First-Principles-Based Study of the Decomposition of Phenol and Hydroquinone on Pt(111) Combined with Quantitative Information from XPS Spectra to Address the Impact of Coverage and Number of Hydroxyl Functional Groups

Hensley AJ, Cardwell N, Jirausch C, Papp C, Denecke R, McEwen JS (2025)

Publication Type: Journal article

Publication year: 2025

Journal

Journal of Physical Chemistry C American Chemical Society

Book Volume: 129

Pages Range: 21938-21954

Journal Issue: 50

DOI: 10.1021/acs.jpcc.5c05126

Abstract

A combined first-principles-based and experimental X-ray photoelectron spectroscopy approach was used to investigate the thermal decomposition of two model biofuel compounds, phenol and hydroquinone, on Pt(111) at both low and high coverages. The DFT-based approach yields adsorption geometries and energies, activation barriers and core-level binding energy shifts for C 1s and O 1s. Increasing the coverage in the theoretical model leads to slight shifts in core-level binding energies─toward higher values for C 1s and lower values for O 1s. It also alters the energy profiles of the decomposition reaction pathway, resulting in weaker adsorption energies and changes in both reaction and activation barriers. At low temperatures, we observe a multilayer for phenol and hydroquinone upon adsorption, with desorption occurring at 200 and 270 K, respectively. Following desorption of the multilayer, decomposition proceeds via initial O–H bond scission, followed by two parallel pathways involving either C–H or C–C bond scission, whereby in the case of phenol C–H bond scission occurs first. We further provide characteristic core level binding energies by theoretical calculations that are subsequently used in experimental analyses, establishing a reference database for key spectra of phenolic functionalities applicable to a range of catalytic reactions.

Authors with CRIS profile

Christian Papp Lehrstuhl für Physikalische Chemie II

Involved external institutions

Stevens Institute of Technology (SIT) US United States (USA) (US) Voiland College of Engineering and Architecture US United States (USA) (US) Universität Leipzig DE Germany (DE)

How to cite

APA:

Hensley, A.J., Cardwell, N., Jirausch, C., Papp, C., Denecke, R., & McEwen, J.S. (2025). First-Principles-Based Study of the Decomposition of Phenol and Hydroquinone on Pt(111) Combined with Quantitative Information from XPS Spectra to Address the Impact of Coverage and Number of Hydroxyl Functional Groups. Journal of Physical Chemistry C, 129(50), 21938-21954. https://doi.org/10.1021/acs.jpcc.5c05126

MLA:

Hensley, Alyssa J.R., et al. "First-Principles-Based Study of the Decomposition of Phenol and Hydroquinone on Pt(111) Combined with Quantitative Information from XPS Spectra to Address the Impact of Coverage and Number of Hydroxyl Functional Groups." Journal of Physical Chemistry C 129.50 (2025): 21938-21954.

BibTeX: Download