Praseodymia–titania mixed oxide supported gold as efficient water gas shift catalyst: modulated by the mixing ratio of oxides

Abstract

Modulating the active sites for controllable tuning of the catalytic activity has been the goal of much research, however, this remains challenging. The O vacancy is well known as an active site in reducible oxides. To modify the activity of O vacancies in praseodymia, we synthesized a series of praseodymia–titania mixed oxides. Varying the Pr : Ti mole ratio (2 : 1, 1 : 2, 1 : 1, 1 : 4) allows us to control the electronic interactions between Au, Pr and Ti cations and the local chemical environment of the O vacancies. These effects have been studied study by X-ray photoelectron spectroscopy (XPS), CO diffuse reflectance Fourier transform infrared spectroscopy (CO-DRIFTS) and temperature-programmed reduction (CO-TPR, H₂-TPR). The water gas shift reaction (WGSR) was used as a benchmark reaction to test the catalytic performance of different praseodymia–titania supported Au. Among them, Au/Pr₁Ti₂O_x was identified to exhibit the highest activity, with a CO conversion of 75% at 300 °C, which is about 3.7 times that of Au/TiO₂ and Au/PrO_x. The Au/Pr₁Ti₂O_x also exhibited excellent stability, with the conversion after 40 h time-on-stream at 300 °C still being 67%. An optimal ratio of Pr content (Pr : Ti 1 : 2) is necessary for improving the surface oxygen mobility and oxygen exchange capability, a higher Pr content leads to more O vacancies, however with lower activity. This study presents a new route for modulating the active defect sites in mixed oxides which could also be extended to other heterogeneous catalysis systems.