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<p>Natural phosphate (NP) is recognized as a highly effective catalyst for organic reactions, though the precise components responsible for its activity remain poorly understood. This study aims to determine whether the catalytic activity of natural phosphate originates from its fluorapatite (FAP) structure, the metal oxides it contains such as CuO, Al<sub>2</sub>O<sub>3</sub>, and Fe<sub>2</sub>O<sub>3</sub>, or a combination of both the FAP structure and these metal oxides. Aldehyde oxidation tests using dioxygen, as a clean oxidant, revealed that natural phosphate demonstrates significantly greater catalytic activity compared to fluorapatite or metal oxides when used separately, emphasizing the presence of a strong synergistic catalytic effect between the components of NP. Furthermore, the NP/O<sub>2</sub>/AcOH-H<sub>2</sub>O system demonstrated effective performance in the oxidation of various linear, aromatic, halogenated, and heterocyclic aldehydes to their corresponding carboxylic acids. Density Functional Theory (DFT) calculations were performed to support the proposed mechanism for the oxidation of aldehydes to their corresponding carboxylic acids in the NP/O<sub>2</sub>/ AcOH-H<sub>2</sub>O heterogeneous catalytic system. This approach not only enhances efficiency in fine chemical synthesis but also aligns with sustainable chemistry principles by employing a clean oxidant and minimizing waste, highlighting NPs potential as an environmentally friendly catalyst for selective oxidation reactions.</p>

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Synergistic Catalysis of Fluorapatite and Trace Metal Oxides Embedded in Natural Phosphate for Efficient Aldehyde Oxidation with Molecular Oxygen Under Green Heterogeneous Conditions

  • 期刊论文

  • 发表日期：

    2025年7月14日

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  • Mohamed Bakhada,
  • Hajar Rouibaa,
  • Mohamed Dakkach,
  • Ahmed Atlamsani

摘要

Natural phosphate (NP) is recognized as a highly effective catalyst for organic reactions, though the precise components responsible for its activity remain poorly understood. This study aims to determine whether the catalytic activity of natural phosphate originates from its fluorapatite (FAP) structure, the metal oxides it contains such as CuO, Al2O3, and Fe2O3, or a combination of both the FAP structure and these metal oxides. Aldehyde oxidation tests using dioxygen, as a clean oxidant, revealed that natural phosphate demonstrates significantly greater catalytic activity compared to fluorapatite or metal oxides when used separately, emphasizing the presence of a strong synergistic catalytic effect between the components of NP. Furthermore, the NP/O2/AcOH-H2O system demonstrated effective performance in the oxidation of various linear, aromatic, halogenated, and heterocyclic aldehydes to their corresponding carboxylic acids. Density Functional Theory (DFT) calculations were performed to support the proposed mechanism for the oxidation of aldehydes to their corresponding carboxylic acids in the NP/O2/ AcOH-H2O heterogeneous catalytic system. This approach not only enhances efficiency in fine chemical synthesis but also aligns with sustainable chemistry principles by employing a clean oxidant and minimizing waste, highlighting NPs potential as an environmentally friendly catalyst for selective oxidation reactions.