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Title: Physi-sorption of H2 on pure and boron-doped graphene monolayers: A dispersion-corrected DFT study

Abstract

Carbon based materials are of interest as potential candidates for H2 storage. Earlier work has been inconclusive on the effect of boron doping on the energy of H2 binding. However, earlier work has been inconclusive on the definitive effect of boron doping on the energy of H2 binding, i.e. isosteric heats of adsorption (Qst). In this work, we completed a systematic DFT study to evaluate this effect, and found that doping graphene with boron provides only minor enhancement in H2 binding. More importantly, the presence of the electron deficient boron into a graphene ring introduces a defect, such as terminal hydrogen or distortion from planarity, which creates hydrogen adsorption sites with slightly increased Qst. The increase is from ~ 5 kJ/mol H2 for the pure carbon matrix to ~6 - 7 kJ/mol for the boron doped system. The more strongly bond H2 is located near the defect and shows little direct interaction with the boron. Most significant enhancement is found in systems where H2 is confined between layers at a distance of about 7Å. In this case, the H2 binding nearly doubles, to ~10 kJ/mol for both pure, undistorted graphene, and the 2% boron doped system, containing tetrahedral C atommore » distortion. Interestingly, at higher doping levels of boron, we found that the Qst decreases compared to the all carbon materials. These finding suggest that interplanar nanoconfinement may be more effective way to enhance H2 binding than boron doping.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1];  [2]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1606402
Alternate Identifier(s):
OSTI ID: 1645104
Report Number(s):
PNNL-SA-147004; PNNL-SA-150699
Journal ID: ISSN 2311-5629
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
C
Additional Journal Information:
Journal Volume: 6; Journal Issue: 1; Journal ID: ISSN 2311-5629
Publisher:
MDPI
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Boron doping; H2 storage; DFT; carbon materials; Boron doping, H2 storage, DFT, carbon materials

Citation Formats

Nayyar, Iffat H., Ginovska, Bojana, Karkamkar, Abhijeet J., Gennett, Tom, and Autrey, S Thomas. Physi-sorption of H2 on pure and boron-doped graphene monolayers: A dispersion-corrected DFT study. United States: N. p., 2020. Web. doi:10.3390/c6010015.
Nayyar, Iffat H., Ginovska, Bojana, Karkamkar, Abhijeet J., Gennett, Tom, & Autrey, S Thomas. Physi-sorption of H2 on pure and boron-doped graphene monolayers: A dispersion-corrected DFT study. United States. doi:https://doi.org/10.3390/c6010015
Nayyar, Iffat H., Ginovska, Bojana, Karkamkar, Abhijeet J., Gennett, Tom, and Autrey, S Thomas. Sun . "Physi-sorption of H2 on pure and boron-doped graphene monolayers: A dispersion-corrected DFT study". United States. doi:https://doi.org/10.3390/c6010015. https://www.osti.gov/servlets/purl/1606402.
@article{osti_1606402,
title = {Physi-sorption of H2 on pure and boron-doped graphene monolayers: A dispersion-corrected DFT study},
author = {Nayyar, Iffat H. and Ginovska, Bojana and Karkamkar, Abhijeet J. and Gennett, Tom and Autrey, S Thomas},
abstractNote = {Carbon based materials are of interest as potential candidates for H2 storage. Earlier work has been inconclusive on the effect of boron doping on the energy of H2 binding. However, earlier work has been inconclusive on the definitive effect of boron doping on the energy of H2 binding, i.e. isosteric heats of adsorption (Qst). In this work, we completed a systematic DFT study to evaluate this effect, and found that doping graphene with boron provides only minor enhancement in H2 binding. More importantly, the presence of the electron deficient boron into a graphene ring introduces a defect, such as terminal hydrogen or distortion from planarity, which creates hydrogen adsorption sites with slightly increased Qst. The increase is from ~ 5 kJ/mol H2 for the pure carbon matrix to ~6 - 7 kJ/mol for the boron doped system. The more strongly bond H2 is located near the defect and shows little direct interaction with the boron. Most significant enhancement is found in systems where H2 is confined between layers at a distance of about 7Å. In this case, the H2 binding nearly doubles, to ~10 kJ/mol for both pure, undistorted graphene, and the 2% boron doped system, containing tetrahedral C atom distortion. Interestingly, at higher doping levels of boron, we found that the Qst decreases compared to the all carbon materials. These finding suggest that interplanar nanoconfinement may be more effective way to enhance H2 binding than boron doping.},
doi = {10.3390/c6010015},
journal = {C},
number = 1,
volume = 6,
place = {United States},
year = {2020},
month = {3}
}

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