While nitrogen and argon isotherms at their respective boiling points are commonly used for the BET analysis of porous materials, CO2 isotherms at 273 K have been suggested as an alternative option for materials containing very small pores in which nitrogen and argon molecules cannot access at cryogenic temperatures. However, it has been known that the BET surface areas obtained from CO2 isotherms are not really meaningful in an absolute sense due to the strong CO2-CO2 interaction. In this study, CO2 isotherms in metal-organic frameworks (MOFs) and zeolites were predicted by grand canonical Monte Carlo (GCMC) simulations and used to evaluate the BET analysis for these materials. For all the microporous materials with varied pore sizes, the BET surface areas calculated from the simulated CO2 isotherms agreed roughly with their geometric surface areas from the crystal structures. Moreover, a clear selection of a proper BET linear region was possible for the material possessing only ultra-micropores. These results indicate that the BET surface areas determined from CO2 isotherms at 273 K may be considered reasonable for adsorbents containing only ultra-micropores where the BET surface areas based on N2 or Ar isotherms at cryogenic temperatures are not available.
Bibliographical noteFunding Information:
This work was supported by In-house Research and Development Program of the Korea Institute of Energy Research (KIER) ( B5-2444 and B5-2603 ). This work was also supported by the Technology Innovation Program ( 10048649 ) funded by the Ministry of Trade, Industry & Energy (MI, Korea) . The authors would like to acknowledge Prof. Randall Q. Snurr for his helpful discussions and comments.
All Science Journal Classification (ASJC) codes
- Materials Science(all)
- Condensed Matter Physics
- Mechanics of Materials