High CO₂/N₂ Selectivity and H₂ Adsorption of a Novel Porous Yttrium Metal–Organic Framework Based on N,N′,N″-Tris(isophthalyl)-1,3,5-benzenetricarboxamide

Abstract

On the basis of a new topology, a novel yttrium metal−organic framework [Y 2 (TPBTM)(H 2 O) 2 ]•xG (TPBTM = N,N′,N″-tris(isophthalyl)-1,3,5-benzenetricarboxamide and G = guest molecule) (NJU-Bai11) has been synthesized and structurally characterized. NJU-Bai11 crystallizes in a chiral space group and in its topological net and exists left of the helical rods, which are constituted from edge-sharing pyramidal polyhedra with points of extension as carboxylic carbon atoms along the a axis. NJU-Bai11 exhibits excellent adsorption capacity for CO 2 (130.0 cm 3 /g at 273 K, 1 bar) and H 2 (160.0 cm 3 /g at 77 K, 1 bar). Remarkably, NJU-Bai11 possesses high H 2 adsorption enthalpy (7.05 kJ/mol), which is approaching the highest value (7.3 kJ/mol) reported among rare-earth metal−organic frameworks (RE-MOFs). In addition, a high selectivity ratio of 30.2 for CO 2 over N 2 makes NJU-Bai11 possess a potential practical application in gas purification.

Chiral Lanthanide Metal-Organic Frameworks

“…Although the ligand H 6 TPBTM used by Tang et al [89] has no chirality, the introduction of Y(III) ions leads to the form of helical chains and the chiral character of the whole structure, [Y 2 (TPBTM)(H 2 O) 2 ]·xG (G ¼ guest molecule). The MOF possesses a chiral space group of P2 1 2 1 2 1 and a new topological net that contains left-helical rods constituted from edge-sharing pyramidal polyhedra with points of extension as carboxylic carbon atoms along the a axis.…”

Lanthanide–Organic Frameworks Constructed from an Unsymmetrical Tricarboxylate for Selective Gas Adsorption and Small‐Molecule Sensing

“…[1][2][3][4][5][6][7][8] Their permanent porosity makes them suitable for applications such as gas storage and separation, [9][10][11][12][13][14] whereas their unique physical properties from the 4f electrons of the lanthanide ions endow them with interesting photophysical, magnetic, and electronic properties. [15][16][17] However, compared to that of their transitional-metal counterparts, the rational design and synthesis of porous Ln-MOFs is more challenging because of the high coordination numbers (usually from 6 to 12) and flexible coordination geometries of lanthanide ions.…”

“…[18] He et al synthesized an aromatic-rich C 3 -symmetric tricarboxylate, benzene-1,3,5-tri(5-naphthoic acid), and used it to construct a Ln-MOF with potential for natural-gas purification. [19] However, compared to those with symmetrical aromatic multicarboxylate ligands, [10,[20][21][22][23][24][25][26] porous Ln-MOFs constructed from unsymmetrical aromatic multicarboxylate ligands are less investigated. [27] On the basis of the abovementioned considerations, we designed and synthesized an unsymmetrical aromatic tricarboxylate organic ligand, namely, 5-(6-carboxynaphthalene-2-yl)isophthalic acid (H 3 L), which is shown in Scheme 1.…”

Lanthanide contraction effects on the structures, thermostabilities, and CO2 adsorption and separation behaviors of isostructural lanthanide–organic frameworks

“…Therefore, MOFs with high thermostability are of practical value. 34,[39][40][41][42][43][44][45] However, almost all of the reports focused on one or several specific lanthanide LOFs and there is still a lack of a systematic study on a series of LOFs for CO 2 separation. 30,31 As a new family of MOFs, lanthanide-organic frameworks (LOFs) with lanthanides as the metal nodes are exactly such porous materials, with desirable properties for their potential application in optical, electronic, sensing, gas separation and catalytic areas.…”

“…Various functionalization methods are available to introduce different metal centers to MOFs to improve their thermostability. Although considerable investigation has been carried out on the gas adsorption properties of LOFs, 31,39,41,[46][47][48][49][50][51][52][53] it is also necessary to prepare LOFs on a large scale for their potential industrial applications. [32][33][34][35][36][37][38] Recently, several lanthanide benzenetricarboxylates (LnBTCs) have been investigated as promising candidates for gas storage and separation.…”