Role of alkali metal in a highly active Pd/alkali/Fe2O3 catalyst for water gas shift reaction

• Pd/K/Fe2O3 catalyst shows high activity for water gas shift (WGS) reaction.
• The K/Pd molar ratio on the catalyst has a remarkable effect on WGS activity.
• The addition of alkali metals (Na, K and Cs) drastically enhanced WGS activity.
• WGS on Pd/K/Fe2O3 catalyst proceeded via redox using lattice oxygen.
• The synergetic effect of Pd and K brought high redox ability and structural stability.

Pd/K/Fe2O3 catalyst shows high activity for water gas shift (WGS) reaction. The K/Pd molar ratio on the catalyst has a remarkable effect on WGS activity. The optimum K/Pd molar ratio is about 2. In this study, to clarify the role of alkali metal (potassium), WGS activities of Pd/alkali/Fe2O3 (alkali: Li, Na, K or Cs) catalysts were investigated and the reaction mechanism over the Pd/K/Fe2O3 catalyst was examined with transient response analyses using a concentration jump method with a quadrupole mass spectrometer (Q-Mass). Results showed that the addition of alkali metals such as Na, K and Cs drastically enhanced WGS activity, except for Li-loaded catalyst. WGS reaction over the highly active Pd/K/Fe2O3 catalyst was found to proceed via reduction–oxidation (redox) using lattice oxygen. Thereby, CO was oxidized by lattice oxygen in Fe2O3. The consumed lattice oxygen was regenerated by H2O. The results of CO-TPR revealed that oxidation of CO by lattice oxygen were enhanced by K, Cs or Na addition. H2-TPR results showed that reduction of Fe2O3 was suppressed by an increment of loading amount of potassium, which brought a high stability for the WGS reaction. The result of CO/H2O-TPR showed that steam can promote the regeneration of consumed lattice oxygen. The synergistic effect brought a high release ability of lattice oxygen for CO oxidation and also high regenerating ability of consumed lattice oxygen by H2O to produce hydrogen, to the Pd/K/Fe2O3 catalyst. It enabled high catalytic performance of the Pd/K/Fe2O3 catalyst with K/Pd molar ratio of 2.

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