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基于自模板还原策略在分级蛋黄壳结构Fe@SiO中原位限域生长高分散镍纳米颗粒作为高效催化剂

In Situ Confined Growth Based on a Self-Templating Reduction Strategy of Highly Dispersed Ni Nanoparticles in Hierarchical Yolk-Shell Fe@SiO Structures as Efficient Catalysts.

作者信息

Jiao Jiao, Wang Haiyan, Guo Wanchun, Li Ruifei, Tian Kesong, Xu Zhaopeng, Jia Yin, Wu Yuehao, Cao Ling

机构信息

Key Laboratory of Applied Chemistry of Hebei Province, College of Environmental and Chemical Engineering, Yanshan University, Qinhuangdao, 066004, P. R. China.

Key Laboratory for Special Fiber and Fiber Sensor of Hebei Province, School of Information Science and Engineering, Yanshan University, Qinhuangdao, 066004, P. R. China.

出版信息

Chem Asian J. 2016 Dec 19;11(24):3534-3540. doi: 10.1002/asia.201601196. Epub 2016 Nov 23.

Abstract

Ni-based magnetic catalysts exhibit moderate activity, low cost, and magnetic reusability in hydrogenation reactions. However, Ni nanoparticles anchored on magnetic supports commonly suffer from undesirable agglomeration during catalytic reactions due to the relatively weak affinity of the magnetic support for the Ni nanoparticles. A hierarchical yolk-shell Fe@SiO /Ni catalyst, with an inner movable Fe core and an ultrathin SiO /Ni shell composed of nanosheets, was synthesized in a self-templating reduction strategy with a hierarchical yolk-shell Fe O @nickel silicate nanocomposite as the precursor. The spatial confinement of highly dispersed Ni nanoparticles with a mean size of 4 nm within ultrathin SiO nanosheets with a thickness of 2.6 nm not only prevented their agglomeration during catalytic transformations but also exposed the abundant active Ni sites to reactants. Moreover, the large inner cavities and interlayer spaces between the assembled ultrathin SiO /Ni nanosheets provided suitable mesoporous channels for diffusion of the reactants towards the active sites. As expected, the Fe@SiO /Ni catalyst displayed high activity, high stability, and magnetic recoverability for the reduction of nitroaromatic compounds. In particular, the Ni-based catalyst in the conversion of 4-nitroamine maintained a rate of over 98 % and preserved the initial yolk-shell structure without any obvious aggregation of Ni nanoparticles after ten catalytic cycles, which confirmed the high structural stability of the Ni-based catalyst.

摘要

镍基磁性催化剂在氢化反应中表现出适度的活性、低成本和磁性可重复使用性。然而,由于磁性载体对镍纳米颗粒的亲和力相对较弱,锚定在磁性载体上的镍纳米颗粒在催化反应过程中通常会出现不良团聚现象。采用自模板还原策略,以分级蛋黄壳结构的Fe₂O₃@硅酸镍纳米复合材料为前驱体,合成了一种具有内部可移动铁核和由纳米片组成的超薄SiO₂/Ni壳层的分级蛋黄壳结构Fe@SiO₂/Ni催化剂。平均尺寸为4nm的高度分散的镍纳米颗粒被空间限制在厚度为2.6nm的超薄SiO₂纳米片内,这不仅在催化转化过程中防止了它们的团聚,还使大量活性镍位点暴露于反应物中。此外,组装的超薄SiO₂/Ni纳米片之间的大内腔和层间空间为反应物向活性位点的扩散提供了合适的介孔通道。正如预期的那样,Fe@SiO₂/Ni催化剂在硝基芳烃化合物的还原反应中表现出高活性、高稳定性和磁性可回收性。特别是,在4-硝基胺转化反应中的镍基催化剂在十个催化循环后保持了超过98%的转化率,并保留了初始的蛋黄壳结构,镍纳米颗粒没有任何明显的聚集,这证实了镍基催化剂的高结构稳定性。

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