二氧化碳电催化剂理论设计方法研究进展

CO_(2)电催化还原(ECR)是一种极具应用前景的CO_(2)利用技术,其关键在于高性能催化剂的开发。采用理论方法可有效指导与加速高效ECR催化剂的设计。从密度泛函理论(DFT)、溶剂化模型、电化学计算模型和机器学习四个方面介绍了ECR催化剂的理论设计方法。DFT、DFT+U、杂化泛函可有效计算ECR反应体系的能量、电子特性等,预测催化剂的性能;对于ECR反应中的溶剂效应,综合计算成本和精度需考虑显式溶剂化模型、隐式溶剂化模型和混合模型;在ECR电化学计算中,恒定电极电位模型比计算氢电极模型更能有效描述CO_(2)还原的能量变化;机器学习可高效、低成本地实现ECR催化剂的性能预测、活性位点设计和组分优化。最后,对CO_(2)电催化剂的理论设计方法进行了展望。

亚硫酸钠在乙硫氮-方铅矿浮选体系中的作用及机理研究

通过方铅矿单矿物浮选试验、吸附量测定、红外光谱检测和电化学计算等手段,研究了亚硫酸钠在乙硫氮-方铅矿浮选体系中的作用及机理。研究结果表明:乙硫氮-方铅矿浮选体系中,方铅矿浮选的较佳乙硫氮浓度为4×10-5 mol/L,方铅矿浮选的较佳pH范围为6 ~ 11;乙硫氮与方铅矿表面相互作用形成的疏水性产物主要为二乙基二硫代氨基甲酸铅(PbD2);中性及碱性条件下在乙硫氮-方铅矿浮选体系中添加亚硫酸钠后红外光谱特征吸收峰增强;乙硫氮-方铅矿浮选体系中的矿浆pH值随着亚硫酸钠的添加而升高,方铅矿的自身氧化反映随着矿浆pH值得升高而受到一定程度的抑制,从而使方铅矿可浮性变好。

Calculation model of edge carbon atoms in graphite particles for anode of lithium-ion batteries

Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in different sites.A spherical close-packed model for graphite particle was developed.The fractions of surface carbon atoms（SCA） and edge carbon atoms（ECA） were derived in the expression of crystallographic parameters and particle size,and the effects of ECA on the initial irreversible capacity and the mechanisms of action were analyzed and verified.The results show that the atoms on the edge are more active for electrochemical reactions,such as electrolyte decomposition and tendency to form stable bond with other atoms and groups.For the practical graphite particle,corresponding modifying factors were introduced to revise the difference in calculating results.The revised expression is suitable for the calculation of the fractions of SCA and ECA for carbon materials such as graphite,disordered carbon and modified graphite.

Influence of freezing rate on microstructure and electrochemical properties of Mg-2%Ga alloys

Equilibrium freezing curve of Mg-2%Ga （mass fraction） alloy was calculated by CALPHALD method. Microstructures of the melted Mg-2%Ga alloys solidified by iron and copper moulds, respectively, were investigated using OM and SEM. Electrochemical properties of the Mg-2%Ga alloys with different freezing rates were measured by galvanostatic, potentiodynamic and electrochemical impedance spectroscopy tests. The results show that solidification by copper mould leads to intergranular MgsGa2 compounds with small size and large number density. Less adsorbent of Mg^＋ and oxide corrosion products occur on the surface of the Mg-2%Ga alloys solidified by copper mould, producing lower corrosion current density of 1.8×10^-5 mA/cm^2. In the galvanostatic tests with 100 mA/cm^2 current density, more negative stable potential of-1.604 V exists in the Mg-2%Ga alloys solidified by iron mould due to the lower freezing rate, which leads to smaller inductive and capacity time constants as well as shorter activity time and better electrochemical activity.

铝空(氧)电池与铝水电池水下应用可行性分析

以铝空(氧)电池与铝水电池为研究对象,详细描述了其工作原理和应用现状,并通过电化学计算,进行与氢氧燃料电池联合发电的水下应用可行性分析。分析结果表明,与氢燃料电池相比,铝空(氧)电池与铝水电池由于工作原理和特点,更加适合小功率、低储能的水下装备。此外,与氢燃料电池联用不仅使系统更加复杂,而且产生的效益也不明显。

Theoretical Investigation on Photoionization and Dissociative Photoionization of Toluene

The photoionization and dissociation photoionization of toluene have been studied using quantum chemistry methods. The geometries and frequencies of the reactants, transition states and products have been performed at B3LYP/6-311＋＋G（d,p） level, and single-point energy calculations for all the stationary points were carried out at DFT calculations of the optimized structures with the G3B3 level. The ionization energies of toluene and the ap- pearance energies for major fragment ions, C7H7＋, C6H5＋, C5H6＋, C5H5＋, are determined to be 8.90, 11.15 or 11.03, 12.72, 13.69, 16.28 eV, respectively, which are all in good agree- ment with published experimental data. With the help of available published experimental data and theoretical results, four dissociative photoionization channels have been proposed： CTHT＋＋H, C6Hs＋＋CH3, C5H6＋WC2H2, CsHs＋＋C2H2＋H. Transition structures and intermediates for those isomerization processes are determined in this work. Especially, the structures of C5H6＋ and C5H5＋ produced by dissociative photoionization of toluene have been defined as chain structure in this work with theoretical calculations.

