While some metal-oxide surfaces can be classified as acidic, after reacting with H2SO4 their acidity can be even higher than the parent sulfuric acid. In this paper, ab initio electronic structure calculations (3–21G+*//3–21G*) were performed on a series of model surfaces to examine these sulfonated species as strong, possibly even superacids. Our results indicate that the polarizing nature of the metal-oxide / sulfonate interaction stabilizes strong Bronsted and Lewis acid sites at the M-O surface and the sulfur center. Thermodynamic analysis has been performed to provide information for experimental verification.
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This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Material Science Division. The Pacific Northwest Laboratory is operated by Battelle Memorial Institute under contract DE-AC06-76RLO 1830.
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Ferris, K.F. Sulfonated Metal-Oxide Surfaces: What Makes them So Acidic?. MRS Online Proceedings Library 318, 539–544 (1993). https://doi.org/10.1557/PROC-318-539