Characterization of the Platinum-Hydrogen Bond by Surface-Sensitive Time-Resolved Infrared Spectroscopy

The Journal of Physical Chemistry Letters
David PalečekPeter Hamm

Abstract

The vibrational dynamics of Pt-H on a nanostructured platinum surface has been examined by ultrafast infrared spectroscopy. Three bands are observed at 1800, 2000, and 2090 cm-1, which are assigned to Pt-CO in a bridged and linear configuration and Pt-H, respectively. Lifetime analysis revealed a time constant of (0.8 ± 0.1) ps for the Pt-H mode, considerably shorter than that of Pt-CO because of its stronger coupling to the metal substrate. Two-dimensional attenuated total reflection infrared spectroscopy provided additional evidence for the assignment based on the anharmonic shift, which is large in the case of Pt-H (90 cm-1), in agreement with the density functional theory calculations. The absorption cross section of Pt-H is smaller than that of the very strong Pt-CO vibration by only a modest factor of ∼1.5-3. Because Pt-H is transiently involved in catalytic water splitting on Pt, the present spectroscopic characterization paves the way for in-operando kinetic studies of such reactions.

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Citations

Sep 28, 2018·Physical Chemistry Chemical Physics : PCCP·Michiel Van DaeleJolien Dendooven
Mar 1, 2021·The Journal of Chemical Physics·Gökçen Tek, Peter Hamm
May 16, 2020·Inorganic Chemistry·Ricardo Fernández-TeránPeter Hamm
Jul 14, 2020·The Journal of Physical Chemistry Letters·Gökçen Tek, Peter Hamm
Mar 4, 2020·The Journal of Physical Chemistry Letters·Luis RebollarMaureen H Tang
Dec 3, 2021·Journal of the American Chemical Society·Xin DengLandong Li

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