Interaction between Molecule and Metal Probed by Vibrational Spectroscopy——Molecular Adsorption and Reaction on Pt Group Metals Probed by SERS and Charge Transfer between Molecule and Metal Probed by

摘要表面增强拉曼光谱（SERS）经过约三十年的发展，已成为研究界面电化学体系的重要谱学技术。但是，迄今已研究体系大部分局限在金、银、铜等币族金属和一些典型的SERS探针分子，且有关表面增强拉曼散射（SERS）的电荷传递机理仍很不清楚。为了将SERS发展为广泛通用的谱学技术，需要克服和解决以上问题。为此，本论文工作主要分为如下两方面：一．拓宽SERS研究体系。苯、甲苯和乙炔等分子因倾向于在过渡金属电极表面平躺吸附而导致其SERS信号微弱，故有关研究极其有限。通过优化拉曼谱仪的灵敏度和电极表面的粗糙方法，成功地获得这些分子在铂、钌、铑、钯金属上的SERS信号，较系统地研究了它们的电化学吸附行为，从...Abstract With a development of nearly three decades, surface-enhanced Raman spectroscopy(SERS) has become one of the most important in-situ spectroscopies and plays important role in interfacial electrochemistry. However, up to now, most of the research are still limited to three noble metals: Au, Ag and Cu with high SERS activity and the classical SERS probe molecules including pyridine, pyraz...学位：理学博士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：B20022502

退火对4-硝基苯硫酚分子常规拉曼峰的影响

文章利用氮气氛围下退火实验实现了4-硝基苯硫酚(PNTP)固体粉末样品中PNTP分子和4,4’-二硝基二苯二硫醚(NPDS)分子的有效分离,考察了不同温度对退火的影响,并利用拉曼光谱对其进行定性分析,同时利用理论计算对NPDS分子的拉曼峰进行了指认.该方法为快速定性PNTP分子中是否含有NPDS提供了快速简便的方法.福建省自然科学基金面上项目(2019J01746

暂态电化学表面增强拉曼光谱研究对硝基苯硫酚分子的电化学还原过程

对硝基苯硫酚是表面增强拉曼光谱研究中最常用的探针分子之一,对硝基苯硫酚在电极表面电化学还原反应的研究有助于对芳香族硝基化合物还原机理的认识.本文应用暂态电化学-表面增强拉曼光谱技术,研究了对硝基苯硫酚在循环伏安和计时电流法过程中的表面增强拉曼光谱.结果表明,实验实现了完全与电化学检测时间分辨率同步的表面增强拉曼光谱检测,以最快5毫秒的时间分辨率研究了对硝基苯硫酚分子在金电极表面的还原过程.结果分析推测其此反应过程极快,在5毫秒的时间分辨率下仍难以捕获其中间物种.本研究为人们更深层次研究和认识硝基苯类化合物电化学还原过程提供了参考和方向

Identification of Colorants in Food by Surface-enhanced Raman Spectroscopy and Wavelet-based Reverse Search

使用金纳米粒子为增强因子的表面增强拉曼光谱技术,通过连续小波变换将拉曼光谱信号转化到小波空间(墨西哥帽小波作为小波基)。该步骤能够减轻信号中基线; 变化及随机噪音的影响并找到峰位置和最佳小波尺度系数。依据小波空间中的信息,对混合物光谱及标准谱光谱进行反向搜索得到反向搜索匹配系数(Revere; match quality,; RMQ),作为判断混合物中目标成分是否存在的依据。该算法可对混合物中的目标物质进行准确定性,并已成功应用于多种食品中色素鉴定。食品中色素的检出率; 达到99%,且结果稳健,其效果明显优于传统的命中质量系数法(Hit quality index,; HQI)。这证实了小波空间反向搜索方法是一种快速而准确的拉曼光谱定性算法。In this study, a gold nanocrystal colloid was used as the enhancement; factor for surfaceenhanced Raman scattering (SERS). Raman spectra were; transformed by continuous wavelet transform (CWT),and Mexican hat; wavelet were chosen as the wavelet basis. This procedure could be used; to alleviate the influence of baseline variations and random noise,and; find peak positions and the best scale wavelet coefficients of signal.; Reverse search method was proposed to compare the spectrum of an unknown; sample with a spectrum of standard using the information in wavelet; space. Reverse match quality (RMQ) could be obtained automatically to; determine whether a substance is present. It was used to identify; colorants in a variety of food successfully. The colorants could be; identified with 99 percent accuracy. It shows a better performance; compared with traditional hit quality index (HQI). The study confirmed; that the wavelet-based reverse search is feasible and accurate in; qualitative analysis.国家自然科学基金资助项目; 国家重大科学仪器设备开发专

