Selective CO₂ Adsorption by a Triazacyclononane‐Bridged Microporous Metal–Organic Framework

Abstract

Metal-organic frameworks constructed by self-assembly of metal ions and organic linkers have recently been of great interest in the preparation of porous hybrid materials with a wide variety of functions. Despite much research in this area and the large choice of building blocks used to fine-tune pore size and structure, it remains a challenge to synthesise frameworks composed of polyamines to tailor the porosity and adsorption properties for CO(2). Herein, we describe a rigid and microporous three-dimensional metal-organic framework with the formula [Zn(2)(L)(H(2)O)]Cl (L=1,4,7-tris(4-carboxybenzyl)-1,4,7-triazacyclononane) synthesised in a one-pot solvothermal reaction between zinc ions and a flexible cyclic polyaminocarboxylate. We have demonstrated, for the first time, that a porous rigid framework can be obtained by starting from a flexible amine building block. Sorption measurements revealed that the material exhibited a high surface area (135 m(2) g(-1)) and was the best compromise between capacity and selectivity for CO(2) over CO, CH(4), N(2) and O(2); as such it is a promising new selective adsorbent for CO(2) capture.

3D Metal–Organic Frameworks Based on Co(II) and Bithiophendicarboxylate: Synthesis, Crystal Structures, Gas Adsorption, and Magnetic Properties

“…The IAST CO 2 /N 2 selectivity values become even greater for the gas mixture composition similar to the real industrial flue gases (CO 2 :N 2 = 15:85 (v/v), Table 2). The CO 2 /O 2 adsorption selectivity factors range from 9.4 to 45.4, depending on the temperature and calculation approach, similarly to results reported for other porous MOFs [37][38][39]. The obtained adsorption selectivity factors for the CO 2 /CO mixture (7.9 ÷ 20.8 at 273 K, 7.2 ÷ 15.1 at 298 K) rival the most prominent results reported for porous MOFs with only a few superior exceptions [40][41][42].…”

Effect of the structural constituents of metal organic frameworks on carbon dioxide capture

“…In this case such functionalization resulted in the presence of many hydrogen donors in the pore structures, increasing CO 2 uptake and the overall stability of the material [145]. with guest molecules of carbon dioxide [146].…”

Molecular Simulation of a Zn–Triazamacrocyle Metal–Organic Frameworks Family with Extraframework Anions

“…It can be seen this high-pressure data is in remarkably good agreement with the low-pressure isotherm reported in ref. 7 (plotted in black on Figure 5). In particular, the Henry constant of both isotherms (i.e.…”

“…5 anions in each system of channels, except for one orientation which has 6 anions. The occurrence of other observed distributions, which are (6,6,4) and (7,5,4), are of much lower probability. They strongly depend on temperature, with their cumulative percentage growing from 5% at 77 K, to 15% at 300 K (and 20% at 1000 K).…”