In Situ Studies of the Formation of MoP Catalysts and Their Structure under Reaction Conditions for Higher Alcohol Synthesis: The Role of Promoters and Mesoporous Supports

Eduardo Valle, Melis Duyar, Jonathan Snider, Samuel Regli, Magnus Ronning, Alessandro Gallo, Thomas Jaramillo
Year of publication: 
The Journal of Physical Chemistry C

Three formulations of a molybdenum phosphide (MoP) catalyst system were characterized for the higher alcohol synthesis (HAS) reaction using in situ X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD), monitoring the chemical phase evolution during activation and under reaction conditions. The in situ study herein provides important insights into the effect of the support and of K that lead to high performance in HAS for K-promoted MoP supported on carbon, as evidenced by previous studies (ethanol selectivity: 29%; conversion: 5%). During the activation process, XAS shows that the carbon-supported samples reduce and reach a highly crystalline state at a lower temperature than the SBA-15-supported sample, indicating a substantial difference in catalyst activation. After activation, the samples are introduced to relevant reaction conditions resulting in spectra fairly similar to one another. XRD results corroborate the difference in the degree of crystallinity of these samples, in alignment with the XAS, and reveal the formation of crystalline potassium pyrophosphate (K4P2O7) during the activation period of the K-promoted samples. This K4P2O7 phase remains present under reaction conditions. Taken together, these results provide insights into the roles played by the carbon support and K promotion, connecting activity to electronic and crystal structure.

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