Flotation behavior and adsorption mechanism of fine wolframite with octyl hydroxamic acid

Flotation behavior and adsorption mechanism of octyl hydroxamic acid(OHA)on wolframite were investigated through flotation experiments,adsorption tests,zeta-potential measurements,infrared spectroscopy and solution chemistry calculations.Results of flotation and adsorption experiments show that the maximum values of flotation recovery and adsorption capacity occur around p H 9.In term of the solution chemistry calculations,the concentration of metal hydroxamate is greater than that of metal tungstate and metal hydroxyl,and metal hydroxamate compounds are identified to be the main species on wolframite surface at p H region of 8-10,contributing to the increase of OHA adsorption and flotation performance.Results of zeta-potential and IR spectra demonstrate that OHA adsorbs onto wolframite surface by chemisorptions.Hydroxamate ions can bond with Mn_2+/Fe_2+cations of wolframite surface,forming metal hydroxamate compounds,which is a key factor in inducing the hydrophobicity of wolframite under the conditions of maximum flotation.

Oxidation of chalcopyrite in air-equilibrated acidic solution: Inhibition with phenacyl derivatives

The effects of 4-(2-hydroxyphenyl)-2-(morpholin-4-yl)-1,3-thiazole(Pr02), 1-(3,5-dibromo-2-hydroxyphenyl)-1-oxoethan-2-yl-N,N-diethyldithiocarbamate(Pr04) and 1-(5-bromo-2-hydroxy-3-methylphenyl)-1-oxoethan-2-yl-Oethyl xanthate(Pr06) on the aqueous oxidation of chalcopyrite(CuFeS2) in air-equilibrated solution at a temperature of 25 ℃ and a pH of 2.5 were studied. The effects were investigated by using potentiodynamic polarization, electrochemical impedance spectroscopy(EIS), scanning electron microscopy coupled with energy dispersive X-ray(SEM/EDX) analysis, aqueous batch experiments, Fourier transform infrared(FTIR) spectroscopy, Raman scattering and quantum chemical calculations. It is found that the anodic current densities decrease in the order of EtOH > Pr02 > Pr04 > Pr06. These results, along with those of the EIS measurements, show that Pr02, Pr04 and Pr06 are effective anodic inhibitors of chalcopyrite aqueous oxidation. Both Raman scattering and FTIR spectroscopy indicate that the elemental sulfur, polysulfide and ferric oxyhydroxides that form on the surface of the mineral are not responsible when it comes to the aqueous oxidation inhibition of chalcopyrite. Quantum chemical calculations show that the adsorption of the tested compounds on the chalcopyrite surface is energetically favorable and so, it can explain the inhibiting effects that were observed.

Optimization study of a PEM fuel cell performance using 3D multi-phase computational fluid dynamics model

An optimization study using a comprehensive 3D, multi-phase, non-isothermal model of a PEM （proton exchange membrane） fuel cell that incorporates significant physical processes and key parameters affecting fuel cell performance is presented and discussed in detail. The model accounts for both gas and liquid phase in the same computational domain, and thus allows for the implementation of phase change inside the gas diffusion layers. The model includes the transport of gaseous species, liquid water, protons, energy, and water dissolved in the ion-conducting polymer. Water is assumed to be exchanged among three phases： liquid, vapottr, and dissolved, with equilibrium among these phases being assumed. This model also takes into account convection and diffusion of different species in the channels as well as in the porous gas diffusion layer, heat transfer in the solids as well as in the gases, and electrochemical reactions. The results showed that the present multi-phase model is capable of identifying important parameters for the wetting behaviour of the gas diffusion layers and can be used to identify conditions that might lead to the onset of pore plugging, which has a detrimental effect on the fuel cell performance. This model is used to study the effects of several operating, design, and material parameters on fuel cell performance. Detailed analyses of the fuel cell performance under various operating conditions have been conducted and examined.

