CAREER: Elucidation of the mechanistic origins of plasmon-induced chemical reactions

职业：阐明等离激元诱导的化学反应的机械起源

• 批准号: 1455011
• 负责人: Prashant Jain
• 金额: $ 65.56万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-08-01 至 2023-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1455011&HistoricalAwards=false
• 关键词: CAREER; Elucidation; mechanistic; origins; plasmon

With this CAREER Award, the Macromolecular, Supramolecular and Nanochemistry Program of the Division of Chemistry is supporting Professor Prashant Jain of the University of Illinois to study the detailed manner in which light energy is converted into chemical energy within metallic materials. This process, if properly understood and controlled, may become a candidate technology for capturing solar energy and for driving energy-intensive processes in the chemical industry with light. Professor Jain aims at preparing strongly light-absorbing materials that can efficiently convert sunlight into chemical energy in fuels. Another effort involves the achievement of light-to-chemical energy conversion using cheaper, more abundant materials. Alongside the laboratory efforts, an interactive software tool is being developed and employed for the purpose of education on the interaction of light with matter. The educational program is aimed at generating early scientific interest in the classroom by means of vivid, hands-on examples from optics, preparing high school, undergraduate, and graduate students for future science and technology careers. Outreach activities seek to foster community awareness of solar energy as a clean, renewable alternative to energy from fossil fuels. Professor Jain investigates the physicochemical mechanism(s) by which the plasmonic excitation of a noble metal-containing heterostructure induces or catalyzes chemical reactions on the surface of the nanostructure. In this project, a plasmonic heterostructure consisting of Au nanoparticles in contact with a semiconducting oxide (titanium dioxide and zinc oxide) is studied for determining the relative contributions of plasmonic near-field enhancement, hot electron transfer, and photothermal heating in photocatalytic reactions. This research aims to elucidate the mechanistic role of the oxide and assess whether near-field-assisted bandgap or sub-bandgap photoexcitation of carriers in the oxide is responsible for the observed photoactivity, or, whether charge separation across the metal/oxide is a more important contributor. Professor Jain uses single-molecule fluoresence to identify whether the photoreaction takes place on the metal, on the semiconducting oxide, or at the metal/oxide interface. Finally, he explores plasmon excitation-induced photocatalysis in a noble metal-free plasmonic oxide, which represents an interface-free system where plasmonic excitation and semiconductor electronic transitions are localized within the same crystallite.

有了这个职业奖，化学系的大分子，超分子和纳米化学计划正在支持伊利诺伊大学的Prashant Jain教授研究光能在金属材料中转化为化学能的详细方式。这一过程，如果正确理解和控制，可能成为一个候选技术，用于捕获太阳能和驱动能源密集型过程中的化学工业与光。Jain教授的目标是制备强吸光材料，可以有效地将阳光转化为燃料中的化学能。 另一项努力涉及使用更便宜，更丰富的材料实现光到化学能的转换。除了实验室的努力，一个互动的软件工具正在开发和使用的目的是教育的光与物质的相互作用。该教育计划旨在通过生动的，动手的例子，从光学，高中，本科和研究生为未来的科学和技术职业准备的手段，在课堂上产生早期的科学兴趣。外联活动力求提高社区对太阳能作为化石燃料能源的清洁、可再生替代能源的认识。Jain教授研究了含贵金属异质结构的等离子激元激发诱导或催化纳米结构表面化学反应的物理化学机制。在这个项目中，一个等离子体异质结组成的Au纳米粒子与半导体氧化物（二氧化钛和氧化锌）接触的研究，以确定等离子体近场增强，热电子转移，和光热加热的光催化反应中的相对贡献。这项研究的目的是阐明氧化物的机械作用，并评估是否近场辅助带隙或子带隙光激发的氧化物中的载流子是负责所观察到的光活性，或者，是否跨金属/氧化物的电荷分离是一个更重要的贡献者。 Jain教授使用单分子荧光来识别光反应是否发生在金属上，半导体氧化物上或金属/氧化物界面上。最后，他探索了无贵金属等离子体氧化物中的等离子体激元激发诱导的电子跃迁，这代表了一种无界面系统，其中等离子体激元激发和半导体电子跃迁位于同一微晶内。

项目成果

Activation Energies of Plasmonic Catalysts

• DOI: 10.1021/acs.nanolett.6b01373
• 发表时间: 2016-05-01
• 期刊: NANO LETTERS
• 影响因子: 10.8
• 作者: Kim, Youngsoo;Torres, Daniel Dumett;Jain, Prashant K.
• 通讯作者: Jain, Prashant K.