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Metal-free Motifs for Oxygen Evolution Catalysis

Zoric, Marija
http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1499074276204656

Abstract Details

2017, Master of Science (MS), Bowling Green State University, Chemistry.
The development of efficient, durable, and low-cost oxygen evolution and oxygen reduction reaction (OER and ORR) catalysts is crucial for several energy storage applications. Here we propose that the metal-free catalysis can be achieved by organic motifs that catalyze OER through alcohol and peroxide intermediates. Particularly, we studied the most difficult step of proposed catalytic cycle for OER: the O-O bond formation. To identify ideal catalytic motifs for this step, we synthesized a series of covalently linked dimers, named DPE, XAN, and BP, investigated their structure using DFT calculations, NMR, and X-ray spectroscopy and identified the efficiency of peroxide formation from their alcohols. This work has shown, for the first time, that the O-O bond can be formed by the oxidation of two organic alcohols, showing a proof-of-principle chemical reactivity that can be utilized for future metal-free graphenic OER catalysts. Remarkably, we are presenting for the first time that even monomeric model MONO upon oxidation formed alkoxy radicals who coupled to make peroxide bond. Furthermore, we show evidence that dimeric model BP formed significantly more peroxide, while DPE and XAN produced no peroxides, demonstrating that choice of right linker is vital for design of efficient catalyst. Spacer should be designed on a way that O-O distance is appropriate for O-O bond formation. Additionally, it also must possess some degree of rigidity to force two -OH groups in close proximity, but still to attain enough flexibility to accommodate dynamically changed distances between active centers over an entire catalytic cycle.
Ksenija Glusac, PhD (Advisor)
R. Marshall Wilson, PhD (Committee Member)
H. Peter Lu, PhD (Committee Member)
51 p.
Chemistry
oxygen evolution; metal-free catalysis; O-O bond formation

Recommended Citations

Citations

  • Zoric, M. (2017). Metal-free Motifs for Oxygen Evolution Catalysis [Master's thesis, Bowling Green State University]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1499074276204656

    APA Style (7th edition)

  • Zoric, Marija. Metal-free Motifs for Oxygen Evolution Catalysis. 2017. Bowling Green State University, Master's thesis. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1499074276204656.

    MLA Style (8th edition)

  • Zoric, Marija. "Metal-free Motifs for Oxygen Evolution Catalysis." Master's thesis, Bowling Green State University, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1499074276204656

    Chicago Manual of Style (17th edition)

bgsu1499074276204656
429
© 2017, all rights reserved.
This open access ETD is published by Bowling Green State University and OhioLINK.