Uncharacteristic Adsorption Breakthrough Behavior of a Core–Shell Copper Hydroxysulfate Metal–Organic Framework Against Gaseous Formaldehyde
Trần Thị Hải Yến, Kumar Vikrant, Jan E. Szulejko, Ki‐Hyun Kim
Abstract
Abstract Core–Shell structured microspheres with a packed nano‐platelet copper hydroxysulfate (CHS) core and an octahedral crystalized metal–organic framework‐199 (CHS@M199) shell are synthesized and tested as adsorbent for gaseous formaldehyde (FA). CHS@M199 outperforms reference materials (e.g., activated carbon (AC), CHS, and M199) with adsorption capacity (Q) of 8.13 mg g −1 and partition coefficient (PC) of 0.263 mol kg −1 Pa −1 against 10 Pa FA at 10% breakthrough (BT) level with the aid of large surface area and copper sites for coordinating with carbonyl group. Contrary to general expectations, CHS@M199 exhibits a unique adsorption behavior in that BT volume increases systematically with the rise in FA inlet partial pressure (e.g., 5–10 Pa). The 10% BT capacity of CHS@M199 decreases noticeably (8.13 to 2.08 mg g −1 ) with increasing relative humidity (0.016 to 10%), reflecting water‐FA competition for hydrophilic adsorption sites. Although FA adsorption on CHS@M199 diminishes with elevated RH levels, such reduction intensifies when simulating ambient conditions (through stepwise addition of competing components: O 2 , CO 2 , and H 2 O). The FA adsorption on CHS@M199 is well described by both pseudo‐first‐order (PFO) and pseudo‐second‐order (PSO) kinetics. Polymerization may play a pivotal role in the adsorption of FA on CHS@M199, as Qi‐LeVan isotherm best fits the experimental data.