Direct hydroxylation of benzene to phenol mediated by nanosized vanadium oxide cluster ions at room temperature

Gas-phase vanadium oxide cluster cations and anions are prepared by laser ablation. The small cluster ions (<1000 amu) are mass-selected using a quadrupole mass filter and reacted with benzene in a linear ion trap reactor; large clusters (>1000 amu) with no mass selection are reacted with C₆H₆ in a fast flow reactor. Rich product variety is encountered in these reactions, and the reaction channels for small cationic and anionic systems are different. For large clusters, the reactivity patterns of (V₂O₅)_n ⁺ (n = 6-25) and (V₂O₅)_nO⁻ (n = 6-24) cluster series are very similar to each other, indicating that the charge state has little influence on the oxidation of benzene. In sharp contrast to the dramatic changes of reactivity of small clusters, a weakly size dependent reaction behavior of large (V₂O₅)_6-25 ⁺ and (V₂O₅)_6-24O⁻ clusters is observed. Therefore, the charge state and the size are not the major factors influencing the reactivity of nanosized vanadium oxide cluster ions toward C₆H₆, which is not common in cluster science. In the reactions with benzene, the small and large reactive vanadium oxide cations show similar reactivity of hydroxyl radicals (OH^•) toward C₆H₆ at higher and lower temperatures, respectively; different numbers of vibrational degrees of freedom and the released energy during the formation of adduct complexes can explain this intriguing correlation. The reactions investigated herein might be used as the models of how to realize the partial oxidation of benzene to phenol in a single step, and the observed mechanisms are helpful to understand the corresponding heterogeneous reactions, such as those over vanadium oxide aerosols and vanadium oxide catalysts.