Study on Films of Organofunctional Silanes on Transition Metal Surfaces——The Structure of γ-Aminopropyltrimethoxysilane Films on Nickel Electrodes

在镍电极表面制备了γ 氨丙基三甲氧基硅烷膜 (γ APS)并对其形成和结构进行了研究 .镍电极表面有机官能团硅烷膜的X射线光电子能谱 (XPS)结果表明氮、硅等元素在电极表面的存在 ,并且氨基在膜中有若干种存在方式 ,包括自由氨基和质子化的氨基 .通过对表面增强拉曼散射光谱 (SERS)谱图的分析 ,发现与电极表面作用的吸附基团硅醇羟基和氨基发生了竞争吸附 ,它们及其邻近基团的拉曼谱峰随着电位的负移除了相对强度发生变化以外 ,还发生了一定的位移 ,这缘于吸附基团吸附的量和吸附取向随电极电位发生了变化并形成了更为复杂的界面结构 ;氨基不同存在方式之间也会随之发生转变 ,这一结果与X射线光电子能谱分析的结果相符合 .原子力显微镜 (AFM)结果表明镍电极表面的有机官能团硅烷膜呈现为一种较规则的多孔结构In the present paper, we prepared the γ-aminopro py ltrimethoxysilane (γ-APS) films on nickel electrode surfaces and studied their formation and structure. XPS results of the films of the organofunctional silan es modified nickel electrodes show the presence of nitrogen and silicon bindin g energy peaks indicating the presence of γ-APS on the metal surface. The result s also in dicate that the amine is presented in several different states, including the free amine and the protonated one. The potential-dependent Raman spectra gave plen ty of information of γ-APS/metal interface, the silanol and amino groups adsor bed competitively on the nickel surfaces. While the applied potential was change d negatively from open circuit potential, the peak intensity of the SERS spectra of these adsorptive groups and the adjacent groups changed and the frequencies of the bands red-shifted. It is assumed that the quantity and adsorptive orien tation of the adsorptive groups changed with the change in the potential and for med more complicated structure of interface. It was also found that the differen t states of amine transformed with the change in the potential, this can be conf irmed by the results of XPS. Atom force microscopy (AFM) was applied to characte rize the silane films. It could be concluded that the films of the organofunctio nal silanes are porous on the microscopic scale.厦门大学固体表面物理化学国家重点实验室开放课题资

Developing On-site,Quick Screening Platform for Artificial Pigments in Food Using Surface-enhanced Raman Spectroscopy

已有研究表明食品加工过程中添加的人工合成色素不仅不能提供营养物质,而且可能是导致小儿多动症的来源之一,影响儿童智力发育.基于表面增强拉曼光谱(SERS)原理和便携式拉曼光谱仪,提出了一种非定向的现场快速筛查方法.该方法只需对疑似含有人工合成色素的固体或液体状食品样品进行简单前处理,即可进行SERS检测.样品前处理和检测的总时长不超过15 min,检出质量浓度在1 mg/L水平,可有效满足政府职能部门的现场执法需求.除具有快速、方便、灵敏度高等特点之外,该检测方法的最大优势在于实现了未知样品的现场非定向测试:在同一种前处理过程和检测方法下,可对食品中常添加的亮蓝、胭脂红、日落黄、柠檬黄、苋菜红和诱惑红6种人工合成色素进行快速鉴定和半定量分析.As widely used additives in food processing,artificial pigments have no any nutrition but are potential sources of hyper-activity and affect the intellectual development of children.On the basis of surface-enhanced Raman spectroscopy( SERS) and portable Raman instrument,we developed a non-targeting,on-site and quick screening platform for artificial pigments in food matrix. SERS measurement could be carried out after the food matrix( either in solid or liquid states) being simply pretreated for 15 min.The detectable concentration is as low as 1 mg / L,a level meeting the demand of the on-site enforcement by the government.Besides the advantages of quick,easy-on-going,and high sensitivity,the most distinguished point of SERS is the non-targeting qualitative on-site detection for the typical pigment additives,including brilliant blue,carmine,sunset yellow,lemon yellow,amaranth and allura red,et al.,while both the pretreatment procedure and the SERS detection remain the same.国家自然科学基金(21473140);; 福建省高校产学合作项目(2016Y4012);; 中央高校基本科研业务费专项(2072016011

