Sorption and Desorption of Vapor of n-Pentane by Porphyrin Aluminum Metal-Organic Framework: Mechanism of Bonding, Kinetics and Stoichiometry by Complementary In-Situ Time-Dependent and Ex-Situ Methods.

Metal-organic frameworks (MOFs) are highly nanostructured coordination polymers that contain metal cations and organic linkers and feature very large pore volumes and surface areas. The sorption and desorption of n-pentane vapor by porphyrin aluminum metal-organic framework Al-MOF-TCPPH 2 where TCPPH 2 is tetrakis(4-carboxyphenyl)porphyrin linker were studied by a novel method of in-situ time-dependent attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy in a controlled atmosphere and complementary in-situ and ex-situ methods. Sorption facilely occurs in the flow of dried air, and in the obtained adsorption complex the adsorbate molecules interact with phenyl and carboxylate groups of the linker and the O-H group. Sorption kinetics follows the pseudo-first-order rate law, as confirmed by in-situ time-dependent gravimetry. Further, an ex-situ (static) sorption of n-pentane vapor results in an adsorption complex with as much as 29.1 wt.% n-pentane with the stoichiometric formula [Al-MOF-TCPPH 2 ] 2 (n-C 5 H 12 ) 7 and a distinct XRD pattern. Finally, in the flow of dried air, the adsorption complex gradually desorbed n-pentane, following the pseudo-first-order rate law. The reversibility of sorption and desorption makes porphyrin aluminum MOF promising for the separation of light hydrocarbons and chemo-sensing. In-situ time-dependent ATR-FTIR spectroscopy in a controlled atmosphere, in combination with in-situ time-dependent gravimetry, is a new approach for the determination of binding sites of sorbents with adsorbate molecules, the stoichiometry of complexes, and chemical kinetics of "solid-gas" interactions.