Collaborative Research: Investigating Photoinduced Charge Transfer Dynamics Across Molecule-Nanocrystal Interfaces

合作研究：研究分子-纳米晶体界面上的光致电荷转移动力学

• 批准号: 1900272
• 负责人: Luis Velarde
• 金额: $ 38.4万
• 依托单位: SUNY at Buffalo
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-08-15 至 2024-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1900272&HistoricalAwards=false
• 关键词: Collaborative; Research; Investigating; Photoinduced; Charge

Plants use sunlight to convert carbon dioxide into energy rich sugar molecules, in a process known as photosynthesis. The development of artificial photosynthetic systems that could use sunlight to make fuels such as alcohol from carbon dioxide and hydrogen from water would have enormous societal benefit. However, the chemical reactions are complicated and involve multiple electron transfer steps and connecting these steps with the absorption of light remains a challenge. With support from the Chemical Structure, Dynamics and Mechanisms A and Macromolecular, Supramolecular and Nanochemistry programs in the Division of Chemistry, Professors David McCamant, Pengfei Huo, and Kathryn Knowles at University of Rochester are teaming up with Professors Luis Velarde and David Watson at the University at Buffalo, State University of New York and Kacie Liwosz at D'Youville College to study light-induced electron transfer reactions between dye molecules and semiconductor nanoparticles. Working with their students, they grow nanoparticles composed of common minerals such as titanium dioxide and iron oxide and coat them with organic dyes. They then combine sophisticated laser spectroscopies with computer modeling to characterize the electron transfer process that occur when the dye molecules absorb light. In addition to training the next generation of scientists, the team is also running educational workshops in Upward Bound summer schools for high-school students with disadvantaged backgrounds. The summer workshops inspire students' curiosity and enthusiasm about renewable energy and chemistry, as well as encourage them to pursue higher education in STEM fields. Photoinduced interfacial charge transfer is a fundamental process underlying the conversion of solar energy to chemical energy and is particularly important in photocatalytic fuel-forming reactions. Detailed knowledge of the conformation and electronic structure of the ground, photoexcited, and charge separated states of molecular species bound to semiconductor surfaces is critical to a mechanistic understanding of the dynamics of such charge transfer reactions. The project combines interdisciplinary expertise in time-resolved electronic and vibrational spectroscopy, sum-frequency generation spectroscopy, quantum dynamics simulation, and the fabrication and characterization of nanostructured semiconductors. These tools are being applied to three important areas relating to interfacial charge transfer: (i) the role of molecular structure in mediating relaxation and energy transfer pathways that precede interfacial charge transfer, (ii) structure-function relationships between the morphology of wide band-gap p-type semiconductors and hole injection from surface-bound molecular sensitizers, and (iii) structure-function relationships between the morphology of narrow band gap semiconductors and charge transfer to surface-bound molecular hole and electron acceptors, such as catalysts for fuel production. Fundamental mechanistic insights generated by this work could enable the rational design of semiconductor/molecule partner systems with improved performance in photocatalytic generation of fuels from sunlight.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.

植物利用阳光将二氧化碳转化为富含能量的糖分子，这一过程被称为光合作用。人工光合系统的发展可以利用阳光从二氧化碳中制造酒精和从水中制造氢气等燃料，这将带来巨大的社会效益。然而，化学反应是复杂的，涉及多个电子转移步骤，将这些步骤与光的吸收联系起来仍然是一个挑战。在化学系的化学结构、动力学和机制A以及大分子、超分子和纳米化学项目的支持下，罗切斯特大学的大卫·麦卡曼特教授、霍鹏飞教授和凯瑟琳·诺尔斯教授与布法罗大学的路易斯·维拉德教授和大卫沃森教授合作，纽约的州立大学和D 'Youville学院的Kacie Liwosz研究染料分子和半导体纳米颗粒之间的光诱导电子转移反应。他们与学生合作，培育由二氧化钛和氧化铁等常见矿物质组成的纳米颗粒，并用有机染料包裹它们。然后，他们将联合收割机复杂的激光光谱与计算机建模相结合，以表征染料分子吸收光时发生的电子转移过程。 除了培训下一代科学家外，该团队还在Upward Bound暑期学校为弱势背景的高中生举办教育研讨会。 暑期工作坊激发学生对可再生能源和化学的好奇心和热情，并鼓励他们在STEM领域接受高等教育。光致界面电荷转移是太阳能转化为化学能的基本过程，在光催化燃料形成反应中尤为重要。详细的知识的构象和电子结构的地面，光激发，和电荷分离状态的分子种类绑定到半导体表面是至关重要的机械理解的动力学，这样的电荷转移反应。该项目结合了时间分辨电子和振动光谱学、和频产生光谱学、量子动力学模拟以及纳米结构半导体的制造和表征方面的跨学科专业知识。这些工具正应用于与界面电荷转移有关的三个重要领域：（i）分子结构在介导界面电荷转移之前的弛豫和能量转移途径中的作用，（ii）宽带隙p型半导体的形态与来自表面结合的分子敏化剂的空穴注入之间的结构-功能关系，以及（iii）窄带隙半导体的形态与电荷转移到表面结合的分子空穴和电子受体（例如用于燃料生产的催化剂）之间的结构-功能关系。这项工作所产生的基本机理见解可以使半导体/分子合作伙伴系统的合理设计与改进性能的光催化发电燃料从sunlight.This奖项反映了NSF的法定使命，并已被认为是值得通过评估使用基金会的智力价值和更广泛的影响审查标准的支持。