Nature of Oxygen Adsorption on Defective Carbonaceous Materials
Abstract
Here, plane-wave density functional theory has been used to study oxygen adsorption on graphene, graphite, and (12,0) zigzag single-walled carbon nanotubes with and without Stone–Wales (SW) and single-vacancy (SV) defects to understand the role of defects on carbonaceous material reactivity. Atomic oxygen adsorption leads to the formation of an epoxide on defect-free graphene and graphite and an ether on the exterior wall of carbon nanotubes and SW-defected materials. O2 chemisorption is endothermic on defect-free graphene and graphite and slightly exothermic on defect-free nanotubes. O2 chemisorption energies are predicted to be –1.1 to –1.4 eV on an SW defect and –6.0 to –8.0 eV on an SV defect. An SW defect lowers the energy barriers by 0.90 and 0.50 eV for O2 chemisorption on graphene and nanotubes, respectively. The formation of a C–O–O–C group is important for O2 dissociation on defect-free and SW-defected materials. The energy barrier is less than 0.30 eV on an SV defect. The more reactive SW defect toward O adsorption on graphene is mostly due to the strained defective carbon atoms being able to donate more electrons to an O to form an ether. The larger 2s character in the hybrid orbitals in an ether than inmore »
- Authors:
-
[1];
[3];
[1];
[4]
- Idaho National Lab. (INL), Idaho Falls, ID (United States). Biological and Chemical Science and Engineering Department
- Boise State Univ., ID (United States); Center for Advanced Energy Studies, Idaho Falls, ID (United States)
- Univ. of Alabama, Tuscaloosa, AL (United States)
- Idaho National Lab. (INL), Idaho Falls, ID (United States). Energy Storage and Advanced Transportation Department
- Publication Date:
- Research Org.:
- Idaho National Laboratory (INL), Idaho Falls, ID (United States)
- Sponsoring Org.:
- USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Nuclear Energy (NE)
- OSTI Identifier:
- 1903576
- Report Number(s):
- INL/JOU-21-63599-Rev000
Journal ID: ISSN 1932-7447; TRN: US2311354
- Grant/Contract Number:
- AC07-05ID14517
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 125; Journal Issue: 37; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 25 ENERGY STORAGE; 36 MATERIALS SCIENCE; defective carbonaceous materials; oxygen adsorption; DFT; two-dimensional materials; ethers; oxygen; carbon nanotubes
Citation Formats
Fang, Zongtang, Li, Lan, Dixon, David A., Fushimi, Rebecca R., and Dufek, Eric J. Nature of Oxygen Adsorption on Defective Carbonaceous Materials. United States: N. p., 2021.
Web. doi:10.1021/acs.jpcc.1c06741.
Fang, Zongtang, Li, Lan, Dixon, David A., Fushimi, Rebecca R., & Dufek, Eric J. Nature of Oxygen Adsorption on Defective Carbonaceous Materials. United States. https://doi.org/10.1021/acs.jpcc.1c06741
Fang, Zongtang, Li, Lan, Dixon, David A., Fushimi, Rebecca R., and Dufek, Eric J. Mon .
"Nature of Oxygen Adsorption on Defective Carbonaceous Materials". United States. https://doi.org/10.1021/acs.jpcc.1c06741. https://www.osti.gov/servlets/purl/1903576.
@article{osti_1903576,
title = {Nature of Oxygen Adsorption on Defective Carbonaceous Materials},
author = {Fang, Zongtang and Li, Lan and Dixon, David A. and Fushimi, Rebecca R. and Dufek, Eric J.},
abstractNote = {Here, plane-wave density functional theory has been used to study oxygen adsorption on graphene, graphite, and (12,0) zigzag single-walled carbon nanotubes with and without Stone–Wales (SW) and single-vacancy (SV) defects to understand the role of defects on carbonaceous material reactivity. Atomic oxygen adsorption leads to the formation of an epoxide on defect-free graphene and graphite and an ether on the exterior wall of carbon nanotubes and SW-defected materials. O2 chemisorption is endothermic on defect-free graphene and graphite and slightly exothermic on defect-free nanotubes. O2 chemisorption energies are predicted to be –1.1 to –1.4 eV on an SW defect and –6.0 to –8.0 eV on an SV defect. An SW defect lowers the energy barriers by 0.90 and 0.50 eV for O2 chemisorption on graphene and nanotubes, respectively. The formation of a C–O–O–C group is important for O2 dissociation on defect-free and SW-defected materials. The energy barrier is less than 0.30 eV on an SV defect. The more reactive SW defect toward O adsorption on graphene is mostly due to the strained defective carbon atoms being able to donate more electrons to an O to form an ether. The larger 2s character in the hybrid orbitals in an ether than in an epoxide makes the ether C–O bond stronger. Stronger C–O binding on an SW-defective carbon nanotube than on a defect-free nanotube is in part due to more flexibility of the defect to release the epoxide ring strain to form an ether.},
doi = {10.1021/acs.jpcc.1c06741},
journal = {Journal of Physical Chemistry. C},
number = 37,
volume = 125,
place = {United States},
year = {Mon Sep 13 00:00:00 EDT 2021},
month = {Mon Sep 13 00:00:00 EDT 2021}
}
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