Temperature-programmed surface reaction (TPSR) of CH4 synthesis by PdxNi100−x nanoparticles

A series of PdxNi100−x nanoparticles were prepared by the co-precipitation method and analyzed using a temperature-programmed surface reaction (TPSR) of their methanation reactions. ESCA measurement suggested that the as-prepared Pd–Ni alloys had Pd-core/Ni-shell structure. Surface Pd segregation occurred during H2 reduction and resulted in a surface composition close to the nominal value. The TPSR experiments were performed by pre-adsorption of CO with H2 to form methane. The peak temperature of methanation increased as Pd content increased, indicating that a methanation reaction is favored on Ni and Ni-rich alloy nanoparticles. For physical mixtures of Pd and Ni nanoparticles, methanation behaviors is similar to those of alloy nanoparticles; but the methanation temperatures of physical mixtures are always higher than those of alloy nanoparticles. This may be due to the formation of a Pd-enriched alloy surface layer during reduction in H2 at 400 °C, or because the CO molecules adsorbed on the Pd sites spill over onto the Ni sites for methanation. Using TPSR technique and measuring methanation temperature, the top-most surface of such bimetallic nanoparticles can be probed.