CAREER: Defining Intrinsic Photophysical and Photocatalytic Properties of Zeolitic Imidazolate Frameworks

职业：定义沸石咪唑酯框架的固有光物理和光催化性能

• 批准号: 1654140
• 负责人: Jier Huang
• 金额: $ 55.56万
• 依托单位: Marquette University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-01-15 至 2022-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1654140&HistoricalAwards=false
• 关键词: CAREER; Defining; Intrinsic; Photophysical; Photocatalytic

Non-Technical DescriptionMetal organic frameworks are an emerging class of nanoporous crystalline materials consisting of metal ions or clusters coordinated to organic ligands. With support from the Solid State and Materials Chemistry program, the Principal Investigator's NSF CAREER grant Dr. Huang will focus on the fundamental design and investigation of a promising type of metal organic framework, which possesses intrinsic photoactivity, i.e. photoactive zeolitic imidazolate frameworks (ZIFs). These materials have potential applications as catalysts in photocatalytic reactions and solar energy conversion. Dr. Huang and her team aim to uncover the unknown photophysical and photochemical properties of these materials and directly correlate these properties with their catalytic functions, thus initiating a new research direction in the field of porous materials for sustainable energy. Furthermore, the proposed research will serve as a basis to raise awareness around the critical issues of global energy production and consumption, and will help train the next generation of solar energy scientists, which are key to the long-term success of this research program and the continued development of the sustainable energy field.Technical DescriptionThe role of zeolitic imidazolate frameworks (ZIFs), an emerging subclass of metal organic frameworks, in heterogeneous catalysis has largely been to act as a simple host or inert medium for dispersing the catalytic species. Inspired by the broad absorption in UV-visible-near IR region of ZIFs with paramagnetic transition metals, this research team hypothesizes that ZIFs could be used as intrinsic photocatalytic materials rather than as inert hosts. The goals of this NSF CAREER project are to fully test this hypothesis through elucidating the photophysical and structure/function relationships of ZIFs, properties essential for their photocatalytic applications. With its focus on elucidating the fundamental understanding of the molecular-level origins of light harvesting, charge separation, photocatalytic properties, and the factors that control the efficiency of these processes, the new insights from this project will be of immense value to the future development of efficient and stable ZIFs for photocatalysis and solar energy conversion. Specific objectives are: i) using the advanced time-resolved optical and X-ray transient absorption spectroscopy to reveal the optical and structural dynamics of ZIF frameworks at the molecular level; ii) systematically exploring framework dimension and chemical composition to reveal the correlation of macroscopic structure to their microscopic properties; iii) encapsulating various chromophores in the framework to enhance the light harvesting and photocatalytic properties of ZIFs; and iv) correlating these photophysical properties with the photocatalytic performance of the designed ZIFs to determine the structure-function relationship in these porous materials.

非技术描述金属有机框架是一类新兴的纳米多孔晶体材料，由与有机配体配位的金属离子或簇组成。在固态与材料化学项目的支持下，主要研究员黄博士将专注于一种有前途的金属有机框架的基础设计和研究，这种框架具有内在的光活性，即光活性沸石咪唑酯框架（ZIF）。这些材料在光催化反应和太阳能转化中具有潜在的应用前景。黄博士和她的团队旨在揭示这些材料未知的物理和光化学性质，并将这些性质与其催化功能直接关联起来，从而在可持续能源多孔材料领域开创一个新的研究方向。此外，拟议的研究将作为提高对全球能源生产和消费的关键问题的认识的基础，并将有助于培养下一代太阳能科学家，这是该研究计划长期成功和可持续能源领域持续发展的关键。技术说明沸石咪唑酯框架（ZIF）的作用，在多相催化中，金属有机骨架的一个新兴的子类在很大程度上充当用于分散催化物质的简单主体或惰性介质。受具有顺磁性过渡金属的ZIFs在紫外-可见-近红外区域的广泛吸收的启发，该研究小组假设ZIFs可以用作固有的光催化材料，而不是惰性主体。这个NSF CAREER项目的目标是通过阐明ZIF的物理和结构/功能关系，以及其光催化应用所必需的特性来充分测试这一假设。由于其重点是阐明对光捕获，电荷分离，光催化特性的分子水平起源以及控制这些过程效率的因素的基本理解，该项目的新见解将对未来开发用于太阳能和太阳能转换的高效稳定的ZIF具有巨大价值。具体目标是：i）使用先进的时间分辨光学和X射线瞬态吸收光谱以在分子水平上揭示ZIF框架的光学和结构动力学; ii）系统地探索框架尺寸和化学组成以揭示宏观结构与其微观性质的相关性; iii）将各种发色团包封在框架中以增强ZIF的光捕获和光催化性质;和iv）将这些物理化学性质与所设计的ZIF的光催化性能相关联，以确定这些多孔材料中的结构-功能关系。

项目成果

Real-Time Visualization of Active Species in a Single-Site Metal–Organic Framework Photocatalyst

• DOI: 10.1021/acsenergylett.8b00062
• 发表时间: 2018-02
• 期刊: ACS energy letters
• 影响因子: 22
• 作者: Sizhuo Yang;B. Pattengale;Sungsik Lee;Jier Huang

Direct Observation of Node-to-Node Communication in Zeolitic Imidazolate Frameworks.

• DOI: 10.1021/jacs.8b06727
• 发表时间: 2018-09
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: B. Pattengale;Daniel J. SantaLucia;Sizhuo Yang;Wenhui Hu;Cunming Liu;Xiaoyi Zhang;J. Berry;Jier Huang

Mechanistic Probes of Zeolitic Imidazolate Framework for Photocatalytic Application

• DOI: 10.1021/acscatal.7b02467
• 发表时间: 2017-11
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: B. Pattengale;Sizhuo Yang;Sungsik Lee;Jier Huang

The Impact of Axial Ligation on the Excited State Dynamics of Cobalt(II) Phthalocyanine

• DOI: 10.1016/j.jpap.2022.100132
• 发表时间: 2022-06
• 期刊: Journal of Photochemistry and Photobiology
• 作者: Wenhui Hu;Denan Wang;Qiushi Ma;Benjamin J. Reinhart;Xiaoyi Zhang;Jie Huang

Dynamic evolution and reversibility of single-atom Ni(II) active site in 1T-MoS2 electrocatalysts for hydrogen evolution

• DOI: 10.1038/s41467-020-17904-z
• 发表时间: 2020-08-17
• 期刊: NATURE COMMUNICATIONS
• 影响因子: 16.6
• 作者: Pattengale, Brian;Huang, Yichao;Huang, Jier
• 通讯作者: Huang, Jier