A more effective catalysis of the CO2 fixation with aziridines: computational screening of metal-substituted HKUST-1

Yan Jiang; Tian-Ding Hu; Li-Ying Yu; Yi-Hong Ding

doi:10.1039/d1na00150g

A more effective catalysis of the CO₂ fixation with aziridines: computational screening of metal-substituted HKUST-1

Nanoscale Adv. 2021 Jun 3;3(14):4079-4088. doi: 10.1039/d1na00150g. eCollection 2021 Jul 13.

Authors

Yan Jiang¹, Tian-Ding Hu¹, Li-Ying Yu¹, Yi-Hong Ding^{1

2}

Affiliations

¹ Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University Changchun 130023 P. R. China [email protected].
² Key Laboratory of Carbon Materials of Zhejiang Province, College of Chemistry and Materials Engineering, Wenzhou University Wenzhou 325035 P. R. China.

Abstract

A vital issue for the fixation and conversion of CO₂ 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 CO₂ 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.