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Modelling Gas Adsorption in Porous Solids: Roles of Surface Chemistry and Pore Architecture

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Abstract

Modelling the adsorption of small molecule gases such as N2, CH4 and CO2 in porous solids can provide valuable insights for the development of next generation materials. Employing a grand canonical Monte Carlo simulation code developed in our group, the adsorption isotherms of CH4 and CO2 in many metal organic frameworks have been calculated and compared with experimental results. The isotherms computed within a force field approach are able to well reproduce the experimental data. Key functional groups in the solids which interact with gas molecules and the nature of their interactions have been identified. The most favorable interaction sites for CH4 and CO2 in the framework solids are located in the linkers which are directed towards the pores. The structure of a perfluorinated conjugated microporous polymer has been modelled and it is predicted to take up 10% more CO2 than its hydrogenated counterpart. In addition, the vibrational, orientational and diffusive properties of CO2 adsorbed in the solids have been examined using molecular dynamics simulations. Intermolecular modes of such adsorbed species exhibit a blue shift with increasing gas pressure.

The adsorption isotherms of CH4 and CO2 in many metal organic frameworks have been calculated using MCIN and compared with experimental results. The most favorable interaction sites for these gases in the framework solids have been observed to be located in the linkers that are directed towards the pores.

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Acknowledgements

We thank DST for support. The first author acknowledges CSIR for a research fellowship. The second author acknowledges SSL for a Senior Fellowship. We thank Prof. Tapas Kumar Maji and his research group at JNCASR for many insightful discussions.

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  1. Chemistry and Physics of Materials Unit, Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore, 560 064, India

    SATYANARAYANA BONAKALA & SUNDARAM BALASUBRAMANIAN

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  1. SATYANARAYANA BONAKALA
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  2. SUNDARAM BALASUBRAMANIAN
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Correspondence to SUNDARAM BALASUBRAMANIAN.

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Supplementary Information

The Supplementary Information associated with this article has sections containing the development of MCIN code and applications of MCIN: validation of MCIN by reproducing simulated and experimental adsorption isotherms, modelling CO2 adsorption in TPE-FCMP, comparison of pair correlation functions of CO2 with respect to MOF sites obtained from MCIN and LAMMPS, vibrational density of states of CO2 in IRMOF-1 and CO2 diffusion in IRMOF-1 and TPE-FCMP at various pressures, comparison of pair correlation functions of adsorbed CO2 with bulk CO2, comparison pair correlation functions of CH4 in FMOF-1 and [Zn2(L)]\(_{\mathrm {\infty } }\) at various pressures and running coordination number of CO2 around carboxylate group of IRMOF-1. The Supplementary Information for this article is available at http://www.ias.ac.in/chemsci.

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BONAKALA, S., BALASUBRAMANIAN, S. Modelling Gas Adsorption in Porous Solids: Roles of Surface Chemistry and Pore Architecture. J Chem Sci 127, 1687–1699 (2015). https://doi.org/10.1007/s12039-015-0939-2

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