Computational Supporting Information for Methane Adsorption on Heteroatom-Modified Maquettes of Porous Carbon Surfaces

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.