Copper nanoparticles exsolution from Sr(Ti, Fe)O3 perovskites : material tuning and probing (electro)catalytic applicability

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Essien, Ubong and Patchaiammal Raju, Swathi and Santos, Keyla and Vicente, Rafael and Ekperechukwu, Chinyere Adaora and Garcia Garcia, Francisco and Fernández, Pablo and Neagu, Dragos (2025) Copper nanoparticles exsolution from Sr(Ti, Fe)O3 perovskites : material tuning and probing (electro)catalytic applicability. Nanoscale Advances. ISSN 2516-0230 (https://doi.org/10.1039/D5NA00426H)

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Abstract

Copper (Cu) is a recyclable, abundant, and promising catalyst for energy transition reactions like electrochemical conversion of nitrate (NO₃RR) and CO2 electroreduction. However, conventional Cu-based electrocatalysts struggle with activity, selectivity, and durability, especially under harsh electrochemical conditions. Exsolution—the in-situ generation of metallic nanoparticles on oxide supports in a single step—enables tightly anchored, size-controlled particles, enhancing stability and performance. Incorporating Cu into Sr1-α(Ti, Fe)O₃-γ perovskites, an earth-abundant system with promising ionic-electronic conductivity and adequate oxygen vacancies, overcomes the limitations of traditional Sr(Ti, Fe)O₃ in facilitating nanoparticle exsolution. This work demonstrates controlled Cu nanoparticle exsolution from Sr₀.₉₅Ti₀.₃Fe₀.₇₋ₓCuₓO₃₋ᵧ perovskites at temperatures as low as 400°C, notably milder than conventional exsolution conditions. By systematically varying reduction parameters, we achieve control over nanoparticle size (13-38 nm) and population density (118-650 particles/μm²). Electrochemical characterisation using nitrate reduction as a probe reaction demonstrates how exsolution conditions directly influence surface reactivity, establishing these materials as tuneable platforms for (electro)catalytic applications.

ORCID iDs

Essien, Ubong, Patchaiammal Raju, Swathi, Santos, Keyla, Vicente, Rafael, Ekperechukwu, Chinyere Adaora, Garcia Garcia, Francisco, Fernández, Pablo and Neagu, Dragos ORCID logoORCID: https://orcid.org/0000-0001-7208-1055;
CORE (COnnecting REpositories)