“Redox” vs “associative formate with –OH group regeneration” WGS reaction mechanism on Pt/CeO2: Effect of platinum particle size

A series of x wt.% Pt/CeO2 catalysts (x = 0.1–2.0) was prepared to investigate for the first time the effect of Pt particle size on important kinetic and mechanistic aspects of the water–gas shift (WGS) reaction, namely the concentration (μmol g−1) and chemical structure of active adsorbed reaction intermediates present in the “carbon-path” and “hydrogen-path” of the WGS reaction at 300 °C. For this, steady-state isotopic transient kinetic analysis (SSITKA) coupled with in situ DRIFTS and mass spectrometry experiments was performed using D2O and 13CO. Α novel transient isotopic experiment performed allowed to quantify the initial transient rates of reactions of adsorbed formate (–COOH) and CO by water, based on which it was concluded that formate should not be considered as an important intermediate. According to the present work, it is proposed that the WGS reaction on ceria-supported Pt at 300 °C occurs largely via the “redox” mechanism, and to a lesser extent via the “associative formate with –OH group regeneration” mechanism. The TOF (s−1) of WGS was found to vary only slightly with Pt particle size (1.3–8.0 nm), while the specific reaction rate based on the length of periphery of Pt–CeO2 interface (μmol cm−1 s−1) was found to significantly increase with increasing platinum loading and mean particle size in the 250–300 °C range.

A novel transient isotopic kinetic technique combined with infrared spectroscopy and mass spectrometry applied to platinum–ceria catalysts in the watergas shift process reveals that a redox mechanism on sites at the Pt–ceria interface dominates the kinetics.Figure optionsDownload high-quality image (146 K)Download as PowerPoint slideResearch highlights
► WGS reaction mechanism on Pt/CeO2 was studied by a novel transient isotopic methodology.
► WGS on Pt/CeO2 at 300 °C largely follows the “redox” mechanism.
► TOFCO of WGS is essentially independent of Pt particle size (1.3–8.0 nm).
► RCO per length of periphery of Pt–ceria interface increases linearly with dPt (nm).
► The “C-path” and “H-path” of WGS consist of small pools of active intermediates.