Ion Beam as an External and Dynamic Metal Reservoir to Induce Nanoparticle Exsolution in Oxides

Abstract

A central theme in solid oxide fuel cells (SOFC) and electrolyzers (SOEC) is to design stable and catalytically active solid/gas interfaces toward desired reactions. A recent advance in this regard is to synthesize nanoparticles decorated electrodes in a process termed “exsolution”. Exsolution generates stable and catalytically active metal nanoparticles via phase precipitation out of a host oxide. Unlike traditional nanoparticle infiltration techniques, the nanoparticle catalysts from exsolution are anchored in the parent oxide. This strong metal-oxide interaction makes the exsolved nanoparticles more resistant against particle agglomeration as compared to the infiltrated ones. In addition, the exsolved particles also open up the possibility of regeneration of catalysts. To date, the concept of exsolution has been successfully applied to a number of applications including SOFC/SOEC, ceramic membrane reactors, chemical looping combustion, and (electro)catalysis.As the exsolution process starts with a solid-solution that contains the to-be-exsolved transition metal ions, this method is often limited by the intrinsic solubility limit of the host oxide. Here, we propose that ion beam irradiation to be a unique tool to promote exsolution as it can introduce defects and dopants into the host oxides and at concentrations higher than thermodynamic limits. Moreover, due to the surface sputtering effect, ion beam irradiation can modulate the surface morphology, creating novel nanostructures.To demonstrate this approach, we chose thin-film perovskite SrTi0.65Fe0.35O3 (STF) and fluorite Ce0.5Zr0.5O2 (CZO) as model systems, both of which are promising materials in SOFC and SOEC. We modulated metal exsolution in both materials with in-situ 10-150 keV Ni irradiation at 800 °C in vacuum. Ni irradiation on STF controllably changed the exsolved particle composition from unitary Fe to bimetallic Fe-Ni. Moreover, it also reduced the particle size down to sub-2 nm, which outperforms other tuning methods thus far in the literature. As a result, the irradiation-modified STF demonstrated superior catalytic activity toward room-temperature oxygen evolution reactions (OER) than the conventional thermally exsolved STF. Regarding CZO, Ni irradiation also decorated the surface with well-dispersed nanoparticles, leading to enhanced high-temperature H2O splitting kinetics. The effective size and composition control over exsolution highlights the utility of metal ion beams in promoting and tailoring exsolved nanocatalysts for a broad range of applications in clean energy and fuel conversion. Figure 1