Porphyrin-Based Aluminum Metal-Organic Framework with Copper: Pre-Adsorption of Water Vapor, Dynamic and Static Sorption of Diethyl Sulfide Vapor, and Sorbent Regeneration.

Metal-organic frameworks (MOFs) are hybrid inorganic-organic 3D coordination polymers with metal sites and organic linkers, which are a "hot" topic in the research of sorption, separations, catalysis, sensing, and environmental remediation. In this study, we explore the molecular mechanism and kinetics of interaction of the new copper porphyrin aluminum metal-organic framework (actAl-MOF-TCPPCu) compound with a vapor of the volatile organic sulfur compound (VOSC) diethyl sulfide (DES). First, compound was synthesized by post-synthetic modification (PSM) of Al-MOF-TCPPH compound by inserting Cu ions into the porphyrin ring and characterized by complementary qualitative and quantitative chemical, structural, and spectroscopic analysis. Second, the interaction of compound with DES vapor was analyzed dynamically by the novel method of in situ time-dependent attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy at controlled humidity levels. The sorbent-adsorbate interactions, as analyzed by the shifts in IR peaks, indicate that the bonding includes the hydroxy O-H, carboxylate COO, and phenyl groups. The kinetics of sorption obeys the Langmuir pseudo-first-order rate law. The pre-adsorption of water vapor by compound at the controlled relative humidity under static (equilibrium) conditions yields the binary stoichiometric adsorption complex (Al-MOF-TCPPCu)(HO). The pre-adsorption of water vapor makes the subsequent sorption of DES slower, while the kinetics obey the same rate law. Then, static pre-adsorption of water vapor was followed by static sorption of DES vapor, and the ternary adsorption complex (Al-MOF-TCPPCu)(HO)(DES). was obtained. Despite the pre-adsorption of significant amounts of water, the binary complex adsorbs a large amount of DES: ca. 36.6 wt. % (per compound ). Finally, the ternary complex is facilely regenerated by gentle heating under vacuum. Compound and related MOFs are promising for adsorptive removal of vapor of DES and related VOSCs from dry and humid air.