In situ solvothermal growth of metal-organic framework-5 supported on porous copper foam for noninvasive sampling of plant volatile sulfides.

Abstract

The present study reported on an in situ solvothermal growth method for immobilization of metal-organic framework MOF-5 on porous copper foam support for enrichment of plant volatile sulfides. The porous copper support impregnated with mother liquor of MOF-5 anchors the nucleation and growth of MOF crystallites at its surface, and its architecture of the three-dimensional channel enables accommodation of the MOF-5 crystallite seed. A continuous and well-intergrown MOF-5 layer, evidenced from scanning electron microscope imaging and X-ray diffraction, was successfully immobilized on the porous metal bar with good adhesion and high stability. Results show that the resultant MOF-5 coating was thermally stable up to 420 °C and robust enough for replicate extraction for at least 200 times. The MOF-5 bar was then applied to the headspace sorptive extraction of the volatile organic sulfur compounds in Chinese chive and garlic sprout in combination with thermal desorption-gas chromatography/mass spectrometry. It showed high extraction sensitivity and good selectivity to these plant volatile sulfides owing to the extraordinary porosity of the metal-organic framework as well as the interaction between the S-donor sites and the surface cations at the crystal edges. Several primary sulfur volatiles containing allyl methyl sulfide, dimethyl disulfide, diallyl sulfide, methyl allyl disulfide, and diallyl disulfide were quantified. Their limits of detection were found to be in the range of 0.2-1.7 μg/L. The organic sulfides were detected in the range of 6.0-23.8 μg/g with recoveries of 76.6-100.2% in Chinese chive and 11.4-54.6 μg/g with recoveries of 77.1-99.8% in garlic sprout. The results indicate the immobilization of MOF-5 on copper foam provides an efficient enrichment formats for noninvasive sampling of plant volatiles.