This dataset is an extensive computational supporting information for the first manuscript of a series of reports from the collaborative work of the carbon materials laboratory of Prof. Nicholas Stadie and the computational laboratory of Prof. Robert Szilagyi at Montana State University. The dataset provide atomic-scale insights into the structure and properties of amorphous carbon materials for reversible gas storage applications. The current report is focused on modeling methane adsorption on zeolite-templated carbon through invoking the concepts of maquettes: simplified models with essential functionalities preserved of the real system. We employed a converging series of explicitly correlated MO theory and density functional theory. The theoretical approach employed is based on our previous publications Ellis E., MacHale L.T., Szilagyi R.K., DuBois J.L.: How Chemical Environment Activates Anthralin and Molecular Oxygen for Direct Reaction Journal of Organic Chemistry, 2020, 85(2), 1315–1321 DOI: 10.1021/acs.joc.9b03133 and Poovathingal S.J., Minton T.K., Szilagyi R.K.: Systematic evaluation of density functionals for electronic and geometric Structures: Chemical speciation of mononuclear Ru-Cl-H-PR3 complexes Journal of Physical Chemistry, Part A. 2019, 123(1), 343–358 DOI: 10.1021/acs.jpca.8b03216 . The level of theories considered here are consistent with an earlier study that was carried out independent from our focus Nishimura Y., Tsuneda T., Sato T., Katouda M., Irle S.: Quantum chemical estimation of acetone physisorption on graphene using combined basis set and size extrapolation schemes. Journal of Physical Chemistry C 2017, 121(16), 8999–9010 DOI: 10.1021/acs.jpcc.6b13002. Moreover, key experimental data are taken from Stadie N.P., Murialdo M., Ahn C.C., Fultz B.: Unusual Entropy of Adsorbed Methane on Zeolite-Templated Carbon Journal of Physical Chemistry C, 2015, 119(47), 26409-26421 DOI: 10.1021/acs.jpcc.5b05021. In addition to a comprehensive evaluation of the methane adsorption on pure-carbon maquette surface, we extended the adsorption studies to B- and N-doped adsorbents. We found consistent preference for N-doped materials for methane storage. In addition to discussing energy differences and structural variations as a function of the nature of dopant, we uncovered details of the electronic structure of methane interactions and its variability along the series of C, B, and N. The predicted heat of adsorption values are now informing on-going experimental synthetic work in the Stadie laboratory toward the optimization of gas storage materials. The results reported in the manuscripts stimulate extension of our work to larger maquettes of porous carbon surfaces with synthetically relevant functional groups, alternative ring sizes, curvature, and other heteroatom substitutional dopants. An additional notable merit is our effort to provide a clear thermodynamic connection among microscopic and macroscopic observables related to physical properties of gas storage materials and interfaces. Version 2.0 of the dataset contains information about a curved blade, large maquette results, extended analysis of electron correlated MO calculations, detailed report on the modified CBS-QD3 results employing MN15 equilibrium structures in place of the B3LYP structures, and updated electronic structure results and a few animations of electron density difference plots.

This work was supported by the U.S. Department of Energy's Office of Energy Efficiency and Renewable Energy (EERE) under the Hydrogen and Fuel Cell Technologies and Vehicle Technologies Offices (DE-EE0008815). We acknowledge support for the analysis of theoretical results by the U.S. Department of Energy's Office of Fossil Energy (FE). Further acknowledgement is to the donors of the American Chemical Society Petroleum Research Fund for partial support of this research. R.R. is thankful for the support by the MSU Undergraduate Scholars Program. We are also grateful for resources provided by the Extreme Science and Engineering Discovery Environment (XSEDE), supported by National Science Foundation grant ACI-1548562.113 Part of the computations were carried out using the Hyalite High Performance Computing System, operated and supported by the University Information Technology Research Cyberinfrastructure at Montana State University.

{"references": ["https://zenodo.org/record/3771172", "https://zenodo.org/record/1478258", "https://doi.org/10.1021/acs.jpca.0c11284"]}