Validation of two contrasting capturing mechanisms for gaseous formaldehyde between two different types of strong metal-organic framework adsorbents.

In this research, the adsorption behavior of formaldehyde (FA) onto two types of metal-organic frameworks (MOFs: MOF-199 [M199] and UiO-66-NH [U6N]) is investigated against changes in the key process variables (e.g., FA partial pressure (0.5-10 Pa), temperature (30-120 °C), and relative humidity (RH: 0%, 50%, and 100%)). The results revealed that the FA adsorption behavior onto both MOFs is exothermic in nature. Besides, their relative dominance for FA uptake varies interactively with the changes in RH and FA partial pressure levels. As the FA levels increase in dry conditions, their breakthrough volumes (BTV (100% BT)) exhibit contrasting trends: The values of U6N decreased noticeably from 5232 and 3792 L·atm·g, while those of M199 increased from 4152 to 5772 L·atm·g. The superiority of U6N over M199 in the lower FA level (at<5 Pa) is supported by the Lewis acid-base interactions with amine groups (U6N) in line with kinetic/isotherm studies. Such superiority is also persistent at higher (10 Pa) FA level under all humid conditions in line with its higher moisture stability. However, in dry conditions, the reversal of relative dominance in which M199 exhibits enhanced efficacy for 10 Pa FA uptake (relative to U6N) should reflect its breathing effects with the potent role of pore-diffusion mechanism. This study offers valuable insights into the construction of tunable adsorbents with enhanced adsorptivity toward key targets.