Glycerol dry reforming on Ni–Fe bimetallic catalysts exsolved from LaNi _{1- <i>X</i>} Fe <i> _X </i> O ₃ perovskites: catalytic activity and resistance to carbon deposition

Abstract Glycerol dry reforming (GDR) is a promising pathway for sustainable hydrogen production; however, its implementation is constrained by thermodynamic limitations, which promote carbon deposition and thermal agglomeration, thereby compromising the performance of conventional Ni-based reforming catalysts. Doping with noble metals and redox exsolution has been proposed to improve the catalytic activity of Ni-based catalysts. However, Ni-based alloy exsolved catalysts remain underexplored for GDR. For the first time, this study investigates the co-exsolution of Ni–Fe nanoparticles from a LaNi 1- X Fe X O 3 platform. The catalysts were characterized by specific surface area ( S BET ), scanning electron microscopy, x-ray diffraction, x-ray photoelectron spectroscopy, temperature programmed reduction (H 2 -TPR) and thermogravimetric analysis. Here, we show that the Fe doping levels significantly influence catalytic performance by inducing surface and structural modifications under reaction conditions, thereby enhancing stability and coking resistance. Our results suggest that Fe doping apparently avoids the excessive oxidation of Ni. H 2 production predominantly proceeds via glycerol decomposition, while the catalyst with 50% Fe doping exhibited the highest performance. These findings offer valuable insights for optimizing the performance of exsolved catalysts in GDR and related processes.