Cs+-modified γ-alumina, titania anatase, and zirconia in
the absence of WS2 are active catalysts for methanol thiolation.
Pyridine and CO adsorptions via IR show that Cs+ cations
induce higher concentrations and strength of base sites. Reaction
rates are similar on all three catalysts, indicating that the Cs+ cations are part of the dominating active sites. Methanol
thiolation shows similar apparent activation energies, decreasing
with Cs+ concentration. Reaction orders close to 0.5 for
both reactants suggest that all three metal oxides and their alkali-metal-modified
counterparts follow the identical base-catalyzed Langmuir–Hinshelwood
mechanism. A reaction between the surface alcoholate and the corresponding
sulfhydryl groups is hypothesized to be the pathway for reaction.
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