State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, No. 2699 Qianjin Street, Changchun 130012, China.
Institute of Theoretical Chemistry, College of Chemistry, Jilin University, No. 2 Liutiao Road, Changchun 130023, China.
Int J Mol Sci. 2024 Jun 20;25(12):6779. doi: 10.3390/ijms25126779.
The oxidative esterification of aldehydes under mild conditions remains a significant challenge. This study introduces a unique defective UiO-66 to achieve gold nanoclusters (AuNCs) for efficient aldehyde oxidation under mild conditions. The construction and characterization of these materials are thoroughly investigated by techniques of XRD, SEM and TEM images, FT-IR, Raman, and XPS spectrum, emphasizing the unique microporous in defective UiO-66 are conducive to the fabrication of AuNCs. The catalytic performance of the prepared materials in aldehyde oxidation reactions is systematically evaluated, demonstrating the remarkable efficiency of dispersed Au@UiO-66-25 with high-content (9.09 wt%) Au-loading and ultra-small size (~2.7 nm). Moreover, mechanistic insights into the catalytic process under mild conditions (70 °C for 1 h) are provided, elucidating the determination of defective UiO-66 in the confined fabrication of AuNCs and subsequent furfural adsorption, which underlie the principles governing the observed enhancements. This study establishes the groundwork for the synthesis of highly dispersed and catalytically active metal nanoparticles using defective MOFs as a platform, advancing the catalytic esterification reaction of furfural to the next level.
在温和条件下实现醛的氧化酯化仍然是一个重大挑战。本研究引入了一种独特的缺陷 UiO-66，以实现在温和条件下高效氧化醛。通过 XRD、SEM 和 TEM 图像、FT-IR、拉曼和 XPS 光谱等技术对这些材料的构建和特性进行了深入研究，强调了缺陷 UiO-66 中的独特微孔有利于 AuNCs 的制备。系统评估了所制备材料在醛氧化反应中的催化性能，证明了具有高含量（9.09wt%）Au 负载和超小尺寸（~2.7nm）的分散 Au@UiO-66-25 的高效性。此外，还提供了在温和条件下（70°C 反应 1 小时）催化过程的机理见解，阐明了缺陷 UiO-66 在受限的 AuNCs 制备和随后糠醛吸附中的决定性作用，这是观察到的增强的基础。本研究为使用缺陷 MOF 作为平台合成高度分散和催化活性的金属纳米粒子奠定了基础，将糠醛的催化酯化反应推进到了一个新的水平。
