Issue 11, 2022

A theoretical approach for homogeneous CO2 reduction by Ni(cyclam): substituents with intra-molecular hydrogen transfer

Abstract

We explore the detailed mechanism for the reduction reaction through systematic theoretical calculations, and the Ni-cyclam catalyst for the homogeneous CO2 reduction reaction exhibits high efficiency. We find that the first hydrogen transfer step is the rate-determining step for the reaction. Our simulation results show that both the acidity of the environment and substituents play critical roles in the CO2 reduction reaction. The strong electron-withdrawing substituent perpendicular to the C atoms at the 5,6,12,14-position of cyclam decreases the energy barrier of the rate-determining step significantly. Moreover, we reveal the mechanism through density functional theory calculations, which exhibits the intra-molecular H-transfer feature and thus explains the extraordinary reactivity seen during the reaction in previous works. All the results ensure a good future for such series of Ni-cyclam catalysts.

Graphical abstract: A theoretical approach for homogeneous CO2 reduction by Ni(cyclam): substituents with intra-molecular hydrogen transfer

Supplementary files

Article information

Article type
Research Article
Submitted
04 Jan 2022
Accepted
13 Apr 2022
First published
15 Apr 2022

Inorg. Chem. Front., 2022,9, 2691-2696

A theoretical approach for homogeneous CO2 reduction by Ni(cyclam): substituents with intra-molecular hydrogen transfer

X. Chen, C. Wang, D. Qi and X. Xing, Inorg. Chem. Front., 2022, 9, 2691 DOI: 10.1039/D2QI00033D

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements