Uddin, Amira Tasnima;
Zhao, Qi;
Toroz, Dimitrios;
Crespo-Otero, Rachel;
Di Tommaso, Devis;
(2024)
Computational screening of metalloporphyrin catalysts for the activation of carbon dioxide.
Molecular Catalysis
, 565
, Article 114386. 10.1016/j.mcat.2024.114386.
Preview |
Text
Crespo Otero_Computational screening of metalloporphyrin catalysts for the activation of carbon dioxide_VoR.pdf Download (3MB) | Preview |
Abstract
Electrocatalytic CO2 reduction (eCO2R) to value-added chemicals offers a promising route for carbon capture and utilization. Metalloporphyrin (M-POR) is a class of catalysts for eCO2R that has drawn attention due to its tuneable electronic and structural properties. This work presents a computational screening, based on density functional theory calculations, of one of the key steps in the eCO2R: the adsorption of CO2 on 110 M-PORs with varying peripheral ligands, metal centres, and oxidation states, to understand how these factors can influence CO2 activation. A set of criteria was used to shortlist M-PORs based on their ability to lengthen the C–O bond, bend the O–C–O angle, bind CO2, and donate charge from the metal of the M-POR to the carbon of CO2. 16 systems were selected for their potential to activate CO2. These systems predominantly have the electron configuration of the metal centre in the d[6] and d[7] configurations. Natural bond orbital analysis revealed the impact of electron-withdrawing groups in the system, which increases orbital splitting and, consequently, lowers the ability of the M-POR to activate CO2. Second-order perturbation theory analysis confirms that the presence of electron-donating groups in the ligand structure enhances CO2 activation. This work demonstrates the interconnected effect of peripheral ligands, metal centres, and oxidation states in M-PORs on their ability to adsorb and activate CO2, thereby establishing structure-activity relationships within M-PORs.
| Type: | Article |
|---|---|
| Title: | Computational screening of metalloporphyrin catalysts for the activation of carbon dioxide |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1016/j.mcat.2024.114386 |
| Publisher version: | http://dx.doi.org/10.1016/j.mcat.2024.114386 |
| Language: | English |
| Additional information: | © 2024 The Author(s). Published by Elsevier B.V. under a Creative Commons license (http://creativecommons.org/licenses/by/4.0/). |
| Keywords: | Electrochemical CO2 reduction, Metalloporphyrin, CO2 activation, Density functional theory |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/10196207 |
Archive Staff Only
 |
View Item |
