Surface Metallization of Glass Fiber(GF)/Polyetheretherketone(PEEK) Composite with Cu Coatings Deposited by Magnetron Sputtering and Electroplating

Surface metallization of glass fiber(GF)/polyetheretherketone(PEEK)[GF/PEEK] is conducted by coating copper using electroplating and magnetron sputtering and the properties are determined by X-ray diffraction(XRD), scanning electron microscopy(SEM), and electron backscatter diffraction(EBSD).The coating bonding strength is assessed by pull-out tests and scribing in accordance with GB/T 9286-1998.The results show that the Cu coating with a thickness of 30 μm deposited on GF/PEEK by magnetron sputtering has lower roughness, finer grain size, higher crystallinity, as well as better macroscopic compressive stress,bonding strength, and electrical conductivity than the Cu coating deposited by electroplating.

Adsorption of Methanol and Methoxy on Cu（111） Surface： A First-principles Periodic Density Functional Theory Study

Adsorption of methanol and methoxy at four selected sites （top, bridge, hcp, fcc） on Cu（111） surface has been investigated by density functional theory method at the generalized gradient approximation （GGA） level. The calculation on adsorption energies, geometry and electronic structures, Mulliken charges, and vibrational frequencies of CH3OH and CH3O on clean Cu（111） surface was performed with full-geometry optimization, and compared with the experimental data. The obtained results are in agreement with available experimental data. The most favorite adsorption site for methanol on Cu（111） surface is the top site, where C-O axis is tilted to the surface. Moreover, the preferred adsorption site for methoxy on Cu（111） surface is the fcc site, and it adsorbs in an upright geometry with pseudo-C2v local symmetry. Possible decomposition pathways also have been investigated by transition-state searching methods. Methoxy radical, CH3O, was found to be the decomposition intermediate. Methanol can be adsorbed on the surface with its oxygen atom directly on a Cu atom, and weakly chemisorbed on Cu（111） surface. In contrast to methanol, methoxy is strongly chemisorbed to the surface.

助剂Ni对Cu(111)表面催化NH_(3)还原NO反应影响的理论研究

针对商用钒钛脱硝催化剂存在的环境污染和易中毒问题,采用无毒环保的单金属铜催化剂并使用助剂Ni掺杂提高其脱硝性能。基于密度泛函理论(DFT),探究了助剂Ni对Cu(111)表面催化NH_(3)还原NO反应的影响。通过分析催化剂表面反应物种的吸附、反应机理和电子结构,对比了助剂Ni掺杂前后Cu(111)表面的催化活性。结果表明,所有反应物种在CuNi(111)表面上的吸附效果均优于在Cu(111)表面的吸附效果。CuNi(111)表面发生的三步基元反应需克服的能垒均低于Cu(111)表面,其中,速控步骤(NH_(2)NO→N_(2)+H_(2)O)的能垒降低了63.6 kJ/mol,可见CuNi(111)表面催化活性明显较高。相比Cu(111)表面,CuNi(111)表面的d带中心更靠近费米能级,说明助剂Ni的掺杂增强了Cu(111)表面电子的活跃性,从而提高了其催化活性。

Wafer-scale 30°twisted bilayer graphene epitaxially grown on Cu_(0.75)Ni_(0.25)(111)

Twisted bilayer graphene(TBG) has been extensively studied because of its novel physical properties and potential application in electronic devices.Here we report the synthesis and characterization of 300 TBG naturally grown on Cu_(0.75)Ni_(0.25)(111) film and investigate the electronic structure by angle-resolved photoemission spectroscopy.Compared with other substrates,our TBG with a wafer scale is acquired with a shorter growth time.The Fermi velocity and energy gap of Dirac cones of TBG are comparable with those of a monolayer on Cu_(0.85)Ni_(0.15)(111).The signature of moré lattices has not been observed in either the low-energy electron diffraction patterns or the Fermi surface map within experimental resolution,possibly due to different Cu and Ni contents in the substrates enhancing the different couplings between the substrate and the first/second layers and hindering the formation of a quasiperiodic structure.

