Strong metal–support interactions between palladium nanoclusters and hematite toward enhanced acetylene dicarbonylation at low temperature. (3rd January 2020) - Wei, Xuemei
Abstract : A four-fold increase in palladium-based acetylene dicarbonylation activity was obtained at low temperature due to the strong metal–support interaction between Pd and the earth-abundant α-Fe2 O3 material. Abstract : Dicarbonylation is an atom-efficient and straightforward method for the direct incorporation of two carbonyl functionalities into organic molecules in a wide range of homogeneous catalytic processes. Preparation of analogously performing heterogeneous supported catalysts is of great importance. Here, a four-fold increase in the acetylene dicarbonylation activity of a palladium-based heterogeneous catalyst was obtained. The strong metal–support interaction (SMSI) between Pd nanoclusters and α-Fe2 O3 support was responsible for enhancing the low temperature catalytic activity, which was confirmed by X-ray photoelectron spectroscopy (XPS) and H2 temperature program reduction (H2 -TPR) analyses. The modified electronic properties of high-valent Pd δ + clusters could lower the CO chemisorption barrier energy. In situ diffuse reflectance infrared Fourier transform spectroscopy ( in situ DRIFTS) was performed to confirm that the interface provided more CO chemisorption and (co-)activation sites. The acetylene dicarbonylation over Pd/α-Fe2 O3 proceeds with a low apparent activation energy (36.26 kJ mol −1 ), which accounted for the high activity toward acetylene dicarbonylation at low temperature. Our study unravels that using a transition metal oxide as a support is a promising strategy for enhancing the efficiency of dicarbonylation and using earth-abundant catalytic materials can reduce the catalyst cost.