Physi-Sorption of H2 on Pure and Boron–Doped Graphene Monolayers: A Dispersion–Corrected DFT Study
"> Figure 1
<p>Coronene (C<sub>24</sub>H<sub>12</sub>) and boron–doped coronene structural models with H<sub>2</sub> adsorbed. The atoms on the central ring are numbered 1 through 6 for ease of discussion in the text and in the data reported in Tables 3 and 4. For the system B, a terminal H is added on the neighboring C atom (C6) denoted as C<sup>d</sup>.</p> "> Figure 2
<p>Binding energy (<math display="inline"><semantics> <mrow> <mo>Δ</mo> <msub> <mi>E</mi> <mi>b</mi> </msub> <mo stretchy="false">)</mo> </mrow> </semantics></math> of H<sub>2</sub> on periodic graphene and different boron–doped concentrations with interlayer spacing of 15 Å along <span class="html-italic">z</span>–axis. Both 2% and 7% B-doping (middle and bottom panel, respectively) show the H<sub>2</sub> interacting near the C<sup>d</sup> atom. The second monolayer at 15 Å along <span class="html-italic">z</span>–axis is not shown here for simplicity. The side and top views are shown in <a href="#app1-carbon-06-00015" class="html-app">Figure S4</a> in the <a href="#app1-carbon-06-00015" class="html-app">Supplementary Materials</a>.</p> "> Figure 2 Cont.
<p>Binding energy (<math display="inline"><semantics> <mrow> <mo>Δ</mo> <msub> <mi>E</mi> <mi>b</mi> </msub> <mo stretchy="false">)</mo> </mrow> </semantics></math> of H<sub>2</sub> on periodic graphene and different boron–doped concentrations with interlayer spacing of 15 Å along <span class="html-italic">z</span>–axis. Both 2% and 7% B-doping (middle and bottom panel, respectively) show the H<sub>2</sub> interacting near the C<sup>d</sup> atom. The second monolayer at 15 Å along <span class="html-italic">z</span>–axis is not shown here for simplicity. The side and top views are shown in <a href="#app1-carbon-06-00015" class="html-app">Figure S4</a> in the <a href="#app1-carbon-06-00015" class="html-app">Supplementary Materials</a>.</p> "> Figure 3
<p>Position of the H<sub>2</sub> molecule between two monolayers of graphene (left) and <b>2%</b> boron–doped graphene (right) at a distance of 7 Å along <span class="html-italic">z</span>–axis. The position and orientation of the H<sub>2</sub> does not change when the spacing between the surfaces is reduced from 15 Å to 7 Å (15 Å not shown), implicating long–range interactions with the second surface. The H<sub>2</sub> is physi-sorbed by both the top and bottom monolayers at a distance of 3.6 and 3.4 Å, respectively.</p> ">
Abstract
:1. Introduction
2. Methods
3. Results
3.1. Coronene Model Calculations
3.1.1. Benchmarking Level of Theory for H2 Binding to Coronene
3.1.2. Effect of Boron Substitution on H2 Binding
3.1.3. Effect of Boron Doping on the Charge Distribution
3.1.4. Effect of Boron Doping on the Bond Order
3.1.5. Other Possibilities for H2 Binding
3.2. Periodic Two–Dimensional and Three–Dimensional Doped Graphene
3.2.1. Benchmarking Level of Theory for H2 Binding on Graphene
