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.

Cycloadditions to Epoxides Catalyzed by Group III–V Transition‐Metal Complexes

“…Through ac omparison witho ther recently reported MOFs for this reaction, such as copper based MMCF-2 [60] or gea-MOF-1, [35] the authors claimed the superior catalytic performance of Hf-NU-1000, howevert he comparison was not based on the turnover frequencies obtained (see also Ta ble 7, entries 3, 5, and 6). [61] Interestingly,a nother MOF containing aZ r 6 cluster has been reported by Feng et al (PCN-224). [59] In this case, the hexanuclear clusterh as been assembled togetherw ith metalloporphyrins containing aN i, Co, or Fe core.…”

“…However,t he contribution of the acidic Zr centers to the conversion of PO has not been taken into account. The catalytic activity of the MOFs reported in this review for the cycloaddition of CO 2 to PO to afford PC are compared in Table 7, along with the catalytic performances of other transition-metal-based MOFs, such as chiral Ni/Cd-based CMOF 1r eported by Jiang and co-workers, [60] Cu-based MMCF-2, [61] and covalento rganic framework Co-CMP. [62] The last two catalysts have been also reported to be active under ambient conditions (Table 7, entries 4-6).…”

Metalated porous porphyrin polymers as efficient heterogeneous catalysts for cycloaddition of epoxides with CO2 under ambient conditions

“…Recently, there are encouraging heterogeneous catalysts such as Cu-MOF [44] and metal-salen based conjugated microporous polymers (metal-salen-CMP) [45], exhibiting excellent catalytic performance for production of cyclic carbonates, and even outperforming the corresponding homogeneous catalysts under real mild conditions such as at room temperature and atmospheric pressure [44][45][46]. However, in these catalysts it is still observed a little metal leaching.…”

Bi-functional heterogeneous catalysts for carbon dioxide conversion: enhanced performances at low temperature

“…20 The use of various metal-organic frameworks (MOF) in combination with ammonium or imidazolium salts was also reported. [21][22][23] The majority of the previously reported examples refer to homogeneous catalysts or systems in which one of the two components (catalyst or cocatalyst) was heterogenized. In the broad list of contributions addressing the synthesis of cyclic carbonates from CO 2 , only a minor number of publications describe the use of a heterogeneous bi-functional catalyst in which both catalyst and Lewis acid co-catalyst are heterogenized on one support and even fewer illustrate the use of inorganic metal centres acting as Lewis acid sites.…”