MOF-5 Metal−Organic Framework as Sorbent for In-Field Sampling and Preconcentration in Combination with Thermal Desorption GC/MS for Determination of Atmospheric Formaldehyde

Abstract

Metal-organic frameworks (MOFs) are one kind of highly porous crystalline materials, which are constructed by metal-containing inorganic nodes and organic linkers. With large surface area and high thermal stability, MOFs have great potential as sorbents for the preconcentration of trace analytes. However, such application of MOFs to the analysis of real samples has not been reported before. Here we report the utilization of MOF-5 as sorbent for in-field sampling and preconcentration of atmospheric formaldehyde before thermal desorption (TD) GC/MS (TD-GC/MS) determination without the need for any chemical derivatization. MOF-5 gave a 53 and 73 times better concentration effect than Tenax TA (organic polymers) and Carbograph 1TD (graphitized carbon black), respectively, for TD-GC/MS determination of formaldehyde. MOF-5 showed good performance for in-field sampling and preconcentration of formaldehyde from air samples with a relative humidity less than 45%. The collected formaldehyde on MOF-5 sorbent was stable for at least 72 h at room temperature before TD-GC/MS analysis. One tube packed with 300 mg of MOF-5 lasted 200 cycles of adsorption/TD without significant loss of collection efficiency. The breakthrough volume of such a tube was 1.2 L of 28.35 mg m(-3) formaldehyde at a sampling flow rate of 100 mL min(-1). The use of MOF-5 for in-field sampling and preconcentration in combination with TD-GC/MS for the determination of formaldehyde offered a linear range covering 3 orders of magnitude, and a detection limit of 0.6 microg m(-3). The precision for six replicate cycles of in-field sampling and preconcentration for TD-GC/MS determination using one 300 mg MOF-5 packed tube ranged from 2.8% to 5.3%. The tube-to-tube reproducibility of three MOF-5 tubes prepared in parallel was 7.7%. The developed method was applied to analysis of local indoor and outdoor air samples for formaldehyde and validated by the standard method TO-11A of the United States Environmental Protection Agency. The concentration of formaldehyde and the recovery of spiked formaldehyde in the air samples ranged from 12 to 48 microg m(-3), and from 93% to 107%, respectively.