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<p>The design of cooperative catalytic systems inspired by nature represents a significant advancement in organic synthesis. In this research, the selective aerobic oxidation of primary and secondary alcohols to the corresponding carbonyl compounds was investigated using molecular oxygen as a green oxidant in the presence of a heterogeneous biomimetic catalytic system consisting of palladium, a sandwich-type polyoxometalate [(OCe)₃(PW₉O₃₄)₂]<sup>12</sup>⁻, and hydroquinone (HQ). In the first method, palladium nanoparticles were immobilized on siliceous mesocellular foam (MCF), while the polyoxometalate (POM) was supported on Nd-doped TiO₂ nanoparticles. Then, the aerobic oxidation of alcohols to the corresponding carbonyl compounds was investigated in the presence of the Pd@MCF/POM@TiO<sub>2</sub>/HQ catalytic system in THF solvent at 40&#xa0;°C. In the second method, both palladium and polyoxometalate were simultaneously immobilized on MCF and POM-Pd@MCF/HQ was used as an efficient biomimetic catalytic system. The second catalyst showed better performance with yields of 84–97% with TOF values up to 111&#xa0;h⁻ <sup>1</sup> in water as solvent at room temperature. Furthermore, the POM-Pd@MCF/HQ system showed the ability to be used for up to 8 consecutive applications with minimal decrease in its catalytic efficiency, indicating its structural stability and recyclability. The Pd@MCF, POM@TiO<sub>2</sub> and POM-Pd@MCF compounds were identified and confirmed by various techniques.</p>

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Palladium/polyoxometalate as a cooperative and reusable catalytic system for room temperature aerobic oxidation of alcohols to the corresponding carbonyl compounds in aqueous media

  • 期刊论文

  • 发表日期：

    2025年12月15日

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  • Sirvan Moradi,
  • Saeed Chehri,
  • Zeinab Shirvandi,
  • Amin Rostami

摘要

The design of cooperative catalytic systems inspired by nature represents a significant advancement in organic synthesis. In this research, the selective aerobic oxidation of primary and secondary alcohols to the corresponding carbonyl compounds was investigated using molecular oxygen as a green oxidant in the presence of a heterogeneous biomimetic catalytic system consisting of palladium, a sandwich-type polyoxometalate [(OCe)₃(PW₉O₃₄)₂]12⁻, and hydroquinone (HQ). In the first method, palladium nanoparticles were immobilized on siliceous mesocellular foam (MCF), while the polyoxometalate (POM) was supported on Nd-doped TiO₂ nanoparticles. Then, the aerobic oxidation of alcohols to the corresponding carbonyl compounds was investigated in the presence of the Pd@MCF/POM@TiO2/HQ catalytic system in THF solvent at 40 °C. In the second method, both palladium and polyoxometalate were simultaneously immobilized on MCF and POM-Pd@MCF/HQ was used as an efficient biomimetic catalytic system. The second catalyst showed better performance with yields of 84–97% with TOF values up to 111 h⁻ 1 in water as solvent at room temperature. Furthermore, the POM-Pd@MCF/HQ system showed the ability to be used for up to 8 consecutive applications with minimal decrease in its catalytic efficiency, indicating its structural stability and recyclability. The Pd@MCF, POM@TiO2 and POM-Pd@MCF compounds were identified and confirmed by various techniques.