Near Ambient Pressure Adsorption of Nickel Carbonyl Contaminated CO on Cu(111) Surface

Formation of volatile nickel carbonyls with CO in catalytic reaction is one of the mechanisms of catalyst deactivation. CO is one of the most popular probe molecules to study the surface properties in model catalysis. Under ultra-high vacuum (UHV) conditions, the problem of nickel carbonyl impurity almost does not exist in the case that a high purity of CO is used directly. While in the near ambient pressure (NAP) range, nickel carbonyl is easily found on the surface by passing through the Ni containing tubes. Here, the NAP techniques such as NAP-X-ray photoelectron spectroscopy and NAP-scanning tunneling microscopy are used to study the adsorption of nickel carbonyl contaminated CO gas on Cu(111) surface in UHV and NAP conditions. By controlling the pressure of contaminated CO, the Ni-Cu bimetallic catalyst can form on Cu(111) surface. Furthermore, we investigate the process of CO adsorption and dissociation on the formed Ni-Cu bi-metal surface, and several high-pressure phases of CO structures are reported. This work contributes to understanding the interaction of nickel carbonyl with Cu(111) at room temperature, and reminds the consideration of CO molecules contaminated by nickel carbonyl especially in the NAP range study.

Surface Alloying of Submonolayer Pb on Cu(111) Studied by Photoemission

The reactions of superthin Pb Hlms on a Cu(111)surface with respect to the coverage of Pb and annealing have been studied by synchrotron radiation photoemission.The submonolayer Pb atoms deposited at room temperature are distributed on the Cu(111)surface as two-dimensional(2D)islands.Annealing to 200℃ gives rise to Pb-Cu surface alloy formation.Analyses show that the surface alloy occurs only in the first layer of the Cu(111)surface.As a surfactant,Pb can promote 2D layer-by-layer growth of thin Hlms on Cu(111),but the Pb~Cu surface alloying may have an unfavorable effect on the activation process.

A DFT Study of CO Adsorption on the Cu_2O(111) Surface with Oxygen Vacancy

First-principles calculations based on density functional theory （DFr） and the generalized gradient approximation （GGA） have been used to study the adsorption of CO molecule on the Cu2O（111） oxygen-vacancy surface. Calculations indicate that the C-O bond is weakened upon adsorption compared with that over perfect surface. In addition, with the density increase of the defective sites, the adsorption energies of the defect-CO configuration increase whereas the C-O bond nearly remains constant.

A density functional theory study on the adsorption of CO and O_2 on Cu-terminated Cu_2O(111) surface

The adsorptions of CO and 02 molecules individually on the stoichiometric Cu-terminatcd Cu20 （111） surface are investigated by first-principles calculations on the basis of the density functional theory. The calculated results indicate that the CO molecule preferably coordinates to the Cu2 site through its C atom with an adsorption energy of-1.69 eV, whereas the 02 molecule is most stably adsorbed in a tilt type with one O atom coordinating to the Cu2 site and the other O atom coordinating to the Cul site, and has an adsorption energy of -1.97 eV. From the analysis of density of states, it is observed that Cu 3d transfers electrons to 2π orbital of the CO molecule and the highest occupied 5σ orbital of the CO molecule transfers electrons to the substrate. The sharp band of Cu 4s is delocalized when compared to that before the CO molecule adsorption, and overlaps substantially with bands of the adsorbed CO molecule. There is a broadening of the 2π orbital of the 02 molecule because of its overlapping with the Cu 3d orbital, indicating that strong 3d-2π interactions are involved in the chemisorption of the 02 molecule on the surface.

The STM Images of Pt (111) (<img src="http://latex.codecogs.com/gif.latex?\sqrt{3}\times&space;\sqrt{3}"title="\sqrt{3}\times \sqrt{3}"/>)R30&deg;/CO Surface by DFT Calculations

In this work we have performed total-energy calculations of the chemisorption properties and STM images of Pt (111) ( × )R30°/CO Surface;STM Image;ChemisorptionR30°/CO surface by using the density functional theory (DFT) and the projector-augmented wave (PAW) method. The calculations show that carbon monoxide molecule (CO) adsorbs on FCC site in the Pt (111) ( × )R30°/ surface is energetically favored by the GGA-PBE XC-functional, this is in agreement with most of the theoretical calculations which is using different XC-functional at the most. However, these results strongly conflicted with the existing experiments. Actually the calculated work function for the FCC adsorption is quite different from the experiments while the atop one is in good agreement with experiments. We speculate that the atop adsorption for (CO is favorable for the adsorption case at the most. Furthermore, we have calculated the scanning tunneling microscopy (STM) images for both adsorption geometries and suggest that there should be existed remarkable differences in the STM images. The present work provides a faithful criterion accounting for the local surface geometry in Pt (111) ( × )R30°/CO surface from surface work functions and STM images instead of totalenergy calculations.

