Phenol is an important chemical material that is widely used in industry. Currently, phenol is dominantly produced by the well−known three−step cumene process, which suffers from severe drawbacks. Therefore, developing a green, sustainable, and economical strategy for the production of phenol directly from benzene is urgently needed. In recent years, the photocatalytic hydroxylation of benzene to phenol, which is economically feasible and could be performed under mild conditions, has attracted more attention, and development of highly efficient photocatalyst would be a key issue in this field. In this review, we systematically introduce the recent achievements of photocatalytic hydroxylation of benzene to phenol from 2015 to mid−2022, and various heterogeneous photocatalysts are comprehensively reviewed, including semiconductors, polyoxometalates (POMs), graphitic carbon nitride (g−C3N4), metal–organic frameworks (MOFs), carbon materials, and some other types of photocatalysts. Much effort is focused on the physical and chemical approaches for modification of these photocatalysts. The challenges and future promising directions for further enhancing the catalytic performances in photocatalytic hydroxylation of benzene are discussed in the end.
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