A more effective catalysis of the CO 2 fixation with aziridines: computational screening of metal-substituted HKUST-1.

A vital issue for the fixation and conversion of CO 2 into useful chemical products is to find effective catalysts. In this work, in order to develop more effective and diverse catalysts, we implemented the first computational screening study (at M06-2X//B3LYP level) on the cycloaddition of CO 2 with aziridines under eighteen metal-substituted HKUST-1 MOFs and tetrabutylammonium bromide (TBAB) as a co-catalyst. For all considered catalytic systems, the ring-opening of aziridine is calculated to be the rate-determining step. Up to 11 M-HKUST-1 systems, i.e. , Rh (31.87 kcal mol -1 ), Y (31.02), Sc (30.50), V (30.02), Tc (29.90), Cd (29.80), Ti (29.32), Mn (29.05), Zn (28.29), Fe (27.85) and Zr (25.09), possess lower ring-opening barrier heights than the original Cu-HKUST-1 (32.90), indicative of their superior catalytic ability to the original Cu-HKUST-1 in theory. With the lowest ring-opening barrier, Zr-HKUST-1 is strongly advocated for future synthetic and catalytic studies.