Exsolution has emerged
as an outstanding route for producing
oxide-supported
metal nanoparticles. For ABO3-perovskite
oxides, various late transition-metal cations can be substituted into
the lattice under oxidizing conditions and exsolved as metal nanoparticles
after reduction. A consistent and comprehensive description of the
point-defect thermodynamics and kinetics of this phenomenon is lacking,
however. Herein, supported by hybrid density-functional-theory calculations,
we propose a single model that explains diverse experimental observations,
such as why substituent transition-metal cations (but not host cations)
exsolve from perovskite oxides upon reduction; why different substituent
transition-metal cations exsolve under different conditions; why the
metal nanoparticles are embedded in the surface; why exsolution occurs
surprisingly rapidly at relatively low temperatures; and why the reincorporation
of exsolved species involves far longer times and much higher temperatures.
Our model’s foundation is that the substituent transition-metal
cations are reduced to neutral species within the
perovskite lattice as the Fermi level is shifted upward within the
bandgap upon sample reduction. The calculations also indicate unconventional
influences of oxygen vacancies and A-site vacancies.
Our model thus provides a fundamental basis for improving existing,
and creating new, exsolution-generated catalysts.