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Unexpected similarities between the surface chemistry of cubic and hexagonal gallia polymorphs

Abstract : γ-Ga2O3 and α-Ga2O3 samples were prepared as single-phase materials having a high surface area. 71Ga NMR showed the simultaneous presence of tetracoordinated (GaIV) and hexacoordinated (GaVI) in γ-Ga2O3, whereas in α-Ga2O3 most of the gallium present was found to be as GaVI. However, the apparent rate of methanol conversion into dimethyl ether (at 473 K) was nearly the same for both samples, when due account was taken of their respective surface area. The unexpected high activity of α-Ga2O3 was explained from IR spectroscopic results obtained by using acidity probes like CO and pyridine. These spectroscopic probe molecules showed, for both samples, the presence of strong Lewis acid sites related to coordinatively unsaturated (cus) GaIV ions which, for the case of α-Ga2O3, strongly suggests surface reconstruction. By contrast, CO2 adsorption revealed a higher basicity for the α-polymorph, as compared to γ-Ga2O3. This basicity can be directly correlated to a larger amount of surface GaVI ions which results in a higher degree of ionicity.
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https://hal-normandie-univ.archives-ouvertes.fr/hal-02399971
Contributor : Guillaume Clet <>
Submitted on : Monday, December 9, 2019 - 12:18:14 PM
Last modification on : Friday, December 13, 2019 - 9:52:42 AM

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J. Lavalley, M. Daturi, V. Montouillout, Guillaume Clet, C. Otero Areán, et al.. Unexpected similarities between the surface chemistry of cubic and hexagonal gallia polymorphs. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2003, 5 (6), pp.1301-1305. ⟨10.1039/b211767n⟩. ⟨hal-02399971⟩

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