High entropy La(Cr0.2Mn0.2Fe0.2Co0.2Ni0.2)O3 with tailored eg occupancy and transition metal-oxygen bond properties for oxygen reduction reaction

doi:10.1016/j.jmst.2023.12.077

Abstract

Abstract: Forming high entropy oxide provides a feasible approach to finding a balance among moderate e_g occupancy, high transition metal-oxygen (TM-O) covalency, and lattice energy, which is essential to ensure efficient and durable oxygen reduction reaction (ORR) process for perovskite lanthanide-transition metal oxides (LaTMO₃). However, due to the compositional complexity, clarifying the relevance among the high entropy components, e_g occupancy, TM-O properties, and ORR performance still remains a challenge. Herein, adopting the B site entropy-driven strategy, a series of LaTMO₃ (TM = Cr, Mn, Fe, Co, Ni) with tunable e_g occupancy and TM-O bond properties are synthesized, and the correlations between high entropy elements, e_g occupancy, TM-O properties, and ORR performances are revealed quantitively based on the crystal field theory and the Phillips-Van Vechten-Levine (P-V-L) valence bond theory. High entropy La(Cr_0.2Mn_0.2Fe_0.2Co_0.2Ni_0.2)O₃ delivers a low overpotential of 493 mV (vs. 503 mV for LaMnO₃) and a minuscule decline by only 1.7% (vs. 4.4% for LaMnO₃) in half wave potential after 10,000 cycles, which can be associated with the tailored e_g occupancy (1.06) and the significant enhancement in both TM-O covalency (4%) and lattice energy (691.75 kJ mol^-1). This work not only demonstrates the prospects of high entropy LaTMO₃ in the ORR field but also provides a new perspective for the quantitative analysis of the structure-activity relationship for high entropy oxide ORR catalysts.

Key words: High entropy oxide, e_g occupancy, TM-O covalency, TM-O lattice energy, LaTMO₃, Oxygen reduction reaction

Wenyi Li, Zhenxin Zhao, Jinyu Zhao, Yongzhen Wang, Xiaomin Wang. High entropy La(Cr_0.2Mn_0.2Fe_0.2Co_0.2Ni_0.2)O₃ with tailored e_g occupancy and transition metal-oxygen bond properties for oxygen reduction reaction[J]. J. Mater. Sci. Technol., 2024, 194: 236-246.

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High entropy La(Cr_0.2Mn_0.2Fe_0.2Co_0.2Ni_0.2)O₃ with tailored e_g occupancy and transition metal-oxygen bond properties for oxygen reduction reaction

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