Haematite (α-Fe₂O₃) has been extensively investigated as a photoanode in photoelectrochemical water oxidation, but the product O₂ has a low economic value. Here we expand its applications to the production of value-added chemicals and report its ability to act as a versatile and efficient oxygen atom transfer catalyst under visible-light irradiation. A variety of organic compounds and inorganic anions were successfully oxidized to the corresponding monooxygenation products with high selectivity and Faradaic efficiency by using water as the sole oxygen source. Photoexcited holes generate iron–oxo species (Fe^IV=O) on α-Fe₂O₃ surfaces and the process of oxygen-atom transfer is proposed to proceed via a concerted two-hole transfer pathway that involves the transfer of oxygen atoms from the surface Fe^IV=O to the substrates. The present study proves α-Fe₂O₃ is an excellent all-inorganic heterogeneous catalyst to drive oxygen atom transfer reactions, and this strategy has significant potential for the synthesis of fine and high-value-added chemicals.

赤铁矿（α-Fe ₂ O ₃）作为光电化学水氧化的光阳极已被广泛研究，但产物O ₂的经济价值较低。在这里，我们将其应用扩展到增值化学品的生产，并报告了它在可见光照射下作为多功能高效氧原子转移催化剂的能力。以水为唯一氧源，成功地将多种有机化合物和无机阴离子氧化成相应的单氧化产物，具有高选择性和法拉第效率。光激发的空穴在 α-Fe ₂ O ₃上产生铁氧物质 (Fe ^IV =O)表面和氧原子转移过程被提议通过协调的双空穴转移途径进行，该途径涉及氧原子从表面 Fe ^IV =O 转移到基板。本研究证明α-Fe ₂ O ₃是一种优异的全无机非均相催化剂来驱动氧原子转移反应，该策略在合成精细和高附加值化学品方面具有巨大潜力。