亚纳米级的Pd团簇的简易合成:Pd/PEG-PNIPAM复合物及其Suzuki反应中的极高催化性能

doi:10.1016/S1872-2067(17)62797-9

催化学报 ›› 2017, Vol. 38 ›› Issue (4): 651-657.DOI: 10.1016/S1872-2067(17)62797-9

亚纳米级的Pd团簇的简易合成:Pd/PEG-PNIPAM复合物及其Suzuki反应中的极高催化性能

陈哲^a, 梁宇^a, 贾大爽^a, 崔志民^b, 宋卫国^c

a 华北电力大学环境科学与工程学院, 北京 102206;
b 北京航空航天大学化学与环境学院, 北京 100191;
c 中国科学院化学研究所分子纳米结构与纳米技术重点实验室, 北京 100190

收稿日期:2017-01-12 修回日期:2017-02-26 出版日期:2017-04-18 发布日期:2017-04-12
通讯作者: 崔志民, 宋卫国
基金资助:
国家自然科学基金（51502089，51302008）；中央高校科研基本业务费（2016MS03）.

Simple synthesis of sub-nanometer Pd clusters: High catalytic activity of Pd/PEG-PNIPAM in Suzuki reaction

Zhe Chen^a, Yu Liang^a, Da-Shuang Jia^a, Zhi-Min Cui^b, Wei-Guo Song^c

a College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, China;
b School of Chemistry and Environment, Beihang University, Beijing 100191, China;
c Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China

Received:2017-01-12 Revised:2017-02-26 Online:2017-04-18 Published:2017-04-12
Supported by:
This work was supported by the National Natural Science Foundation of China (51502089, 51302008) and the Fundamental Research Funds for the Central Universities (2016MS03).

摘要/Abstract

摘要：

由于纳米材料的小尺寸效应，在异相催化剂中，超小的催化剂颗粒往往具有很好的催化性能，多种多样的合成稳定的小纳米颗粒的方法如百花齐放地报道出来.在这些合成方法中，为了防止小颗粒的长大，往往需要稳定剂，常用的稳定剂如功能性纳米材料，树枝状分子等.但是，由于其稳定性较差，制备超小的纳米颗粒往往非常困难，表面吸附的稳定剂也会影响其催化活性.Suzuki反应在现代精细化工合成中具有非常重要的地位.合成容易回收分离的且足以催化氯苯的异相Pd催化剂，将是一个重大的突破.
我们使用单电子转移活性自由基聚合（SET-LRP）方法，合成了夹心型的PEG-PNIPEM聚合物，PNIPAM聚合在PEG-1的两端，两端都连接了25个NIPAM分子.通过氢核磁共振（¹H NMR），凝胶渗透色谱（GPC）和傅里叶变化红外光谱（FTIR），我们证明了PNIPAM已经成功地接枝在PEG的两端，PEG-PNIPAM的数均分子量Mn，GPC为7841.通过简单的负载流程，我们将Pd纳米颗粒成功的地负载在PEG-PNIPAM共聚物上，得到Pd/PEG-PNIPAM催化剂，Pd的负载量为4.4 wt%.在透射照片中，PEG-PNIPAM看起来像一个薄薄的片层.Pd的团簇颗粒很小，最大约2 nm.我们测量了制得的催化剂Pd/PEG-PNIPAM水溶液随着温度变化的光透过率曲线，最后确定该材料的LCST为41℃.我们认为在温度高于LCST进行反应时，催化剂的载体由亲水变成亲油，这样亲油的反应物分子将容易向催化剂载体扩散并富集.催化剂会形成一个亲油的微环境富集反应物，并形成反应微环境将大大提高催化速率.
该催化剂在Suzuki反应中表现出了极好的催化能力.使用该催化剂催化Suzuki反应，我们发现苯硼酸和碘苯在80℃反应时10 s内即可完全转化，TOF为4.3×10⁴ h^-¹.对于异相Pd催化剂而言，达到这个TOF是非常难得的，可与活性很高的均相催化剂比拟.室温下催化速率明显减慢，但也仍在1 min内转化完全，TOF为7.2×10³ h^-¹.当加大反应物的量，反应物/催化剂的比从120增加到1600，反应在3 min内达到100%转化，TOF为3.2×10⁴ h^-¹.即使使用苯硼酸和氯苯进行反应，也在5 min内达到了65%的转化.异相Pd催化剂催化氯苯的Suzuki反应是很难进行的，表明该纳米材料具有极佳的催化活性.然而，在催化苯硼酸与碘苯的连续3次反应中，催化剂的活性明显降低，直至失活.使用后的催化剂颗粒长大至几百纳米，许多小颗粒被包裹于其中.Pd颗粒有所长大，PEG-PNIPAM相互缠绕发生团聚，这也就是催化剂失活的原因.由于Pd/PEG-PNIPAM复合物可以通过其温度响应性回收，我们认为其在高效催化方面具有很好的应用前景.

关键词: 温度响应性, 亲水聚合物, 钯纳米团簇, Suzuki反应

Abstract:

Ultra-small metal nanoclusters have high surface energy and abundant active sites, and therefore their catalytic activities are usually significantly higher than those of larger nanoparticles. A temperature-responsive copolymer, namely poly(ethylene glycol)-co-poly(N-isopropylacrylamide) (PEG-PNIPAM) was synthesized as the first step, and then ultra-small Pd clusters stabilized within PEG-PNIPAM copolymer micelles were formed by direct reduction. Pd nanoclusters of size less than 2 nm showed outstanding catalytic activity in the Suzuki coupling reaction. The reaction between iodobenzene and phenylboronic acid was completed in as little as 10 s (turnover frequency=4.3×10⁴ h^-1). A yield of 64% was achieved in 5 min in the reaction between chlorobenzene and phenylboronic acid. The catalyst showed significant deactivation during three consecutive runs. However, this composite catalyst consisting of Pd/PEG-PNIPAM can be easily recycled based on the reversible phase transition of temperature-responsive PEG-PNIPAM. This catalyst therefore has good potential for practical applications.

Key words: Temperature responsive, Hydrophilic polymer, Pd nanoclusters, Suzuki reaction

陈哲, 梁宇, 贾大爽, 崔志民, 宋卫国. 亚纳米级的Pd团簇的简易合成:Pd/PEG-PNIPAM复合物及其Suzuki反应中的极高催化性能[J]. 催化学报, 2017, 38(4): 651-657.

Zhe Chen, Yu Liang, Da-Shuang Jia, Zhi-Min Cui, Wei-Guo Song. Simple synthesis of sub-nanometer Pd clusters: High catalytic activity of Pd/PEG-PNIPAM in Suzuki reaction[J]. Chinese Journal of Catalysis, 2017, 38(4): 651-657.

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亚纳米级的Pd团簇的简易合成:Pd/PEG-PNIPAM复合物及其Suzuki反应中的极高催化性能

Simple synthesis of sub-nanometer Pd clusters: High catalytic activity of Pd/PEG-PNIPAM in Suzuki reaction

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