Structural and Bonding Properties of Al_(n)C_(4)^(−/0)(n=2−4)Clusters:Anion Photoelectron Spectroscopy and Theoretical Calculations

We measured the photoelectron spectra of Al_(n)C_(4)^(−)(n=2−4)clusters by using size-selected anion photoelectron spectroscopy.The structures of Al_(n)C_(4)^(−/0)(n=2−4)clusters were explored with quantum chemistry calculations and were determined by comparing the theoretical results with the experimental spectra.It is found that the most stable structure of Al_(2)C_(4)^(−) anion is a C_(2v)symmetry planar structure with two Al atoms interacting with two C_(2)units.In addition,Al_(2)C_(4)^(−) anion also has a D∞h symmetry linear structure with two Al atoms located at the two ends of a C_(4)chain,which is slightly higher in energy than the planar structure.The most stable structure of neutral Al_(2)C_(4)has a D∞h symmetry linear structure.The most stable structure of Al_(3)C_(4)^(−) anion is a planar structure with three Al atoms interacting with two C_(2)units.Whereas neutral Al_(3)C_(4)cluster has a C_(2v)symmetric V-shaped bent structure.The global minima structures of both Al_(4)C_(4)^(−) and neutral Al_(4)C_(4)are C_(2)h symmetry planar structures with four Al atoms interacting with the ends of two C_(2)units.Adaptive natural density partitioning analyses of Al_(n)C_(4)^(−)(n=2−4)clusters show that the interactions between the Al atoms and C_(2)units have bothσandπcharacters.

Waveforms analysis and optimization of new electro-hydraulic excitation technology

A new electro-hydraulic exciter that consists of rotary valve and micro-displacement double-functioned hydraulic cylinder was proposed to realize different kinds of waveforms.Calculated fluid dynamics(CFD) simulation of rotary valve orifice reveals that orifice exists the two-throttle phenomenon.According to the finding,the revised flow area model was established.Vibration waveforms analysis was carried out by means of mathematic model and the related experiments were validated.Furthermore,as a new analysis indicator,saturation percentage was introduced first.The experimental results indicate that the revised flow area model is more accurate compared to the original one,and vibration waveforms can be optimized through suitable spool parameters and the revised cylinder structure.

Nonlinear Optical Response of Conjugated Polymer to Elec tric Field

The organic π-conjugate d polymers are of major interest materials for the use in electro-optical and no nlinear optical devices. In this work, for a selected polyacetylene chain, the optical absorption spectra in UV/Vis regime as well as the linear polarizabiliti y and nonlinear hyperpolarizability are calculated by using quantum chemical ab initio and semiempirical methods. The relationship of its optical property to el ectric field is obtained. Some physical mechanism of electric field effect on mo lecular optical property is discussed by means of electron distribution and intr amolecular charge transfer.

Molecular Dipole Moment Computed with Ab Initio MKS Charges

Molecular dipole moments computed at the levels of HF/STO-3G, HF/6-31G(d, p), HF/6-311+G(2d, 2p), MP2/6-31G(d, p) and MP2/6-311+G(2d, 2p) have been investigated. HF/6-311+G(2d, 2p) was found to be the relatively good choice to compute MKS charges for reproducing the experimental values of molecular dipole moments. Root mean square deviation of computed dipole moments for 21 small polar molecules is about 0.1969 D.

Density Functional Theory and Electrochemistry Studies on LiFexMn1-xPO4 Solid Solutions

The thermodynamic stability and lithiated/delithiated potentials of LiFexMn1-xPO4 were studied with density functional theorical calculations. The results show that the formation free energy of the LiFexMn1-xPO4 solid solution is slightly higher than that of the phase-separated mixture of LiFePO4 and LiMnPO4, and the two forms may co-exist in the actual LiFexMn1-xPO4 materials. The calculation manifests that the lithiated/delithiated potentials of LiFexMn1-xPO4 solid solutions vary via the Mn/Fe ratio and the spatial arrangements of the transition metal ions, and the result is used to explain the shape of capacity-voltage curves. Experimentally, we have synthesized the LiFexMn1-xPO4 materials by solid-phase reaction method. The existence of the LiFexMn1-xPO4 solid solution is thought to be responsible for the appearance of additional capacity-voltage plateau observed in the experiment.

Corrosion behaviour of 6061 Al-15vol. Pct. SiC composite and its base alloy in sulphuric acid medium

In this paper the corrosion characteristics of Silicon carbide particulate-reinforced 6061 aluminum composite （ 6061 AI/SiCp composite ） and the base alloy are experimentally assessed. The corrosion tests are carried out at different temperatures in the concentration range of 0.01N to 1N sulphuric acid as corrosion media using Tafel extrapolation technique and Electrochemical Impedance Spectroscopy （EIS）. The results obtained from Tafel extrapolation technique and Electrochemical Impedance Spectroscopy are in good agreement. The results show an increase in the corrosion rate with increase in temperature as well as with increase in the concentration of the corrosion media. The thermodynamic parameters like energy of activation are calculated using Arrhenius theory equation and, enthalpy of activation and entropy of activation are calculated using transition state theory equation.

