Effect of Oxygen Spillover on Stable Ni₃Fe₁ Alloy for High-Performance Dry Reforming of Methane

Ni–Fe alloy catalysts represent promising alternatives for dry reforming of methane (DRM). However, the strong affinity of Fe for oxygen caused progressive Fe segregation on the alloy, leading to a decline in catalytic properties. Herein, we explored an efficient approach to create highly dispersed CeO2 clusters on an Al2O3 support for anchoring the stable Ni3Fe1 alloy using the oxygen spillover effect. CH4 and CO2 conversions as well as the H2/CO ratio were maintained at 73.7%, 81.6%, and 0.87 at 700 °C, respectively, on the optimal Ni3Fe1/1CeO2–16Al2O3. This catalyst featured plentiful oxygen vacancies, strong interactions between the metal and support, and moderate CO2 activation centers. These collective effects enable the oxygen spillover from FeOx toward the proximate vacancies on CeO2. These oxygen species were consumed along with the generation of vacancies by carbon species. The oxygen spillover effect could not only stabilize the alloy structures but alleviate carbon deposition in DRM.