期刊
ACS CATALYSIS
卷 13, 期 10, 页码 6549-6561出版社
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.3c01021
关键词
XANES; StoBe; gallium catalyst; oxidation state; propane dehydrogenation
In this study, the experimental characteristics of Ga(I) oxidation state were investigated by recording Ga K-edge X-ray absorption spectra for several well-defined molecular and crystalline Ga(I) compounds. Compared to trigonal Ga(III)-containing materials, Ga(I) spectra displayed a significantly more intense white line feature. Theoretical simulations confirmed this observation and revealed that the strong XANES intensity originated from transitions to several empty, nearly degenerate p-like 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 degrees C, accompanied by a dramatic reduction in the Ga/gamma-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. 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/gamma-Al2O3 point to, at most, a minor fraction of Ga(I) sites.
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