Rigorous Oxidation State Assignments for Supported Ga-Containing Catalysts Using Theory-Informed X-ray Absorption Spectroscopy Signatures from Well-Defined Ga(I) and Ga(III) Compounds

Li, Li; Chalmers, Jason A.; Bare, Simon R.; Scott, Susannah L.; Vila, Fernando D.

doi:10.1021/acscatal.3c01021

Rigorous Oxidation State Assignments for Supported Ga-Containing Catalysts Using Theory-Informed X-ray Absorption Spectroscopy Signatures from Well-Defined Ga(I) and Ga(III) Compounds

Journal Article · Fri Apr 28 00:00:00 EDT 2023 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.3c01021· OSTI ID:1991527

Li, Li ^[1]; Chalmers, Jason A. ^[2]; ^[3]; ^[2]; ^[4]

Univ. of California, Santa Barbara, CA (United States); SLAC
Univ. of California, Santa Barbara, CA (United States)
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Univ. of Washington, Seattle, WA (United States)

Gallium-based heterogeneous catalysts originally developed for commercial use in propane dehydroaromatization have been explored extensively as potential replacements for Pt- and Cr-based catalysts used in propane dehydrogenation for on-demand propylene production. In a large number of experimental and theoretical studies, active sites with a variety of Ga nuclearities, coordination environments, and oxidation states have been proposed. Isolated Ga(I) ions are often invoked, despite the scarcity of well-defined molecular species and their well-documented instability. In this study, we investigate the appearance of a high-intensity, low-energy white line at the Ga K-edge upon reduction of Ga/HZSM-5 by H₂ at a temperature of ca. 500 °C, accompanied by a dramatic reduction in the extended X-ray absorption fine structure (EXAFS) intensity. In contrast, Ga/γ-Al₂O₃ does not show such behavior. In order to lay a rigorous foundation for characterizing these types of systems and to establish experimental signatures for the elusive Ga(I) oxidation state, we recorded Ga K-edge X-ray absorption spectra [including high-energy-resolution fluorescence detection-X-ray absorption near-edge spectroscopy (HERFD-XANES)] for several well-defined molecular and crystalline Ga(I) compounds. XANES is essential to establishing the presence of Ga(I), despite the overlap in edge energies with organoGa(III) compounds, because Ga(I)-containing oxide materials show very weak EXAFS scattering. Compared to the XANES of trigonal Ga(III)-containing materials, Ga(I) spectra display a significantly more intense white line feature. Theoretical simulations agree well with this experimental observation and reveal that the strong XANES intensity originates from the superposition of transitions to several empty, nearly degenerate p-like states. Finally, these signatures provide compelling evidence for assigning the intense white line and dramatic loss of EXAFS intensity in Ga/HZSM-5 to the near-quantitative reduction of Ga(III) to Ga(I), while the weaker white line and conventional EXAFS signal of Ga/γ-Al₂O₃ point to, at most, a minor fraction of Ga(I) sites.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)

Sponsoring Organization:: 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; AC02-76SF00515; FG02-03ER15467

OSTI ID:: 1991527

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 10 Vol. 13; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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