When Photoelectrons Meet Gas Molecules: Determining the Role of Inelastic Scattering in Ambient Pressure X-ray Photoelectron Spectroscopy

Li, Haoyi; Jana, Asmita; Garcia-Esparza, Angel T.; Li, Xiang; Kaminsky, Corey J.; Hamlyn, Rebecca; Prabhakar, Rajiv Ramanujam; Atwater, Harry A.; Ager, Joel W.; Sokaras, Dimosthenis; Yano, Junko; Crumlin, Ethan J.

doi:10.1021/acscentsci.4c01841

Title: When Photoelectrons Meet Gas Molecules: Determining the Role of Inelastic Scattering in Ambient Pressure X-ray Photoelectron Spectroscopy

Journal Article · 19 December 2024 · ACS Central Science

DOI: https://doi.org/10.1021/acscentsci.4c01841 · OSTI ID:2504527

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^[2]; Li, Xiang ^[2]; Kaminsky, Corey J. ^[1];

^[1]; Prabhakar, Rajiv Ramanujam ^[1];

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^[4]; Sokaras, Dimosthenis ^[5];

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Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
California Institute of Technology (CalTech), Pasadena, CA (United States)
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States); University of California, Berkeley, CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Inelastic photoelectron scattering (IPES) by gas molecules, a critical phenomenon observed in ambient pressure X-ray photoelectron spectroscopy (APXPS), complicates spectral interpretation due to kinetic energy loss in the primary spectrum and the appearance of additional features at higher binding energies. In this study, we systematically investigate IPES in various gas environments using APXPS, providing detailed insights into interactions between photoelectrons emitted from solid surfaces and surrounding gas molecules. Corelevel XPS spectra of Au, Ag, Zn, and Cu metals were recorded over a wide kinetic energy range in the presence of CO₂, N₂, Ar, and H₂ gases, demonstrating the universal nature of IPES across different systems. Additionally, we analyzed spectra of scattering effects induced by gas-phase interactions without metal solids. In two reported CO₂-reduction systems (p-GaN/ Au/Cu and p-Si/TaO_x/Cu), we elucidated that IPES is independent of the composition, structure, or size of the solid materials. Using metal foil platforms, we further developed an analytical model to extract electron excitation cross sections of gas molecules. These findings enhance our understanding of IPES mechanisms and enable the predictions of IPES structures in other solid–gas systems, providing a valuable reference for future APXPS studies and improving the accuracy of spectral analysis in gas-rich catalytic interfaces.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: US Department of Energy; USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22), Scientific User Facilities Division (SC-22.3 ); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-05CH11231; SC0021266

OSTI ID:: 2504527

Journal Information:: ACS Central Science, Journal Name: ACS Central Science Journal Issue: 1 Vol. 11; ISSN 2374-7943

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: When Photoelectrons Meet Gas Molecules: Determining the Role of Inelastic Scattering in Ambient Pressure X-ray Photoelectron Spectroscopy

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