基于密度泛函理论计算分析磺胺类抗生素的拉曼光谱

最近我们研究组发现磺胺类抗生素在不同团聚剂作用下的表面增强拉曼光谱(SERS)会发生明显的差异。为了研究产生差异的原因,我们采用密度泛函理论(DFT)计算的方法,讨论了磺胺类分子的构型变化、构象变化、质子化以及分子间二聚体等方面的变化对其在金纳米粒子上的SERS变化的影响。国家自然科学基金项目(21533006,21621091)资

Study on films of organofunctional silanes on transition metal surfaces - The structure of gamma-aminopropyltrimethoxysilane films on nickel electrodes

In die present paper, we prepared the gamma-aminopropyltrimethoxysilane (gamma-APS) films on nickel electrode surfaces and studied their formation and structure. XPS results of the films of the organofunctional silanes modified nickel electrodes show the presence of nitrogen and silicon binding energy peaks indicating the presence of gamma-APS on the metal surface. The results also indicate that the amine is presented in several different states, including the free amine and the protonated one. The potential-dependent Raman spectra gave plenty of information of gamma-APS/metal interface, the silanol and amino groups adsorbed competitively on the nickel surfaces. While the applied potential was changed negatively from open circuit potential, the peak intensity of the SERS spectra of these adsorptive groups and the adjacent groups changed and the frequencies of the bands red-shifted. It is assumed that the quantity and adsorptive orientation of the adsorptive groups changed with the change in the potential and formed more complicated structure of interface. It was also found that the different states of amine transformed with the change in the potential, this can be confirmed by the results of XPS. Atom force microscopy (AFM) was applied to characterize the silane films. It could be concluded that the films, of the organofunctional silanes are porous on the microscopic scale

Developing fast laboratory screening platform for sulfate dioxide in food by surface-enhanced Raman spectroscopy

基于表面增强拉曼光谱(SERS)的指纹图谱的高能量分辨率,以位于~630; cm~(-1)亚硫酸根的特征峰为定性和定量依据,本文开展了食品中滥用和非法添加二氧化硫的直接检测研究:一种检测流程实现了不同食品基质中二氧化硫的; 高灵敏检测,最低检出浓度达1 mg; kg~(-1)的水平.针对实际样本的传统蒸馏法前处理流程的一些不足以及SERS检测的指纹图谱优势,本文进行了三方面显著改进:; (1)碳酸钙和沸石取代氮气以提高二氧化硫的挥发提取效率; (2)草酸取代盐酸酸化蒸馏溶液,以有效避免挥发性强酸对操作环境的危害;; (3)氢氧化钠溶液代替乙酸铅溶液作为吸收液,以防止二次污染.环境友好、灵敏度高和不受基质干扰等特点使得本方法有望取代经典蒸馏法和比色法,用于食品; 中非法添加二氧化硫类添加剂的快速高效筛查.The direct detection of sulphur dioxide has been realized in various; food matrixes with high sensitivity and high selectivity, on the basis; of the integration of the high energy resolution of the finger-print; spectrum of surface-enhanced Raman spectroscopy and the universal but; easy-on-going pretreatment procedure. The characteristic peak of sulphur; dioxide at ~630 cm~(-1) was applied as the qualitative and quantitative; standard, which displayed a lowest detectable concentration at the 1 mg; kg~(-1) level for the spiked food samples. The key point of the high; sensitivity and selectivity is the effective pretreatment born out of; the standard distillation one, which has been improved in the three; parts. (1) Using CaCO_3 and Zeolite instead of N_2 gas as the bubbling; reagent. (2) Using oxalic acid as the acidic distillation solution to; eliminate the hazards from acid volatilization, such as hydrochloric; acid. (3) Using diluted sodium hydroxide solution as the absorption; reagent instead of lead acetate solution to avoid the secondary; pollution. With the three distinguished advantages of environment; friendly, high sensitivity and free of matrix interference, the proposed; method has great potential to replace the traditional ones for the fast; screening of the illegal or abused sulphur dioxide in food.国家自然科学基金; 福建省高校产学合作项目; 中央高校基本科研业务费专项资