The sol–gel autocombustion as a route towards highly CO2-selective, active and long-term stable Cu/ZrO2 methanol steam reforming catalysts

Abstract

The adaption of the sol–gel autocombustion method to the Cu/ZrO₂ system opens new pathways for the specific optimisation of the activity, long-term stability and CO₂ selectivity of methanol steam reforming (MSR) catalysts. Calcination of the same post-combustion precursor at 400 °C, 600 °C or 800 °C allows accessing Cu/ZrO₂ interfaces of metallic Cu with either amorphous, tetragonal or monoclinic ZrO₂, influencing the CO₂ selectivity and the MSR activity distinctly different. While the CO₂ selectivity is less affected, the impact of the post-combustion calcination temperature on the Cu and ZrO₂ catalyst morphology is more pronounced. A porous and largely amorphous ZrO₂ structure in the sample, characteristic for sol–gel autocombustion processes, is obtained at 400 °C. This directly translates into superior activity and long-term stability in MSR compared to Cu/tetragonal ZrO₂ and Cu/monoclinic ZrO₂ obtained by calcination at 600 °C and 800 °C. The morphology of the latter Cu/ZrO₂ catalysts consists of much larger, agglomerated and non-porous crystalline particles. Based on aberration-corrected electron microscopy, we attribute the beneficial catalytic properties of the Cu/amorphous ZrO₂ material partially to the enhanced sintering resistance of copper particles provided by the porous support morphology.