表面增强拉曼光谱:应用和发展

表面增强拉曼光谱技术(Surface-enhanced Raman spectroscopy,SERS)是一种具有超高灵敏度的指纹光谱技术,目前已广泛应用于表面科学、材料科学、生物医学、药物分析、食品安全、环境检测等领域,是一种极具潜力的痕量分析技术。本文对SERS技术及相关的针尖增强拉曼光谱(Tip-enhanced Raman spectroscopy,TERS),壳层隔绝纳米粒子增强拉曼光谱(Shell-isolated nanoparticle-enhanced Raman spectroscopy,SHINERS)技术的发展及应用进行了综合评述,并探讨了其未来的研究热点及发展方向。国家自然科学基金项目(21533006,21522508,21775127)~

In situ dynamic tracking of heterogeneous nanocatalytic processes by shell-isolated nanoparticle-enhanced Raman spectroscopy

原位监测纳米催化反应过程对深入认识反应机理、设计高效催化剂具有重要意义。作为一种具有超高灵敏度的表面分析技术，表面增强拉曼光谱（SERS）是可提供反应过程中催化剂表面吸附物种的丰富信息。然而，仅有Au、Ag、Cu等少数金属在形成特定纳米结构时才能提供较强的拉曼增强，且它们会对催化剂的性质及反应过程产生严重干扰。这就极大地限制了SERS在实际多相催化体系中的应用。鉴于此，该论文发展了一种利用壳层隔绝纳米粒子增强拉曼光谱原位监测纳米催化过程的方法。通过将纳米催化剂组装于壳层隔绝纳米粒子表面，形成SHIENRS卫星结构，利用内核Au纳米粒子增强催化剂表面的拉曼信号，SiO2壳层隔绝Au对催化剂及反应的影响，从而直接获得了纳米催化剂表面物种的真实信息。利用这种SHINERS卫星策略，他们实现了CO氧化反应的原位监测，直接观测到了反应条件下催化剂表面吸附物种。并结合DFT计算，对反应机理进行了阐述。该研究表明SHINERS卫星策略可作为原位跟踪催化反应过程的有效方法，为纳米催化的原位研究提供了一种新的思路。 同时，我校也将在今年12月5-9日举办表面增强拉曼光谱国际会议(International Conference on SERS)，讨论SERS领域的最新进展。会议期间，SERS领域的先驱与权威Richard P. Van Duyne、Martin Moskovits、Andreas Otto以及相关学科的顶级学者Peter G. Bruce、Stefan A. Maier等将作大会报告（会议官方网站http://sers2017.xmu.edu.cn/）。【Abstract】Surface molecular information acquired in situ from a catalytic process can greatly promote the rational design of highly efficient catalysts by revealing structure-activity relationships and reaction mechanisms. Raman spectroscopy can provide this rich structural information, but normal Raman is not sensitive enough to detect trace active species adsorbed on the surface of catalysts. Here we develop a general method for in situ monitoring of heterogeneous catalytic processes through shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) satellite nanocomposites (Au-core silica-shell nanocatalyst-satellite structures), which are stable and have extremely high surface Raman sensitivity. By combining operando SHINERS with density functional theory calculations, we identify the working mechanisms for CO oxidation over PtFe and Pd nanocatalysts, which are typical low- and high-temperature catalysts, respectively. Active species, such as surface oxides, superoxide/peroxide species and Pd–C/Pt–C bonds are directly observed during the reactions. We demonstrate that in situ SHINERS can provide a deep understanding of the fundamental concepts of catalysis.This work was supported by the NSFC (21522508, 21427813, 21373167, 21521004, 21573178 and 21673187), Natural Science Foundation of Guangdong Province (2016A030308012), the Fundamental Research Funds for the Central Universities (20720150039 and 20720160046), ‘111’Project (B16029), and the Thousand Youth Talents Plan of China。 研究工作得到国家自然科学基金优秀青年基金、谱学分析创新研究群体和青年千人计划等资助

