Plasmon-enhanced Raman Spectroscopic Studies: From Interfacial Electronic Structure and Electrochemical Reactions to Heterogeneous Photoreactions

表面增强拉曼散射（Surface-enhancedRamanscattering，SERS）主要基于可在某些金属表面产生光电场增强的表面等离激元共振（Surfaceplasmonresonance，SPR）而具有检测表面物种的超高灵敏度。电化学-表面增强拉曼光谱(Electrochemicalsurface-enhancedRamanspectroscopy，EC-SERS)技术在经历了约40年的发展后成为了为数不多的原位研究电极/溶液界面结构和过程的强有力工具。尽管如此，迄今应用EC-SERS技术研究电化学反应机理的成功实例却少之又少。这是由于电化学反应远远复杂于电化学吸附，实验和理论计算方...Surface-enhanced Raman scattering (SERS) is highly sensitive to the surface species, which primarily originates from the giant enhanced optical field generated by surface plasmon resonance (SPR) on some metallic surfaces. Experienced the development in the past four decades, electrochemical surface-enhanced Raman spectroscopy (EC-SERS) has been one of a few powerful in-situ techniques for the inve...学位：理学博士院系专业：化学化工学院_物理化学(含化学物理)学号：2052010015366

Surface-enhanced Raman Spectroscopy and Plasmon-Assisted Photocatalysis of p-Aminothiophenol

对氨基苯硫酚(PATP)是表面增强拉曼光谱(SErS)研究中最重要的探针分子之一.PATP吸附体系具有非常特征且异常强的SErS信号,但人们对其SErS信号的理解仍存在较大争议.本文结合文献,总结了我们为了理解PATP分子异常的SErS光谱所开展的系统的理论和实验工作.首先介绍PATP的SErS增强机理方面开展的理论工作,研究表明PATP分子的异常SErS信号不是来自PATP分子本身,而是来自其表面催化偶联反应产物二巯基偶氮苯(dMAb).通过实验和dMAb合成两个方面,验证了dMAb是异常SErS信号的根源.其次总结了各种实验条件对PATP转化为dMAb的影响,并从实验和理论两个角度探讨PATP的表面催化偶联反应机理.最后,通过对PATP体系的SErS和等离激元增强化学反应的总结,展望表面等离激元增强化学反应的未来发展方向.p-Aminothiophenol(PATP) is one of the most important probe molecules in surface-enhanced Raman spectroscopy(SERS).Adsorbed PATP exhibits very unique and abnormally intense SERS signals.However, the understanding toward the abnormal SERS signals is still in debate.In this review, we overview our theoretical and experimental studies to understand the abnormal SERS of PATP.We first introduce the theoretical investigation on the SERS enhancement mechanism of PATP.The theoretical study shows that the abnormal SERS signals of PATP are not from PATP itself but arise from its surface catalytic coupling product p,p'-dimercaptoazobenzene(DMAB).The assumption is supported by carefully designed experiments of PATP and the SERS signal of the synthesized DMAB molecule.Then, we summarize the experimental factors that influence the photochemical conversion of PATP to DMAB on the surfaces of metal nanostructures.We then explore the reaction mechanisms for the surface catalytic coupling reaction of PATP in both experimental and theoretical aspects.Finally, we proposed the further direction of surface plasmon enhanced chemical reaction on the basis of our systematically studies of SERS and plasmon photocatalysis of PATP

Electrochemical Surface-Enhanced Raman Spectroscopic Studies on Nickel Ultramicroelectrode

