Direct Hydroxylation of Benzene to Phenol on Solid‐State Catalyst

Phenol is a very important chemical raw material. The traditional phenol production process is not environment friendly with a large amount of by-products. Therefore, the direct oxidation of benzene is a promising route to produce phenol. In this chapter, we systematically review the direct hydroxylation of benzene to phenol with nitrous oxide, oxygen, and hydrogen peroxide as oxidant, especially the environment-friendly hydrogen peroxide system. In the liquid-phase benzene hydroxylation reaction, we mainly introduce the commonly used heterogeneous catalysts from the type of silica- and silicate-based catalysts, carbon-based catalysts to metal-oxide-based catalysts. Also, new methods of benzene hydroxylation reaction are introduced, including electrolytic synthesis, photocatalysis, and biosynthesis. In addition, the reaction mechanism is briefly discussed.