双金属纳米材料催化的有机反应进展

Chinese Journal of Catalysis 34 (2013) 1964–1974

催化学报 2013年 第34卷 第11期 | http://doc.guandang.net 

available at http://doc.guandang.net 

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Review (Dedicated to Professor Yi Chen on the occasion of his 80th birthday) 

Progress in organic reactions catalyzed by bimetallic nanomaterials

Shuangfei Cai a,b, Dingsheng Wang a, Zhiqiang Niu a, Yadong Li a,*

Department of Chemistry, Tsinghua University, Beijing 100084, China b National Center for Nanoscience and Technology, Beijing 100190, China

a

ARTICLE INFO

ABSTRACT

Article history:

Received 20 July 2013

Accepted 2 September 2013 Published 20 November 2013 Keywords:

Bimetallic nanomaterial Catalyst

Organic reaction

Heterogeneous catalysis

Nanocatalysis, which is also known as semi‐heterogeneous catalysis, sits at the boundary between homogeneous catalysis and heterogeneous catalysis and has been the subject of increasing interest during the course of the last few years. Significant progress has recently been made towards the catalytic applications of bimetallic nanomaterials, which show high levels of activity, selectivity and recyclability. This review provides a summary of bimetallic nanomaterial‐catalyzed organic trans‐formations, including selective oxidation, hydrogenation, and coupling reactions, as well as dechlo‐rination, amidation, reductive amination, and hydrogenolysis reactions, and the asymmetric 1,4‐addition reactions of arylboronic acids to enones. The complex organic molecules using bimetal‐lic nanocatalysis would be anticipated soon. There is significant scope for bimetallic nanocatalysts to be further developed in terms of our general understanding of their fundamental properties and practical applications. Future development may benefit from the rational design and controllable synthesis of bimetallic nanomaterials, as well as a deeper understanding of their reaction mecha‐nisms and further progress towards the development of sophisticated computational studies in‐volving catalysis, which would require interdisciplinary collaborations.

© 2013, Dalian Institute of Chemical Physics, Chinese Academy of Sciences.

Published by Elsevier B.V. All rights reserved.

1. Introduction

The field of heterogeneous catalysis, with particular empha‐sis on catalysis involving bimetallic nanomaterials (BNMs) that contain two different materials in the same nanoparticle, has seen many advances over the past few years. For example, sig‐nificant progress has been made with regard to the preparation and characterization of a variety of different BNMs with well‐defined size, shape, and composition properties [1–5]. Fur‐thermore, to allow for the development of a deeper under‐standing of the origins of their novel catalytic properties, ex‐tensive mechanistic studies have been directed towards heter‐ogeneous catalysis, as summarized in several reviews [6–12]. BNMs not only combine the properties of their individual

constituents but also show unique properties that are superior to those of the ordinary materials, and therefore provide an opportunity for the development of novel catalysts with en‐hanced activity, selectivity, and stability. The term “bimetallic clusters” was introduced by Sinfelt [13] in the early 1980s. The synergistic catalytic effects of BNMs have been attributed to the “ligand” and “ensemble” effects of bimetallic clusters [14,15]. The ligand effect results from changes in the properties of the cluster surface that are caused by the exchange of electrons between the core metal and surface metal particles, whereas the ensemble effect is derived from the independent activation of substrates on each metal atom on the cluster surface. In this review, we will focus on recent progress in the field of BNM‐catalyzed organic reactions.

* Corresponding author. Tel: +86‐10‐62772350; Fax: +86‐10‐62788765; E‐mail: ydli@http://doc.guandang.net

This work was supported by the State Key Project of Fundamental Research for Nanoscience and Nanotechnology (2011CB932401, 2011CBA00500, 2012CB224802) and the National Natural Science Foundation of China (21221062, 21171105, 21322107, 21131004).

DOI: 10.1016/S1872‐2067(12)60701‐3 | http://doc.guandang.net/science/journal/18722067 | Chin. J. Catal., Vol. 34, No. 11, November 2013

Shuangfei Cai et al. / Chinese Journal of Catalysis 34 (2013) 1964–1974 1965

2. Organic reactions catalyzed by bimetallic nanomaterials 2.1. Selective oxidations

Oxidation reactions, especially the catalytic oxidations of hydrocarbons using molecular oxygen as an oxidant, are of considerable industrial importance [16,17], and research to‐wards improving the efficiency and selectivity of oxidation reactions for valuable commercial products remains a chal‐lenge. For this reason, the development of effective catalysts that can activate oxygen is highly desirable [18].

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