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氮掺杂有序介孔碳负载钯纳米颗粒用于以氧气为氧化剂在无溶剂条件下将苯甲醇选择性氧化为苯甲醛

Nitrogen-Dopped Ordered Mesoporous Carbon Anchored Pd Nanoparticles for Solvent Free Selective Oxidation of Benzyl Alcohol to Benzaldehyde by Using O.

作者信息

Song Hongbing, Liu Zong, Gai Hengjun, Wang Yongjie, Qiao Lin, Zhong Caiyun, Yin Xiangyang, Xiao Meng

机构信息

State Key Laboratory Base for Eco-Chemical Engineering in College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao, China.

出版信息

Front Chem. 2019 Jun 27;7:458. doi: 10.3389/fchem.2019.00458. eCollection 2019.

Abstract

Introducing electron-rich nitrogen atoms to ordered mesoporous carbons (OMC) as supports for noble metal catalysts, not only improves the hydrophilic properties of a mesoporous carbon surface, but also enhances the coordination and binding abilities of metal ion. In the present work, nitrogen-doped ordered mesoporous carbons (NOMCs) were successfully fabricated via a facile hydrothermal self-assembly. The prepared NOMCs were characterized through powder X-ray diffraction (XRD), Raman spectroscopy, transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption-desorption isotherm. The analyses demonstrated that the NOMCs prepared at a pyrolysis temperature of 750°C possessed an ordered 2D hexagonal mesoporous structure, a high graphitization degree, large surface area, and a well-distributed pore size. In particular, NOMCs could anchor Pd nanoparticles uniformly because of the introducing N atoms with strong electronegativity, which were selected as efficient catalysts for the partial oxidation of benzyl alcohol to benzaldehyde. Approximately 24.63% conversion with 85.71% selectivity to benzaldehyde was obtained without using any solvent by molecular O oxidation. Most importantly, the TOF value of the catalyst in the reaction system was up to 8698 h. After five runs reaction, TOF and selectivity of the catalyst remained essentially same. Hence, the proposed catalyst has a potential engineering application value.

摘要

将富电子的氮原子引入有序介孔碳(OMC)作为贵金属催化剂的载体,不仅能改善介孔碳表面的亲水性,还能增强金属离子的配位和结合能力。在本工作中,通过简便的水热自组装成功制备了氮掺杂有序介孔碳(NOMC)。通过粉末X射线衍射(XRD)、拉曼光谱、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和氮吸附-脱附等温线对制备的NOMC进行了表征。分析表明,在750℃热解温度下制备的NOMC具有有序的二维六方介孔结构、高石墨化程度、大表面积和分布均匀的孔径。特别是,由于引入了具有强电负性的N原子,NOMC能够均匀地锚定Pd纳米颗粒,这些NOMC被选为将苯甲醇部分氧化为苯甲醛的高效催化剂。通过分子氧氧化,在不使用任何溶剂的情况下,获得了约24.63%的转化率和85.71%的苯甲醛选择性。最重要的是,反应体系中催化剂的TOF值高达8698 h⁻¹。经过五次循环反应后,催化剂的TOF和选择性基本保持不变。因此,所提出的催化剂具有潜在的工程应用价值。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/af64/6610524/518dcbc4b829/fchem-07-00458-g0001.jpg

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