Highly selective oxidation of benzene to phenol with air at room temperature promoted by water

Phenol is one of the most important fine chemical intermediates in the synthesis of plastics and drugs with a market size of ca. $30b¹ and the commercial production is via a two-step selective oxidation of benzene, requiring high energy input (high temperature and high pressure) in the presence of a corrosive acidic medium, and causing serious environmental issues^2-5. Here we present a four-phase interface strategy with well-designed Pd@Cu nanoarchitecture decorated TiO₂ as a catalyst in a suspension system. The optimised catalyst leads to a turnover number of 16,000-100,000 for phenol generation with respect to the active sites and an excellent selectivity of ca. 93%. Such unprecedented results are attributed to the efficient activation of benzene by the atomically Cu coated Pd nanoarchitecture, enhanced charge separation, and an oxidant-lean environment. The rational design of catalyst and reaction system provides a green pathway for the selective conversion of symmetric organic molecules.