Capture Fluorocarbon and Chlorofluorocarbon from Air Using DUT‐67 for Safety and Semi‐Quantitative Analysis

Abstract Fluoro‐ and chlorofluorocabons (FC/CFCs) are important refrigerants, solvents, and fluoropolymers in industry while being toxic and carrying high global warming potential. Detection and reclamation of FC/CFCs based on adsorption technology with highly selective adsorbents is important to labor safety and environmental protection. Herein, the study reports an integrated method to combine capture, separation, enrichment, and analysis of representative FC/CFCs (chlorodifluoromethane(R22) and 1,1,1,2‐tetrafluoroethane (R134a)) by using the highly stable and porous Zr‐MOF, DUT‐67. Gas adsorption and breakthrough experiments demonstrate that DUT‐67 has high R22/R134a uptake (124/116 cm3 g−1) and excellent R22/R134a/CO2 separation performance (IAST selectivities of R22/CO2 and R134a/CO2 ranging from 51.4 to 33.3, and 31.1 to 25.8), even in rather low concentration and humid conditions. A semi‐quantitative analysis protocol is set up to analyze the low concentrations of R22/R134a based on the high selective R22/R134a adsorption ability, fast adsorption kinetics, water‐resistant utility, facile regeneration, and excellent recyclability of DUT‐67. In situ single‐crystal X‐ray diffraction, theoretical calculations, and in situ diffuse reflectance infrared Fourier transform spectra have been employed to understand the adsorption mechanism. This work may provide a potential adsorbent for purge and trap technique under room temperature, thus promoting the application of MOFs for VOCs sampling and quantitative analysis.