Comparing the oxygen reduction reaction on selectively edge halogen doped graphene from quantum mechanics
Abstract
Recently, edge halogenated graphene-nanosheets (EH-GNS) have been discovered to provide low cost oxygen reduction reaction (ORR) catalysis for alkaline fuel cells. Particularly important is that EH-GNS lead to water as the preferred product whereas undoped graphene leads to peroxide. In order to understand the ORR mechanism, we use density functional theory (DFT) to determine the most probable conformations of the doped graphene after synthesis by ball-milling, to calculate the binding energies of each species, and then to obtain the barriers of each step of the ORR. Our results predict that ORR occurs on the edge of the zigzag with onset potentials of 0.62 (chlorine), 0.66 (bromine), and 0.75 V (iodine) vs. the reversible hydrogen electrode (RHE). Based on our validated theoretical framework, we surveyed other molecules (TeH, BiH₂, SbH₂, OCH₃, SCH₃, SeCH₃) as graphene edge molecules to test for promising ORR catalysts, predicting that SCH₃ would be best.
Additional Information
© 2019 Published by Elsevier Inc. Received 13 March 2019, Revised 7 October 2019, Accepted 18 October 2019, Available online 27 November 2019. This research was supported by the National Institute of General Medical Sciences of the National Institutes of Health under Award Nos. 8UL1GM118979-02, 8TL4GM118980-02, and 8RL5GM118978-02 (T.H.Y., E.T., and R.R.) and Office of Naval Research under award N000141812155 (W.A.G. and B.V.M.). The content is solely the responsibility of the authors and does not necessarily represent the official views of the National Institutes of Health. This work is supported by the grants of CSULB Office of Research and Sponsored Program (ORSP) Grant, RSCA Faculty Small Grant, CSULB Start Up Grant, and Southern California Air Quality Management District Grant, Hispanic Serving Institute-STEM (T.H.Y., E.M., and N.H.). We would like to thank In-Yup Jeon for fruitful discussions. We would like to thank the members of Shahab Derakhshan's lab for x-ray diffraction of EH-GNS. Declaration of Competing Interest: None.Attached Files
Supplemental Material - 1-s2.0-S0021951719305317-mmc1.pdf
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Additional details
- Eprint ID
- 100104
- DOI
- 10.1016/j.jcat.2019.10.022
- Resolver ID
- CaltechAUTHORS:20191127-113547020
- National Institute of General Medical Sciences
- 8UL1GM118979-02
- NIH
- 8TL4GM118980-02
- NIH
- 8RL5GM118978-02
- NIH
- N000141812155
- Office of Naval Research (ONR)
- California State University, Long Beach
- Southern California Air Quality Management District
- Hispanic Serving Institute
- Created
-
2019-11-27Created from EPrint's datestamp field
- Updated
-
2021-11-16Created from EPrint's last_modified field
- Other Numbering System Name
- WAG
- Other Numbering System Identifier
- 1361