Highly efficient synergistic CO₂ conversion with epoxide using copper polyhedron-based MOFs with Lewis acid and base sites

Abstract

Jiaming Gu,a Xiaodong Sun,b Xinyao Liu,a Yang Yuan,a Hongyan Shan,a and Yunling Liu*a To systematically study the effect of Lewis acid sites (LASs) and Lewis basic sites (LBSs) in MOFs...

Lanthanide Coordination Polymers through Design for Exceptional Catalytic Performances in CO2 Cycloaddition Reactions

“…The coexistence of the Lewis acidic Eu III with vacant coordination sites and the Brønsted acidic −COOH and −OH as well as the Lewis basic −NN– bond, the phenyl rings, and the lone-paired electron containing O atoms in the vicinity of Eu III (Figure ) should, in principle, promote the catalytic activities of Ib and IIb. − …”

“…The copresence of Lewis acidic and basic motifs within the frameworks was also reported to enhance the catalysis since the Lewis basic motifs can help in transfixing CO 2 in close vicinity of the Lewis acid. Some previous CPs/MOFs devised based on this strategy were through the use of, for instance, the lone-paired electron containing N atom of 1,1′-(propane-1,3-diyl)­bis­(1 H -pyrazole-3,5-dicarboxylic acid) (PDC) in [Zn 3.5 (PDC) 2 (H 2 O) 10 ] and (5-5′-(1 H -1,2,4-triazole-3,5-diyl) diisophthalic acid in copper-based MOFs and the uncoordinated carboxylate O atoms in {[(CH 3 ) 2 NH 2 ]­[Zn II Tb III (TDP)­(H 2 O)]·3DMF·3H 2 O} n . Apart from the Lewis acidic and basic motifs, the catalytic activities of CPs/MOFs can also be improved in the presence of Brønsted acids, which may interact with both CO 2 and epoxide, e.g., −OH in [Zn 5 (OH) 2 (DBTA) 2 (H 2 O) 4 ] (H 4 DBTA = 2,2′-dihydroxy-1,1′-binaphthyl-3,3′,6,6′-tetrakis-(4-benzoic acid)) and −NH 2 as well as −COOH in [Zn 3 (L) 3 (H 2 L)·2DMF·H 2 O] (L = 2-aminoterephthalic acid) …”

Construction of a 3D porous Zn(II) compound with (3,4)‐connected topology: luminescent and gas sorption properties

“…In this 3D framework, there exists two different 1D nanotube substructures: one is constructed by the Zn(II) ions and L À ligands (Figure 1b) and the other is constructed by Zn(II) ions, L À ligands and oxalate anions (Figure 1c). Topologically speaking, if the L À ligands and Zn(II) ions can be reduced into 3-, 4-connected nodes, respectively, and the oxalate anions can be viewed as linear linkers, the network topology of this 3D framework can be described as a binodal (3,4)-connected topological network with the Schläfli symbol of {6 3 }{6 5 • 8}(Figure 1e). Viewing along crystallographical a axis, The 1D nanotubes in the 3D framework are so large that it can accommodate another identical one.…”

“…As a new type of hybrid crystalline materials, metal-organic frameworks (MOFs) built from the metal ions or clusters with diverse organic ligands have attracted considerable scientific research interest owing to their huge potential applications in magnetism, chemical sensing, luminescence, catalysis, gas storage and separation, and so on. [1][2][3][4][5] Of particular interest is the construction of porous MOFs for gas storage and separation. [6][7][8] Compared with traditional adsorbent materials, such as zeolites, activated carbons, or diatomite, porous MOFs materials are more advantageous in terms of high surface area, adjustable pore size, as well as unique functional groups modified pore environment.…”

“…In summary, a new 3D porous Zn(II) compound has been successfully constructed under solvothermal conditions. The overall structure of 1 is 2-fold interpenetrated and can be regarded as a(3,4)-connected topological network with the Schläfli symbol of {6 3 }{6 5 • 8}. The 1D nanotube channels that occupied by the disordered DMA molecules contribute its high solvent-accessible free volume.…”