Gas-Permeable Iron-Doped Ceria Shell on Rh Nanoparticles with High Activity and Durability

Strong metal-support interaction (SMSI) is a promising strategy to control the structure of the supported metal catalyst. Especially, encapsulating metal nanoparticles through SMSI can enhance resistance against sintering but typically blocks the access of reactants onto the metal surface. Here, we report gas-permeable shells formed on Rh nanoparticles with enhanced activity and durability for the surface reaction. First, Fe species were doped into ceria, enhancing the transfer of surface oxygen species. When Rh was deposited onto the Fe-doped ceria (FC) and reduced, a shell was formed on Rh nanoparticles. Diffuse reflectance infrared Fourier-transform spectroscopy (DRIFTS) results show that the shell is formed upon reduction and removed upon oxidation reversibly. CO adsorption on the Rh surface through the shell was confirmed by cryo-DRIFTS. The reverse water gas shift (RWGS) reaction (CO₂ + H₂ → CO + H₂O) occurred on the encapsulated Rh nanoparticles effectively with selective CO formation, whereas bare Rh nanoparticles deposited on ceria produced methane as well. The CO adsorption became much weaker on the encapsulated Rh nanoparticles, and H₂-spillover occurred more on the FC, resulting in high activity for RWGS. The exposed Rh nanoparticles deposited on ceria presented degradation at 400 °C after 150 h of RWGS, whereas the encapsulated Rh nanoparticles showed no degradation with superior durability. Enhancing surface oxygen transfer can be an efficient way to form gas-permeable overlayers on metal nanoparticles with high activity and durability.