Exsolution trends and co-segregation aspects of self-grown catalyst nanoparticles in perovskites

Ohhun Kwon, Sivaprakash Sengodan, Kyeounghak Kim, Gihyeon Kim, Hu Young Jeong, Jeeyoung Shin, Young-Wan Ju, Jeong Woo Han () and Guntae Kim ()
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Ohhun Kwon: Ulsan National Institute of Science and Technology (UNIST)
Sivaprakash Sengodan: Ulsan National Institute of Science and Technology (UNIST)
Kyeounghak Kim: University of Seoul
Gihyeon Kim: Ulsan National Institute of Science and Technology (UNIST)
Hu Young Jeong: UNIST Central Research Facilities and School of Materials Science and Engineering, UNIST
Jeeyoung Shin: Sookmyung Women’s University
Young-Wan Ju: Wonkwang University
Jeong Woo Han: University of Seoul
Guntae Kim: Ulsan National Institute of Science and Technology (UNIST)

Nature Communications, 2017, vol. 8, issue 1, 1-7

Abstract: Abstract In perovskites, exsolution of transition metals has been proposed as a smart catalyst design for energy applications. Although there exist transition metals with superior catalytic activity, they are limited by their ability to exsolve under a reducing environment. When a doping element is present in the perovskite, it is often observed that the surface segregation of the doping element is changed by oxygen vacancies. However, the mechanism of co-segregation of doping element with oxygen vacancies is still an open question. Here we report trends in the exsolution of transition metal (Mn, Co, Ni and Fe) on the PrBaMn2O5+δ layered perovskite oxide related to the co-segregation energy. Transmission electron microscopic observations show that easily reducible cations (Mn, Co and Ni) are exsolved from the perovskite depending on the transition metal-perovskite reducibility. In addition, using density functional calculations we reveal that co-segregation of B-site dopant and oxygen vacancies plays a central role in the exsolution.

Date: 2017
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DOI: 10.1038/ncomms15967

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