Mechanistic studies of CO₂/CH₄ reforming over Ni–La₂O₂/5A

Abstract

The mechanism of CO₂/CH₄ reforming over Ni–La₂O₃/5A has been studied. The results of the CO₂‐pulsing experiments indicated that the amount of CO₂ converted was roughly proportional to the amount of H present on the catalyst, implying that CO₂ activation could be H‐assisted. Pulsing CH₄ onto a H₂‐reduced sample and a similar sample pretreated with CO₂, we found that CH₄ conversion was higher in the latter case. Hence, the idea of oxygen‐assisted CH₄ dissociation is plausible. The fact that the amount of CO produced in 10 pulses of CO₂/CH₄ was larger than that produced in 5 pulses of CO₂ followed by 5 pulses of CH₄, indicated that CO₂ and CH₄ could activate each other synergistically. In the chemical trapping experiments, following the introduction of CD₃I onto a Ni–La₂O₃/5A sample pretreated with CH₄/CO₂, we observed CD₃COOH, CD₃CHO, and CD₃OCD₃. In the in situ DRIFT experiments, IR bands attributable to formate and formyl were observed under working conditions. These results indicate that formate and formyl are intermediates for syngas generation in CO₂/CH₄ reforming, and active O is generated in the breaking of a C–O bond. Based on these results, we suggest that during CO₂/CH₄ reforming, CO₂ activation is H‐promoted and surface O species generated in CO₂ dissociation reacts with CH_x to give CO. A reaction scheme has been proposed.