单原子Ge助剂修饰Cu(111)晶面上CO_(2)加氢制甲醇的机理研究

针对CO_(2)热催化转化制甲醇过程中CO_(2)吸附、活化较困难及副产物较多的问题,提出采用单原子Ge助剂修饰Cu(111)晶面的解决思路,通过密度泛函理论(DFT)计算研究了CO_(2)在Ge-Cu(111)晶面上加氢合成甲醇的反应机理。结果表明,单原子Ge助剂的电子调控增加了与其相邻的Cu原子的电子云密度,使CO_(2)分子在含Ge活性界面上的吸附能力显著增强:CO_(2)在GeCu(111)晶面上的吸附能约为Cu(111)晶面的1.5倍,约为Pd改性Cu(111)晶面的2.4倍,进而使逆水煤气变换(RWGS)反应路径速控步骤的活化能降低了近20 kJ·moL^(-1),同时衍生出3条生成甲醇的RWGS新路径;此外,Ge-Cu(111)晶面上甲酸盐路径由于速控步骤活化能大幅上升而被禁阻,进而CO及烃类等副产物选择性大幅降低,Ge-Cu(111)晶面上CO_(2)加氢制甲醇选择性升高。

鸡蛋壳生物炭对Cu(Ⅱ)和苯胺吸附研究

针对印染废水有机物和重金属混合污染物难以有效去除的问题,本研究以鸡蛋壳为原料制备生物炭吸附剂,利用SEM、XRD和BET等方法分析生物炭理化性能,采用响应曲面法优化最佳吸附条件,研究其对苯胺和Cu(Ⅱ)吸附性能和吸附机理。试验结果表明:磁性鸡蛋壳生物炭的比表面积为改性前的3.98倍,孔隙结构及吸附点位得到优化,多方位提升生物炭的吸附性能。pH是最显著影响因素,pH和生物炭投加量的交互作用对Cu(Ⅱ)和苯胺去除率的影响较大,最佳吸附条件为pH=6.0,吸附剂投加量0.015 g/mL,接触时间24 h,生物炭对Cu(Ⅱ)、苯胺吸附容量为2.00、0.97 mg/g。MESBC对污染物的吸附过程是以化学吸附为主的多分子层混合吸附,符合准二级动力学模型和Freundlich吸附等温模型。MESBC具有较好的循环再生稳定性,重复利用次数不宜超过5次。

高温退火Cu(111)衬底上生长高质量厘米尺寸单晶石墨烯

二维(2D)石墨烯具有原子层厚度,在电子器件中展示出突破摩尔定律限制的巨大潜力。目前,化学气相沉积(CVD)是一种广泛应用于石墨烯生长的方法,满足低成本、大面积生产和易于控制层数的需求。然而,由于催化金属(例如Cu)衬底一般为多晶特性,导致CVD法生长的石墨烯晶体质量相对较差。为此,通过高温退火工艺制备了Cu(111)单晶衬底,使石墨烯的初始成核过程得到了很好的控制,从而实现了厘米尺寸的高质量单晶石墨烯的制备。根据二者的晶格匹配关系,Cu(111)衬底为石墨烯生长提供了唯一的成核取向,相邻石墨烯成核岛的边界能够缝合到一起。单晶石墨烯具有高电导率,相较于原始多晶Cu上生长的石墨烯(1415.7Ω·sq^(-1)),其平均薄层电阻低至607.5Ω·sq^(-1)。高温退火能够清洁铜箔,从而获得表面粗糙度较低的洁净石墨烯。将石墨烯用于场效应晶体管(FET),器件的最大开关比为145.5,载流子迁移率为2.31×10^(3)cm^(2)·V^(-1)·s^(-1)。基于以上结果,相信本工作中的单晶石墨烯还满足其他高性能电子器件的制备。

