The Promoting Role of Ni on In2O3 for CO2 Hydrogenation to Methanol.

Ni-promoted indium oxide (In2O3) is a promising catalyst for the selective hydrogenation of CO2 to CH3OH, but the nature of the active Ni sites remains unknown. By employing density functional theory and microkinetic modeling, we elucidate the promoting role of Ni in In2O3-catalyzed CO2 hydrogenation. Three representative models have been investigated: (i) a single Ni atom doped in the In2O3(111) surface, (ii) a Ni atom adsorbed on In2O3(111), and (iii) a small cluster of eight Ni atoms adsorbed on In2O3(111). Genetic algorithms (GAs) are used to identify the optimum structure of the Ni8 clusters on the In2O3 surface. Compared to the pristine In2O3(111) surface, the Ni8-cluster model offers a lower overall barrier to oxygen vacancy formation, whereas, on both single-atom models, higher overall barriers are found. Microkinetic simulations reveal that only the supported Ni8 cluster can lead to high methanol selectivity, whereas single Ni atoms either doped in or adsorbed on the In2O3 surface mainly catalyze CO formation. Hydride species obtained by facile H2 dissociation on the Ni8 cluster are involved in the hydrogenation of adsorbed CO2 to formate intermediates and methanol. At higher temperatures, the decreasing hydride coverage shifts the selectivity to CO. On the Ni8-cluster model, the formation of methane is inhibited by high barriers associated with either direct or H-assisted CO activation. A comparison with a smaller Ni6 cluster also obtained with GAs exhibits similar barriers for key rate-limiting steps for the formation of CO, CH4, and CH3OH. Further microkinetic simulations show that this model also has appreciable selectivity to methanol at low temperatures. The formation of CO over single Ni atoms either doped in or adsorbed on the In2O3 surface takes place via a redox pathway involving the formation of oxygen vacancies and direct CO2 dissociation.

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 (∼0.25 gMeOH/(gcat h), 250 °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 %). H2-TPR points to a higher surface density of oxygen vacancy (Ov) 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 H2 dissociation on the reduced Ni surface species, facilitating hydrogenation of adsorbed CO2 on Ov.