Compositional Engineering of NiSe2Precatalysts with IrOxfor Controlled Reconstruction toward Improved Alkaline OER

Rodrigues PS, Priamushko T, de Araújo MA, da Silva GC, Cherevko S, Ticianelli EA (2025)

Publication Type: Journal article

Publication year: 2025

Journal

ACS Applied Materials and Interfaces American Chemical Society

Book Volume: 17

Pages Range: 66554-66568

Journal Issue: 49

DOI: 10.1021/acsami.5c15821

Abstract

The development of efficient and durable oxygen evolution reaction (OER) electrocatalysts remains a challenge in alkaline water electrolysis. Nickel-based materials are well explored as OER precatalysts due to their ability to undergo structural reconstruction into an active nickel oxyhydroxide phase (NiOOH) under anodic conditions. Interestingly, nickel-based chalcogenides, such as nickel selenides, also undergo reconstruction but form a more active surface compared to conventional nickel oxide catalysts, making them appealing for water electrolysis application in alkaline media. Here, we explore a strategy to modulate the chemical composition of nickel selenide by incorporating small amounts of iridium oxide (IrOx) nanoparticles. A series of catalysts with varying Ni:Ir ratio proportions were synthesized, and we demonstrate that IrOxincorporation leads to a reduction in particle size, an increase in surface area, and a modification of surface composition, resulting in a lower OER overpotential. Online electrochemical dissolution measurements reveal that selenium acts as a sacrificial species during the structural reconstruction to form the NiOOH phase, while IrOxsuppresses excessive Se leaching. This behavior is rationalized using hard–soft acid–base theory, where the replacement of soft-base Se22–by hard-base oxygen species is driven by stronger interactions with Ni3+, a hard acid. The optimal composition (IrOx-NiSe2with Ir atomic percentage of 2.4%) achieves a balance between accessible active sites and favorable intermediate adsorption. In contrast, higher IrOxcontent led to performance decline due to site blocking, as predicted by Sabatier’s principle. This work highlights how compositional control and surface reconstruction can guide the design of OER precatalysts, while also deepening the understanding of oxidative transformation mechanisms in nickel chalcogenides, particularly selenides.

Involved external institutions

University of São Paulo / Universidade de São Paulo (USP) BR Brazil (BR) Universidade Federal de Viçosa (UFV) BR Brazil (BR) Forschungszentrum Jülich / Research Centre Jülich (FZJ) DE Germany (DE)

How to cite

APA:

Rodrigues, P.S., Priamushko, T., de Araújo, M.A., da Silva, G.C., Cherevko, S., & Ticianelli, E.A. (2025). Compositional Engineering of NiSe2Precatalysts with IrOxfor Controlled Reconstruction toward Improved Alkaline OER. ACS Applied Materials and Interfaces, 17(49), 66554-66568. https://doi.org/10.1021/acsami.5c15821

MLA:

Rodrigues, Pâmella S., et al. "Compositional Engineering of NiSe2Precatalysts with IrOxfor Controlled Reconstruction toward Improved Alkaline OER." ACS Applied Materials and Interfaces 17.49 (2025): 66554-66568.

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