H2 Oxidation over Supported Au Nanoparticle Catalysts: Evidence for Heterolytic H2 Activation at the Metal-Support Interface.

Water adsorbed at the metal-support interface (MSI) plays an important role in multiple reactions. Due to its importance in CO preferential oxidation (PrOx), we examined H2 oxidation kinetics in the presence of water over Au/TiO2 and Au/Al2O3 catalysts, reaching the following mechanistic conclusions: (i) O2 activation follows a similar mechanism to that proposed in CO oxidation catalysis; (ii) weakly adsorbed H2O is a strong reaction inhibitor; (iii) fast H2 activation occurs at the MSI, and (iv) H2 activation kinetics are inconsistent with traditional dissociative H2 chemisorption on metals. Density functional theory (DFT) calculations using a supported Au nanorod model suggest H2 activation proceeds through a heterolytic dissociation mechanism, resulting in a formal hydride residing on the Au and a proton bound to a surface TiOH group. This potential mechanism was supported by infrared spectroscopy experiments during H2 adsorption on a deuterated Au/TiO2 surface, which showed rapid H-D scrambling with surface hydroxyl groups. DFT calculations suggest that the reaction proceeds largely through proton-mediated pathways and that typical Brønsted-Evans Polanyi behavior is broken by introducing weak acid/base sites at the MSI. The kinetics data were successfully reinterpreted in the context of the heterolytic H2 activation mechanism, tying together the experimental and computational evidence and rationalizing the observed inhibition by physiorbed water on the support as blocking the MSI sites required for heterolytic H2 activation. In addition to providing evidence for this unusual H2 activation mechanism, these results offer additional insight into why water dramatically improves CO PrOx catalysis over Au.