Ethylene Hydrogenation over Pt/TiO<sub>2</sub>: A
Charge-Sensitive Reaction
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Abstract
Controlled
charge transfer between a support and small metal particles
provides unique opportunities to tune the activity of supported metal
catalysts, as first proposed by Schwab [G. M. Schwab et al., <i>Angew. Chem</i>. <b>1959</b>, <i>71</i>, 101β104]. By controlling the thickness
of polycrystalline anatase TiO<sub>2</sub> films, the TiO<sub>2</sub> carrier concentration can be manipulated by an order of magnitude.
When 1 nm Pt particles are deposited on these TiO<sub>2</sub> films,
the variation in the charge transfer between the TiO<sub>2</sub> support
and the Pt particles is found to dramatically increase the ethylene
hydrogenation activity. The sensitivity of ethylene hydrogenation
to charge transfer was anticipated from the large effect of the Pt
charge on the ethylene and ethylidyne adsorption energy, e.g., compared
to CO and H. Our results demonstrate that the controllable Schwab
effect provides a powerful tool to tune catalytic activity. An even
larger effect can be expected for supported sub-nanometer clusters,
and for the selectivity of hydrogenation reactions