Reactivity (psychology)

Catalysis

Physical chemistry

Inorganic chemistry

Alternative medicine

Transition metal

Medicine

Density functional theory

Hydrodeoxygenation

Metal

Selectivity

Organic chemistry

Dissociation (chemistry)

Computational chemistry

Chemistry

Pathology

ACS Catalysis

Atomically dispersed late transition-metal cations have attracted significant attention as next-generation heterogenous catalysts. However, relationships between the catalytic behavior of atomically dispersed metal cations and active sites on metal nanoparticles have been difficult to establish, in large part because of the difficulty in characterizing the local atomic structure of these metal species. Here, we use the hydrodeoxygenation (HDO) of m-cresol, a model bio-oil compound, to understand relationships between metal structure and reactivity down to the limit of atomically dispersed active sites. Through a combination of kinetic studies, spectroscopic characterization, and density functional theory calculations, we find that isolated Pt cations supported on TiO2 are significantly less active than small Pt clusters for m-cresol HDO due to their lower activity for hydrogen dissociation and their weaker interaction with m-cresol. We demonstrate that m-cresol HDO reaction kinetics are particularly sensitive...

Relationship between Atomic Scale Structure and Reactivity of Pt Catalysts: Hydrodeoxygenation of <i>m</i>-Cresol over Isolated Pt Cations and Clusters

Relationship between Atomic Scale Structure and Reactivity of Pt Catalysts: Hydrodeoxygenation of m-Cresol over Isolated Pt Cations and Clusters