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担载于氮掺杂碳修饰的氧化铈上的 Pt 纳米粒子用于 5-羟甲基糠醛的无碱有氧氧化。

Pt Nanoparticles Supported on Nitrogen-Doped-Carbon-Decorated CeO for Base-Free Aerobic Oxidation of 5-Hydroxymethylfurfural.

机构信息

State Key Laboratory of Chemical Resource Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, P. O. BOX 98, Beijing, 100029, P. R. China.

出版信息

Chem Asian J. 2018 Sep 17;13(18):2714-2722. doi: 10.1002/asia.201800738. Epub 2018 Aug 15.

Abstract

Currently, the base-free aerobic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF) to produce 2,5-furandicarboxylic acid (FDCA) is attracting intense interest due to its prospects for the green, sustainable, and promising production of biomass-based aromatic polymers. Herein, we have developed a new Pt catalyst supported on nitrogen-doped-carbon-decorated CeO (NC-CeO ) for the aerobic oxidation of HMF in water without the addition of any homogeneous base. It was demonstrated that the small-sized Pt particles could be well dispersed on the surface of the hybrid NC-CeO support, and the activity of the supported Pt catalyst depended strongly on the surface structure and properties of the catalysts. The as-fabricated Pt/NC-CeO catalyst, with abundant surface defects, enhanced basicity, and favorable electron-deficient metallic Pt species, enabled an almost 100 % yield of FDCA in water with molecular oxygen (0.4 MPa) at 110 °C for 8 h without the addition of any homogeneous base, which is indicative of exceptional catalytic performance. Furthermore, this Pt/NC-CeO catalyst also showed good stability and reusability owing to strong metal-support interactions. An understanding of the role of surface structural defects and basicity of the hybrid NC-CeO support provides a basis for the rational design of high-performance and stable supported metal catalysts with practical applications in various transformations of biomass-derived compounds.

摘要

目前,由于其在绿色、可持续和有前途的生物基芳香族聚合物生产方面的前景,无基底有氧氧化生物质衍生的 5-羟甲基糠醛(HMF)生产 2,5-呋喃二甲酸(FDCA)引起了人们的极大兴趣。在此,我们开发了一种新型的氮掺杂碳修饰的 CeO 负载的 Pt 催化剂(NC-CeO),用于在水中有氧氧化 HMF,无需添加任何均相碱。结果表明,小尺寸的 Pt 颗粒可以很好地分散在混合 NC-CeO 载体的表面上,负载型 Pt 催化剂的活性强烈依赖于催化剂的表面结构和性质。所制备的 Pt/NC-CeO 催化剂具有丰富的表面缺陷、增强的碱性和有利的缺电子金属 Pt 物种,在 110°C 下,在水中以 0.4 MPa 的分子氧(O2)反应 8 小时,几乎可以 100%地将 FDCA 作为产物得到,无需添加任何均相碱,这表明其具有优异的催化性能。此外,由于强的金属-载体相互作用,该 Pt/NC-CeO 催化剂还表现出良好的稳定性和可重复使用性。对混合 NC-CeO 载体表面结构缺陷和碱性的认识为合理设计具有实际应用价值的高性能和稳定的负载型金属催化剂提供了依据,可用于生物质衍生化合物的各种转化。

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