ABSTRACT
Indoor air contamination by phthalate ester (PAE) derivatives has become a significant concern since traces of PAEs can cause endocrine disruption, among other health issues. PAE abatement from the environment is thus mandatory to further ensure a good quality of indoor air. Herein, we explored the physisorption-based capture of volatile PAEs by metal-organic frameworks (MOFs). A high-throughput computational screening approach was first applied on databases compiling more than 20,000 MOF structures in order to identify the best MOFs for adsorbing traces of dimethyl phthalate (DMP), considered as a representative molecule of the family of PAE contaminants. Among the 20 top candidates, MOF-74(Ni), which combines substantial DMP uptake at the 10 ppm concentration level (â¼0.20 g g-1) with high adsorption enthalpy at infinite dilution (-ΔHads(DMP),0 = 109.9 kJ mol-1), was revealed as an excellent porous material to capture airborne DMP. This prediction was validated by further experiments: gravimetric sorption isotherms were carried out on MOF-74(Ni), replacing DMP by dimethyl maleate (DMM), a molecule with a higher vapor pressure and indeed easier to manipulate compared to DMP while mimicking the adsorption behavior of DMP by MOFs, as evidenced by Monte Carlo calculations. Notably, saturation of DMM by MOF-74(Ni) (â¼0.35 g g-1 at 343 K) occurs at very low equivalent concentration of the sorbate, i.e., 15 ppm, while half of the DMM molecules remain trapped in the MOF pores, even by heating the system up to 473 K under vacuum. This computational-experimental study reveals for the first time the potential of MOFs for the capture of phthalate ester contaminants as vapors of key importance to address indoor air quality issues.
ABSTRACT
The pollution of indoor air is a major worldwide concern in our modern society for people's comfort, health, and safety. In particular, toluene, present in many substances including paints, thinners, candles, leathers, cosmetics, inks, and glues, affects the human health even at very low concentrations throughout its action on the central nervous system. Its prevalence in many workplace environments can fluctuate considerably, which led to firm regulation with exposure limits varying between 50 and 400 ppm depending on exposure time. This therefore requires the development of technologies for an accurate detection of this contaminant. Metal-organic frameworks have been proposed as promising candidates to detect and monitor a series of molecules at even extremely low concentrations owing to the high tunability of their functionality. Herein, a high-throughput Monte Carlo screening approach was devised to identify the best MOFs from the computation-ready, experimental (CoRE) metal-organic framework (MOF) density-derived electrostatic and chemical (DDEC) database for the selective capture of toluene from air at room temperature, with the consideration of a ternary mixture composed of extremely low-level concentration of toluene (10 ppm) in oxygen and nitrogen to mimic the composition of air. An aluminum MOF, DUT-4, with channel-like micropores was identified as an excellent candidate for the selective adsorption of toluene from air with a predicted adsorption uptake of 0.5 g/g at 10 ppm concentration and room temperature. The toluene adsorption behavior of DUT-4 at low equivalent concentrations, alongside its sensing performance, was further experimentally investigated by its incorporation in a quartz crystal microbalance sensor, confirming the promises of DUT-4. Decisively, the resulting high sensitivity and fast kinetics of our developed sensor highlight the applicability of this hand-in-hand computational-experimental methodology to porous material screening for sensing applications.
ABSTRACT
Volatile methylsiloxanes (VMSs) are common silicone degradation byproducts that cause serious concern for the contamination of sensitive electronics and optics, among others. With the goal of fast, online detection of VMS, we herein highlight the mesoporous MIL-101(Cr) MOF as a promising mass sensing layer for integration with a quartz crystal microbalance (QCM), using an in-house modified gravimetric adsorption system capable of achieving extremely low concentrations of siloxane D4 (down to 0.04 ppm), targeting applications for monitoring in indoor spaces and spacecraft. Our developed MIL-101(Cr)@QCM sensor achieves near-perfect reversibility with no hysteresis alongside excellent repeatability over cycling and fast response/recovery times under 1 min. We attribute this capability to optimum host/guest interactions as uncovered through molecular simulations.
