Sulfoxides, a class of pharmaceuticals and fine chemicals of significant importance, are readily peroxidized to sulfones in the H₂O₂ system. Altering the intermediate oxygen species is the key to achieving selectivity regulation. Herein, Zr(OH)₄ was used to support Mo species, after calcining at 500 °C, obtaining a unique amorphous composite oxide with Mo uniformly dispersed in the ZrO₂ matrix (Mo_aZr_0.8O_x-500). Mo_aZr_0.8O_x-500 demonstrates enhanced catalytic proficiency, enabling the synthesis of sulfoxides within 30 minutes at 30 °C. Reactive oxygen species (ROS) quenching experiments and EPR spectra indicate that Mo_aZr_0.8O_x-500 possesses the ability to rapidly and directly participate in the heterolytic cleavage of H₂O₂ to produce ¹O₂ without passing through the intermediate ˙O²⁻, preventing the peroxidation of sulfoxides to sulfones. Additionally, the prevalence of basic sites in Mo_aZr_0.8O_x-500 is conducive to proton transfer, which plays a significant role in the heterolytic cleavage of H₂O₂. Furthermore, Mo_aZr_0.8O_x-500 exhibits excellent reproducibility, scalability, and broad substrate applicability. This study provides new insights into the selective regulation of the sulfide oxidation reaction, as well as the preparation of amorphous solid solution.

中文翻译：

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无定形 MoaZr0.8Ox-500 催化 H2O2 直接异质裂解 1O2 介导的硫化物选择性氧化为亚砜


亚砜是一类非常重要的药物和精细化学品，在 H₂O₂ 系统中很容易过氧化成砜类。改变中间氧是实现选择性调节的关键。本文用 Zr（OH）₄ 支持钼属，在 500 °C 下煅烧后，得到独特的无定形复合氧化物，其中钼均匀分散在 ZrO₂ 基体中 （Mo_aZr_0.8O _x-500）。Mo_aZr_0.8O _x-500 表现出增强的催化熟练度，能够在 30 °C 下在 30 分钟内合成亚砜。 活性氧 （ROS） 淬灭实验和 EPR 光谱表明，Mo_aZr_0.8O _x-500 具有快速直接参与 H₂O₂ 的异质裂解产生 ¹O₂ 的能力，而无需通过中间体 ̇O²⁻，防止亚砜过氧化为砜类。此外，Mo_aZr_0.8O _x-500 中碱性位点的普遍存在有利于质子转移，这在 H₂O₂ 的异质分解裂解中起重要作用。此外，Mo_aZr_0.8O _x-500 具有出色的重现性、可扩展性和广泛的基材适用性。本研究为硫化物氧化反应的选择性调控以及无定形固溶体的制备提供了新的见解。