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 PrBaMn₂O_5+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.

Solid oxide fuel cells (SOFC) are the cleanest, most efficient, and cost-effective option for direct conversion to electricity of a wide variety of fuels. While significant progress has been made in anode materials with enhanced tolerance to coking and contaminant poisoning, cathodic polarization still contributes considerably to energy loss, more so at lower operating temperatures. Here we report a synergistic effect of co-doping in a cation-ordered double-perovskite material, PrBa_0.5Sr_0.5Co_2−xFe_xO_5+δ, which has created pore channels that dramatically enhance oxygen ion diffusion and surface oxygen exchange while maintaining excellent compatibility and stability under operating conditions. Test cells based on these cathode materials demonstrate peak power densities ~2.2 W cm⁻² at 600°C, representing an important step toward commercially viable SOFC technologies.

Exsolution has been intensively studied in the fields of energy conversion and storage as a method for the preparation of catalytically active and durable metal nanoparticles. Under typical conditions, however, only a limited number of nanoparticles can be exsolved from the host oxides. Herein, we report the preparation of catalytic nanoparticles by selective exsolution through topotactic ion exchange, where deposited Fe guest cations can be exchanged with Co host cations in PrBaMn_1.7Co_0.3O_5+δ. Interestingly, this phenomenon spontaneously yields the host PrBaMn_1.7Fe_0.3O_5+δ, liberating all the Co cations from the host owing to the favorable incorporation energy of Fe into the lattice of the parent host (ΔE_{incorporation} = −0.41 eV) and the cation exchange energy (ΔE_exchange = −0.34 eV). Remarkably, the increase in the number of exsolved nanoparticles leads to their improved catalytic activity as a solid oxide fuel cell electrode and in the dry reforming of methane.