DFT Investigation of the Adsorption/dissociation Mechanisms of Methyl Nitrite on the Pd(111) Surface

The adsorption behavior of methyl nitrite （MN） on the closed-packed Pd（111） sur- face has been investigated in detail by using density functional theory （DFT）. MN binds to the surface in two alternative forms, using the nitrogen atom attached to the surface. An overall net charge transfer from the substrate to the cis-MN molecule is also confirmed. In addition, the reaction mechanism for the dissociation of MN on the Pd（111） surface has been identified and compared with the methanol decomposition via O-H scission. The results demonstrate that MN is a more active reactant than methanol for the oxidative addition to the Pd catalyst. The possible reason has been analyzed from the adsorption behaviors and reaction barriers, that is, MN is chemically absorbed on the Pd（111） surface; the CHaO-NO bond scission, leading to the formation of adsorbed methoxy species, is much more favorable than that of the O-H bond scission and has a large exothermic behavior.

A Periodic Density Functional Study on Adsorption Properties of Methoxy on Au(111) Surface

Adsorption of CH3O at four sites （top, bridge, hcp, fcc） on Au（111） surface has been investigated by density functional theory method at the generalized gradient approximation level. We have performed calculations on adsorption energies, structures, Mulliken charges and vibrational frequencies of CH3O on Au（111） surface with full-geometry optimization. The predicted results are compared with the available experimental observation. The calculated CH3O adsorption structure and stretching vibrational frequencies agree well with experimental ones, and precise determinations of adsorption sites are carded out. The most favorite adsorption on Au（111） occurs at the bridge site, and O-C axis is tilted to the surface. However, on hollow sites （hcp, fcc） the species is adsorbed in an upright geometry （pseudo-C3v local symmetry）.

Theoretical investigation of lithium ions’ nucleation performance on metal-doped Cu surfaces

Lithium metal batteries(LMBs)of an ultrahigh theoretical energy density have attracted lots of attentions for a wide range of practical applications.However,there are still numerous challenges in LMBs system,such as poor cycling performance,complicated interfacial reactions,low Coulombic efficiency,and uncontrollable lithium dendrites.Understanding Li^+ions’nucleation mechanism is essential to tackle the uncontrolled growth of lithium dendrites.However,the nucleation behavior of Li+ions is interfered by the structural complexities of existing substrates during the reduplicative plating/stripping process and the rational mechanism of uniform nucleation of Li^+ions has not been clearly understood from the theoretical point of view.In our work,first-principles theoretical calculations are carried out to investigate the Li^+ions nucleation performance on metal-doped Cu surfaces(MDCSs)and the key descriptors that determines the properties of various MDCSs are systematically summarized.It is found that the introduction of heterogeneous doping Ag and Zn atoms will induce a gradient adsorption energy on MDCSs,and such gradient deposition sites can reduce the diffusion barriers and accelerate the diffusion rates of Li+ions dynamically.By maneuvering the Li+ions nucleation on MDCSs,a dendrite-free lithium metal anode can be achieved without the use of porous matrixes and complex synthesis process,which can be attributed to suppress the uncontrollable lithium dendrites for realizing the high-efficiency LMBs.

First-principles Study on Geometric and Electronic Structures of Si（111）-√7× √3-In Surface Reconstruction

In order to determine the structures of Si（111）-√7 √3-In surfaces and to understand their electronic properties, we construct six models of both hexagonal and rectangular types and perform first-principles calculations. Their scanning tunneling microscopic images and work functions are simulated and compared with experimental results. In this way, the hex-H3＇ and rect-T1 models are identified as the experimental configurations for the hexagonal and rectangular types, respectively. The structural evolution mechanism of the In/Si（lll） surface with indium coverage around 1.0 monolayer is discussed. The 4×1 and -√7× √3 phases are suggested to have two different types of evolution mechanisms, consistent with experimental results.

