
NSF Org: |
CHE Division Of Chemistry |
Recipient: |
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Initial Amendment Date: | July 30, 2019 |
Latest Amendment Date: | July 30, 2019 |
Award Number: | 1900476 |
Award Instrument: | Standard Grant |
Program Manager: |
Richard Johnson
CHE Division Of Chemistry MPS Directorate for Mathematical and Physical Sciences |
Start Date: | August 1, 2019 |
End Date: | July 31, 2022 (Estimated) |
Total Intended Award Amount: | $450,000.00 |
Total Awarded Amount to Date: | $450,000.00 |
Funds Obligated to Date: |
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History of Investigator: |
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Recipient Sponsored Research Office: |
2550 NORTHWESTERN AVE # 1100 WEST LAFAYETTE IN US 47906-1332 (765)494-1055 |
Sponsor Congressional District: |
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Primary Place of Performance: |
525 Northwestern Ave West Lafayette IN US 47907-2036 |
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): | CMFP-Chem Mech Funct, and Prop |
Primary Program Source: |
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Program Reference Code(s): |
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Program Element Code(s): |
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Award Agency Code: | 4900 |
Fund Agency Code: | 4900 |
Assistance Listing Number(s): | 47.049 |
ABSTRACT
In this project supported by the Chemical Structure, Dynamic & Mechanism,B Program of the Chemistry Division, Professor Yulia Pushkar of the Department of Physics and Astronomy at Purdue University studies the time-resolved mechanism of dioxygen (O2) formation in artificial photosynthesis. In artificial photosynthesis, solar energy is converted into chemical energy through generation of the clean fuels hydrogen and oxygen, a process which requires rearrangement of chemical bonds. Fundamental understanding of this process is required for the development of new catalysts and devices which are able to mimic natural photosynthesis. The development of artificial photosynthesis and its large-scale implementation can address energy needs of modern society. This research lies at the interface of physics, chemistry and materials science, with results expected to impact diverse fields and contribute to fundamental science, education and national energy security. Planned research and educational activities are designed to increase participation of under-represented students from economically disadvantaged backgrounds, improve experiences of female students in STEM (Science, Technology, Engineering and Mathematics), enhance training of students via integration of research results into curricula and to deliver teaching modules to schools.
Research in this project focuses on the complex multi-electron chemical process of artificial photosynthesis. A major project goal is to determine the structure, electronic configurations and dynamics of the critical intermediates involved in water oxidation. In this multi-scale approach, time-resolved techniques monitor the evolution of structure and electronic states in newly designed ruthenium catalysts, with a focus on the key mechanism of oxygen-oxygen bond formation and its dependence on ligand structure. The relationship between molecular structure and catalytic activity is tested by a combination of experiments and quantum-mechanical computational models. Experimental techniques in this study of in situ catalytic water oxidation are synchrotron-based X-ray spectroscopy, including X-ray absorption near edge structure (XANES), extended X-ray absorption fine structure (EXAFS), electron paramagnetic resonance (EPR) and multi-wavelength kinetic resonance Raman spectroscopy. These experimental techniques deliver information on the structure of the intermediates and their electronic configuration as they evolve during the catalytic process.
This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.
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.
In this project supported by the Chemical Structure, Dynamic & Mechanism Program of the Chemistry Division, Professor Yulia Pushkar of the Department of Physics and Astronomy at Purdue University studied mechanisms of dioxygen (O2) formation in multiple systems capable of water oxidation reaction – a key reaction required to realize artificial photosynthesis. In artificial photosynthesis, solar energy is converted into chemical energy through generation of the clean fuels such as hydrogen, a process which requires rearrangement of chemical bonds and extraction of hydrogen ions from water. Fundamental understanding of this process is required for the development of new catalysts and devices which are able to mimic natural photosynthesis. The development of artificial photosynthesis and its large-scale implementation can address energy needs of modern society. This research lies at the interface of physics, chemistry and materials science, with results expected to impact diverse fields and contribute to fundamental science, education and national energy security.
Research in this project focused on the complex multielectron chemical process of artificial photosynthesis. A major project goal was to determine the structure, electronic configurations and dynamics of the critical intermediates involved in water oxidation. In our multi-scale approach, we used in situ techniques to monitor the evolution of structure and electronic states in newly designed molecular ruthenium, iron and cobalt based catalysts and single Ir atom heterogeneous electrode based electrocatalysts. With a focus on the key mechanism of oxygen-oxygen bond formation we detected key chemical species capable of activating relatively inert water molecule. These species contain metal center with activated oxygen fragment. Using X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) we determined electronic configurations of such species and metal-oxygen bond lengths. Electron paramagnetic resonance (EPR) and multi-wavelength kinetic resonance Raman spectroscopy were also used to obtain additional information about studied reactions. The relationships between molecular structure and catalytic activity were tested by a combination of experiments and quantum-mechanical computational models. To minimize the use of expensive ruthenium and iridium metals electrodes were produced via incorporation of molecular catalysts into metal organic frameworks or deposited as single site catalysts on the electrodes.
Conducted research and educational activities allowed to increase participation of undergraduate students in research, improve experiences of female students in STEM (Science, Technology, Engineering and Mathematics), enhance training of students via integration of research results into curricula and to deliver teaching modules to schools.
Last Modified: 09/05/2022
Modified by: Yulia Pushkar
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