镍（Ni）电极在电化学中应用广泛。原位表征Ni电极表面的吸附物种有益于帮助理解电极反应历程、指导发展高效电催化剂。应用超微电极作为工作电极的电化学表面增强拉曼光谱技术结合了超微电极表面的传质特性和分子水平的高灵敏度表征,是研究Ni电化学的有力手段。本文所述的研究工作通过在金（Au）超微电极表面电吸附具有SERS活性的Au纳米粒子并恒电流沉积金属Ni薄层,制备并表征了具有SERS活性的Ni超微电极。在氢氧化钠溶液中的循环伏安实验和以4-甲基苯硫酚分子作为探针分子的SERS实验结果表明,沉积速率和沉积电量是影响超微电极表面Ni的覆盖度和SERS活性的关键因素。在吸附了直径为55 nm Au纳米粒子的、直径为10 μm Au的超微电极表面,以100 μA·cm-2电流密度电沉积厚度约为5个原子层Ni的条件下,可获得Ni覆盖完好的、具有最强SERS活性的Ni超微电极。Nickel (Ni) electrodes are widely used in electrochemical researches. Understanding electrochemical processes on Ni electrodes through in-situ characterization of adsorbed species on their surfaces is helpful for rational optimization and application of Ni electrochemistry. Microelectrochemical surface-enhanced Raman spectroscopy (μEC-SERS) combines the mass transfer feature of ultramicroelectrode with high-sensitivity characterizations of molecular structures, which is a powerful method for studying Ni electrochemistry on polarization and non-equilibrium conditions. The key point of performing μEC-SERS is to make a SERS-active Ni ultramicroelectrode. Here, we demonstrate a method of preparing a SERS-active Ni ultramicroelectrode through electrochemical deposition of several atomic layers of metallic Ni onto a SERS-active gold (Au) ultramicroelectrode. Firstly, a SERS-active Au ultramicroelectrode was made through electrochemical adsorption of Au nanoparticles. A smooth polycrystalline Au ultramicroelectrode with a diameter of 10 μm was made by sealing a Au wire into a glassy tube. The Au nanoparticles of 55 nm in diameter were adsorbed from Au sol onto the Au ultramicroelectrode under an electrochemical polarization at 1.8 V. The scanning electron microscopic (SEM) images showed that Au nanoparticles aggregated on surface. On the prepared Au ultramicroelectrode adsorbed by Au nanoparticles, a thin and compact Ni layer was deposited by using galvanostatic method in 5 mmol·L-1 Ni(NO3)2 electrolyte. The thickness of Ni layer was controlled via the charge. The voltammograms of the prepared SERS-active Ni ultramicroelectrode in 0.1 mol·L-1 NaOH showed the characters of polycrystalline Ni electrode. Since the SERS activity decreased as a result of the increase in the thickness of Ni layer, the SERS measurements of 4-methylthiophenol in air were carried out for evaluating SERS activity. The comparisons in the intensity of the band at 1077 cm-1 from the 4-methylthiophenol adsorbed on the ultramicroelectrode made by using 10 μA·cm-2, 50 μA·cm-2, 100 μA·cm-2, 500 μA·cm-2 and 1000 μA·cm-2 indicated that the rate and charge of deposition are key in determining the coverage status of Ni layer and the SERS activity. An optimized SERS activity on a compact Ni was obtained by electrodepositing 5 atomic layers of Ni at a current density of 100 μA·cm-2. To demonstrate the application of Ni ultramicroelectrode in the in-situ μEC-SERS measurement, the molecule of 4-methylthiophenol, employed as a probe, was adsorbed onto the prepared Ni ultramicroelectrode through spontaneous adsorption in the methanol solution of 4-methylthiophenol. The obtained SERS spectra showed characteristic bands of 4-methylthiophenol. In addition, stark effect of the bands was observed, indicating the successful application of Ni ultramicroelectrode in the in-situ μEC-SERS measurement.The preparation methodology of SERS-active ultramicroelectrode enables the in-situ μEC-SERS measurement on Ni under electrochemical polarization or non-equilibrium reaction conditions, which exhibits a good potential application in studying Ni electrochemistry.国家自然科学基金项目(21872094);国家自然科学基金项目(21991152);国家自然科学基金项目(21802057)通讯作者:黄逸凡E-mail:[email protected]:Yi-FanHuangE-mail:[email protected].上海科技大学物质科学与技术学院,上海 2012102.井冈山大学化学化工学院,江西 吉安 3430091. School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China2. College of Chemistry and Chemical Engineering, Jinggangshan University, Ji’an 343009, Jiangxi, Chin

从日本对华 ODA 看中日关系的互动 = The bilateral interaction of Sino-Japan relations : a study of Japan’s ODA to China

