Fe<sub>3</sub>O<sub>4</sub>修饰的Pt-Ru/C纳米催化剂的制备及其在无溶剂条件下邻氯硝基苯选择性加氢的催化性能

引用本文: 王亚南, 杨玉霞, 李永文, 赖俊华, 孙鲲鹏. Fe₃O₄修饰的Pt-Ru/C纳米催化剂的制备及其在无溶剂条件下邻氯硝基苯选择性加氢的催化性能[J]. 物理化学学报, 2013, 29(10): 2239-2244. doi: 10.3866/PKU.WHXB201308151 shu

Citation: WANG Ya-Nan, YANG Yu-Xia, LI Yong-Wen, LAI Jun-Hua, SUN Kun-Peng. Preparation of Fe₃O₄ Modified Pt-Ru/C Nanocatalysts and Their Catalytic Properties for the Selective Hydrogenation of ortho-Chloronitrobenzene under Solvent-Free Conditions[J]. Acta Physico-Chimica Sinica, 2013, 29(10): 2239-2244. doi: 10.3866/PKU.WHXB201308151 shu

Fe₃O₄修饰的Pt-Ru/C纳米催化剂的制备及其在无溶剂条件下邻氯硝基苯选择性加氢的催化性能

摘要:

采用浸渍法制备了一系列Pt/Ru质量比不同的Fe₃O₄修饰的Pt-Ru/Fe₃O₄/C催化剂, 运用透射电镜(TEM)、能量弥散X射线谱(EDX)、X射线光电子能谱(XPS)、X射线粉末衍射(XRD)等手段对Pt-Ru/Fe₃O₄/C一系列催化剂进行了表征, 并考察了Pt/Ru质量比不同对催化剂Pt-Ru/Fe₃O₄/C在无溶剂条件下催化邻氯硝基苯(o-CNB)选择性加氢制备邻氯苯胺(o-CAN)催化性能的影响. 研究结果表明, 催化剂的催化活性和对目标产物的选择性跟活性组分Pt、Ru比例有关. 随着Pt/Ru比例的减小, 目标产物o-CAN的选择性有所升高, 然而反应物o-CNB的转化率有所下降. 当Pt/Ru的质量比为2时, o-CNB的转化率降为76.5%, 而目标产物o-CAN的选择性仍然为100%. 与此同时, 我们还对Pt-Ru/Fe₃O₄/C催化剂高的催化活性和目标产物的高选择性可能的原因进行了分析.

关键词:

English

Preparation of Fe₃O₄ Modified Pt-Ru/C Nanocatalysts and Their Catalytic Properties for the Selective Hydrogenation of ortho-Chloronitrobenzene under Solvent-Free Conditions

1.
1 Centre for Green Chemistry and Catalysis, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China;
2 University of Chinese Academy of Sciences, Beijing 100049, P. R. China;
3 Cold and Arid Regions Environmental and Engineering Research Institute, Chinese Academy of Sciences, Lanzhou 730000, P. R. China
Received Date: 10 April 2013
Available Online: 26 September 2013

Abstract:

Aseries of Fe₃O₄-modified Pt-Ru/C nanocomposite catalysts were prepared by impregnation and hydrazine hydrate reduction of Pt and Ru precursors. Various Pt/Ru mass ratios of the catalysts were examined in terms of catalytic activity. They were characterized by transmission electron microscopic measurements (TEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD). The average diameters of the catalysts with different mass ratios of Pt/Ru were in a range of 2.2-2.5 nmwith narrowsize distributions. The valence states of the nanoparticles indicate strong interactions between the Pt and the carbon support or with Fe₃O₄. The XRDpatterns of the 8Pt-1Ru/Fe₃O₄/C, 6Pt-1Ru/Fe₃O₄/ C, 4Pt-1Ru/Fe₃O₄/C, and 2Pt-1Ru/Fe₃O₄/Ccatalysts have similar profiles, which are attributed to the cubic phase of pure Fe₃O₄ (i.e., no Pt or Ru present). These catalysts selectively hydrogenate ortho-chloronitrobenzene (o-CNB) to the corresponding ortho-chloroaniline (o-CAN) under solvent-free conditions that not only allowed high substrate concentrations promoting the hydrogenation reaction, but also enabled easy product separation and purification. They exhibited excellent catalytic activity (turnover frequency (TOF) range: 0.98-2.09 mol·mol^-1·s^-1) and up to 100% o-CAN selectivity, which was composition-dependent. The o-CAN yield selectivity monotonically increased with the proportion of Ru; however, the catalytic activity decreased. The high catalytic activity and selectivity of Pt-Ru/Fe₃O₄/Cnanoparticles are attributed to electron transfer between the two metals and Fe₃O₄.

Key words:

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

Fe₃O₄修饰的Pt-Ru/C纳米催化剂的制备及其在无溶剂条件下邻氯硝基苯选择性加氢的催化性能

English

Preparation of Fe₃O₄ Modified Pt-Ru/C Nanocatalysts and Their Catalytic Properties for the Selective Hydrogenation of ortho-Chloronitrobenzene under Solvent-Free Conditions

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Fe3O4修饰的Pt-Ru/C纳米催化剂的制备及其在无溶剂条件下邻氯硝基苯选择性加氢的催化性能

English

Preparation of Fe3O4 Modified Pt-Ru/C Nanocatalysts and Their Catalytic Properties for the Selective Hydrogenation of ortho-Chloronitrobenzene under Solvent-Free Conditions

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Fe₃O₄修饰的Pt-Ru/C纳米催化剂的制备及其在无溶剂条件下邻氯硝基苯选择性加氢的催化性能

Preparation of Fe₃O₄ Modified Pt-Ru/C Nanocatalysts and Their Catalytic Properties for the Selective Hydrogenation of ortho-Chloronitrobenzene under Solvent-Free Conditions

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs