Applicability of the BET method for determining surface areas of microporous metal-organic frameworks.

The surface area is one of the most important quantities for characterizing novel porous materials. The BET analysis is the standard method for determining surface areas from nitrogen adsorption isotherms and was originally derived for multilayer gas adsorption onto flat surfaces. Metal-organic frameworks (MOFs) are a relatively new class of crystalline, porous materials that have been shown to exhibit very large BET surface areas. These materials are microporous and possess surfaces that are far from flat. In some MOFs, adsorption occurs through a pore-filling mechanism rather than by layer formation. Thus, it is unclear whether BET surface area numbers reported for these materials are truly meaningful. Given the standard practice of reporting BET surface areas for novel porous materials, a critical test of the BET method is much needed. In this work, grand canonical Monte Carlo simulations were used to predict adsorption isotherms for nitrogen in a series of MOFs. The predicted isotherms were used as pseudoexperimental data to test the applicability of the BET theory for obtaining surface areas of microporous MOFs. BET surface areas calculated from the simulated isotherms agree very well with the accessible surface areas calculated directly from the crystal structures in a geometric fashion. In addition, the surface areas agree well with experimental reports in the literature. These results provide a strong validation that the BET theory can be used to obtain surface areas of MOFs.