International Collaboration in Chemistry: Nucleation/Growth of Catalytic Nanoclusters

化学国际合作：催化纳米团簇的成核/生长

• 批准号: 1026582
• 负责人: Michael Mirkin
• 金额: $ 35.54万
• 依托单位: CUNY Queens College
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2010
• 资助国家: 美国
• 起止时间: 2010-10-01 至 2014-09-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1026582&HistoricalAwards=false
• 关键词: International; Collaboration; Chemistry; Nucleation; Growth

The Chemical Catalysis Program in the Chemistry Division and the Office of International Science and Engineering's (OISE) East Asia and Pacific Program support Professor Michael Mirkin of CUNY Queens College in the US, in collaboration with Professor Bin Ren of Xiamen University in China. The proposal for which this award was granted was submitted in response to Program Announcement NSF 09-608: International Collaboration in Chemistry between US investigators and their Counterparts Abroad (ICC). The research of Professor Ren is supported by the National Natural Science Foundation of China. The researchers propose to prepare catalytic metal clusters by electrodeposition at nanoelectrodes and to produce even smaller (a few atoms) metal deposits in thin layer nanocells. The first part of this project will focus on electrodeposition at nanoelectrodes (research conducted by the CUNY group). Mercury, used as a model to validate the methodology, and solid catalytic metals (e.g., Ru, Pd, Ag, Co, and Ni) will be deposited on Au and Pt nanoelectrodes of various sizes (from 5 nm to 200 nm). The size and shape of deposited metal nanostructures will be characterized by electrochemistry, scanning electrochemical microscopy (SECM) and scanning electron microscopy (SEM). The mechanism of nucleation/growth of metals on nanoelectrodes will be investigated. Preliminary results point to the new features of these processes that could not be observed in conventional experiments at macroscopic electrodes. Meanwhile, the Xiamen group will develop methodology for using modified disk-type Au nanoelectrodes as tip-enhanced Raman spectroscopy (TERS) tips to generate the Raman active species in real time. Next, the groups will focus on electrodeposition and TERS experiments in nanometer-sized thin layer cells (nano-TLCs). The catalytic activities of deposited metal clusters for several electrocatalytic reactions (hydrogen evolution reaction [HER], oxygen reduction reaction [ORR], and oxidation of methanol) will be characterized by electrochemical methods and a SECM-TERS hybrid technique. The combination of SECM and TERS will provide much more comprehensive information about electrocatalysis than that obtained from electrochemical and spectroscopic experiments individually. The proposed research intends to address fundamental aspects of the electrocatalysis of extremely small metal clusters. It should contribute to better understanding of the electrocatalytic process and its current limitations. In addition, it is expected to advance knowledge of nanoelectrochemistry, scanning electrochemical microscopy (SECM) and tip enhanced Raman Spectroscopy (TERS). In addition to fundamental importance, the anticipated results will have significant implications for fuel cells and other alternative energy systems relying on electrocatalysis. The results of this research will be broadly disseminated through publications and professional presentations. The proposed activities will enhance the infrastructure for research and education at CUNY by stimulating the development of new instrumentation and forging the new international partnership. The undergraduate and graduate students involved in this project will gain valuable experience in multidisciplinary fundamental research. The proposed international collaboration will provide additional training opportunities for students in both research groups and expose them to a wide range of electroanalytical and spectroscopic methods, as well as theoretical and computational approaches. Being a part of the international collaborative project will prepare them for future leadership positions in research, both nationally and internationally.

化学系的化学催化项目和国际科学与工程办公室（OISE）的东亚和太平洋项目支持美国纽约市立大学皇后学院的Michael Mirkin教授与中国厦门大学的任斌教授合作。该奖项是根据NSF 09-608计划公告：美国研究人员与国外同行（ICC）之间的化学国际合作而提交的。任教授的研究得到了国家自然科学基金的资助。研究人员建议通过在纳米电极上电沉积来制备催化金属簇，并在薄层纳米细胞中产生更小（几个原子）的金属沉积物。该项目的第一部分将重点关注纳米电极的电沉积（由纽约市立大学小组进行的研究）。汞（用作验证方法的模型）和固体催化金属（例如，Ru、Pd、Ag、Co和Ni）将沉积在各种尺寸（从5 nm到200 nm）的Au和Pt纳米电极上。沉积的金属纳米结构的尺寸和形状将通过电化学、扫描电化学显微镜（SECM）和扫描电子显微镜（SEM）来表征。将研究纳米电极上金属的成核/生长机制。初步结果指出，这些过程的新特点，不能在传统的实验中观察到宏观电极。与此同时，厦门研究组将开发使用修饰的圆盘型Au纳米电极作为尖端增强拉曼光谱（TERS）尖端的方法，以真实的实时产生拉曼活性物质。接下来，小组将专注于纳米尺寸的薄层电池（nano-TLC）中的电沉积和TERS实验。沉积的金属簇的催化活性的几个电催化反应（析氢反应[HER]，氧还原反应[ORR]，和甲醇的氧化）将其特征在于电化学方法和SECM-TERS混合技术。SECM和TERS的结合将提供比单独从电化学和光谱实验获得的更全面的关于电催化的信息。拟议的研究旨在解决极小金属簇的电催化的基本方面。它应有助于更好地了解电催化过程及其目前的局限性。此外，预计将推进纳米电化学，扫描电化学显微镜（SECM）和尖端增强拉曼光谱（TERS）的知识。除了基本的重要性，预期的结果将对燃料电池和其他依赖于电催化的替代能源系统产生重大影响。这项研究的结果将通过出版物和专业介绍广泛传播。拟议的活动将通过促进新仪器的开发和建立新的国际伙伴关系，加强纽约市立大学的研究和教育基础设施。参与该项目的本科生和研究生将获得多学科基础研究的宝贵经验。拟议的国际合作将为两个研究小组的学生提供额外的培训机会，并使他们接触到广泛的电分析和光谱方法，以及理论和计算方法。作为国际合作项目的一部分，将为他们未来在国内和国际研究中的领导地位做好准备。