Abstract Atomic‐scale engineering of chromite spinels featuring redox‐active tetrahedral A‐sites and strong Cr–O covalency offers a promising route to superior platinum‐group‐metal‐free oxygen evolution reaction (OER) catalysts. However, comprehensive studies addressing how cation substitution influences surface chemistry and governs OER activity and durability in chromite spinels remain limited. Here, a systematic investigation of the multicationic chromite series NixFeyCr3−x−yO4is presented, identifying composition‐dependent Lewis acidity as a descriptor of superior OER performance. It is further demonstrated that tuning surface acidity directly controls dynamic reconstruction processes and lattice‐oxygen participation during spinel‐based electrocatalysis. Following activation, the optimized Ni0.8Fe0.3Cr1.9O4catalyst delivers a current density of 10 mA cm−2at an overpotential of 235 mV, surpassing RuO2, with excellent long‐term stability. Integrating microscopic and spectroscopic analysis with operando impedance spectroscopy, it shows that activation generates an oxyhydroxide overlayer and reveals a previously unrecognized link between surface Lewis acidity and the growth kinetics and activity of these shells. Density functional theory calculations indicate that Fe incorporation at octahedral sites raises the O 2p‐band center and lowers oxygen‐vacancy formation energy, promoting lattice‐oxygen activation and triggering reconstruction, yielding enhanced OER. This work integrates cation‐driven surface‐acidity modulation, acidity‐governed reconstruction, and OER activity enhancement into a unified predictive framework for designing earth‐abundant spinel‐based catalysts.
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Improving the Activity for Oxygen Evolution Reaction by Tailoring Oxygen Defects in Double Perovskite Oxides
Abstract Developing low‐cost, high‐performance electro‐catalysts is essential for large‐scale application of electrochemical energy devices. In this article, reported are the findings in understanding and controlling oxygen defects in PrBa0.5Sr0.5Co1.5Fe0.5O5+δ(PBSCF) for significantly enhancing the rate of oxygen evolution reaction (OER) are reported. Utilizing surface‐sensitive characterization techniques and first‐principle calculations, it is found that excessive oxygen vacancies promote OH−affiliation and lower the theoretical energy for the formation of O* on the surface, thus greatly facilitating the OER kinetics. On the other hand, however, oxygen vacancies also increase the energy band gap and lower the O 2pband center of PBSCF, which may hinder OER kinetics. Still, careful tuning of these competing effects has resulted in enhanced OER activity for PBSCF with oxygen defects. This work also demonstrates that oxygen defects generated by different techniques have very different characteristics, resulting in different impacts on the activity of electrodes. In particular, PBSCF nanotubes after electrochemical reduction exhibit outstanding OER activity compared with the recently reported perovskite‐based catalysts.
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- Award ID(s):
- 1742828
- PAR ID:
- 10460354
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Functional Materials
- Volume:
- 29
- Issue:
- 34
- ISSN:
- 1616-301X
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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