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，研究人员将研究一种相对较新的材料，称为金属有机框架（MOF），以适合其作为催化剂生产氢作为阳光和水的可持续燃料的催化剂。该项目的具体目标是研究光敏剂和催化中心在基于锆基的MOF中的放置如何影响光催化发生的机制以及光催化反应的相应效率。 从更广泛的角度来看，该研究将创建一个结构模型，用于对其他光活性材料的实时结构 - 功能相关性的未来研究，从而广泛影响诸如光催化，光电设备和太阳能转化技术等领域。反过来，这项研究将有助于确定最终由太阳能驱动的最终碳中性，经济可行的燃料行业的材料。该项目将包括在光催化研究中对研究生和本科生的培训和指导，这将加强美国科学教育的学生渠道，准备解决材料科学，可持续化学和能源科学方面的下一代问题。 该项目侧重于对MOF的实时光谱研究，其中光敏剂和催化中心在MOF中组织良好。 PI已确定基于ZR的高度健壮的MOF，其中包含协调不饱和的ZR6簇作为结构原型。结构拓扑将以可控的，逐步的方式将光敏剂和催化剂插入MOF结构中，以生成新的混合MOF光催化剂。将使用时间分辨的光学和X射线吸收光谱以及原位X射线吸收光谱法研究杂交材料的电荷分离和结构动力学。 这些技术将用于建立杂化催化剂结构与氢生产的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，该活动将为本科生提供机会，并鼓励妇女从事研究和科学职业。 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