自从大平正芳首相在 1979 年访华时宣布对中国的第一笔日元贷款,日本对华 ODA 的历史业已超过三十年时间。随着时间的推移,对华 ODA 在成为中国经济发展 的重要推动力同时,也逐渐成长为中日关系中十分关键的一环。但是纵观对华 ODA 演变历史,它的发展算不上一帆风顺。随着在 1990 年代,日本逐渐在对华 ODA 决 策过程中加入政治色彩,从而影响到了中日关系的发展。随之而来的是,中日之间 不断产生摩擦的声音。而也正是在这一时期,中国重新拿出历史问题向日本问责。 而在此之后,中日两国人民也逐渐产生种种隔阂与误解。到了 21 世纪之后,对华 ODA 失去增进两国关系的政治功能,反而成为制约中日关系发展的政治砝码。而因 此,对华 ODA 也最终与 2008 年宣告终结。在这样的背景之下,本文讨论了在对华 ODA 演变过程之中,中日双方的背后动 因,以及对华 ODA 又是如何影响中日关系的发展。同时,通过对于 1972 年中日邦 交正常化至今的历史梳理,本文也尝试去总结中日关系中的互动机制。Japan’s Official Development Assistance (ODA) policy towards China has been more than 30-year history, since Japanese Prime Minster Ohira announced the first yen loan to China in 1979. It has made a significant progress to Chinese economy, and become critical components of Sino-Japanese bilateral relations today. However, the history of ODA to China was not going well all the time. It became more controversial, especially after Japan made adjustments to the policy-making process in 1990s. The bilateral relations get influenced because of those adjustments, and more tension was caused between China and Japan. Also since then, China started to bring up historical issues to Japan, and misunderstandings and gaps were emerged between Chinese and Japanese. After 21st Century, ODA no longer played as incentive role in Sino-Japan relations as before. It became more as political leverages that jeopardize the development of the bilateral relations. Because of this, China and Japan had both confirmed to terminate the yen loan in 2008. Under this background, this essay is trying to examine the motivations for both China and Japan throughout the ODA history, and how development of ODA process influenced Sino-Japan relations. Above that, by exploring the history from normalization process in 1972 to today, this essay also tries to sum up the mechanism of interaction process between China and Japan.Bachelor of Art

Electrochemical Surface-Enhanced Raman Spectroscopy—Current Status and Perspective

通讯作者，Tel: (86-592)2186532， E-mail: bren@xmu．edu．cn[中文文摘]许多和能源、生命相关的过程都强烈依赖于电化学荷电界面的结构和性能.自从表面增强拉曼光谱效应发现后,就很快地被应用于电化学界面的原位研究,即从分子水平上深入表征各种表面(或界面)的结构和过程,如鉴别物种在表面的键合、构型和取向等.最近十年,纳米科技的飞速发展为SERS技术提供了丰富的基底以及检测和表征方法,从而推动了与纳米科学密切相关的电化学SERS领域令人瞩目的发展.本文系统介绍Au和Ag的SERS、过渡金属薄层SERS、纯过渡金属SERS、核壳结构SERS和已经可以应用于单晶表面研究的gap-modeSERS、TERS和SHINERS,其中穿插着介绍电化学SERS的历史发展、现状和存在的问题及其展望,为电化学SERS研究提供较为全面的详细的参考.[英文文摘]Electrochemical interface is a very important interface closely related to various energy and life processes. Surface-enhanced Raman scattering was widely used in electrochemistry soon after its discovery to understand the surface bonding,configuration,and orientation of the surface species. In recent 10 years,the fast development of nanoscience and nanotechnology has offered SERS with abundant substrates and characterization methods,which has allowed impressive development of electrochemical SERS. This articles will follow the time line to make systematically overview of SERS on Au and Ag， thin-layer transition-metal SERS，pure transition metal SERS，core-shell SERS and those methods for studying single crystal surfaces， including gap-mode SERS， TERS and SHINERS． Emphasis will be put on the history，present status and existing problems and perspectives of electrochemical SERS． We hope the present article will provide a comprehensive overview of the electrochemical SERS．国家自然科学基金(20825313和20827003); 科技部973项目(2009CB930703和2007CB935603)资

基于时间特性视角的视觉审美和愉悦感受研究

美感和愉悦感受的关系是近些年审美研究者们十分关注的话题。虽然行为和核磁实验都提示美感和愉悦感受有非常紧密的关系,但由于刺激材料选择的局限性,二者是否可以等同还有较大争议。本研究招募了30名无长期美术培训经验的被试,通过预实验建立了四种不同美感-愉悦度组合的图片库(美-愉悦、美-不愉悦、不美-愉悦和不美-不愉悦),旨在从时间特性的角度探索了审美和愉悦感受的关系。实验过程中,每张图片的呈现时间有8种条件,分别为17ms、34ms、50ms、100ms、200ms、400ms和自由呈现时间,被试对所有图片进行美感、愉悦感受和唤醒度的打分。结果发现,被试欣赏所有图片时美感和愉悦感受的评分结果同前期进行分类图片时其他被试评分的结果相近。对于美-愉悦和不美-不愉悦两种类型的图片而言,美感和愉悦感受评分在所有呈现时间条件下都呈现显著的正相关;而对于不美-愉悦和美-不愉悦两种类型的图片,图片带给被试的美感和愉悦感受则呈现显著的负相关。将美感和愉悦感受在控制呈现时间条件和自由呈现时间条件下的相关系数作为此感受趋于稳定的程度,我们探究了形成稳定的美感和愉悦感受所需要的最短时间。结果表明美感和愉悦感受评价一般在图片呈现50～100ms后逐渐趋于稳定。对于美-愉悦和不美-不愉悦类型的图片而言,愉悦感受和美感在所有控制呈现时间条件下和不控制呈现时间条件下的相关系数的差异均不显著;对于美-不愉悦和不美-愉悦两种类型的图片,当呈现时间为200ms时,相关系数表现出显著差异。我们的结果表明美感和和愉悦感受的极性并不总是一致的,在时间特性上可以出现分离,提示二者虽然可美感和和愉悦感受具有部分独立的神经基础,一定程度上挑战了前人对美感来源于欣赏作品时产生的愉悦体验的解释。</p

