Decoding the Promotional Effect of Iron in Bimetallic Pt-Fe-Nanoparticles for the Low Temperature Reverse Water-Gas Shift Reaction

The reverse water-gas shift reaction (RWGS) is a key technology of the chemical industry, central to the emerging circular carbon economy. Pt-based catalysts have previously been shown to effectively promote the RWGS, especially when modified by promoter elements. However, their active state is still poorly understood. Here, we show that the intimate incorporation of an iron promoter into metal-oxide supported Pt-based nanoparticles can increase their activity and selectivity for the low temperature reverse water-gas shift (LT-RWGS) substantially and drastically outperform unpromoted Pt-based materials. Specifically, the study explores the promotional effect of iron in Pt-Fe bimetallic systems supported on silica (PtxFey@SiO2) prepared by surface organometallic chemistry (SOMC). The most active catalyst (Pt1Fe1@SiO2) shows high selectivity (>99% CO) towards CO at a formation rate of 0.192 molCO h-1 gcat-1, which is significantly higher than that of monometallic Pt@SiO2 (96% sel. and 0.022 molCO h-1 gcat-1). In-situ diffuse reflectance FT-IR spectroscopy (DRIFTS) and X-ray absorption spectroscopy (XAS) indicate a dy-namic process at the catalyst surface under reaction conditions, revealing distinct reaction pathways for the monometallic Pt@SiO2 and bime-tallic PtxFey@SiO2 systems.