Collaborative Research: Real Time Spectroscopic Studies of Hybrid MOF Photocatalysts for Solar Fuel Production

合作研究：用于太阳能燃料生产的混合 MOF 光催化剂的实时光谱研究

• 批准号: 1706632
• 负责人: Jian Zhang
• 金额: $ 22.48万
• 依托单位: University of Nebraska-Lincoln
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-08-01 至 2021-07-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1706632&HistoricalAwards=false
• 关键词: Collaborative; Research; Real; Time; Spectroscopic

In this project, the researchers will investigate a relatively new class of materials known as metal-organic frameworks (MOFs) as to their suitability as catalysts for the production of hydrogen as a sustainable fuel from sunlight and water. The specific goals of this project are to examine how placement of the photosensitizer and catalytic centers within zirconium-based MOFs influence both the mechanism by which photocatalysis occurs and the corresponding efficiency of the photocatalytic reaction. More broadly, the research will create a structural model for future studies of real-time structure-function correlations for other photoactive materials, impacting broadly on fields such as photocatalysis, optoelectronic devices, and solar energy conversion technologies. In turn, this research will help identify efficient materials for an eventual carbon-neutral, economically-viable fuel industry driven by solar energy. The project will include training and mentoring of graduate and undergraduate students in photocatalysis research, which will strengthen the U.S. pipeline of science-educated students prepared to tackle next-generation problems in materials science, sustainable chemistry, and energy science. The project focuses on real-time spectroscopic studies of MOFs in which the photosensitizer and catalytic center are well-organized within MOFs. The PIs have identified highly robust Zr-based MOFs that contain coordinately unsaturated Zr6-clusters as the structural prototype. Structural topology will be used as a guide to insert both the photosensitizer and catalyst into the MOF structure, in a controllable, step-wise fashion, to generate new hybrid MOF photocatalysts. The charge separation and structural dynamics of the hybrid materials will be investigated using time resolved optical and X-ray absorption spectroscopies as well as in situ X-ray absorption spectroscopy. These techniques will be used to establish a direct correlation between the structure of the hybrid catalysts and their catalytic efficiency for hydrogen production. The proposed research will be integrated with educational activities that will provide opportunities for undergraduate students, and encourage women to pursue research and science careers. The graduate and undergraduate students working on the project will receive interdisciplinary training in the fields of materials chemistry, physical chemistry, and solar energy science.

在这个项目中，研究人员将研究一类相对较新的材料，即金属有机框架（MOFs），以确定它们是否适合作为催化剂，用于从阳光和水中生产氢作为可持续燃料。该项目的具体目标是研究锆基MOFs中光敏剂和催化中心的位置如何影响光催化反应的发生机制和相应的光催化反应效率。 更广泛地说，该研究将为未来研究其他光活性材料的实时结构-功能相关性创建一个结构模型，广泛地影响太阳能电池、光电器件和太阳能转换技术等领域。反过来，这项研究将有助于确定由太阳能驱动的最终碳中和，经济可行的燃料行业的有效材料。该项目将包括对研究生和本科生的培训和指导，这将加强美国受过科学教育的学生的管道，以解决材料科学，可持续化学和能源科学的下一代问题。 该项目的重点是MOFs的实时光谱研究，其中光敏剂和催化中心在MOFs中组织良好。PI已经确定了高度稳健的Zr基MOF，其含有配位不饱和的Zr 6簇作为结构原型。结构拓扑结构将被用作指导，以可控的、逐步的方式将光敏剂和催化剂两者插入到MOF结构中，以产生新的混合MOF光催化剂。混合材料的电荷分离和结构动力学将使用时间分辨光学和X射线吸收光谱以及原位X射线吸收光谱进行研究。 这些技术将用于建立混合催化剂的结构和它们的制氢催化效率之间的直接相关性。拟议的研究将与教育活动相结合，为本科生提供机会，并鼓励妇女从事研究和科学事业。 从事该项目的研究生和本科生将接受材料化学，物理化学和太阳能科学领域的跨学科培训。

项目成果

Selective Excited-State Dynamics in a Unique Set of Rationally Designed Ni Porphyrins

一组独特的合理设计的镍卟啉的选择性激发态动力学

• DOI: 10.1021/acs.jpcc.9b05413
• 发表时间: 2019
• 期刊: The Journal of Physical Chemistry C
• 作者: Pattengale, Brian;Liu, Qiuhua;Hu, Wenhui;Yang, Sizhuo;He, Peilei;Tender, Sir Lawrence;Wang, Yingqi;Zhang, Xiaoyi;Zhou, Zaichun;Zhang, Jian
• 通讯作者: Zhang, Jian