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具有超薄壁的磁性空心铂纳米笼作为用于催化转移氢化反应的高度集成纳米反应器。

Magnetically Hollow Pt Nanocages with Ultrathin Walls as a Highly Integrated Nanoreactor for Catalytic Transfer Hydrogenation Reaction.

作者信息

Ai Yongjian, Hu Zenan, Liu Lei, Zhou Junjie, Long Yang, Li Jifan, Ding Mingyu, Sun Hong-Bin, Liang Qionglin

机构信息

Key Laboratory of Bioorganic Phosphorus Chemistry & Chemical Biology (Ministry of Education) Beijing Key Lab of Microanalytical Methods & Instrumentation Department of Chemistry Center for Synthetic and Systems Biology Tsinghua University Beijing 100084 P. R. China.

Department of Chemistry Northeastern University Shenyang 110819 P. R. China.

出版信息

Adv Sci (Weinh). 2019 Feb 7;6(7):1802132. doi: 10.1002/advs.201802132. eCollection 2019 Apr 3.

Abstract

Fabricating efficient and stable nanocatalysts for chemoselective hydrogenation of nitroaromatics is highly desirable because the amines hold tremendous promise for the synthesis of nitrogen containing chemicals. Here, a highly reactive and stable porous carbon nitride encapsulated magnetically hollow platinum nanocage is developed with subnanometer thick walls (FeO@Pt@PCN) for this transformation. This well-controlled nanoreactor is prepared via the following procedures: the preparation of core template, the deposition of platinum nanocage with subnanometer thick walls, oxidative etching, and calcination. This highly integrated catalyst demonstrates excellent performance for the catalytic transfer hydrogenation of various nitroaromatics and the reaction can reach >99% conversion and >99% selectivity. With the ultrathin wall structure, the atom utilization of platinum atoms is highly efficient. The X-ray photoelectron spectroscopy results indicate that partial electrons transfer from the iron oxides to Pt nanowalls, and this increases the electron density of Pt nanoparticles, thus promoting the catalytic activity for the transfer hydrogenation of nitroaromatics. For the reduction of 4-nitrophenol, the reaction rate constant is 0.23 min and the turnover frequency (TOF) is up to 3062 h. Additional reaction results illustrate that this magnetic nanoreactor can be reused more than eight times and it is a promising catalytic nanoplatform in heterogeneous catalysis.

摘要

制备用于硝基芳烃化学选择性加氢的高效稳定纳米催化剂非常有必要,因为胺类化合物在含氮化学品的合成中具有巨大潜力。在此,我们开发了一种具有亚纳米厚壁的高活性且稳定的多孔氮化碳包覆磁性空心铂纳米笼(FeO@Pt@PCN)用于这种转化反应。这种精确控制的纳米反应器通过以下步骤制备:制备核模板、沉积具有亚纳米厚壁的铂纳米笼、氧化蚀刻和煅烧。这种高度集成的催化剂在各种硝基芳烃的催化转移加氢反应中表现出优异的性能,反应转化率可达>99%,选择性>99%。由于具有超薄壁结构,铂原子的原子利用率很高。X射线光电子能谱结果表明,部分电子从铁氧化物转移到铂纳米壁上,这增加了铂纳米颗粒的电子密度,从而提高了硝基芳烃转移加氢的催化活性。对于4-硝基苯酚的还原反应,反应速率常数为0.23 min,周转频率(TOF)高达3062 h。其他反应结果表明,这种磁性纳米反应器可以重复使用八次以上,是多相催化中一种很有前景的催化纳米平台。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f3a3/6446610/260a46e92390/ADVS-6-1802132-g001.jpg

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