Utilization of metal-organic frameworks for the adsorptive removal of an aliphatic aldehyde mixture in the gas phase

摘要

Considerable efforts have been undertaken in the domain of air quality management for the removal of hazardous volatile organic compounds, particularly carbonyl compounds (CCs). In this study, the competitive sorptive removal of six CCs (namely, formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) was assessed using selected metal-organic frameworks (MOFs: MOF-5, MOF-199, UiO-66, and UiO-66-NH2) and inexpensive commercial activated carbon as a reference sorbent. The sorption experiments were conducted using a mixture of the six CCs (formaldehyde and acetaldehyde at similar to 1 Pa and propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde at similar to 0.2 Pa) together with 15 Pa water and 2.6 Pa methanol in 1 bar nitrogen. For all of the carbonyl compounds other than formaldehyde, MOF-199 showed the best 10% breakthrough performance ranging from 34 L g(-1) and 0.14 mol kg(-1) Pa-1 for acetaldehyde to 1870 L g(-1) and 7.6 mol kg(-1) Pa-1 for isovaleraldehyde. Among all the sorbents tested, UiO-66-NH2 exhibited the best 10% breakthrough performance metrics towards the lightest formaldehyde which remains to be one of the most difficult targets for sorptive removal (breakthrough volume: 285 L g(-1) and partition coefficient: 1.1 mol kg(-1) Pa-1). Theoretical density functional theory (DFT)-based computations were also conducted to provide better insights into the adsorbate-adsorbent interactions. Accordingly, the magnitude of adsorption energy increased with an increase in the CC molar mass due to an enhancement in the synergetic interaction between C & xe001;O groups (in adsorbate molecules) and the MOF active centers (open metallic centers and/or NH2 functionality) as the adsorbent. Such interactions were observed to result in strong distortion of MOF structures. In contrast, weak van der Waals attraction between the hydrocarbon "tail" of CC molecules and MOF linkers were seen to play a stabilizing role for the sorbent structure. The presence of the NH2 group in the MOF structure was suspected to play a key role in capturing lighter CCs, while such an effect was less prominent for heavier CCs. Overall, the results of this study provided a basis for the establishment of an effective strategy to enhance the sorption capacity of MOFs against diverse carbonyl species.