CuNi纳米晶的可控合成及Pt/CuNi催化剂催化肉桂醛加氢性能

doi:10.16085/j.issn.1000-6613.2019-1320

摘要/Abstract

摘要：

采用水热法制备了CuNi二元金属纳米晶。以水合肼为还原剂，探究水热合成温度、表面活性剂[乙二胺（EDA）、聚乙烯吡咯烷酮（PVP）、十六烷基三甲基溴化铵（CTAB）]对CuNi纳米晶形貌的影响。随水热合成温度的升高（60℃、90℃、120℃、150℃），Cu²⁺、Ni²⁺的还原速率加快，有利于形成Cu@Ni核壳结构。以EDA为表面活性剂时，制备的CuNi二元金属纳米晶在120℃和150℃时分别呈现花状和海胆状。此外，以CuNi纳米晶为催化剂载体，采用化学置换法负载贵金属Pt合成了Pt/CuNi三元金属催化剂。X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、扫描电镜X射线能谱（SEM-EDS）、X射线光电子能谱（XPS）、高角度环形暗场扫描透射（HAADF-STEM）和元素面扫（STEM-EDS）表征结果表明，Pt/CuNi催化剂纳米结构为小岛状的Pt纳米团簇负载于CuNi纳米晶。其中，Pt/CuNi-120-EDA（120为水热合成温度，EDA为制备CuNi纳米晶时添加的表面活性剂）催化剂表面具有较丰富的缺陷位和活性位点，使其在肉桂醛加氢反应中表现出最佳的催化性能（80℃下对苯丙醇的产率达100%）。

关键词: 纳米结构, 水热, 加氢, 催化剂, 形貌

Abstract:

CuNi bimetallic nanocrystals were prepared by hydrothermal synthesis method with hydrazide hydrate as reductant, and the effects of hydrothermal synthesis temperature and surfactants (EDA, PVP and CTAB) on the morphology of the CuNi nanocrystals were investigated. With the increase of temperature from 60℃ to 150℃, the reduction of Cu²⁺ and Ni²⁺ were accelerated, which was beneficial to the formation of Cu@Ni core-shell structure. When the hydrothermal temperatures were 120℃ and 150℃ respectively and EDA was used as surfactant, the CuNi bimetallic nanocrystals with flower-like and urchin-like morphologies were obtained accordingly. In addition, the Pt/CuNi tri-metallic catalysts were synthesized via the galvanic replacement reaction by using the CuNi nanocrystals as support. The characterization results of X-ray powder diffraction (XRD), scanning electron microscopy (SEM), scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS), X-ray photoelectron spectroscopy (XPS), high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM) and scanning transmission electron microscopy energy dispersive X-ray spectroscopy (STEM-EDS) mapping confirmed that the nanostructure of the Pt/CuNi catalysts was Pt nanoclusters in the form of small islands supported on the CuNi nanocrystals. Furthermore, the surface of the Pt/CuNi-120-EDA catalyst (synthesized at 120℃ with EDA as the surfactant) had abundant defects and active sites, showing the highest catalytic activity in cinnamaldehyde hydrogenation with the yield to phenyl propanol reaching 100% at 80℃.

Key words: nanostructure, hydrothermal, hydrogenation, catalyst, morphology

中图分类号:

O643.36

张欢, 阮露娜, 裴安, 艾文斌, 吴锋顺, 熊晚枫, 朱丽华. CuNi纳米晶的可控合成及Pt/CuNi催化剂催化肉桂醛加氢性能[J]. 化工进展, 2020, 39(5): 1774-1783.

Huan ZHANG, Luna RUAN, An PEI, Wenbin AI, Fengshun WU, Wanfeng XIONG, Lihua ZHU. Controlled synthesis of CuNi nanocrystals and the catalytic performance of Pt/CuNi catalysts for cinnamaldehyde hydrogenation[J]. Chemical Industry and Engineering Progress, 2020, 39(5): 1774-1783.

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