Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary CH Bonds

Zhang, Feng; Pan, Li; Choi, Juhee; Mehar, Vikram; Diulus, John T.; Asthagiri, Aravind; Weaver, Jason F.

doi:10.1002/ange.201505237

Propane σ‐Complexes on PdO(101): Spectroscopic Evidence of the Selective Coordination and Activation of Primary CH Bonds (in German)

Journal Article · Wed Sep 30 00:00:00 EDT 2015 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201505237· OSTI ID:1785750

Zhang, Feng; Pan, Li; Choi, Juhee; Mehar, Vikram; Diulus, John T.; Asthagiri, Aravind; Weaver, Jason F.

Abstract

Achieving selective CH bond cleavage is critical for developing catalytic processes that transform small alkanes to value‐added products. The present study clarifies the molecular‐level origin for an exceptionally strong preference for propane to dissociate on the crystalline PdO(101) surface via primary CH bond cleavage. Using reflection absorption infrared spectroscopy (RAIRS) and density functional theory (DFT) calculations, we show that adsorbed propane σ‐complexes preferentially adopt geometries on PdO(101) in which only primary CH bonds datively interact with the surface Pd atoms at low propane coverages and are thus activated under typical catalytic reaction conditions. We show that a propane molecule achieves maximum stability on PdO(101) by adopting a bidentate geometry in which a HPd dative bond forms at each CH ₃ group. These results demonstrate that structural registry between the molecule and surface can strongly influence the selectivity of a metal oxide surface in activating alkane CH bonds.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FG02-03ER15478

OSTI ID:: 1785750

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 47 Vol. 127; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: German

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