Amination of 1-hexanol on bimetallic AuPd/TiO2 catalysts

AuPd/TiO2 catalysts, synthesized using controlled surface reactions, are active for the gas-phase amination of 1-hexanol using ammonia. The bimetallic active sites for these catalysts have been characterized using CO chemisorption and XAS techniques, and the absence of monometallic Pd species in the AuPd catalysts was confirmed using UV-vis and STEM-EDS analysis. The bimetallic catalysts exhibit synergy between Au and Pd, as the rate of hexanol conversion increases from 8.7 mol ks(-1) (mol total Pd)(-1) over Pd/TiO2 to up to 42 mol ks(-1) (mol total Pd)(-1) over AuPd/TiO2 with a Pd/Au atomic ratio of 0.06. The rate of hexanol conversion is also enhanced with respect to Au content, with a 5-fold increase in the total Au-normalized rate from Au/TiO2 to AuPd0.67/TiO2. As Pd is added to Au/TiO2 in increasing quantities, the production rate of primary species (i.e., hexylamine and hexanenitrile) is preferentially increased. The rate of dihexylamine production increases to a lesser extent, while trihexylamine formation remains relatively constant across Pd loadings. Moreover, trihexylamine, which cannot be formed via the condensation of dihexylamine and hexanol, is shown to be produced via the secondary aldimine, N-hexylidene hexylamine. The AuPd bimetallic catalysts also exhibit reduced hydrogenolysis activity compared to monometallic Pd/TiO2.