| 高贵琪,崇汉宝,李广.选择性控制的配体工程在金团簇催化中的作用[J].分子催化,2018,32(6):546-554 |
| 选择性控制的配体工程在金团簇催化中的作用 |
| Mediating the Catalytic Selectivity of Au Nanoclusters by Ligand Engineering |
| 投稿时间：2018-09-27 修订日期：2018-10-10 |
| DOI： |
| 中文关键词: 配体效应 选择性 金团簇 催化 纳米 |
| 英文关键词:ligand effect selectivity Au nanoclusters nanocatalysis |
| 基金项目:Supported by Doctoral Startup Foundation of Anhui University (grant no. 10113190077), the Anhui Provincial Natural Science Foundation (grant no. 1608085QB39), and the National Natural Science Foundation of China (grant no. 51402001). |
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| 摘要点击次数: 1910 |
| 全文下载次数: 1879 |
| 中文摘要: |
| 金团簇表面的硫醇配体影响着团簇的催化性质，尤其是选择性.我们采用在真空条件下通过程序升温的方法逐渐剥除金团簇表面的硫醇配体来制备催化剂，利用透射电镜，红外光谱对催化剂结构进行表征，以硝基化合物催化还原反应为模型反应，详细研究了配体对催化活性和选择性的影响.研究发现因配体被剥离导致底物更容易接近团簇表面，最终使得反应转换率大幅升高.实验结果还表明金团簇催化剂催化不同官能团取代的底物显示了良好的官能团兼容性，有吸电子效应的硫配体使团簇表面带正电荷，进而避免苯胺衍生物的产生. |
| 英文摘要: |
| It was well-established that the thiolate ligands laid significant influence on the catalytic properties of protected Au nanoclusters (NCs for short), especially the selectivity. In this work, catalytic nitro reduction is investigated over nanocluster catalyst. The electron-withdrawing property of thiolates renders the surface positively charged, which results in less aniline derivatives. The conversion is found to augment a lot after complete removal of capping thiolates, owing to the accessibility of active sites on Au NCs. Furthermore, a range of functionalized substrates are investigated for the universality of this catalytic reaction, and the composite catalysts show good tolerance to functional groups. Moreover, the exterior ligands were gradually peeled off by thermal treatment through controlling the temperature under vacuum, and the as-prepared catalysts were characterized by TEM, FTIR measurements. Using these catalysts, the relationship between the extent of ligand removal and the catalytic activity/selectivity was investigated. |
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