A series of high-quality M2(BDC)2(DABCO) metal–organic frameworks (abbreviated as M-DABCO; M=Zn, Co, Ni, Cu; BDC=1,4-benzene dicarboxylate; DABCO=1,4-diazabicyclo[2.2.2]octane), were synthesized by using a solvothermal (SV) method, and their catalytic activity for the cycloaddition of CO2 to epoxides in the absence of a co-catalyst or solvent was demonstrated. Of these metal–organic frameworks (MOFs), Zn-DABCO exhibited very high activity and nearly complete selectivity under moderate reaction conditions. The other members of this MOF series (Co-DABCO, Ni-DABCO, and Cu-DABCO) displayed lower activity in the given sequence. Samples of Zn-DABCO, Co-DABCO, and Ni-DABCO were recycled at least three times without a noticeable loss in catalytic activity. The reaction mechanism can be attributed to structural defects along with the acid–base bifunctional characteristics of these MOFs. Moreover, we illustrate that the synthetic method of M-DABCO influences the yield of the reaction. In addition to the SV method, Zn-DABCO was synthesized by using spray drying due to its industrial attractiveness. It was found that the synthesis procedure clearly influenced the crystal growth and thus the physicochemical properties, such as surface area, pore volume, and gas adsorption, which in turn affected the catalytic performance. The results clarified that although different synthetic methods can produce isostructural MOFs, the application of MOFs, especially as catalysts, strongly depends on the crystal morphology and textural properties and, therefore, on the synthesis method.
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