI3/Ag interfaces,which may further facilitate iodide ion diffusion,resulting in the decomposition of perovskite layers and the corrosion of Ag electrode.

Adsorption of H2O, OH, and O on CUCl（111） Surface： A Density Functional Theory Study

The adsorption of H2O molecule and its dissociation products, O and OH, on CuCl（111） surface was studied with periodic slab model by PW91 approach of GGA within the framework of density functional theory. The results of geometry optimization indicate that the top site is stable energetically for H2O adsorbed over the CuCl（111） surface. The threefold hollow site is found to be the most stable adsorption site for OH and O, and the calculated adsorption energies are 309.5 and 416.5 kJ/mol, respectively. Adsorption of H20 on oxygen-precovered CuCl（111） surface to form surface hydroxyl groups is predicted to be exothermic by 180.1 kJ/mol. The stretching vibrational frequencies, Mulliken population analysis and density of states analysis are employed to interpret the possible mechanism for the computed results.

Diagrammatic Representation of Electronic Correlations in Photoionization Process: Application to Scandium

The conversion rules under which an algebraic expression can be obtained from a corresponding photoionizationGoldstone diagram have been given systematically in the present work.The electronic correlations in thephotoionization processes then could be studied diagrammatically.The application to atomic scandium shows that thepresent theoretical scheme can give reasonable photoionization cross sections,which agree well with the experimentalresults.

Effect of surface nanocrystallization and PPEC time on complex nanocrystalline hard layer fabricated by plasma electrolysis

Size distribution of nano-carbides produced by duplex treatments of surface nanocrystallization(by surface severe plastic deformation) and plasma electrolytic carburizing on CP-Ti was investigated.Skewness and kurtosis of Gussian shape distribution curves were studied and the effect of time was determined.The usage of longer time is more suitable for achieving less size of complex nano-carbides.Surface roughness of treated samples was measured.It is observed that there is an optimum level for time on surface roughness increasing(difference between two measured data).

Partition Equilibrium Between Charged Membrane and Single Electrolyte Aqueous Solution

Ionic partition equilibrium in charged membrane immersed in solution of single electrolyte with monovalence or multi-valence is systematically investigated and several expressions are established for determination of partition coefficients. On this basis, the effects of the ratio of membrane charge density to bulk electrolyte solution concentration, the charge sign and valence of electrolyte ions and the type of membrane on the partition equilibrium were analyzed and simulated within chosen parameters. It is revealed that ion partition is not related solely with the respective concentrations but also definitely with the concentration ratio of fixed group to bulk solution in addition to the charge sign and the valence. For a counterion, the partition coefficient increases with this ratio and the valence; while for a coion, the partition coefficient decreases with this ratio and the valence. The theoretical calculations were compared with the experimental data and a good agreement was observed.

Resonant Effects of FPL and SPP for Light Transmitting through Subwavelength Metallic Gratings

A new model is proposed to explain the physical mechanism of the extraordinary transmission enhancement in subwavelength metallic grating.The extraordinary transmission enhancement is described by the co-operation of Fabry-Perot-like(FPL) resonance and the surface plasmon polariton(SPP) resonance.The rigorous coupled-wave analysis(RCWA) and the finite difference time domain(FDTD) method are employed to illustrate the model by calculating the transmission and the field distributions in the subwavelength metallic grating,respectively.And the numerical calculations show that transmission enhancement is achieved when the coupling resonance of the incident light,the surface plasmon polariton mode and the Fabry-Perot-Like mode is happened,which are in good agreement with the proposed model.

Surface-Induced Dissociation of Low Energy H_2^(+) Impact on a Carbon Surface: A Monte Carlo Simulation

A Monte Carlo simulation based on the classical binary collision approximation is performed to investigate the interaction of W2 ions with the carbon target. The incident H2^＋ ion is characterized by its translational energy, eigenenergy and population of the vibrational state, and orientation of the ion with respect to the target surface. It is shown that experimentally determined energy resolved mass spectrum of H＋ can be nicely reproduced with the help of the proposed model. These simulations predict that translational to vibrational （T → V） energy transfer efficiency increases nonlinearly with translational energy of the incident ion. T → V energy transfer efficiency along with the initial vibrational energy of the incident H＋ ion found to play an important role in dissociation. Our simulations also show that the fraction of absorbed, reflected, and dissociated ions depends on the translational energy. The average vibrational energy of reflected H＋ increases with its initial translational energy. Moreover, average number of collisions required for dissociation varies inversely with the initial translational energy of the H2^＋.

丙烯醛在外电场中的解离性质

利用密度泛函理论(DFT)计算方法,在6-31G+(d,p)基组上,讨论C_(3)H_(4)O气体分子在受到外加电场(-10.28 V·nm^(-1)~10.28 V·nm^(-1))作用时的结构特征和解离特性。计算发现,沿分子共轭单键的方向电场增强时,总能量增大,碳碳双键和碳碳单键的键长减小,碳氧双键键长增大,偶极矩减小;能隙E_(G)增加,红外吸收峰在不同的频率分别发生红移和蓝移,同时IR强度发生变化。分子解离性能表现为:势能壁垒随着外电场增大而降低,达到25.71 V·nm^(-1)时势能壁垒几乎消失,解离能随着电场增加而逐渐降低,说明在电场作用下解离难度逐渐减小。研究结果为C_(3)H_(4)O气体分子或含有该成分的混合物在外电场下的解离特性研究提供参考。

外电场作用下BrCl分子的物理特性与光谱

采用HF（Hartree-Fock）方法,在6-31＋G（d,p）基组水平上优化不同外电场（0-0.035 a.u.）下氯化溴分子的基态稳定构型,在此基础上计算氯化溴分子的分子结构、偶极矩、分子总能量、分子键长、分子电荷分布、分子能隙、红外光谱及解离势能面等.结果表明：随着Z轴（平行于Br-Cl连线）方向外电场的增加（0-0.035 a.u.）,分子总能量先小幅度增加后又降低,键长先减小后增大,分子偶极矩先减小后单调增加,原子电荷分布递增,分子能隙逐渐减小,分子红外光谱先蓝移后红移.通过对解离势能面的计算分析发现,强度为0.045 a.u.的外电场使得Br-Cl键断裂而降解,该结果对氯化溴进行电场降解提供参考依据.

Photoelectrode for water splitting: Materials,fabrication and characterization

Photoelectorchemical（PEC） water splitting is an attractive approach for producing sustainable and environment-friendly hydrogen. An efficient PEC process is rooted in appropriate semiconductor materials, which should possess small bandgap to ensure wide light harvest, facile charge separation to allow the generated photocharges migrating to the reactive sites and highly catalytic capability to fully utilize the separated photocharges. Proper electrode fabrication method is of equal importance for promoting charge transfer and accelerating surface reactions in the electrodes. Moreover,powerful characterization method can shed light on the complex PEC process and provide deep understanding of the rate-determining step for us to improve the PEC systems further. Targeting on high solar conversion efficiency, here we provide a review on the development of PEC water splitting in the aspect of materials exploring, fabrication method and characterization. It is expected to provide some fundamental insight of PEC and inspire the design of more effective PEC systems.