DFT Study of Thiophene Adsorption on the Pd(111) and Pt(111) Surfaces

Thiophene adsorption on the（111） surfaces of Pd and Pt have been investigated by density functional theory.The results indicate that the adsorption at the hollow sites is the most stable.To our interest,the molecular plane of thiophene ring is distorted with C=C bond being elongated to 1.450 and C–C bond being shortened to 1.347 ,and the C–H bonds tilt 13.91～44.05o away from this plane.Furthermore,analysis on population and density of states verified the calculated adsorption geometries.Finally,charge analysis suggests that thiophene molecule is an electron acceptor,reflecting the interaction between the lone pair of sulfur and the d-orbitals of metal.

基于Cr-O-C钝化层改变多晶Cu表面能和表层位错的脱模力与脱模精度

Cr-O-C钝化层可以提高精密电铸脱模精度,但Cr-O-C钝化层对基底表面的钝化规律和对表层的影响尚未清楚。利用分子动力学方法,在多晶Cu表面沉积离散的Cr、O和C原子,获得不同比例和数量的Cr-O-C钝化层。计算结果表明,不同比例的Cr、O和C原子均可以大幅降低多晶Cu的表面能;随着原子数量的增加,多晶Cu的表面能呈下降趋势;Cr-O-C钝化层增加了多晶Cu表层的位错密度;新增加的位错以Shockley位错为主;在一定沉积原子数量内,位错密度有极值。在多晶Cu表面电沉积不同密度的Cr、O和C原子,通过接触角测试验证了Cr-O-C钝化层降低多晶Cu表面能的结论。电沉积脱模强度和脱模表面粗糙度结果显示,随着沉积原子数的增加,脱模强度和脱模表面粗糙度均降低。研究结果可为利用离散Cr-O-C界面辅助精密电铸脱模提供一种解释。

Surface Topography and Roughness of High-speed Milled AlMn1Cu

The aluminum alloy AlMn1Cu has been broadly applied for functional parts production because of its good properties. But few researches about the machining mechanism and the surface roughness were reported. The high-speed milling experiments are carried out in order to improve the machining quality and reveal the machining mechanism. The typical topography features of machined surface are observed by scan electron microscope（SEM）. The results show that the milled surface topography is mainly characterized by the plastic shearing deformation surface and material piling zone. The material flows plastically along the end cutting edge of the flat-end milling tool and meanwhile is extruded by the end cutting edge, resulting in that materials partly adhere to the machined surface and form the material piling zone. As the depth of cut and the feed per tooth increase, the plastic flow of materials is strengthened and the machined surface becomes rougher. However, as the cutting speed increases, the plastic flow of materials is weakened and the milled surface becomes smoother. The cutting parameters （e.g. cutting speed, feed per tooth and depth of cut） influencing the surface roughness are analyzed. It can be concluded that the roughness of the machined surface formed by the end cutting edge is less than that by the cylindrical cutting edge when a cylindrical flat-end mill tool is used for milling. The proposed research provides the typical topography features of machined surface of the anti-rust aluminum alloy AlMn1Cu in high speed milling.

Theoretical Study on the Adsorption and Decomposition of Methanol over the Pt-Mo(111)/C Surface

The density functional theory（DFT） and self-consistent periodic calculation were used to investigate the methanol adsorption on the Pt-Mo（111）/C surface.The adsorption energies,equilibrium geometries and vibration frequencies of CH3OH on nine types of sites on the Pt-Mo（111）/C surface were predicted and the favorite adsorption site for methanol is the top-Pt site.Both sites of valence and conduction bands of doped system have been broadened,which are favorable for electrons to transfer to the cavity.The possible decomposition pathway was investigated with transition state searching and the calculation results indicate that the O-H bond is first broken,and then the methanol decomposes into methoxy.The activation barrier of O-H bond breaking with Pt-Mo catalyst is only 104.8 kJ mol-1,showing that carbon supported Pt-Mo alloys have promoted the decomposition of methanol.Comparing with the adsorption energies of CH3OH on the Pt（111）/C surface and that of CO,the adsorption energies of CO are higher,and Pt（111）/C is liable to be oxidized and loses the activity,which suggests that the catalyst Pt-Mo（111）/C is in favor of decomposing methanol and has better anti-poisoning ability than Pt（111）/C.