The role of ceria in promoting Ni catalysts supported on phosphate‐modified zirconia for the partial oxidation of methane

The catalytic partial oxidation of methane (POM) is aimed at the mitigation of CH4 (a highly potent greenhouse gas) from the environment and the synthesis of syngas with a high H2/CO ratio. Herein, to enhance the POM reaction, Ni‐supported phosphate‐modified‐zirconia were synthesized with promotor “Ce” to achieve high H2/CO ratio (2.4–3.2). The catalysts were characterized by surface area and porosity, X‐ray diffraction, RAMAN, temperature‐programmed experiments (TPR, CO2‐TPD, and TPO), and TEM. Increasing the ceria addition over 10Ni/PO4 + ZrO2 resulted in lower crystallinity, higher dispersion of active sites, and enhanced the surface area of catalyst. The unique and prominent reducibility and basicity of NiO‐species and surface oxide ions, respectively, are particularly notable at 4 wt.% ceria loading. At a reaction temperature of 600°C, the highest concentration of active sites and a unique concentration of moderate strength basic sites can be achieved with 4 wt.% ceria loading over 10Ni/PO4 + ZrO2. This leads to 44% conversion of CH4, 36% yield of H2, 35% yield of CO2, and H2/CO ratio of 3.16 for the POM reaction. The cyclic H2TPR‐O2TPO‐H2TPR experiment confirms the reorganization of the active site towards high temperature under oxidizing gas O2 and reducing gas H2 gas stream during the POM reaction. PO4 + ZrO2 is found excellent support for stabilizing Ni (active sites) derived from NiO and Ni2P2P7. Upon promotional addition of 4 wt% ceria over Ni/PO4 + ZrO2, the concentration of moderate strength basic sites and reducible species have grown which induce the highest activity majorly through an indirect pathway of partial oxidation of methane.