Experimental methods in chemical engineering: specific surface area and pore size distribution measurements—BET,BJH, and DFT

Gas physisorption is an experimental technique based on equilibrium Van der Waals interactions between gas molecules and solid particles, that quantifies the specific surface area (SSA), pore size distribution (PSD), and pore volume of solids and powders. The performance of catalysts, absorbents, chromatography column materials, and polymer resins depends on these morphological properties. Here we introduce the basic principles and procedures of physical adsorption, especially nitrogen physisorption, as a guide to students and researchers unfamiliar with the field. The Brunauer‐Emmett‐Teller theory (BET) is a common approach to estimate SSA that extends the Langmuir monolayer molecular adsorption model to multilayer layers. It relies on an equilibrium adsorption isotherm, measured at the normal boiling point of the adsorbate, eg, 77 K or 87 K for N₂ and Ar, respectively. Web of Science indexed 45 400 articles in 2016 and 2017 that mentioned N₂ adsorption porosimetry—BET and BJH (Barrett‐Joyner‐Halenda) keywords. The VOSViewer bibliometric tool grouped these articles into four research clusters: adsorption, activated carbon in aqueous solutions for removal of heavy metal ions; synthesis of nanoparticles and composites; catalysts performance in oxidation and reduction processes; and photocatalytic degradation with TiO₂. According to the literature, the accuracy of the density function theory (DFT) method is higher than with the BJH theory and it is more reliable.