TY - JOUR

T1 - Cu-doped perovskite-type oxides

T2 - A structural deep dive and examination of their exsolution behaviour influenced by B-site doping

AU - Berger, Tobias

AU - Drexler, Hedda

AU - Ruh, Thomas

AU - Lindenthal, Lorenz

AU - Schrenk, Florian

AU - Bock, Johannes

AU - Rameshan, Raffael

AU - Föttinger, Karin

AU - Irrgeher, Johanna

AU - Rameshan, Christoph

N1 - Publisher Copyright: © 2024 The Authors

PY - 2024/5/8

Y1 - 2024/5/8

N2 - Perovskite-type oxides have gained significant attention in the scientific community due to their unique properties and potential applications. Their ability to exsolve reducible B-site cations (e.g. Co, Ni, Cu) combined with their flexibility regarding A-site and B-site composition allows for the tailoring of novel catalytic materials. This study focuses on B-site doped perovskite-type oxides with a general formula of Nd0.6Ca0.4Fe1-xCuxO3 and Pr0.6Ca0.4Fe1-xCuxO3 (x = 0.0, 0.03, 0.05, 0.10) for potential use as a catalyst for Methanol Steam Reforming via the exsolution of catalytically active Cu nanoparticles. The atomic and electronic structure, morphology, and exsolution behaviour of these materials were investigated experimentally and with density functional theory, with a specific emphasis on the impact of B-site doping with varying Cu content as well as choice of A-site element. Both parameters influenced the crystal structure, surface area, and morphology of the materials. The exsolution behaviour of the materials was observed using in-situ XRD at DESY beamline P02.1 at PETRA III, with nanoparticles forming after reductive treatments on the host oxide surface. The quantity and size of the nanoparticles were found to be adjustable by selecting the A-site ion, doping content at the B-site, and the choice of reducing agent. Materials with higher Cu content on the B-site exhibited facilitated exsolution. Furthermore, exsolution was promoted with Nd as the A-site element compared to Pr. In conclusion, the controlled exsolution of Cu nanoparticles introduces Cu-doped perovskite-type oxides as promising candidates for developing novel catalytic systems. The findings underscore the importance of fine-tuning the oxide composition (A-site element, amount of B-site dopant) to achieve tailored exsolution of nanoparticles, which is crucial for rational material design. By leveraging this knowledge, catalysts with finely tuned properties can be created for specific applications and operational environments.

AB - Perovskite-type oxides have gained significant attention in the scientific community due to their unique properties and potential applications. Their ability to exsolve reducible B-site cations (e.g. Co, Ni, Cu) combined with their flexibility regarding A-site and B-site composition allows for the tailoring of novel catalytic materials. This study focuses on B-site doped perovskite-type oxides with a general formula of Nd0.6Ca0.4Fe1-xCuxO3 and Pr0.6Ca0.4Fe1-xCuxO3 (x = 0.0, 0.03, 0.05, 0.10) for potential use as a catalyst for Methanol Steam Reforming via the exsolution of catalytically active Cu nanoparticles. The atomic and electronic structure, morphology, and exsolution behaviour of these materials were investigated experimentally and with density functional theory, with a specific emphasis on the impact of B-site doping with varying Cu content as well as choice of A-site element. Both parameters influenced the crystal structure, surface area, and morphology of the materials. The exsolution behaviour of the materials was observed using in-situ XRD at DESY beamline P02.1 at PETRA III, with nanoparticles forming after reductive treatments on the host oxide surface. The quantity and size of the nanoparticles were found to be adjustable by selecting the A-site ion, doping content at the B-site, and the choice of reducing agent. Materials with higher Cu content on the B-site exhibited facilitated exsolution. Furthermore, exsolution was promoted with Nd as the A-site element compared to Pr. In conclusion, the controlled exsolution of Cu nanoparticles introduces Cu-doped perovskite-type oxides as promising candidates for developing novel catalytic systems. The findings underscore the importance of fine-tuning the oxide composition (A-site element, amount of B-site dopant) to achieve tailored exsolution of nanoparticles, which is crucial for rational material design. By leveraging this knowledge, catalysts with finely tuned properties can be created for specific applications and operational environments.

KW - DFT

KW - Exsolution

KW - In-situ XRD

KW - Perovskite

KW - Synchrotron

UR - http://www.scopus.com/inward/record.url?scp=85192961212&partnerID=8YFLogxK

U2 - 10.1016/j.cattod.2024.114787

DO - 10.1016/j.cattod.2024.114787

M3 - Review article

AN - SCOPUS:85192961212

VL - 437.2024

JO - Catalysis today

JF - Catalysis today

SN - 0920-5861

IS - 1 July

M1 - 114787

ER -