TY - JOUR
T1 - Unraveling the effects of Fe and Mn promoters on the tungstated zirconia catalyst
T2 - A DFT study
AU - Madrigal-Carrillo, Karina G.
AU - Rodríguez, Juan I.
AU - Hernández-Pichardo, Martha L.
AU - Jimenez-Izal, Elisa
N1 - Publisher Copyright:
© 2022 The Author(s)
PY - 2022/10/15
Y1 - 2022/10/15
N2 - Periodic DFT calculations are performed to unravel the effect of the incorporation of Fe and Mn into the tungstated zirconia catalyst, (WO3)x/ZrO2 (x = 1,3), in their electronic, geometric, and catalytic properties. Our results suggest that both Mn and Fe have a proclivity to occupy the same positions and thus both metals will compete for the same adsorption sites. The addition of Fe or Mn slightly destabilizes the WO3 monomer while stabilizes the (WO3)3 trimer. Hence, medium size clusters, which are the most catalytically active species, will be more sinter resistant in the presence of the promoters, leading to catalysts with longer lifetimes. The computed deprotonation energies evidence that the overall Brønstead acidity is increased upon the addition of the dopant atoms. It is proposed that the metals lead to a reduction of WZ and induce a local spin density imbalance.The function as redox initiators of these metals is confirmed.
AB - Periodic DFT calculations are performed to unravel the effect of the incorporation of Fe and Mn into the tungstated zirconia catalyst, (WO3)x/ZrO2 (x = 1,3), in their electronic, geometric, and catalytic properties. Our results suggest that both Mn and Fe have a proclivity to occupy the same positions and thus both metals will compete for the same adsorption sites. The addition of Fe or Mn slightly destabilizes the WO3 monomer while stabilizes the (WO3)3 trimer. Hence, medium size clusters, which are the most catalytically active species, will be more sinter resistant in the presence of the promoters, leading to catalysts with longer lifetimes. The computed deprotonation energies evidence that the overall Brønstead acidity is increased upon the addition of the dopant atoms. It is proposed that the metals lead to a reduction of WZ and induce a local spin density imbalance.The function as redox initiators of these metals is confirmed.
KW - Alkane isomerization
KW - Catalysis
KW - DFT
KW - Deprotonation
KW - Tungstated zirconia
KW - WOx clusters
UR - http://www.scopus.com/inward/record.url?scp=85133836552&partnerID=8YFLogxK
U2 - 10.1016/j.apsusc.2022.154052
DO - 10.1016/j.apsusc.2022.154052
M3 - Artículo
AN - SCOPUS:85133836552
SN - 0169-4332
VL - 599
JO - Applied Surface Science
JF - Applied Surface Science
M1 - 154052
ER -