Observing atomic layer electrodeposition on single nanocrystals surface by dark field spectroscopy

从单颗粒水平研究电化学表面和界面过程，特别是欠电位沉积是电化学领域的一个重要挑战。欠电位沉积通常仅涉及单原子层到亚单原子层的物种，但是能够显著调控金属表面电子结构，是制备高效电催化剂的一个重要的方法。然而目前在电化学环境下表征单个粒子表面单层原子的变化仍然是个巨大的挑战，针对上述挑战，任斌教授课题组发展了一套高灵敏的电化学暗场散射光谱装置，在不使用特殊光源的情况下，可以使得检测的粒径小至10-15 nm，灵敏度提高到亚单层原子。该工作是在任斌教授指导下，主要由化学化工学院已毕业博士生胡树（第一作者）完成。李剑锋教授及其课题组的博士生张月皎在单晶电化学实验上提供了重要帮助。已毕业博士生易骏在理论计算方面提供了有力支持。Underpotential deposition offers a predominant way to tailor the electronic structure of the catalytic surface at the atomic level, which is key to engineering materials with a high activity for (electro)catalysis. However, it remains challenging to precisely control and directly probe the underpotential deposition of a (sub)monolayer of atoms on nanoparticle surfaces. In this work, we in situ observe silver electrodeposited on gold nanocrystals surface from submonolayer to one monolayer by designing a highly sensitive electrochemical dark field scattering setup. The spectral variation is used to reconstruct the optical “cyclic voltammogram” of every single nanocrystal for understanding the underpotential deposition process on nanocrystals, which cannot be achieved by any other methods but are essential for creating novel nanomaterials.The authors thank Dr. Hai-Xin Lin for helpful discussion of nanoparticle synthesis and characterization. The authors acknowledge support from the Natural Science Foundation of China (21633005, 21790354, and 21711530704) and the Ministry of Science and Technology of China (2016YFA0200601).该研究工作得到了国家自然科学基金委和科技部等的资助和支持

Synthesis of Ultra-Uniform Gold Spherical Nanoparticles with Different Sizes and Their SERS Effects Study

以氯金酸为原料,抗坏血酸为还原剂,柠檬酸钠为保护剂,用化学还原(种子生长)法制备了不同粒径、超均匀的球形金纳米粒子溶胶,并通过紫外可见吸收光谱(UV-Vis)和扫描电子显微镜(SEM)进行表征。结果表明,随着金纳米粒子粒径的增大,其UV-Vis光谱中的吸收峰发生红移并出现四极峰。为进一步研究金纳米粒子表面增强拉曼散射(SERS)效应的作用机理并优化其灵敏度,我们以罗丹明6G(R6G)为探针分子,对不同粒径的金纳米粒子进行SERS表征,发现R6G的SERS信号随着金纳米粒子的增大先增强后减弱。当金纳米粒子的平均粒径达到120nm时,产生最强SERS信号增强,增强因子约为1.1×10~7。三维时域有限差分法(3D-FDTD)理论模拟纳米粒子阵列电磁场分布结果与实验数据的趋势一致。A series of ultra-uniform gold spherical nanoparticles with different sizes were synthesized using gold chloride acid as precursor,ascorbic acid as reductant and sodium citrate hydrate as surfactant.The prepared Au nanoparticles were characterized by scanning electron microscope(SEM)and UV-visible spectroscopy.The results showed that the absorption peak of UV-Vis spectroscopy red-shifted along with size increasing of the nanoparticles and finally appeared a quadrupole peak.To further explore the mechanism of surface enhanced Raman spectroscopy(SERS)effect and optimize the sensitivity,SERS on Au nanoparticles with different sizes were measured using Rhodamine 6G(R6G)as probe molecule.We found the SERS signals of R6 Gon the Au nanoaprtciles were highly size dependent.When the particles sizes are close to~120nm,it will generate the highest enhancement,the enhancement factor is about 1.1×10~7.The 3D-FDTD simulation results correlated with the experimental data very well.国家自然科学基金项目(21473140)资