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多孔立方聚集 Co3O4 微球负载金纳米粒子用于一氧化碳和甲苯的氧化。

Porous cube-aggregated Co3O4 microsphere-supported gold nanoparticles for oxidation of carbon monoxide and toluene.

机构信息

Laboratory of Catalysis Chemistry and Nanoscience, Department of Chemistry and Chemical Engineering, College of Environmental and Energy Engineering, Beijing University of Technology, Beijing 100124 (PR China), Fax: (+86) 10-6739-1983.

出版信息

ChemSusChem. 2014 Jun;7(6):1745-54. doi: 10.1002/cssc.201400050. Epub 2014 Jun 5.

Abstract

Porous cube-aggregated monodisperse Co3O4 microspheres and their supported gold (xAu/Co3O4 microsphere, x=1.6-7.4 wt %) nanoparticles (NPs) were fabricated using the glycerol-assisted solvothermal and polyvinyl alcohol-protected reduction methods. Physicochemical properties of the materials were characterized by means of numerous analytical techniques, and their catalytic activities were evaluated for the oxidation of toluene and CO. It is shown that the cubic Co3O4 microspheres were composed of aggregated cubes with a porous structure. The gold NPs with a size of 3.2-3.9 nm were uniformly deposited on the surface of Co3O4 microspheres. Among the Co3O4 microsphere and xAu/Co3O4 microsphere samples, the 7.4Au/Co3O4 microspheres performed the best, giving T90 % values (the temperature required for achieving a CO or toluene conversion of 90 % at a weight hourly space velocity of 20 000 mL g(-1)  h(-1)) of -8 and 250 °C for CO and toluene oxidation, respectively. In the case of 3.0 vol % water vapor introduction, a positive effect on CO oxidation and a small negative effect on toluene oxidation were observed over the 7.4Au/Co3O4 microsphere sample. The apparent activation energies obtained over the xAu/Co3O4 microsphere samples were in the ranges of 40.7-53.6 kJ mol(-1) for toluene oxidation and 21.6-34.6 kJ mol(-1) for CO oxidation. It is concluded that the higher oxygen adspecies concentration, better low-temperature reducibility, and stronger interaction between gold NPs and Co3O4 as well as the porous microspherical structure were responsible for the excellent catalytic performance of 7.4Au/Co3O4 microsphere.

摘要

多孔立方聚集体单分散 Co3O4 微球及其负载的金(xAu/Co3O4 微球,x=1.6-7.4wt%)纳米颗粒(NPs)是通过甘油辅助溶剂热和聚乙烯醇保护还原方法制备的。通过多种分析技术对材料的物理化学性质进行了表征,并评价了它们在甲苯和 CO 氧化反应中的催化活性。结果表明,立方 Co3O4 微球由具有多孔结构的聚集体立方组成。金 NPs 的尺寸为 3.2-3.9nm,均匀沉积在 Co3O4 微球的表面上。在 Co3O4 微球和 xAu/Co3O4 微球样品中,7.4Au/Co3O4 微球的性能最好,CO 和甲苯氧化的 T90%值(在重量空速为 20000mL·g-1·h-1 时达到 CO 或甲苯转化率 90%所需的温度)分别为-8 和 250°C。在引入 3.0vol%水蒸气的情况下,在 7.4Au/Co3O4 微球样品上观察到对 CO 氧化的正效应和对甲苯氧化的小负效应。在 xAu/Co3O4 微球样品上获得的表观活化能范围分别为甲苯氧化的 40.7-53.6kJ·mol-1 和 CO 氧化的 21.6-34.6kJ·mol-1。结论是,较高的氧吸附物种浓度、更好的低温还原性、金 NPs 与 Co3O4 之间更强的相互作用以及多孔微球结构是 7.4Au/Co3O4 微球具有优异催化性能的原因。

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