The Efficient and Environmentally Friendly Chlorination of Arene, Alcohol, Halobenzene, and Peroxide Catalyzed by Fe–Ba Binary Oxides Using Hydrochloric Acid as Chlorine Source and Aqueous H₂O₂ as Oxidant

A series of Fe–Ba mixed oxides, including a pure Fe-containing sample as a reference, have been synthesized via a sol–gel process using Fe³⁺ or Fe²⁺ salts and BaSO₄ as raw materials, with Pluronic P123 serving as a template. These oxides have been thoroughly characterized and subsequently utilized as catalysts for the chlorination of various organic molecules. Commercial hydrochloric acid, known for its relative safety, and environmentally friendly aqueous hydrogen peroxide were employed as the chlorine source and oxidant, respectively. The pure Fe-containing catalyst displays excellent thermal stability between 600 and 800 °C and exhibited moderate to high conversions in the chlorination of toluene, benzene, and tert-butyl hydroperoxide, with remarkable ortho-selectivity in chlorination of toluene. The combination of Fe³⁺ salt with BaSO₄ in the sol–gel process results in a Fe–Ba mixed oxide catalyst composed of BaO₂, BaFe₄O₇, and Fe₂O₃, significantly enhancing the chlorination activity compared to that displayed by the pure Fe catalyst. Notably, the chlorination of tert-butyl hydroperoxide (TBHP) does not require additional oxidants such as H₂O₂, and involves both electrophilic substitution and nucleophilic addition. Notably, the chlorination of bromobenzene yields chlorobenzene as the sole product, a transformation that has not been previously reported. Overall, this catalytic chlorination system holds promise for advancing the chlorination industry and enhancing pharmaceutical production.