Rowsey, RylanTaylor, Erin E.Irle, StephanStadie, Nicholas P.Szilagyi, Robert K.2022-09-162022-09-162021-07Rylan Rowsey, Erin E. Taylor, Stephan Irle, Nicholas P. Stadie, and Robert K. Szilagyi The Journal of Physical Chemistry A 2021 125 (28), 6042-6058 DOI: 10.1021/acs.jpca.0c112841089-5639https://scholarworks.montana.edu/handle/1/17165This document is the unedited Author’s version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.0c11284Experimental and theoretical studies disagree on the energetics of methane adsorption on carbon materials. However, this information is critical for the rational design and optimization of the structure and composition of adsorbents for natural gas storage. The delicate nature of dispersion interactions, polarization of both the adsorbent and the adsorbate, interplay between H-bonding and tetrel bonding, and induced dipole/Coulomb interactions inherent to methane physisorption require computational treatment at the highest possible level of theory. In this study, we employed the smallest reasonable computational model, a maquette of porous carbon surfaces with a central site for substitution and methane binding. The most accurate predictions of methane adsorption energetics were achieved by electron-correlated molecular orbital theory CCSD(T) and hybrid density functional theory MN15 calculations employing a saturated, all-electron basis set. The characteristic geometry of methane adsorption on a carbon surface (“lander approach”) arises due to bonding interactions of the adsorbent π-system with the proximal H–C bonds of methane, in addition to tetrel bonding between the antibonding orbital of the distal C–H bond and the central atom of the maquette (C, B, or N). The polarization of the electron density, structural deformations, and the comprehensive energetic analysis clearly indicate a ∼3 kJ mol–1 preference for methane binding on the N-substituted maquette. The B-substituted maquette showed a comparable or lower binding energy than the unsubstituted, pure C model, depending on the level of theory employed. The calculated thermodynamic results indicate a strategy for incorporating electron-enriched substitutions (e.g., N) into carbon materials as a way to increase methane storage capacity over electron-deficient (e.g., B) modifications. The thermochemical analysis was revised for establishing a conceptual agreement between the experimental isosteric heat of adsorption and the binding enthalpies from statistical thermodynamics principles.en-UScopyright American Chemical Society 2021http://web.archive.org/web/20190502075603/http://pubs.acs.org/paragonplus/copyright/jpa_form_a.pdfmethane adsorptionporous carbon surfacesArticle