Publication date: 10th April 2024
The exsolution process from perovskite oxides has emerged as a promising alternative to achieve highly dispersed and stable metallic nanoparticles by annealing in a hydrogen-containing atmosphere. The great advantage is that exsolved metallic nanoparticles remain anchored to the oxide backbone, preventing sintering [1]. Besides, they improve electrode resistance against carbon deposition, providing a better long-term performance under catalytic tests compared to commercial noble metal-supported catalysts. Additionally, by careful compositional control, it is possible to exsolve metallic alloy nanoparticles in a facile manner, which can trigger unprecedented electrocatalytic properties.
This work focuses on the exsolution of multicomponent metallic Ni-Co-Fe alloys from Sr2FeCo0.2Ni0.2Mn0.1Mo0.5O6-δ perovskite electrodes in which we carried out a microstructural optimization by a careful adjustment of the exsolution treatment conditions. In a previous work, these materials were tested as fuel electrodes for CO2 electrolysis, exhibiting high Faradaic efficiencies and lower polarization resistance when functionalized with ternary alloy exsolved nanoparticles of 10 nm size [2]. Here, we prove that by carefully choosing the exsolution processing conditions (temperature and pressure), it is possible to further adjust the Ni/Co/Fe content of the exsolved nanoparticles. Interestingly, high-pressure exsolution (up to 100 bar), unexplored to date, was found to have a volcano-like trend, for a fixed temperature, on both the exsolution extent and the elemental composition of the nanoparticles, which helped in identifying the optimum pressure. Additionally, high pressure allowed for exsolution at low temperatures, resulting in high nanoparticle dispersions (ca. 7000 particles /μm2) at 300 ºC, which were one order of magnitude higher than at 600 º C.
In summary, this talk will provide useful processing guidelines for further development of multi-component metallic exsolution that could be extended to other perovskite compounds or other oxides (fluorites, spinels) to design more efficient exsolved nanocatalysts.
The project that gave rise to these results received the support of a fellowship from “la Caixa” Foundation (ID 100010434). The fellowship code is LCF/BQ/PI20/11760015. Financial support by the Spanish Ministry of Science and Innovation (CEX2021-001230-S grant funded by MCIN/AEI/10.13039/501100011033) and by Generalitat Valenciana (CIPROM/2022/10) is gratefully acknowledged.
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