A comparison of the results of catalytic and electrocatalytic oxidation of aniline using VS-1 in the presence of 1-1202 and TBHP indicates remarkable differences in conversion and selectivity. VS-1 catalyzes the oxidation of aniline selectively to nitrobenzene (73%) in the presence of t-butyl hydroperoxide (TBHP), while azoxybenzene (95.2%) is formed selectively when H202 is used. Cyclic voltammetrie studies show a three-step oxidation of aniline to nitrobenzene in H202 but in the presence of TBHP only one step is observed. Electrocatalytic oxidation of aniline to nitrobenzene occurs at a potential 700 mV less than that corresponding to H~.O2 as oxidant along with a selectivity of 91.8%. The enhancement of e, lectrocatalytic rate is attributed to the stabilization of electron deficient transition state.
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