Molecular Dynamics Simulation of Copper Nanofilm Self-Assembly on Silicon Substrate under Gas-Discharge Plasma Conditions

High Energy Chemistry - Using the molecular dynamics method, the sputtering of a copper target and the subsequent formation of a copper nanofilm on a silicon substrate has been modeled. The process...     

Electrochemically Mediated Atom Transfer Radical Polymerization from a Substrate Surface Manipulated by Bipolar Electrolysis: Fabrication of Gradient and Patterned Polymer Brushes

We report the first ever use of electrochemically mediated atom transfer radical polymerization (eATRP) employing a bipolar electrochemical method for the fabrication of both gradient and patterned polymer brushes. A potential gradient generated on a bipolar electrode allowed the formation of a concentration gradient of a Cu^I polymerization catalyst through the one‐electron reduction of Cu^II, resulting in the gradient growth of poly(NIPAM) brushes from an initiator‐modified substrate surface set close to a bipolar electrode. These polymer brushes could be fabricated in three‐dimensional gradient shapes with control over thickness, steepness, and modified area by varying the electrolytic conditions. Moreover, by site‐selective application of potential during bipolar electrolysis, a polymer brush with a circular pattern was successfully formed. Polymerization was achieved using both a polar monomer (NIPAM) and a nonpolar monomer (MMA) with the eATRP system.     

Surface Water as an Initial Proton Source for the Electrochemical CO Reduction Reaction on Copper Surfaces

We have employed in situ electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) and density functional theory (DFT) calculations to study the CO reduction reaction (CORR) on Cu single-crystal surfaces under various conditions. Coadsorbed and structure-/potential-dependent surface species, including *CO, Cu−O_ad, and Cu−OH_ad, were identified using electrochemical spectroscopy and isotope labeling. The relative abundance of *OH follows a “volcano” trend with applied potentials in aqueous solutions, which is yet absent in absolute alcoholic solutions. Combined with DFT calculations, we propose that the surface H₂O can serve as a strong proton donor for the first protonation step in both the C₁ and C₂ pathways of CORR at various applied potentials in alkaline electrolytes, leaving adsorbed *OH on the surface. This work provides fresh insights into the initial protonation steps and identity of key interfacial intermediates formed during CORR on Cu surfaces.     

Dynamic Surface Tension and Adsorption/Desorption Kinetics for Mixtures on Planar Surfaces: I. Under Nonflow Conditions

The adsorption/desorption kinetics for individual polymers and polymer mixtures of the water-soluble associative polymers with molecular weights of 12, 62, and 100 kg/mol onto SiO2 planar substrate have been studied by ellipsometry at room temperature under nonflow conditions. Equations were derived to predict behaviors of the adsorption/desorption kinetics and dynamic surface tension onto planar surfaces for any times. It is shown that the desorption kinetics of the water-soluble associative polymers onto planar SiO2 surface is an irreversible process due to strong interaction between polymer molecules and an interface. Copyright 1999 Academic Press.     

用电解法评估纯铜和普通黄铜样品的质量

在用电解法采集纯铜和 普通黄铜样品时，根据样品的牌号确定样品的近似电化摩尔质量ｋ，选择合适的电解条件使电流效率为１００％，用Ｆａｒａｄａｙ定律ｍ＝ｋＩｔ计算采集样品的质量。     

Modeling Structural Changes in the Deposit during Galvanostatic Electrolysis and Contact Deposition of Metals

The crystallization of dendritic deposits during a galvanostatic electrolysis and a contact deposition of metals from aqueous solutions is modeled. Structural changes in a deposit are characterized by its distribution by radii of apexes of growing dendrites. The calculation is carried out by solving a set of differential equations by the Runge–Kutta method within the Mathcad Plus 6 package. The reduction of metals with different exchange currents during electrolysis and with different exchange currents of the component being reduced during cementation is considered. The calculated results qualitatively conform to available experimental data.     

Effect of Surface Depressions on Wetting and Interactions between Hydrophobic Pore Array Surfaces

The surface structure is known to significantly affect the long-range capillary forces between hydrophobic surfaces in aqueous solutions. It is, however, not clear how small depressions in the surface will affect the interaction. To clarify this, we have used the AFM colloidal probe technique to measure interactions between hydrophobic microstructured pore array surfaces and a hydrophobic colloidal probe. The pore array surfaces were designed to display two different pore spacings, 1.4 and 4.0 μm, each with four different pore depths ranging from 0.2 to 12.0 μm. Water contact angles measured on the pore array surfaces are lower than expected from the Cassie-Baxter and Wenzel models and not affected by the pore depth. This suggests that the position of the three-phase contact line, and not the interactions underneath the droplet, determines the contact angle. Confocal Raman microscopy was used to investigate whether water penetrates into the pores. This is of importance for capillary forces where both the movement of the three-phase contact line and the situation at the solid/liquid interface influence the stability of bridging cavities. By analyzing the shape of the force curves, we distinguish whether the cavity between the probe and the surfaces was formed on a flat part of the surface or in close proximity to a pore. The pore depth and pore spacing were both found to statistically influence the distance at which cavities form as surfaces approach each other and the distance at which cavities rupture during retraction.     

