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Ni-doping effects on formation and migration of oxygen vacancies in SrFe 1- x Ni x O 3- δ oxygen carriers.

Ting JiaYinuo HaoHua HaoZhi Zeng
Published in: RSC advances (2024)
Ni is a promising B-site doping element capable of improving the oxygen carrier performance of SrFeO 3 perovskite. In this work, the effect of Ni doping on the formation and migration of oxygen vacancies in SrFe 1- x Ni x O 3- δ ( x = 0, 0.0625, 0.125, 0.1875, and 0.25) is investigated using density functional theory calculations. Our results show that the oxygen vacancies formed from Ni-O-Fe chains exhibit lower formation energy ( E f ) compared to those from Fe-O-Fe chains in each doping system. Additionally, E f generally decreases with an increase of Ni content. This Ni-promoted formation of V O is attributed to three factors: weakened Ni-O bonding, the closure of O-2p states to the Fermi level by Ni-O hybridization, and Ni 3+ decreasing the positive charges to be compensated by V O formation. Due to these multiple advantages, a modest Ni doping of x = 0.25 can induce a higher P O 2 and a lower T comparted to the relatively larger Co doping of x = 0.5, thermodynamically. Kinetically, Ni-doping appears to be a disadvantage as it hinders oxygen migration, due to a higher oxygen migration barrier through SrSrNi compared to the SrSrFe pathway. However, the overall oxygen ion conduction would not be significantly influenced by hopping through a nearby pathway of SrSrFe with a low migration barrier in a system doped with a small amount of Ni. In a word, a small amount of Ni doping has an advantage over Co doping in terms of enhancing the oxygen carrier performance of the parent SrFeO 3 system.
Keyphrases
  • transition metal
  • metal organic framework
  • density functional theory
  • mass spectrometry
  • single molecule
  • ionic liquid