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，由金属离子或与有机配体协调的簇组成。在固态和材料化学计划的支持下，首席研究员的NSF职业授予黄博士将重点介绍具有有希望的金属有机框架类型的基本设计和研究，该框架具有内在的光效率，即光活动的Zeolitic Zeolitic Imidazy框架（ZIFS）。这些材料在光催化反应和太阳能转化率中具有潜在的应用作为催化剂。黄博士和她的团队旨在揭示这些材料的未知的光物理和光化学特性，并将这些特性与它们的催化功能直接相关，从而在多孔材料领域启动了新的研究方向，以实现可持续能量。 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在很大程度上是作为分散催化物种的简单宿主或惰性培养基。该研究团队受到具有顺磁过渡金属的紫外可见率 - near IR区域的广泛吸收的启发，该研究团队假设ZIF可以用作固有的光催化材料，而不是惰性宿主。 NSF职业项目的目标是通过阐明ZIF的光体物理和结构/功能关系，对其光催化应用必不可少的属性充分检验这一假设。侧重于阐明对光收集，电荷分离，光催化特性的分子水平起源的基本理解，以及控制这些过程效率的因素，该项目的新见解将对有效且稳定的ZIF的未来发展具有光载分析和太阳能能量转化的效率发展。特定目标是：i）使用先进的时间分辨光学和X射线瞬态吸收光谱，以揭示分子水平ZIF框架的光学和结构动力学； ii）系统地探索框架维度和化学成分，以揭示宏观结构与它们的微观特性的相关性； iii）将各种发色团包裹在框架中，以增强ZIF的光收集和光催化特性； iv）将这些光物理特性与设计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

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

Zeolitic imidazolate frameworks as intrinsic light harvesting and charge separation materials for photocatalysis

• DOI: 10.1063/5.0048720
• 发表时间: 2021-06-28
• 期刊: JOURNAL OF CHEMICAL PHYSICS
• 影响因子: 4.4
• 作者: Hu, Wenhui;Pattengale, Brian;Huang, Jier
• 通讯作者: Huang, Jier

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

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