Ni-In Synergy in CO2 Hydrogenation to Methanol

Indium oxide (In2O3) is a promising catalyst for selective CH3OH synthesis from CO2 but displays insufficient activity at low reaction temperatures. By screening a range of promoters (Co, Ni, Cu, and Pd) in combination with In2O3 using flame spray pyrolysis (FSP) synthesis, Ni is identified as the most suitable first-row transition-metal promoter with similar performance as Pd-In2O3. NiO-In2O3 was optimized by varying the Ni/In ratio using FSP. The resulting catalysts including In2O3 and NiO end members have similar high specific surface areas and morphology. The main products of CO2 hydrogenation are CH3OH and CO with CH4 being only observed at high NiO loading (>= 75 wt %). The highest CH3OH rate (similar to 0.25 g(MeOH)/(g(cat) h), 250 degrees C, and 30 bar) is obtained for a NiO loading of 6 wt %. Characterization of the as-prepared catalysts reveals a strong interaction between Ni cations and In2O3 at low NiO loading (<= 6 wt %). H-2-TPR points to a higher surface density of oxygen vacancy (O-v) due to Ni substitution. X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, and electron paramagnetic resonance analysis of the used catalysts suggest that Ni cations can be reduced to Ni as single atoms and very small clusters during CO2 hydrogenation. Supportive density functional theory calculations indicate that Ni promotion of CH3OH synthesis from CO2 is mainly due to low-barrier H-2 dissociation on the reduced Ni surface species, facilitating hydrogenation of adsorbed CO(2 )on O-v.

Automated summary

This study investigates the promotion of Ni on In2O3 and optimization of NiO-In2O3 catalyst for CO2 hydrogenation. Ni facilitates the synthesis of CH3OH by reducing the dissociation barrier of H2, leading to reduced activation energy for CO2 hydrogenation. The interaction between Ni cations and In2O3 at low NiO loading enhances the surface density of oxygen vacancy, promoting the hydrogenation of adsorbed CO2 on O-v.