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

Abstract

A previous work has shown that doping the TiC (001) surface with early transition metals significantly affects CO2 adsorption and activation, which opens up a possible way to control this interesting chemistry. In this work, we explore other possibilities, which include nontransition metal elements (Mg, Ca, Sr., Al, Ga, In, Si, and Sn) as well as late transition metals (Pd, Pt, Rh, and Ir) and lanthanides (La and 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. This can increase desorption temperature by up to 230 K, 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 the 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 CO2 adsorption energy in transition metal carbide surfaces without the need for DFT calculations.