Size-Dependent Strong Metal–Support Interactions of Rutile TiO2-Supported Ni Catalysts for Hydrodeoxygenation of m-Cresol

Abstract

A series of rutile TiO2-supported Ni catalysts with varying Ni sizes were prepared and reduced at 650 °C to explore the effect of Ni size on the strong metal–support interactions (SMSI) and its consequences on the hydrodeoxygenation (HDO) of m-cresol at 350 °C and atmospheric pressure. When the Ni size increases from 4 to 29.1 nm, the SMSI becomes stronger, e.g., the thickness of the TiOx overlayer and the coverage extent of TiOx on the Ni particle surface increase. Direct deoxygenation to toluene is the dominant pathway on Ni/TiO2 catalysts with varying Ni loadings, with almost no CH4 being formed. These results indicate that the TiOx overlayer significantly alters the property of Ni. That is, the C-C hydrogenolysis activity on bare Ni is completely inhibited due to SMSI, while the deoxygenation activity is improved at the Ni-TiOx interfacial perimeter sites. Meanwhile, the turnover frequency of HDO on small Ni particles of 4 nm is > 2 times higher than that on large Ni particles of 29.1 nm, indicating that the small Ni particle with moderate SMSI appears to be optimal for the direct deoxygenation of m-cresol to toluene. The results suggest HDO activity may be enhanced by tuning the metal particle size and SMSI degree.