Crystal Engineering of an nbo Topology Metal–Organic Framework for Chemical Fixation of CO₂ under Ambient Conditions

Abstract

Crystal engineering of the nbo metal–organic framework (MOF) platform MOF‐505 with a custom‐designed azamacrocycle ligand (1,4,7,10‐tetrazazcyclododecane‐N,N′,N′′,N′′′‐tetra‐p‐methylbenzoic acid) leads to a high density of well‐oriented Lewis active sites within the cuboctahedral cage in MMCF‐2, [Cu2(Cu‐tactmb)(H2O)3(NO3)2]. This MOF demonstrates high catalytic activity for the chemical fixation of CO2 into cyclic carbonates at room temperature under 1 atm pressure.

3d-4f Heterometal–Organic Frameworks for Efficient Capture and Conversion of CO2

“…It is proposed that metal ions serve as Lewis acid sites to efficiently activate epoxide and TBAB is employed as a cocatalyst in the experiment in the previous reports. 50,51 The synergistic effect of compound 1 and TBAB is the main reason of high catalytic activity of the catalyst system under mild conditions. Generally, Lewis acid sites are widely considered to be responsible for CO 2 conversion with epoxides.…”

Cycloaddition of CO 2 and epoxides catalyzed by dicationic ionic liquids mediated metal halide: Influence of the dication on catalytic activity

“…Nevertheless, CO2 is an unreactive molecule and high energy barrier of the noncatalyzed cycloaddition associated with CO2 is necessary for the reaction to occur spontaneously [7,8]. So far, a plethora of catalytic systems for producing cyclic carbonates has been successfully developed in order to reduce the activation energy of the cycloaddition reaction, including metal oxides [9,10], alkali metal salts [11,12], metal-salen complexes [13,14], metal-organic framework (MOF) [15,16], microporous polymer [17], graphitic carbon nitride [18,19] and ionic liquids [20][21][22][23][24].…”

“…In the case of DBU-based dication (entries[13][14][15], the steric hindrance played the leading role in the catalytic activity and 2d with the shortest aliphatic chain bridge showed the best catalytic activity. With the same linkage chain length, the catalytic efficiency decreased in the order of 4b > 4a > 4d > 4c, this was ZnI2 displayed the most efficient activity for further investigation on the coupling reaction.…”

Synthesis of a Pyridine–Zinc‐Based Porous Organic Polymer for the Co‐catalyst‐Free Cycloaddition of Epoxides

“…Up to now,s everal types of heterogeneousc atalysts have been developed, including metal oxides, [17] functional graphene oxide, [18] supportedc atalysts, [19] zeolitic imidazolate frameworks (ZIFs) and metal-organic frameworks (MOFs), [20][21][22][23][24][25][26][27] and porous organic polymers (POPs). [28][29][30][31][32][33][34] Recently,t he potential applicationso fP OPs in gas storage and separation, [35][36][37][38] energy transfer and conversions, [39,40] sensing, [41,42] and heterogeneous catalysis [28][29][30][31][32][33][34][43][44][45][46][47] were demonstrated.…”