中国婴幼儿（0～36月）光感发育研究

光感是基本的视觉功能,包含基本的原始光刺激反射和对不同波长光的辨别能力,反映了神经发育状态,临床上多用于判断异常发育、预后、死亡、自主反应等。由于研究方法和刺激选择等差异,光感的发育过程尚有争议。本研究研制了一套标准的光感测试体系(笔式手电筒和5种不同颜色反光板),招募了来自中国5个不同省份868名0～36个月婴幼儿,测量了由光线增强引起的瞳孔收缩和眼睑闭合反应,以及对不同颜色光斑的注视和躲避等光斑感知反应。结果发现,婴幼儿的瞳孔对光反射、光刺激瞬目反射、白色、红色、黄色、绿色、蓝色光反应的通过率均值分别为76.7%(&plusmn;1.4%)、67.4%(&plusmn;1.6%)、62.4%(&plusmn;1.6%)、60.1%(&plusmn;1.6%)、59.9%(&plusmn;1.7%)、54.3%(&plusmn;1.7%)、52.0%(&plusmn;1.7%);在每个项目中,7～12个月通过率都高于均值以及其他年龄组。分层卡方检验表明,瞳孔对光反射在0～7个月发育速度显著快于其他项目,7个月之后一致,且总体通过率高于其他功能;光刺激瞬目反射的发育节奏与不同颜色光反射一致,但总体通过率略高;白色和长波长光(红色和黄色)在项目通过率和发育节奏上均无显著差异,短波长光(绿色和蓝色)在项目通过率和发育节奏上也无显著差异,但前者总体通过率略高于后者。本研究在较大样本范围内证实了不同光感功能发育的异步性,瞳孔对光反射优先发育,光刺激瞬目反射和其他色光反射步调一致,都在12个月以后发育相对成熟;在不同色光中,长波长光感与短波长光感的发育节奏一致,但其成熟度高于短波长光感,表明长短波长光感的发育可能存在一定的不均衡。</p

Electrochemical Surface-Enhanced Raman Spectroscopy—Current Status and Perspective

许多和能源、生命相关的过程都强烈依赖于电化学荷电界面的结构和性能.自从表面增强拉曼光谱效应发现后,就很快地被应用于电化学界面的原位研究,即从分子水平上深入表征各种表面(或界面)的结构和过程,如鉴别物种在表面的键合、构型和取向等.最近十年,纳米科技的飞速发展为SERS技术提供了丰富的基底以及检测和表征方法,从而推动了与纳米科学密切相关的电化学SERS领域令人瞩目的发展.本文系统介绍Au和Ag的SERS、过渡金属薄层SERS、纯过渡金属SERS、核壳结构SERS和已经可以应用于单晶表面研究的gap-modeSERS、TERS和SHINERS,其中穿插着介绍电化学SERS的历史发展、现状和存在的问题及其展望,为电化学SERS研究提供较为全面的详细的参考.Electrochemical interface is a very important interface closely related to various energy and life processes. Surface-enhanced Raman scattering was widely used in electrochemistry soon after its discovery to understand the surface bonding,configuration,and orientation of the surface species. In recent 10 years,the fast development of nanoscience and nanotechnology has offered SERS with abundant substrates and characterization methods,which has allowed impressive development of electrochemical SERS. This articles will follow the time line to make systematically overview of SERS on Au and Ag,thin-layer transition-metal SERS,pure transition metal SERS,core-shell SERS and those methods for studying single crystal surfaces,including gap-mode SERS, TERS and SHINERS. Emphasis will be put on the history,present status and existing problems and perspectives of electrochemical SERS. We hope the present article will provide a comprehensive overview of the electrochemical SERS.作者联系地址：厦门大学化学化工学院化学系,固体表面物理化学国家重点实验室;Author's Address: State Key Laboratory of Physical Chemistry of Solid Surfaces,Department of Chemistry, College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,Fujian,Chin