| NSF Org: |
CBET Division of Chemical, Bioengineering, Environmental, and Transport Systems |
| Recipient: |
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| Initial Amendment Date: | July 18, 2017 |
| Latest Amendment Date: | July 18, 2017 |
| Award Number: | 1706971 |
| Award Instrument: | Standard Grant |
| Program Manager: |
Robert McCabe
CBET Division of Chemical, Bioengineering, Environmental, and Transport Systems ENG Directorate for Engineering |
| Start Date: | August 1, 2017 |
| End Date: | July 31, 2021 (Estimated) |
| Total Intended Award Amount: | $224,999.00 |
| Total Awarded Amount to Date: | $224,999.00 |
| Funds Obligated to Date: |
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| History of Investigator: |
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| Recipient Sponsored Research Office: |
313 N 13TH ST MILWAUKEE WI US 53233-2244 (414)288-7200 |
| Sponsor Congressional District: |
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| Primary Place of Performance: |
WI US 53201-1881 |
| Primary Place of
Performance Congressional District: |
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| Unique Entity Identifier (UEI): |
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| Parent UEI: |
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| NSF Program(s): | Catalysis |
| Primary Program Source: |
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| Program Reference Code(s): | |
| Program Element Code(s): |
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| Award Agency Code: | 4900 |
| Fund Agency Code: | 4900 |
| Assistance Listing Number(s): | 47.041 |
ABSTRACT
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.
PUBLICATIONS PRODUCED AS A RESULT OF THIS RESEARCH
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PROJECT OUTCOMES REPORT
Disclaimer
This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.
Significance and Objective. Metal organic framework (MOFs) represent promising photocatalytic materials that currently lack synthetic control at the atomic level, preventing a meaningful mechanistic understanding of their structural dynamics and photocatalytic functions. This project aims to address this challenge through collaborative efforts between the Huang group at the Marquette University (MU) and the Zhang group at University of Nebraska-Lincoln (UNL), which combines the expertise of materials design and synthesis (Zhang) and time resolved and in situ spectroscopy (Huang).
Scientific Accomplishment. During the course of this project, there are multiple major scientific findings that provided important insight on the development of novel MOF based photocatalytic systems for photocatalytic applications: 1) Using symmetry guided approach, we have successfully inserted two photoactive ligands to Zr-MOF, which significantly improved the light absorption ability of Zr-MOF through energy transfer process; 2) We were able to construct a photocatalytic Zr-MOF through sequentially inserting photosensitizer and catalyst to Zr-MOF; 3) Using time resolved absorption spectroscopy, we unraveled the excited state and charge separation dynamics in a series of hybrid MOFs and the model compounds that have potentials to be inserted into MOFs as photosensitizers and catalysts; 4) We have demonstrated that the designed hybrid MOFs can be used as photocatalysts for photoredox reactions and solar fuel conversion; 5) Based on these fundamental studies, we were able to unravel the structure-property-function relationship trough directly correlating the structure of the MOFs with their photophysical and photocatalytic properties.
Educational Accomplishment. This project has provided unique interdisciplinary research opportunities to multiple graduate and undergraduate students, where the students gained the experience not only in materials synthesis but also sophisticated spectroscopic methods. The research has also been incorporated to undergraduate physical chemistry laboratory curriculum and shared with woman students/postdoctoral researchers through virtual breakfast/brown bag lunch.
Last Modified: 11/28/2021
Modified by: Jier Huang
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