Abstract
We investigate the CO2 electroreduction reaction (CO2ERR) using first principles calculations, for the active site tuning of cobalt phthalocyanine (CoPc) via distinct atomic linker species which immobilize CoPc on a carbon nanotube (CNT) substrate. Eight different linker species are studied, along with the effect of linker hydrogenation. Superior reaction performance is predicted for the NH, S and PH linkers, which show activated CO2 adsorption. This results from spin polarization causing unoccupied dz2 spin-down states of the cobalt active site at, or above, the Fermi level. Using an ‘on-catalyst’ reaction scheme, calculated activation barriers for COOH formation and CO desorption are lower for the CoPc-PH-CNT system compared to the CoPc-NH-CNT system and CoPc remains attached to PH-CNT throughout the reaction. We thus expect the PH linker system to have similar or better CO2ERR performance compared to the NH and S linker systems but at a slightly higher electrode potential.
Original language | English |
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Pages (from-to) | 43-55 |
Number of pages | 13 |
Journal | Journal of Catalysis |
Volume | 422 |
Early online date | 8 Apr 2023 |
DOIs | |
Publication status | Published - Jun 2023 |
Keywords
- Activation barriers
- Active site
- Catalyst
- CO electroreduction
- Cobalt
- Density of states
- DFT
- First principles
- Free energy
- Phthalocyanine