Experimental and molecular simulation study of CO2 adsorption in ZIF-8: Atomic heat contributions and mechanism

Abstract

We successfully synthesised ZIF-8 using the solvothermal method at room temperature to study CO2 adsorption storage at 273 and 298 K up to 35 bar. Characterisation methods such as BET, SEM-EDS, XRD, and TGA were used to measure the physical and composition properties of ZIF-8. Grand canonical Monte Carlo (GCMC) simulation was conducted to compare with experimental data and get inside of the CO2 adsorption mechanism by calculating the isosteric heat and its fluid–fluid and solid–fluid contributions. The second was also split into fluid–solid atom contributions to understand in detail the interaction between CO2 and ZIF-8. The analyses revealed that there are three main stages during the CO2 adsorption gas–solid atom contributions, developing, pore-filling and densification. During the developing and pore-filling stages the largest fluid–solid atom contribution to the isosteric heat is CO2-C2 interactions, indicating that the CO2 is adsorbed close to the hexagonal windows of the ZIF-8 structure, while during the densification stage the largest contribution is CO2-N interactions. Where C2 and N refers to C-atom and N-atom, respectively in NCH group of the solid framework. This is because CO2 changes its orientation to be able to accommodate more molecules in the pore cavity. This work provides a better understanding of the adsorption mechanism of CO2 on ZIF-8 and shows how molecular simulation can be used to improve the understanding gas adsorption storage on metal–organic frameworks.