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用于高效无碱有氧氧化葡萄糖的羟基磷灰石与钙铝层状双氢氧化物负载金纳米粒子的混合复合材料。

A hybrid composite of hydroxyapatite and Ca-Al layered double hydroxide supported Au nanoparticles for highly efficient base-free aerobic oxidation of glucose.

作者信息

Zhuge Yunfeng, Fan Guoli, Lin Yanjun, Yang Lan, Li Feng

机构信息

State Key Laboratory of Chemical Resources Engineering, Beijing Advanced Innovation Center for Soft Matter Science and Engineering, Beijing University of Chemical Technology, Beijing, 100029, China.

出版信息

Dalton Trans. 2019 Jun 25;48(25):9161-9172. doi: 10.1039/c9dt00985j.

Abstract

In this work, a new hybrid composite of hydroxyapatite and Ca-Al layered double hydroxide (HAP-LDH) was successfully assembled via an in situ growth route, by which large quantities of small needle-like HAP crystals in situ grew over the lateral surface of large platelet-like CaAl-LDH particles, and applied to immobilize Au nanoparticles for base-free aerobic glucose oxidation in water to produce gluconic acid using molecular oxygen. A combination of characterization techniques and catalytic experiments revealed that the activity of supported Au catalysts was strongly associated with the composition of supports, and the hybrid HAP-LDH supported one with a Au loading amount of about 0.2 wt% delivered a high gluconic acid yield of >98% under optimal reaction conditions, along with a quite high turnover frequency value of ∼20 225 h-1. High efficiency of the as-formed Au/HAP-LDH was mainly ascribed to cooperation between favorable surface Au species (Au0/Auδ+) and abundant basic sites. Furthermore, the present catalyst also presented good structural stability, because of the novel hybrid three-dimensional nano/microstructure of the HAP-LDH composite support facilitating the stabilization of active Au species and components of the support. The present synthesis strategy of employing a hybrid composite support provides a new way to design stable and high-performance supported metal nanocatalysts for a variety of advanced heterogeneous catalytic processes.

摘要

在本工作中,通过原位生长路线成功组装了一种新型的羟基磷灰石与钙铝层状双氢氧化物的杂化复合材料(HAP-LDH),大量小针状的HAP晶体在大的片状CaAl-LDH颗粒的侧面原位生长,并将其用于固定金纳米颗粒,以在水中进行无碱需氧葡萄糖氧化反应,利用分子氧生成葡萄糖酸。表征技术与催化实验相结合表明,负载型金催化剂的活性与载体的组成密切相关,在最佳反应条件下,负载量约为0.2 wt%的HAP-LDH杂化负载型催化剂的葡萄糖酸产率高达>98%,同时周转频率值相当高,约为20225 h-1。所形成的Au/HAP-LDH具有高效性,主要归因于良好的表面金物种(Au0/Auδ+)与丰富的碱性位点之间的协同作用。此外,由于HAP-LDH复合载体新颖的三维纳米/微观结构有助于活性金物种和载体成分的稳定,本催化剂还表现出良好的结构稳定性。采用杂化复合载体的当前合成策略为设计用于各种先进多相催化过程的稳定且高性能的负载型金属纳米催化剂提供了一种新方法。

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