Photo of Glusac, Ksenija

Ksenija Glusac

Associate Professor

Address:

5105 SES

Office Phone Voice:

(312) 413-8867

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About

We study conceptually new catalytic approaches for solar fuel-forming reactions. The mainstream research in this area explores transition-metal-based systems to catalyze O2/H2 evolution and CO2 reduction. These catalysts are often made of rare and toxic metals, which disables their wide usage. To provide less expensive and more environmentally friendly alternatives, we aim to discover earth-abundant catalytic motifs that utilize solely organic compounds made of C, H, N and O.

Two projects are currently under investigation in our labs:

Metal-free motifs for electrocatalytic oxygen-evolution reaction (OER) and oxygen-reduction reaction (ORR). This research endeavor is driven by the hypothesized mechanism involving iminium ions, pseudobases and peroxides as key catalytic intermediates (see figure). Our studies have shown promising results for metal-free OER catalysis, and have provided important insights into the recent findings by other groups on OER by metal-free doped carbon-based nanostructures. In the future, we aim to investigate the OER/ORR bi-functionality of our model structures as an approach towards more efficient catalysis. In addition to these mechanistic studies, the chemical methodology to graft the well-defined catalytic motifs onto the edges of graphene nanoribbons will be explored to form functional 3D materials for OER/ORR. This project is currently funded by NSF.
A picture of electrons moving into and out of organic molecules.

Photocatalytic CO2 reduction using NAD+/NADH analogs. In this biomimetic approach, the CO2 reduction is expected to occur by a sequence of three hydride transfer steps from NADH analogs, which are photo-generated from the corresponding NAD+ analog dyes (see figure). The advantage of such approach is that the selectivity for methanol production will be achieved, while the undesired proton reduction will be suppressed by metal-free catalysts. We recently demonstrated the efficient photoreduction of NAD+ analog dyes on GaP, while our current efforts aim to evaluate the hydricities of model NADH analogs and their reactivity toward CO2 reduction. This study will provide important mechanistic insights into the CO2 reduction catalysis observed by others using simple organic catalysts (such as pyridinium ion). This project is currently funded by ACS PRF.
A molecule accepts electrons from a substrate so that it can transform CO2 into methanol.

While this research is motivated by the applications in energy storage, our approach is quite fundamental in nature and addresses the key aspects of important chemical processes, such as O-O bond formation and hydride transfer. Our aim is to facilitate the discovery of a new generation of catalysts by providing fundamental mechanistic insights.

Selected Publications

  1. S. Ilic, U. Padey, G. N. Hargenrader, Y. Huang, M. Zoric, K. D. Glusac, Metal-Free Motifs for Solar Fuels, Ann. Rev. Phys. Chem, 2017, 68, 14.1-14.27  DOI: 10.1146/annurev-physchem-052516-050924.
  2. K. D. Glusac, What Has Light Ever Done for Chemistry?, Nat. Chem., 2016, 8, 734-735 DOI:10.1038/nchem.2582.
  3. M. R. Zoric, U. P. Kadel, K. A. Korvinson, H. L. Luk, A. Nimthong-Roldan, M. Zeller, K. D. Glusac, Conformational Flexibility of Xanthene-based Covalently-linked Dimers, J. Phys. Org. Chem, 2016, DOI: 10.1002/poc.3572.
  4. S. Ilic, E. S. Brown, Y. Xie, S. Maldonado, K. D. Glusac, Sensitization of p-GaP with Monocationic Dyes: The Effect of Dye Excited-State Lifetime on Hole Injection Efficiencies, J. Phys. Chem. C, 2016, 120, 3145-3155, DOI: 10.1021/acs.jpcc.5b10474.
  5. J. Walpita, Y. Xin, R. Khatmullin, H. L. Luk, C. Hadad, K. D. Glusac, Proton-Coupled Electron Transfer in Weakly Coupled Systems: A Case Study Involving Acridinol and Phenanthridinol Pseudobases, J. Phys. Org. Chem, 2015, DOI: 10.1002/poc.3516.
  6. X. Yang, J. Walpita, E. Mirzakulova, S. Vyas, S. F. Manzer, C. M. Hadad, K. D. Glusac, Mechanistic Studies of Electrode-Assisted Catalytic Oxidation by Flavinium and Acridinium Cations, ACS Catal, 2014, 4, 2635-2644. DOI: 10.1021/cs5005135.
  7. X. Yang, J. Walpitha, D. Zhou, H. L. Luk, S. Vyas, R. S. Khnayzer, S. Chandra, C. M. Hadad, F. N. Castellano, A. I. Krylov, K. D. Glusac, Toward Organic Photohydrides: Excited-State Behavior of 10-Methyl-9-Phenyl-9.10-dihydroacridine, J. Phys. Chem. B, 2013, 117, 49, 15290. DOI: 10.1021/jp401770e. Part of the Michael D. Fayer Festschrift.
  8. R. Khatmullin, D. Zhou, T. Corrigan, E. Mirzakulova, K. D. Glusac, Thermolysis and Photolysis of 2-Ethyl-4-nitro-1(2H)-isoquinolinium Hydroperoxide, J. Phys. Org. Chem., 2013, 26, 440-450. DOI: 10.1002/poc.3107.            
  9. E. Mirzakulova, R. Khatmullin, J. Walpita, T. Corrigan, N. M. Vargas-Barbosa, S. Vyas, S. Ottikkal, S. Manzer, C. M. Hadad, K. D. Glusac, Electrode-assisted Catalytic Water Oxidation by a Flavin Derivative, Nat. Chem., 2012, 4, 794. DOI: 10.1038/nchem.1439. This work was highlighted by C&EN News, 2012, Vol. 90, Issue 35, p. 10:http://cen.acs.org/articles/90/i35/Organocatalyst-Splits-Water.html
  10. V. Sichula, Y. Hu, E. Mirzakulova, S. F. Manzer, S. Vyas, C. M. Hadad, K. D. Glusac, Mechanism of N(5)-Ethyl-flavinium Cation Formation Upon Electrochemical Oxidation of N(5)-Ethyl-4a-hydroxyflavin Pseudobase, J. Phys. Chem. B., 2010, 114, 9452-9461. DOI: 10.1021/jp104443y.

Education

B.A., University of Belgrade, Serbia 1999
Ph.D., University of Florida 2003
ACS PRF Postdoctoral Fellow, Stanford University 2004-2006