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Predicting the Effect of Dopants on CO2 Adsorption on Transition Metal Carbides: Case Study on TiC (001)

submitted on 01.05.2020, 08:51 and posted on 04.05.2020, 12:26 by Marti Lopez, Francesc Vines, Michael Nolan, Frances Illas
Previous work has shown that doping the TiC(001) surface with early transition metals significantly affects CO2 adsorption and activation which opens a possible way to control this interesting chemistry. In this work we explore other possibilities which include non-transition metals elements (Mg, Ca, Sr, Al, Ga, In, Si, Sn) as well as late transition metals (Pd, Pt, Rh, Ir) and lanthanides (La, Ce) often used in catalysis. Using periodic slab models with large supercells and state-of-the-art density functional theory (DFT) based calculations, we show that, in all the studied cases, CO2 appears as bent and, hence, activated. However, the effect is especially pronounced for dopants with large ionic crystal radii. These can increase desorption temperature by up to 230K, almost twice the value predicted when early transition metals are used as dopants. However, a detailed analysis of the results shows that the main effect does not come from electronic structure perturbations but from the distortion that the dopant generates into the surface atomic structure. A simple descriptor is proposed that would allow predicting the effect of the dopant on the CO2 adsorption energy in transition metal carbide surfaces without requiring DFT calculations.


MICIUN/FEDER RTI2018-095460-B-I00

María de Maeztu MDM-2017-0767

Generalitat de Catalunya 2017SGR13

COST Action 18234

Horizon 2020 2 co-fund program grant agreement No 685451

Science Foundation Ireland 16/M-ERA/3418

Horizon 2020 HPC-EUROPA3 INFRAIA-2016-1-730897


Email Address of Submitting Author


Tyndall National Institute, UCC



ORCID For Submitting Author


Declaration of Conflict of Interest

No conflict of interest

Version Notes

Submitted version