TY - JOUR
T1 - Dual role of Fe boost lattice oxygen oxidation of Mo-based materials from kinetics and thermodynamics
AU - Liu, Qingcui
AU - Su, Qiaohong
AU - Cheng, Wenhua
AU - Ding, Juan
AU - Zhang, Wenjun
AU - Wang, Jiulin
AU - Wang, Yonggang
AU - Wang, Xingchao
AU - Huang, Yudai
PY - 2024/1
Y1 - 2024/1
N2 - High-valent Mo-based oxides are easily dissolved in alkaline electrolyte resulting in complete surface reconstruction of catalyst. Therefore, there are few researches on the oxygen evolution reaction (OER) process of this material, especially the reaction mechanism. Herein, Fe-Mo2C@CN was synthesized by introducing 3d metal Fe into the Mo-based catalyst, which inhibited the complete dissolution of Mo. The overpotential is only 226 mV at a current density of 10 mA cm−2. Experimental and density functional theory (DFT) results demonstrate that excellent electrocatalytic performance derives from the dual role of Fe and the thermodynamically favorable single-site lattice oxygen oxidation mechanism (LOM). Electronic-rich pure Fe inhibits the molybdenum dissolution while enhancing the reaction kinetics. And the doped Fe decreases the d-band center, weakens the M-O (metal-oxygen) bond, and promotes the involvement of lattice oxygen in the OER process. This work provides theoretical basis for the engagement of Mo-based catalysts in water splitting. © 2023 Elsevier B.V.
AB - High-valent Mo-based oxides are easily dissolved in alkaline electrolyte resulting in complete surface reconstruction of catalyst. Therefore, there are few researches on the oxygen evolution reaction (OER) process of this material, especially the reaction mechanism. Herein, Fe-Mo2C@CN was synthesized by introducing 3d metal Fe into the Mo-based catalyst, which inhibited the complete dissolution of Mo. The overpotential is only 226 mV at a current density of 10 mA cm−2. Experimental and density functional theory (DFT) results demonstrate that excellent electrocatalytic performance derives from the dual role of Fe and the thermodynamically favorable single-site lattice oxygen oxidation mechanism (LOM). Electronic-rich pure Fe inhibits the molybdenum dissolution while enhancing the reaction kinetics. And the doped Fe decreases the d-band center, weakens the M-O (metal-oxygen) bond, and promotes the involvement of lattice oxygen in the OER process. This work provides theoretical basis for the engagement of Mo-based catalysts in water splitting. © 2023 Elsevier B.V.
KW - Dual role of Fe
KW - Electrocatalyst
KW - Lattice oxygen oxidation
KW - Mo2C
KW - Oxygen evolution reaction
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UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-85168725849&origin=recordpage
U2 - 10.1016/j.apcatb.2023.123188
DO - 10.1016/j.apcatb.2023.123188
M3 - RGC 21 - Publication in refereed journal
SN - 0926-3373
VL - 340
JO - Applied Catalysis B: Environmental
JF - Applied Catalysis B: Environmental
M1 - 123188
ER -