Optimizing Pd:Zn molar ratio in PdZn/CeO2 for CO2 hydrogenation to methanol

O.A. Ojelade, S.F. Zaman, M.A. Daous, A.A. Al-Zahrani, A. S.Malik, H. Drissa, G. Shterk, J. Gascon
Applied Catalysis A General, volume 584, 117185, (2019)

Optimizing Pd:Zn molar ratio in PdZn/CeO2 for CO2 hydrogenation to methanol

Keywords

PdZn alloy, CeO2, Citric acid, Chelating agent, Methanol synthesis, DRIFTS

Abstract

​We report the compositional optimization of Pd:Zn/CeO2 catalysts prepared via sol-gel chelatization for the hydrogenation of CO2 under mild reaction conditions. The formation of a PdZn alloy, which is the main active phase for this reaction, was maximized for the catalyst with a Pd to Zn ratio close to 1. For this catalyst, a maximum conversion of 14%, close to thermodynamic equilibrium, and high selectivity to methanol (95%) were achieved at 220 °C, 20 bar, 2400 h−1 GHSV and H2:CO2 stoichiometric ratio of 3:1. The formation of PdZn alloys was achieved by reducing the catalyst precursor at 550 °C under hydrogen flow and confirmed by XRD. XPS study confirmed the presence of Pd°, being maximum for the optimized catalyst composition. At lower temperature, i.e. 180 °C, 1.0PdZn catalyst showed 100% selectivity to methanol with 8% CO2 conversion. RWGS reaction is responsible for the production of CO and its selectivity increases with temperature. In situ DRIFTS suggests that CO2 is activated as adsorbed CO3- species over CeO2. Surface micro-kinetics demonstrates that methanol can be formed either via formaldehyde or formic acid surface intermediates.

Code

DOI: 10.1016/j.apcata.2019.117185

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