Theoretical Evaluation of the Microporosity of Pillared Layered Double Hydroxides

Over the last ten years, the concept of pillaring has frequently been applied on layered double hydroxides (LDHs). Due to the variety of possible anionic pillaring species and the adjustable layer charge density, LDHs offer good perspectives with regard to the creation of porous adsorbents and catalysts. But despite these possibilities, their porosity properties can still not compete with those of industrially applicable materials like zeolites. In this study, theoretical calculations based on geometrical models and performed on both Fe(CN)₆-MgAl-LDHs (A) and [PV₂W¹⁰ O⁴⁰]-ZnAl-LDHs (B) were reported. Properties such as the micropore volume and the interpillar distance were calculated, and compared to experimental data. For a M(II)/M(III) ratio in the layers of 3, the theoretical maximum micropore volumes were 0.3843 cm³/g (A) and 0.1497 cm³/g (B), respectively. By implementing parameters like the stack size, pillars on the outside of the stacks and the possibility of collapse, the model was adjusted in order to create a realistic picture of the microstructure of pillared LDHs. This led to a better understanding of the limiting factors, and gave an explanation for the relatively low micropore volumes of pillared LDHs. For the Fe(CN)₆-MgAl-LDHs, small interpillar distances were responsible for the partial inaccessibility of the interlayer regions by N₂. This effect was the most pronounced for high charge density LDHs. The situation for the [PV₂W¹⁰O⁴⁰]-ZnAl-LDHs is more complex. Probably due to an incomplete pillaring process, the theoretical maximum values are not reached.