An experimental and computational study of CO₂adsorption in the sodalite-type M-BTT (M = Cr, Mn, Fe, Cu) metal–organic frameworks featuring open metal sites

Abstract

The work provides molecular level insight into the CO2 adsorption properties of an isostructural series of MOFs, known as M-BTT.

Unraveling Structure and Dynamics in Porous Frameworks via Advanced In Situ Characterization Techniques

“…Rising levels of atmospheric CO 2 motivated Long and co‐workers to search for the optimal materials for CO 2 capture. In situ NPD on a series of sodalite type frameworks with composition [(M 4 Cl) 3 (BTT) 8 ] 3− (M = Cr, Mn, Fe, Co, Ni, Cu, and Cd; BTT 3− = 1,3,5‐benzenetristetrazolate), loaded with CO 2 , provided an information of the adsorption sites, well reflecting molecular simulation data, which additionally supported experimental results . A series of in situ NPD experiments was conducted on a mesoporous MOF, DUT‐49 and their isoreticular networks, showing a novel counterintuitive phenomenon named “negative gas adsorption” (NGA).…”

“…In situ NPD on a series of sodalite type frameworks with composition [(M 4 Cl) 3 (BTT) 8 ] 3− (M = Cr, Mn, Fe, Co, Ni, Cu, and Cd; BTT 3− = 1,3,5-benzenetristetrazolate), loaded with CO 2 , provided an information of the adsorption sites, well reflecting molecular simulation data, which additionally supported experimental results. [138] A series of in situ NPD experiments was conducted on a mesoporous MOF, DUT-49 and their isoreticular networks, showing a novel counterintuitive phenomenon named "negative gas adsorption" (NGA). In situ NPD in this case gives important information on the pore filling mechanism in these frameworks with trimodal pore size distribution and its impact on NGA.…”

Selective CO2 Sorption Using Compartmentalized Coordination Polymers with Discrete Voids**

“…With the aim of increasing the sorption capacity of compartmentalized coordination polymers, the ligands btztp and btztzine were designed to obtain larger cavities, based on the previously reported ligands btzx and btzbp (see Scheme 1). These reported ligands have been used for the preparation of CCP‐1 and CCP‐2 (btzx), [19, 20] and CCP‐3 and CCP‐4 (btzbp) [21] . The ligands btztp and btztzine were prepared adapting previously reported protocols for the formation of tetrazoles [22] and tetrazines [23] (see Supporting Information).…”

“…In addition, the large chemical versatility of these PCPs allows to modify the framework inner space to incorporate different functionalities and promote favourable host‐guest interactions [12, 13] . In this sense, the introduction of specific binding sites for CO 2 , including open‐metal sites [14] or Lewis basic sites, [15–17] has been demonstrated as an efficient solution to separate CO 2 from mixtures of gases [18, 19] …”

A Stable Amine‐Functionalized Microporous Metal–Organic Framework for Thermodynamically and Kinetically Selective Gas Separations

“…The IAST selectivity of CO 2 /N 2 remains nearly constant at all pressures, with a value of ∼26. Also, very slight change can be observed for the different compositions (50/50, 30/70, 15/75), which has also been reported on various MOFs . Similarly, for the case of CO 2 ‐ CH 4 mixtures, the IAST selectivity remains nearly constant, with a value of ∼4 at all pressures, and displays little change for different compositions (50/50, 20/80, 5/95).…”