Lattice Oxygen Exchange Pathways in Nickel–Iron Metal–Organic Framework-Based Oxygen Evolution Electrocatalysts

Zheng DJ, McCormack K, Peng J, Garcia-Diez R, Kataev EY, Schwarz F, Nehzati S, Thyr J, Quevedo-Garzón W, Howchen B, Bär M, Román-Leshkov Y, Shao-Horn Y, Görlin M (2026)

Publication Type: Journal article

Publication year: 2026

Journal

ACS Applied Materials and Interfaces American Chemical Society

Book Volume: 18

Pages Range: 1062-1076

Journal Issue: 1

DOI: 10.1021/acsami.5c12947

Abstract

The oxygen evolution reaction (OER) is crucial for electrofuel production. Metal–hydroxide organic frameworks (MHOFs), a subset of metal–organic frameworks with oxyhydroxide-like layers interconnected via organic linkers, have shown great promise as OER electrocatalysts. This study investigates lattice oxygen exchange in four Ni- and Fe-substituted MHOFs with varying linker stabilities using ¹⁸O isotope labeling combined with operando Raman spectroscopy. A negative correlation between ¹⁸O/¹⁶O lattice oxygen exchange and the OER activity is shown, with Fe ions further suppressing exchange. Operando X-ray spectroscopy (XAS) and UV–vis further reveals that lattice oxygen exchange primarily proceeds on reduced Ni²⁺ sites, with higher linker stability preserving more Ni²⁺ sites and promoting greater lattice oxygen exchange. Supported by density functional theory, the MHOF surface transforms into an OER-active MOxHy-like phase, explaining the negative correlation of lattice exchange with the OER activity. This work also identifies a noninnocent role of the Raman laser in inducing lattice oxygen exchange and offers critical insights into various lattice oxygen exchange pathways in MHOFs, demonstrating their distinction from the catalytic lattice oxygen evolution reaction mechanism.

Authors with CRIS profile

Marcus Bär

Involved external institutions

Helmholtz-Zentrum Berlin für Materialien und Energie (HZB)

Germany (DE) Massachusetts Institute of Technology (MIT)

United States (USA) (US) Diamond Light Source

United Kingdom (GB) Uppsala University

Sweden (SE)

How to cite

APA:

Zheng, D.J., McCormack, K., Peng, J., Garcia-Diez, R., Kataev, E.Y., Schwarz, F.,... Görlin, M. (2026). Lattice Oxygen Exchange Pathways in Nickel–Iron Metal–Organic Framework-Based Oxygen Evolution Electrocatalysts. ACS Applied Materials and Interfaces, 18(1), 1062-1076. https://doi.org/10.1021/acsami.5c12947

MLA:

Zheng, Daniel J., et al. "Lattice Oxygen Exchange Pathways in Nickel–Iron Metal–Organic Framework-Based Oxygen Evolution Electrocatalysts." ACS Applied Materials and Interfaces 18.1 (2026): 1062-1076.

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