Delocalizedπ_(3)^(6) Bond in OX_(2) (X=Halogen) Molecules

OX_(2)(X=halogen)molecules was studied theoretically.Calculation results show that delocalizedπ_(3)^(6) bonds exist in their electronic structures and O atoms adopt the sp^(2) type of hybridization,which violates the prediction of the valence shell electron pair repulsion theory of sp^(3) type.Delocalization stabilization energy is proposed to measure the contribution of delocalizedπ_(3)^(6) bond to energy decrease and proves to bring extra-stability to the molecule.These phenomena can be summarized as a kind of coordinating effect.

First principles calculation on electronic structure,chemical bonding,elastic and optical properties of novel tungsten triboride

The electronic structures,chemical bonding,elastic and optical properties of the novel hP24 phase WB3 were investigated by using density-functional theory(DFT) within generalized gradient approximation(GGA).The calculated energy band structures show that the hP24 phase WB3 is metallic material.The density of state(DOS) and the partial density of state(PDOS) calculations show that the DOS near the Fermi level is mainly from the W 5d and B 2p states.Population analysis suggests that the chemical bonding in hP24-WB3 has predominantly covalent characteristics with mixed covalent-ionic characteristics.Basic physical properties,such as lattice constant,bulk modulus,shear modulus and elastic constants Cij were calculated.The elastic modulus E and Poisson ratio υ were also predicted.The results show that hP24-WB3 phase is mechanically stable and behaves in a brittle manner.Detailed analysis of all optical functions reveals that WB3 is a better dielectric material,and reflectivity spectra show that WB3 can be promised as good coating material in the energy regions of 8.5-11.4 eV and 14.5-15.5 eV.

Fuel Cells as Energy Systems： Efficiency, Power Limits and Thermodynamic Behavior

Steady-state model of a high-temperature solid oxide fuel cell （SOFC） is considered, which refers to constant chemical potentials of incoming hydrogen fuel and oxidant. Lowering of the cell voltage below its reversible value is attributed to polarizations and imperfect conversions of reactions. An imperfect power formula summarizes the effect of transport laws, irreversible polarizations and efficiency of power yield. Reversible electrochemical theory is extended to the case with dissipative chemical reactions; this case includes systems with incomplete conversions, characterized by ＂reduced affinities＂ and an idle run voltage. Efficiency drop is linked with thermodynamic and electrochemical irreversibilities expressed in terms of polarizations （activation, concentration and ohmic）. Effect of incomplete conversions is modeled by assuming that substrates can be remained after the reaction and that side reactions may occur. Optimum and feasibility conditions are discussed for basic input parameters of the cell. Calculations of maximum power show that the data differ for power generated and consumed and depend on current intensity, number of mass transfer units, polarizations, electrode surface area, average chemical rate, etc.. These data provide bounds for SOFC energy generators, which are more exact and informative than reversible bounds for electrochemical transformation.

基于元胞自动机模型的镍基合金点蚀模拟（英文）

为了深入理解核电蒸汽发生器传热管的点蚀,发展了利用元胞自动机(CA)模型模拟点蚀过程。元胞自动机的4个基本元素由电化学反应,化学反应和扩散过程决定。模拟结果通过定性和定量的方式与试验和已有文献进行了对比。结果显示:元胞自动机模拟能够较好的模拟出点蚀的萌生和亚稳态扩展过程,得到了点蚀坑的形状、腐蚀电流密度和Cl-对点蚀的影响,这些结果对蒸汽发生器传热管的结构完整性预测有重要影响。

A multiphase nickel iron sulfide hybrid electrode for highly active oxygen evolution

Development of highly active electrocatalysts for oxygen evolution reaction(OER)is one of the critical issues for water splitting,and most reported catalysts operate at overpotentials above 190 mV.Here we present a multiphase nickel iron sulfide(MPS)hybrid electrode with a hierarchical structure of iron doped NiS and Ni3S2,possessing a benchmark OER activity in alkaline media with a potential as low as 1.33 V(vs.reversible hydrogen electrode)to drive an OER current density of 10 mA cm^-2.The Fe doped NiS,combined with highly conductive disulfide phase on porous Ni foam,is believed to be responsible for the ultrahigh activity.Furthermore,density functional theory simulation reveals that partially oxidized sulfur sites in Fe doped NiS could dramatically lower the energy barrier for the rate-determining elementary reaction,thus contributing to the active oxygen evolution.