Award Abstract # 1900476
Advanced Time-Resolved Studies of the O-O Bond Formation Mechanisms: Interplay of the Metal and Ligand Redox Reactivity

NSF Org: CHE
Division Of Chemistry
Recipient: PURDUE UNIVERSITY
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: FY 2019 = $450,000.00
History of Investigator:
  • Yulia Pushkar (Principal Investigator)
Recipient Sponsored Research Office: Purdue University
2550 NORTHWESTERN AVE # 1100
WEST LAFAYETTE
IN  US  47906-1332
(765)494-1055
Sponsor Congressional District: 04
Primary Place of Performance: Purdue University
525 Northwestern Ave
West Lafayette
IN  US  47907-2036
Primary Place of Performance
Congressional District:
04
Unique Entity Identifier (UEI): YRXVL4JYCEF5
Parent UEI: YRXVL4JYCEF5
NSF Program(s): CMFP-Chem Mech Funct, and Prop
Primary Program Source: 01001920DB NSF RESEARCH & RELATED ACTIVIT
Program Reference Code(s): 8396, 8397, 8607, 8650, 8990
Program Element Code(s): 910200
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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(Showing: 1 - 10 of 11)
Bury, Gabriel and Pushkar, Yulia "Computational Analysis of StructureActivity Relationships in Highly Active Homogeneous RutheniumBased Water Oxidation Catalysts" Catalysts , v.12 , 2022 https://doi.org/10.3390/catal12080863 Citation Details
Ezhov, Roman and Karbakhsh Ravari, Alireza and Page, Allison and Pushkar, Yulia "Water Oxidation Catalyst cis- [Ru(bpy)(5,5-dcbpy)(H 2 O) 2 ] 2+ and Its Stabilization in MetalOrganic Framework" ACS Catalysis , v.10 , 2020 10.1021/acscatal.0c00488 Citation Details
Ezhov, Roman and Ravari, Alireza Karbakhsh and Bury, Gabriel and Smith, Paul F. and Pushkar, Yulia "Do multinuclear 3d metal catalysts achieve OO bond formation via radical coupling or via water nucleophilic attack? WNA leads the way in [Co4O4]n+" Chem Catalysis , 2021 https://doi.org/10.1016/j.checat.2021.03.013 Citation Details
Ezhov, Roman and Ravari, Alireza Karbakhsh and Pushkar, Yulia "Characterization of the Fe V =O Complex in the Pathway of Water Oxidation" Angewandte Chemie , v.132 , 2020 10.1002/ange.202003278 Citation Details
Hong, Young Hyun and Jang, Yuri and Ezhov, Roman and Seo, Mi Sook and Lee, Yong-Min and Pandey, Bhawana and Hong, Seungwoo and Pushkar, Yulia and Fukuzumi, Shunichi and Nam, Wonwoo "A Highly Reactive Chromium(V)Oxo TAML Cation Radical Complex in Electron Transfer and Oxygen Atom Transfer Reactions" ACS Catalysis , v.11 , 2021 https://doi.org/10.1021/acscatal.1c00079 Citation Details
Ibrahim, Iskander M. and Wu, Huan and Ezhov, Roman and Kayanja, Gilbert E. and Zakharov, Stanislav D. and Du, Yanyan and Tao, Weiguo Andy and Pushkar, Yulia and Cramer, William A. and Puthiyaveetil, Sujith "An evolutionarily conserved iron-sulfur cluster underlies redox sensory function of the Chloroplast Sensor Kinase" Communications Biology , v.3 , 2020 https://doi.org/10.1038/s42003-019-0728-4 Citation Details
Karbakhsh Ravari, Alireza and Pineda-Galvan, Yuliana and Huynh, Alexander and Ezhov, Roman and Pushkar, Yulia "Facile Light-Induced Transformation of [Ru II (bpy) 2 (bpyNO)] 2+ to [Ru II (bpy) 3 ] 2+" Inorganic Chemistry , v.59 , 2020 https://doi.org/10.1021/acs.inorgchem.0c01446 Citation Details
Karmalkar, Deepika G. and Sankaralingam, Muniyandi and Seo, Mi Sook and Ezhov, Roman and Lee, YongMin and Pushkar, Yulia N. and Kim, WonSuk and Fukuzumi, Shunichi and Nam, Wonwoo "A HighValent Manganese(IV)OxoCerium(IV) Complex and Its Enhanced Oxidizing Reactivity" Angewandte Chemie International Edition , v.58 , 2019 https://doi.org/10.1002/anie.201910032 Citation Details
Lebedev, Dmitry and Ezhov, Roman and Heras-Domingo, Javier and Comas-Vives, Aleix and Kaeffer, Nicolas and Willinger, Marc and Solans-Monfort, Xavier and Huang, Xing and Pushkar, Yulia and Copéret, Christophe "Atomically Dispersed Iridium on Indium Tin Oxide Efficiently Catalyzes Water Oxidation" ACS Central Science , v.6 , 2020 https://doi.org/10.1021/acscentsci.0c00604 Citation Details
Patel, Jully and Bury, Gabriel and Ravari, Alireza K. and Ezhov, Roman and Pushkar, Yulia "Systematic Influence of Electronic Modification of Ligands on the Catalytic Rate of Water Oxidation by a SingleSite RuBased Catalyst" ChemSusChem , v.15 , 2022 https://doi.org/10.1002/cssc.202101657 Citation Details
Ravari, Alireza Karbakhsh and Zhu, Guibo and Ezhov, Roman and Pineda-Galvan, Yuliana and Page, Allison and Weinschenk, Whitney and Yan, Lifen and Pushkar, Yulia "Unraveling the Mechanism of Catalytic Water Oxidation via de Novo Synthesis of Reactive Intermediate" Journal of the American Chemical Society , v.142 , 2019 10.1021/jacs.9b10265 Citation Details
(Showing: 1 - 10 of 11)

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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