Coating Pd/Al2O3 catalysts with FeOx enhances both activity and selectivity in 1,3-butadiene hydrogenation

Abstract

Pd-based catalysts are widely used in hydrogenation reactions, and it is essential to improve the selectivity of these catalysts to give the desired products, especially at high conversions. However, improvements in selectivity have generally been achieved at the expense of catalytic activity. Here, we report that deposition of FeOx onto a Pd/Al2O3 catalyst using atomic layer deposition with precise, near atomic control provides a remarkable improvement in both activity and butene selectivity in the selective hydrogenation of 1,3-butadiene under mild conditions. Diffuse reflectance infrared Fourier transform spectroscopy for CO chemisorption measurements illustrate that FeOx preferentially nucleates on Pd (111) facets and divides the Pd surface atoms into small ensembles. X-ray photoelectron spectroscopy measurements revealed that the Pd became electron deficient after FeOx deposition owing to the strong Pd–FeOx interaction. Our results suggest that a geometric effect, that is, the formation of small Pd ensembles, is the main contributor to the improvement in butene selectivity, whereas the enhancement in hydrogenation activity may be attributed to both electronic effects and the newly generated Pd–FeOx interface.