Hydrogen Production through Bi-Reforming of Methane: Improving Ni Catalyst Performance via an Exsolution Approach

Hydrogen production through the bi-reforming of methane over exsolution-derived Ni catalysts has been studied. Nickel-based catalysts were prepared through the activation of (CeM)1−xNixOy (M = Al, La, Mg) solid solutions in a reducing gaseous medium. Their performance and resistance to coking under the reaction conditions were controlled by regulating their textural, structural, morphological, and redox properties through adjustments to the composition of the oxide matrix (M/Ce = 0–4; x = 0.2–0.8; y = 1.0–2.0). The role of the M-dopant type in the genesis and properties of the catalysts was established. The efficiency of the catalysts in the bi-reforming of methane increased in the following series of M: M-free < La < Al < Mg, correlating with the structural behavior of the nickel active component and the anti-coking properties of the support matrix. The preferred M-type and M/Ce ratio determined the best performance of (CeM)1−xNixOy catalysts. At 800 °C the optimum Ce0.6Mg0.2Ni0.2O1.6 catalyst provided a stable H2 yield of 90% at a high level of CO2 and CH4 conversions (>85%).