Limiting Current of Copper Electrodeposition from a Copper Sulfate Solution under Conditions of Natural Convection: The Space Charge Effect

Copper electrodeposition from a copper sulfate solution under conditions of natural convection is analyzed theoretically and examined experimentally. The space charge, which forms in the near-cathode layer, is shown to affect the limiting current density and to change its concentration dependence.     

The Effect of Polymer Substrate Surface Basicity on the Adsorption of a Cationic Polyacrylamide

The adsorption of a cationic polyacrylamide onto polytetrafluoroethylene, bisphenol-A based epoxy resins, and acrylate substrates was characterized with X-ray photoelectron spectroscopy (XPS) and dynamic contact angle measurement in water. Surface acidity-basicity was quantified via dynamic contact angle measurement in water, ethylene glycol, and diiodomethane. The epoxy resins exhibited intermediate surface basicity and adsorbed the most polyelectrolyte, suggesting that specific substrate-adsorbate acid-base interactions govern adsorption of the cationic polyacrylamide onto surfaces of low to intermediate basicity. In general polar interactions appear to dominate the adsorption process. Advancing contact angle measurements have yielded quantitative fractional surface coverage information for polymer-on-polymer adsorption comparable to that obtained via XPS. Copyright 1999 Academic Press.     

抗结冰涂层: 从表面化学到功能化表面

在交通运输、航空航天、电力通信等诸多领域,结冰给人类和社会带来很大危害和安全隐患。现有的抗结冰方法如机械除冰、加热除冰以及喷洒化学试剂等虽然有效,但是存在耗能大和环境污染等问题。在基体表面涂装具有抗结冰性能的功能涂层被认为是一种必要的切实有效的方法,近年来备受关注。本文在介绍了涂层抗结冰原理及基体表面结冰影响因素的基础上,详细综述了近年来各类抗结冰涂层取得的研究成果,主要包括牺牲性涂层、疏冰涂层和超疏水涂层。重点介绍了制备抗结冰涂层所用的材料及方法,并分析了各种抗结冰涂层的优缺点,指出了抗结冰涂层目前存在的问题,最后对抗结冰涂层的发展趋势进行了分析和展望。     

铜表面二硫代氨基甲酸改性葡萄糖自组装膜的缓蚀作用

合成了一种环境友好型的缓蚀剂--二硫代氨基甲酸改性葡萄糖（DTCG）。 采用该缓蚀剂在铜表面制备了自组装膜,并运用电化学阻抗谱、极化曲线方法研究了该膜在3%NaCl溶液中对铜的缓蚀性能。 研究结果表明,DTCG自组装膜对铜有良好的缓蚀效果,在自组装时间为4 h、自组装浓度为120 mg/L的缓蚀效率接近于97%。 量子化学计算结果也证明了DTCG具有优异的缓蚀性能。     

碱式硫酸铜与氢氧化铜的相互转化及纯净氢氧化铜的制备条件

通过实验定量研究了Cu4(OH)6SO4与Cu(OH)2相互转化的特点及纯净Cu(OH)2制备的条件。研究结果表明,Cu4(OH)6SO4与Cu(OH)2之间能够相互转化,且转化相对缓慢;提高CuSO4浓度有利于Cu(OH)2向Cu4(OH)6SO4转化,提高NaOH浓度有利于Cu4(OH)6SO4向Cu(OH)2转化;纯净Cu(OH)2的制备方法为CuSO4溶液滴加到NaOH溶液中,且NaOH过量15%以上。     

聚合物基板表面状态对异相接枝的影响研究

研究了对于羟丙基纤维素（HPC）基板进行表面修饰时,基板表面状态的调控 对基板表面化学接枝的影响。用双官能团化合物2,4-甲苯二异氰酸酯（TDI）作为 接枝桥梁,其对位的异氰酸酯基先和基板上的羟基反应,保留的邻位异氰酸酯基进 一步再与丙烯酸的羟基反应,让接枝在基板上的活性丙烯酸分子继续和丙烯酸溶液 聚合,通过这种途径在基板表面修饰聚丙烯酸。基板制备时,由于不同介质对HPC 基板表面的不同诱导作用,导致表面组成各异,大大影响了接枝反应的效果。红外 光谱和二次离子飞行时间质谱均证明了可以用2,4-甲苯-二异氰酸酯（TDI）分子 做接枝桥梁在基板表面异相接枝上羟基并进一步接枝聚丙烯酸,从而达到修饰基板 的目的。     

铜催化剂有效表面积的测定

 综述了几种测定铜催化剂有效表面积的方法．N2O前沿反应色谱法（RFC）对设备要求简单，操作简便，测定结果重现性好，是测定铜催化剂中铜的表面积的有效方法．给出了装置原理图和适当的实验条件．     