3.2.2. Effect of Boron Doping Concentration on H2 Binding
3.2.3. Effect of Interlayer Distance Between Graphene Monolayers on the H2 Binding
4. Discussion and Conclusion
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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System | Binding Energy of H2 | Reference |
---|---|---|
Pure Graphene | −5.1 kJ/mol H2 | [2,3] |
Microporous B/C | −10.8 kJ/mol (0.62 wt %) | [30] |
B doped Carbon Scaffolds | −8.6 kJ/mol (zero coverage) | [31] |
Porous BCx | −12 to −20 kJ/mol (high coverage) | [32] |
B doped CMK-3 | −5 kJ/mol H2 | [34] |
B doped C | NA | [36] (increased capacity to 5 wt% at 298 K) |
C36 Fullerenes | −19.2 kJ/mol H2 | [18] * |
C–Nanotubes | Reduced from −10.3 kJ/mol H2 in pristine | [19] * |
B doped Graphene | −1.35 kJ/mol H2 | [20] * |
Pure Coronene | −5.7 kJ/mol H2 | [27] * |
Pure Graphene | −5.9 kJ/mol H2 | [27] * |
Pure Graphene | −5.5 kJ/mol H2, −4.6 kJ/mol H2 | [28] * |
XC Functional | (D3 Corrected) | |
---|---|---|
PBE | −0.3 | −9.8 |
PBE0 | −0.7 | −7.3 |
B3LYP | 3.1 | −6.2 |
vdW–DF2 (solid state) [27] | −5.7 |
System | Nomenclature | |
---|---|---|
C24 H12 | C | −6.2 |
B C23 H13 | B | −7.6 |
B2 C22 H12 | BB ortho | −6.6 |
BB meta | −5.9 | |
BB para | −5.6 |
Atom # | C | B | BB ortho | BB meta | BB para |
---|---|---|---|---|---|
1 | 0.10 | 0.01 b | −0.22 | 0.51 b | 0.56 b |
2 | 0.06 | −0.28 | 0.13 | −0.22 | −0.21 |
3 | 0.06 | 0.11 | 0.13 | 0.16 | −0.12 |
4 | 0.11 | 0.09 | −0.27 | −0.22 | 0.37 b |
5 | 0.04 | 0.14 | −0.03 b | 0.50 b | −0.19 |
6 | 0.05 | −0.54 Cd | −0.03 b | −0.56 | −0.20 |
Bond Order | C | B | BB ortho | BB meta | BB para |
---|---|---|---|---|---|
1–2 | 1.25 | 1.12 * | 1.24 | 1.01 * | 0.95 * |
2–3 | 1.21 | 1.30 | 1.06 | 1.16 | 1.43 |
3–4 | 1.25 | 1.14 | 1.25 | 1.17 | 1.00 * |
4–5 | 1.26 | 1.30 | 1.04 * | 1.01 * | 1.01 * |
5–6 | 1.23 | 1.06 Cd | 1.24 ** | 1.13 * | 1.42 |
6–1 | 1.26 | 1.00 *Cd | 1.02 * | 1.13 * | 0.96 * |
DFT Exchange | Dispersion Method | |
---|---|---|
PBE | no dispersion | −0.75 |
PBE | D3—no damping | −0.8 |
PBE | D3—Becke-Johnson damping | −0.75 |
PBE | vdW–DF1 | −9.5 |
PBE | vdW–DF2 | −6.0 |
revPBE | vdW–DF2 | −3.8 |
optPBE | vdW–DF2 | −4.6 |
RPBE | vdW–DF2 | −5.2 |
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Nayyar, I.; Ginovska, B.; Karkamkar, A.; Gennett, T.; Autrey, T. Physi-Sorption of H2 on Pure and Boron–Doped Graphene Monolayers: A Dispersion–Corrected DFT Study. C 2020, 6, 15. https://doi.org/10.3390/c6010015
Nayyar I, Ginovska B, Karkamkar A, Gennett T, Autrey T. Physi-Sorption of H2 on Pure and Boron–Doped Graphene Monolayers: A Dispersion–Corrected DFT Study. C. 2020; 6(1):15. https://doi.org/10.3390/c6010015
Chicago/Turabian StyleNayyar, Iffat, Bojana Ginovska, Abhijeet Karkamkar, Thomas Gennett, and Thomas Autrey. 2020. "Physi-Sorption of H2 on Pure and Boron–Doped Graphene Monolayers: A Dispersion–Corrected DFT Study" C 6, no. 1: 15. https://doi.org/10.3390/c6010015