Ligand Dynamics and Chemistry on Locally Curved Metallic Nanoparticle Surfaces

局部弯曲金属纳米颗粒表面的配体动力学和化学

• 批准号: 2202928
• 负责人: Hui Wang
• 金额: $ 48.71万
• 依托单位: University of South Carolina at Columbia
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-08-15 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2202928&HistoricalAwards=false
• 关键词: Ligand; Dynamics; Chemistry; Locally; Curved

With the support of the Macromolecular, Supramolecular and Nanochemistry Program in the Division of Chemistry, Dr. Hui Wang of University of South Carolina aims at developing quantitative understanding of the dynamic interactions between molecular ligands and nanoparticle surfaces as well as surface curvature-dependent ligand chemistry and photochemistry. The inorganic cores and the organic ligand shells are two structurally distinct but strongly interplaying components that synergistically determine the collective optical, electronic, and catalytic properties of the nanoparticles. The insights to be gained from this research project will serve as a central knowledge framework that guides the rational optimization of the surface functionalities of colloidal nanoparticles toward targeted applications in catalysis, photocatalysis, photonics, sensing, and biomedicine. This project will create valuable research training opportunities for students at various levels and will be further integrated with outreach activity development. Specifically, Dr. Wang will develop a highly interdisciplinary research and education program on nanoparticle surface chemistry involving broad participation of graduate, undergraduate, and high school students. In addition, Dr. Wang and his students will collaborate with Benedict College, a Historically Black College and University (HBCU) in South Carolina, to develop a long-term partnership on both research and education. Furthermore, the Wang group will work closely with the Electron Microscopy Center at the University of South Carolina on developing educational outreach activities that specifically target the students from local public schools and the participants of the South Carolina State Science Fair.Virtually all chemically synthesized inorganic colloidal nanoparticles, regardless of their dimensions, crystalline structures, and chemical compositions, are coated with a thin layer of organic molecular ligands. This research project involves systematic comparative studies of several deliberately selected nanoparticle-ligand systems to investigate the interfacial dynamics and chemical/photochemical transformations of molecular adsorbates on locally curved metallic nanoparticle surfaces through integrated experimental and computational research efforts. Dr. Wang and his research team will utilize surface-enhanced Raman spectroscopy (SERS) as an ultrasensitive plasmon-enhanced spectroscopic tool to quantitatively correlate the interfacial ligand dynamics with detailed molecular structures under a diverse set of ligand adsorption, desorption, and exchange conditions. SERS will also be used as an in situ spectroscopic tool to fine-revolve detailed structural evolution of the transforming molecular adsorbates on structurally tailored metallic nanoparticle surfaces in real time during chemical and photochemical reactions. The thermodynamic and kinetic results obtained through deliberately designed SERS measurements will be further corroborated by density functional theory calculations to fully unravel how the chemical nature of nanoparticle-adsorbate interactions and the local curvature of nanoparticle surfaces profoundly influence the dynamic interfacial behaviors and the chemical/photochemical reactivities of various types of surface-bound ligand molecules, such as organothiols, isocyanide compounds, terminal alkynes, and diazonium-derived aryl ligands.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系大分子、超分子和纳米化学计划的支持下，南卡罗来纳大学的王辉博士致力于定量了解分子配体和纳米颗粒表面之间的动态相互作用，以及表面曲率相关的配体化学和光化学。无机核和有机配位体壳层是两个结构截然不同但相互作用很强的成分，它们协同决定了纳米粒子的集体光学、电子和催化性质。从这一研究项目中获得的见解将作为一个核心知识框架，指导胶体纳米颗粒表面功能的合理优化，从而达到在催化、光催化、光子学、传感和生物医学中的目标应用。该项目将为各级学生创造宝贵的研究培训机会，并将进一步与外联活动的发展相结合。具体地说，王博士将开发一个高度跨学科的纳米颗粒表面化学研究和教育计划，让研究生、本科生和高中生广泛参与。此外，王博士和他的学生将与南卡罗来纳州历史上的黑人学院和大学(HBCU)本尼迪克特学院合作，在研究和教育方面发展长期合作伙伴关系。此外，WANG小组将与南卡罗来纳大学电子显微镜中心密切合作，开展专门针对当地公立学校学生和南卡罗来纳州科学博览会参与者的教育推广活动。实际上，所有化学合成的无机胶体纳米颗粒，无论其尺寸、晶体结构和化学成分，都覆盖着一层薄薄的有机分子配体。该研究项目包括对几个精心选择的纳米颗粒-配体系统进行系统的比较研究，通过实验和计算相结合的研究工作，研究分子在局部弯曲的金属纳米颗粒表面上的界面动力学和化学/光化学转化。Wang博士和他的研究团队将利用表面增强拉曼光谱(SERS)作为一种超灵敏的等离子体增强光谱工具，在不同的配体吸附、解吸和交换条件下，将界面配体动力学与详细的分子结构定量关联。SERS还将作为一种原位光谱工具，在化学反应和光化学反应过程中实时精细地研究结构定制的金属纳米颗粒表面上转化分子吸附的详细结构演变。通过精心设计的SERS测量获得的热力学和动力学结果将进一步得到密度泛函理论计算的证实，以充分揭示纳米颗粒-吸附相互作用的化学本质和纳米颗粒表面的局部曲率如何深刻地影响各种表面结合的配体分子的动态界面行为和化学/光化学反应活性，如有机硫醇、异氰化物化合物、末端炔和重氮衍生的芳基配体。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，认为值得支持。

项目成果

Effects of Cascading Optical Processes: Part II: Impacts on Experimental Quantification of Sample Absorption and Scattering Properties

• DOI: 10.1021/acs.analchem.2c05055
• 发表时间: 2023-02-14
• 期刊: ANALYTICAL CHEMISTRY
• 影响因子: 7.4
• 作者: Wathudura，Pathum;Wamsley，Max;Zhang，Dongmao
• 通讯作者: Zhang，Dongmao

Origin of Superlinear Power Dependence of Reaction Rates in Plasmon-Driven Photocatalysis: A Case Study of Reductive Nitrothiophenol Coupling Reactions

• DOI: 10.1021/acs.nanolett.3c00195
• 发表时间: 2023-03-15
• 期刊: NANO LETTERS
• 影响因子: 10.8
• 作者: Chen, Kexun;Wang, Hui
• 通讯作者: Wang, Hui