Quantum state and surface-site-resolved studies of methane chemisorption by vibrational spectroscopies. Issue 31 (29th July 2020)

• Record Type: Journal Article
• Authors: Gutiérrez-González, Ana; Beck, Rainer D.
• Is Part Of: Physical chemistry chemical physics. Volume 22:Issue 31(2020)
• Page Start: 17448
• Page End: 17459
• Publication Date: 2020-07-29
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/d0cp03134h
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : Infrared spectroscopic methods enable quantum-state-specific and surface-site-selective studies of methane chemisorption on stepped platinum surfaces. Abstract : -The combination of quantum state-specific reactant preparation by infrared laser pumping with surface-site-resolved detection of chemisorbed reaction products by Reflection Absorption Infrared Spectroscopy (RAIRS) enables highly detailed studies of molecule/surface reactivity. In this perspective, we review the methodologies developed for simultaneous quantumstate and surface-site-resolved reactivity measurements and their application towards the chemisorption of methane on stepped and kinked platinum surfaces. We demonstrate that RAIRS allows for surface-site-resolved detection of methane dissociation, which serves to measure surface-site-resolved product uptake curves, sticking probabilities, and dissociation barrier heights. For the dissociation of C–H stretch excited singly deuterated CH3 D on a stepped Pt surface such as Pt(211), RAIRS was used to detect bond selectivity in methane chemisorption and to reveal how the bond-selective dissociation proceeds from the step to the terrace sites with increasing incident kinetic energy of the CH3 D reactant. Extension to site-selective RAIRS detection of methane dissociation to other vicinal surfaces such as Pt(210), Pt(531), and Pt(110)-(2 × 1) is also presented.