TY - JOUR
T1 - Predicting the Effect of Dopants on CO2Adsorption in Transition Metal Carbides
T2 - Case Study on TiC (001)
AU - López, Martí
AU - Viñes, Francesc
AU - Nolan, Michael
AU - Illas, Francesc
PY - 2020/7/23
Y1 - 2020/7/23
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85089419260&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.0c03893
DO - 10.1021/acs.jpcc.0c03893
M3 - Article
AN - SCOPUS:85089419260
SN - 1932-7447
VL - 124
SP - 15969
EP - 15976
JO - Journal Of Physical Chemistry C
JF - Journal Of Physical Chemistry C
IS - 29
ER -