Formation of Benzonitrile from the Reaction of Styrene with Nitrogen on the Pt(111) Surface

Abstract

Temperature-programmed reaction spectroscopy (TPRS) and reflection absorption infrared spectroscopy (RAIRS) were used to investigate the adsorption and reaction chemistry of styrene with clean and nitrogen covered Pt(111). The RAIR spectra indicate that the adsorption geometry of styrene is altered by both coverage effects and by the presence of nitrogen atoms on the surface. For an annealed monolayer of styrene on the clean Pt(111) surface, the most intense peaks correspond to out-of-plane bending vibrations indicating that the molecular plane is oriented parallel to the surface. For monolayer styrene on the nitrogen-precovered surface and for an unannealed monolayer of styrene, the in-plane and out-of-plane vibrations have comparable intensities indicating a more random orientation of the molecular plane. Upon heating, styrene reacts with the coadsorbed nitrogen atoms to form benzonitrile, which desorbs at 380 K. When benzonitrile is directly adsorbed on the Pt(111) surface, TPRS and RAIRS reveal that it desorbs at 350 K, indicating that its desorption at 380 K when formed from the reaction of styrene with nitrogen is reaction limited.

Adsorption of Acetonitrile, Benzene, and Benzonitrile on Pt(111): Single Crystal Adsorption Calorimetry and Density Functional Theory

“…Near-edge X-ray absorption spectroscopy (NEXAFS) shows that benzonitrile is lying flat and parallel to the surface upon adsorption . Another study investigating the reaction of styrene and nitrogen to form BN by Yin et al is available . In their TPD and infrared reflection absorption spectroscopy (IRRAS) experiments a rather weakly bound adsorption state desorbing at 87 K is found.…”

“…52 Another study investigating the reaction of styrene and nitrogen to form BN by Yin et al is available. 53 In their TPD and infrared reflection absorption spectroscopy (IRRAS) experiments a rather weakly bound adsorption state desorbing at 87 K is found. Only weak IRRAS signals are obtained in the C−N region.…”

Capture of Bridging Imido and Azavinylidene Intermediates Engaged in Nitrogen Functionality Changes from Primary Azide to Nitrile on a Copper Surface

“…The N 3 bands disappear after annealing to 210 K (around the N 2 TPD peak temperature), and several different IR bands are observed, suggesting that new species are formed at the expense of the azido functionality. It is known that vibrational spectra for submonolayer coverage of benzonitrile on metal surfaces are relatively featureless (see Figure S2 in the Supporting Information); therefore, interference from the PhCN impurity is not a concern in interpreting the RAIR spectra. Here, eight major vibration bands, 3066, 1527, 1490, 1446, 1336, 1155, 1055, and 1026 cm –1 , are clearly visible, and their intensities vary as a function of temperature.…”