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Tuning Oxide Properties by Oxygen Vacancy Control During Growth and Annealing

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Enhancing Water Oxidation Performance of Transition Metal Oxides by Atomically Precise Heteroatom Doping.

Zhipu Zhang^1,2, Shanshan Lu^1,2, Moshuqi Zhu^3,4

¹State Key Laboratory of Advanced Materials for Intelligent Sensing & Key Laboratory of Organic Integrated Circuits, Ministry of Education & Tianjin Key Laboratory of Molecular Optoelectronic Sciences, Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China.

Journal of the American Chemical Society

|June 16, 2025

Summary

Atomically precise doping of iron oxide with chromium enhances oxygen evolution reactions (OERs) by stabilizing active sites and improving catalyst stability. This method offers a scalable approach for efficient, cost-effective catalyst development.

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Area of Science:

Materials Science
Electrochemistry
Catalysis

Background:

Non-noble transition metal oxides are crucial for cost-efficient oxygen evolution reactions (OERs).
Conventional doping methods for these oxides often result in unpredictable doping sites and phase separation.
Precise control over heteroatom doping is essential for optimizing catalyst performance and stability.

Purpose of the Study:

To develop an atomically precise doping strategy for 3d transition metal oxides.
To investigate the effect of uniform chromium doping on the OER performance and stability of Fe2O3.
To elucidate the mechanism behind the enhanced catalytic activity and durability.

Main Methods:

Development of an interfacial diffusion strategy based on the lattice-match principle for uniform heteroatom doping.
Synthesis of atomically precise chromium-doped iron oxide (FeCrO3) using Fe2O3 as a model.
Electrochemical characterization of FeCrO3 for OER activity and stability testing in 1.0 M KOH.

Main Results:

FeCrO3 exhibited a significantly reduced overpotential (258 mV at 10 mA cm-2) compared to Fe2O3 (438 mV).
The catalyst demonstrated excellent long-term stability, operating for over 1100 hours with minimal performance decay.
Ordered Cr doping induced electron flux, stabilized active Fe2+ species, and accelerated the redox cycle, promoting water activation.

Conclusions:

Atomically precise doping via interfacial diffusion is an effective strategy for enhancing OER catalysts.
Ordered Cr doping in Fe2O3 improves catalytic activity and stability by modifying electronic structure and reaction mechanisms.
This scalable doping approach is extendable to other transition metal oxides, highlighting the importance of precise surface engineering.