Nonthermal Plasma-Stimulated C–N Coupling from CH4 and N2 Depends on the Presence of Surface CHx and Plasma-Phase CN Species

Lee, Garam; Go, David B.; O’Brien, Casey P.

doi:10.1021/acsami.4c01830

Nonthermal Plasma-Stimulated C–N Coupling from CH₄ and N₂ Depends on the Presence of Surface CH_x and Plasma-Phase CN Species

Journal Article · Mon May 20 00:00:00 EDT 2024 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.4c01830· OSTI ID:2564870

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University of Notre Dame, IN (United States)

Formation of C–N containing compounds from plasma-catalytic coupling of CH₄ and N₂ over various transition metals (Ni, Pd, Cu, Ag, and Au) is investigated using a multimodal spectroscopic approach, combining polarization-modulation infrared reflection–absorption spectroscopy (PM-IRAS) and optical emission spectroscopy (OES). Through sequential experiments utilizing CH₄ and N₂ nonthermal plasmas, we minimize plasma-phase reactions and identify key intermediates for C–N coupling on metal surfaces. Results show that simultaneous CH₄ and N₂ exposure with plasma stimulation produces surface C–N species. However, N₂–CH₄ sequential exposure does not lead to C–N species formation, while CH₄–N₂ sequential exposure reveals the presence of CH_x surface species and CN radical species as key precursors to C–N species formation. From further analysis using X-ray photoelectron spectroscopy and liquid chromatography–mass spectrometry, the influence of exposure conditions on the degree of nitrogen incorporation and the nature of C–N species formed were revealed. The work highlights the importance of surface chemistry and exposure conditions in surface C–N coupling with plasma stimulation.

View Accepted Manuscript (DOE)

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: FE0031862

OSTI ID:: 2564870

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 22 Vol. 16; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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