疏水性钯纳米团簇的合成及其作为表面增强拉曼散射基底的应用

doi:10.16085/j.issn.1000-6613.2019-0707

摘要/Abstract

摘要：

以醋酸钯为前体、有机氢硅烷为还原剂开发了一种简单温和的疏水性钯纳米颗粒制备方法。通过调节前体、保护剂和还原剂的配比，在氯仿溶液中室温条件下合成了疏水性的钯纳米团簇和钯纳米球。运用透射电子显微镜（TEM）、X射线衍射（XRD）、光学接触角测试仪、循环伏安法（CV）、表面增强拉曼光谱（SERS）对这两种钯纳米材料进行了测试表征。TEM观察表明这两种钯纳米材料粒径分布均匀，分散性良好。接触角测试表明钯纳米团簇与钯纳米球均具有疏水性。CV测定结果显示这两种钯纳米材料具有良好的电催化稳定性，钯纳米团簇比钯纳米球对乙醇氧化具有更突出的电催化性能，表明钯纳米团簇结构稳定并具有更大的比表面积。SERS测试表明钯纳米团簇是一种优良的疏水性表面增强拉曼散射基底，利用这种基底对疏水性致癌物3,4-苯并芘和联苯胺进行了SERS快速检测，检测限为0.1mg/mL。

关键词: 钯纳米团簇, 钯纳米球, 合成, 表面增强拉曼光谱, 基底

Abstract:

A simple and mild approach for the synthesis of hydrophobic palladium nanomaterials using palladium acetate as a precursor and hydrosilane as a reducing agent was developed. Hydrophobic Pd nanoclusters and spherical Pd nanoparticles were prepared in chloroform at room temperature by adjusting the molar ratio of precursor, protective agent and reducing agent, respectively. Transmission electron microscope (TEM), optical contact angle tester, X-ray diffraction (XRD), cyclic voltammetry (CV) and surface enhanced Raman scattering (SERS) were employed to characterize the obtained palladium nanomaterials. TEM images displayed that the two Pd nanomaterials had uniform particle size distribution and good dispersion, and the contact angle measurements showed that both Pd nanoclusters and Pd nanoparticles were hydrophobic. CV tests indicated that the Pd nanoclusters exhibited more notable electrocatalytic performance than spherical Pd nanoparticles for ethanol oxidation, and the two Pd nanomaterials demonstrated good electrocatalytic stability, showing that Pd nanoclusters possessed stable structures and larger specific surface area than spherical Pd nanoparticles. The Pd nanoclusters were found to be an excellent hydrophobic substrate for surface-enhanced Raman scattering. Hydrophobic carcinogens such as 3,4-benzopyrene and benzidine were detected via SERS using the Pd nanoclusters as a substrate. The limit of detection for 3,4-benzopyrene and benzidine was 0.1mg/mL.

Key words: Pd nanoclusters, Pd spherical nanoparticles, synthesis, SERS, substrate

中图分类号:

O614.82

欧阳杰,朱文仙,张小会,唐华东,黄荣斌. 疏水性钯纳米团簇的合成及其作为表面增强拉曼散射基底的应用[J]. 化工进展, 2019, 38(11): 5048-5056.

Jie OUYANG,Wenxian ZHU,Xiaohui ZHANG,Huadong TANG,Rongbin HUANG. Synthesis of hydrophobic palladium nanocluster and its application as a substrate for surface enhanced raman scattering[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 5048-5056.

图/表 11

图1 钯纳米球的TEM图片与EDX谱图

图2 钯纳米团簇的TEM图片与EDX谱图

图3 钯纳米团簇与钯纳米球的疏水性表征

图4 钯纳米球与钯纳米团簇的XRD 谱图

图5 钯纳米球与钯纳米团簇在1.0mol·L–1 NaOH溶液中的循环伏安曲线

图6 钯纳米球与钯纳米团簇在1.0mol·L–1 NaOH + 1.0mol·L–1 EtOH溶液中的循环伏安曲线

图7 钯纳米球与钯纳米团簇在1.0mol·L–1 NaOH + 1.0mol·L–1 EtOH溶液中，连续循环扫描50次的循环伏安曲线

图8 1.0mg·mL–1联苯胺在钯纳米球与钯纳米团簇基底上的SERS谱图

图9 不同浓度的联苯胺在钯纳米团簇基底上的SERS谱图

图10 1.0mg·mL–1 3,4-苯并芘在钯纳米球与钯纳米团簇

图11 不同浓度的3,4-苯并芘在钯纳米团簇基底上的SERS谱图

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