Crystal-Plane-Dependent Guaiacol Hydrodeoxygenation Performance of Au on Anatase TiO2

TiO2-supported catalysts have been widely used for a range of both liquid-phase and gas-phase hydrogenation reactions. However, little is known about the effect of their different crystalline surfaces on their activity during the hydrodeoxygenation process. In this work, Au supported on anatase TiO2, mainly exposing 101 or 001 facets, was investigated for the hydrodeoxygenation (HDO) of guaiacol. At 300 °C, the strong interaction between the Au and TiO2-101 surface resulted in the facile reduction of the TiO2-101 surface with concomitant formation of oxygen vacancies, as shown by the H2-TPR and H2-TPD profiles. Meanwhile, the formation of Auδ−, as determined by CO-DRIFT spectra and in situ XPS, was found to promote the demethylation of guaiacol producing methane. However, this strong interaction was absent on the Au/TiO2-001 catalyst since TiO2-001 was relatively difficult to be reduced compared with TiO2-101. The Au on TiO2-001 just served as the active site for the dissociation of hydrogen without the formation of Auδ−. The hydrogen atoms spilled over to the surface of TiO2-001 to form a small amount of oxygen vacancies, which resulted in lower activity than that over Au/TiO2-101. The catalytic activity of the Au/TiO2 catalyst for hydrodeoxygenation will be controlled by tuning the crystal plane of the TiO2 support.