基于光子晶体带边效应的表面增强拉曼基底

将光子晶体的带边效应与金纳米粒子的拉曼散射增强作用相结合,制备了一种新型光子晶体表面增强拉曼散射基底(PC-AuNPs),利用罗丹明B(RhB)作为报告分子,对所得基底性能进行检测.PC-AuNPs基底的制备包括3个步骤:在SiO2微球表面修饰氨基,再通过垂直沉降自组装得到蛋白石结构光子晶体(PC), 最后, 在光子晶体表面负载金纳米粒子(AuNPs).结果表明,光子晶体的带隙范围及AuNPs的负载量直接影响了PC-AuNPs基底的检测效果;以所得的PC-AuNPs基底测定RhB分子,其拉曼散射特征峰强度与浓度对数值呈现良好的线性关系,线性方程为I=1711lg[RhB(mol/L)]+15244,线性相关系数R2=0.9994,检出限为1×10-8 mol/L,表明此PC-AuNPs基底可用于目标物的定性及定量检测.本方法提高了传统拉曼散射光谱检测灵敏度,操作简单,具有良好的重现性,可为其它新型检测基底的制备提供.     

纳米ZnO的表面增强拉曼散射效应来源研究

表面增强拉曼光谱（SERS）的广泛应用源于优良的基底,目前主要局限在粗糙贵金属及胶体纳米颗粒材料.而半导体的光谱高稳定性和再现性,使其成为制备SERS基底的新型材料,但对于其SERS增强机理的研究仍存在极大挑战.本工作以典型的形貌新颖、尺寸均一的扫帚状n型纳米半导体ZnO为SERS基底材料,通过调节激发光的波长和选用具有不同对位取代基的对硝基苯硫酚（PNTP）、苯硫酚（TP）、对氨基苯硫酚（PATP）为探针分子,系统地研究了纳米ZnO的SERS增强行为,估算了其表面增强因子（EF）,分离了化学增强作用中非共振增强效应和电荷转移效应对SERS的贡献.研究表明三种分子在不同激发光作用下的增强因子为10至35,其中PNTP分子约10倍的增强主要来自于因吸附而造成极化率变化的非共振增强效应,TP和PATP分子20~35倍的增强则是由非共振增强效应与光子驱动电荷转移效应共同作用所致,光子能量越高,SERS增强效应越强.且因分子与ZnO间电荷转移的速率较慢导致ZnO表面电荷转移增强效应较贵金属低1~2个数量级.本研究结果为新型半导体SERS基底的制备及调控提供了新思路.     

Dehydrogenative Homocoupling of Terminal Alkenes on Copper Surfaces: A Route to Dienes

Homocouplings of hydrocarbon groups including alkynyl (sp¹), alkyl (sp³), and aryl (sp²) have recently been investigated on surfaces with the interest of fabricating novel carbon nanostructures/nanomaterials and getting fundamental understanding. Investigated herein is the on‐surface homocoupling of an alkenyl group which is the last elementary unit of hydrocarbons. Through real‐space direct visualization (scanning tunneling microscopy imaging) and density functional theory calculations, the two terminal alkenyl groups were found to couple into a diene moiety on copper surfaces, and is contrary to the common dimerization products of alkenes in solution. Furthermore, detailed DFT‐based transition‐state searches were performed to unravel this new reaction pathway.     

低自由能固体表面的制备及其应用*

低自由能表面具有一些独特的性能,在工业和日常生活中具有广泛的应用,本文就低自由能表面的制备及其发展概况进行综述,共引用文献83篇。     

基质表面多环芳烃的化学单层组装及其荧光传感特性

经由柔性连接臂化学单层组装于基质表面的多环芳烃,在基质表面有限区域内可以形成特定的超分子结构,并呈现相应的荧光光谱.这类结构及其光谱性质可因环境条件的变化而变化,基于这种变化可以设计制备传感薄膜材料.本文在概述此类研究工作的基础上,重点介绍了笔者实验室近年来,通过改变基质类型、调节连接臂长度和结构、优化多环芳烃的固定化密度等途径,设计制备对有关化学物质敏感且既可用于液相也可用于气相的荧光传感薄膜材料方面的研究工作.     

分子自组装法制备具有可控浸润性的铜表面简

通过简单浸泡的方法在铜基底上制备出了具有微纳米复合结构的氧化铜,再利用混合硫醇溶液[含HS(CH2)9CH3和 HS(CH2)11OH]对浸泡后的表面进行修饰,通过控制溶液中HS(CH2)11OH的浓度,制备出一系列具有不同浸润性的铜表面,实现表面从超疏水到超亲水的有效调控. 研究发现,表面浸润的可控性源于表面复合结构与不同化学组成的协同作用,微纳米复合结构的存在为表面浸润性的调节提供了必要的条件.