Dry reforming of methane by La2NiO4 perovskite oxide: B-site substitution improving reactivity and stability

Abstract

The development of highly active and stable catalyst materials is the focus of dry reforming of methane (DRM) technology. The effect of substituting transition metals (Mn, Fe, Co, and Cu) on the B-site of La2NiO4 perovskite on the DRM catalytic performance was investigated. Compared to the unsubstituted sample, the Co-substituted sample exhibited reduced reactivity but increased carbon deposition; the Mn-substituted and Fe-substituted samples demonstrated decreased reactivity and carbon deposition; the Cu-substituted sample displayed a slight decrease in CH4 conversion but a substantial increase in carbon resistance. The effect of the substitution ratios of Cu elements was further investigated. The results showed that Cu substitution could maintain the perovskite phase in the samples. In the 5-h DRM reaction, the reactivity of the samples exhibited a decreasing trend as Cu substitution ratios increased. All Cu-containing samples displayed carbon deposition rates lower than 0.4 mg/(g*h), resulting in an over 90-fold improvement in carbon resistance compared to the La2NiO4 sample. Further investigations revealed that the La2Ni0.6Cu0.4O4 sample exhibited stable activity during the 50-h DRM reaction with only a small amount of amorphous carbon in the reacted sample (no obvious carbon nanotubes were observed). Characterization results indicated that the enhanced carbon resistance in Cu-substituted samples was attributed to the Ni-Cu alloy formation, which inhibited CH4 decomposition reactions and reduced solid carbon generation rates. Density functional theory (DFT) calculations showed that the partial substitution of Cu could increase the energy barrier of the CH* dehydrogenation step, which in turn reduced the rate of solid carbon generation.