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利用微波原位生成钯铂核壳纳米粒子在还原氧化石墨烯上(Pd@Pt/rGO):在脱卤反应和烯烃还原中的应用。

In Situ Generation of Pd-Pt Core-Shell Nanoparticles on Reduced Graphene Oxide (Pd@Pt/rGO) Using Microwaves: Applications in Dehalogenation Reactions and Reduction of Olefins.

机构信息

Regional Centre of Advanced Technologies and Materials, Department of Physical Chemistry, Faculty of Science, Palacky University , Šlechtitelů 27, 783 71 Olomouc, Czech Republic.

出版信息

ACS Appl Mater Interfaces. 2017 Jan 25;9(3):2815-2824. doi: 10.1021/acsami.6b13138. Epub 2017 Jan 11.

DOI:10.1021/acsami.6b13138
PMID:28035800
Abstract

Core-shell nanocatalysts are a distinctive class of nanomaterials with varied potential applications in view of their unique structure, composition-dependent physicochemical properties, and promising synergism among the individual components. A one-pot microwave (MW)-assisted approach is described to prepare the reduced graphene oxide (rGO)-supported Pd-Pt core-shell nanoparticles, (Pd@Pt/rGO); spherical core-shell nanomaterials (∼95 nm) with Pd core (∼80 nm) and 15 nm Pt shell were nicely distributed on the rGO matrix in view of the choice of reductant and reaction conditions. The well-characterized composite nanomaterials, endowed with synergism among its components and rGO support, served as catalysts in aromatic dehalogenation reactions and for the reduction of olefins with high yield (>98%), excellent selectivity (>98%) and recyclability (up to 5 times); both Pt/rGO and Pd/rGO and even their physical mixtures showed considerably lower conversions (20 and 57%) in dehalogenation of 3-bromoaniline. Similarly, in the reduction of styrene to ethylbenzene, Pd@Pt core-shell nanoparticles (without rGO support) possess considerably lower conversion (60%) compared to Pd@Pt/rGO. The mechanism of dehalogenation reactions with Pd@Pt/rGO catalyst is discussed with the explicit premise that rGO matrix facilitates the adsorption of the reducing agent, thus enhancing its local concentration and expediting the hydrazine decomposition rate. The versatility of the catalyst has been validated via diverse substrate scope for both reduction and dehalogenation reactions.

摘要

核壳纳米催化剂是一类具有独特结构的纳米材料,由于其独特的结构、组成依赖性的物理化学性质以及各组分之间的协同作用,具有广泛的潜在应用。本文描述了一种在微波(MW)辅助下的一锅法制备还原氧化石墨烯(rGO)负载的钯-铂核壳纳米粒子(Pd@Pt/rGO)的方法;选择合适的还原剂和反应条件,可得到具有 Pd 核(∼80nm)和 15nmPt 壳的球形核壳纳米材料(∼95nm),且 Pt 壳均匀分布在 rGO 基质上。该复合材料具有协同作用和 rGO 支撑,在芳族脱卤反应和烯烃还原中作为催化剂表现出高收率(>98%)、高选择性(>98%)和可回收性(高达 5 次);Pt/rGO 和 Pd/rGO 甚至它们的物理混合物在 3-溴苯胺的脱卤反应中转化率(20%和 57%)要低得多。同样,在苯乙烯还原为乙苯的反应中,与 Pd@Pt/rGO 相比,Pd@Pt 核壳纳米粒子(无 rGO 支撑)的转化率(60%)要低得多。Pd@Pt/rGO 催化剂的脱卤反应机制是基于 rGO 基质促进了还原剂的吸附,从而提高了其局部浓度并加快了联氨的分解速率。通过对还原和脱卤反应的多种底物范围的验证,证明了催化剂的多功能性。

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