纳米二硫化钼及其复合材料的制备和分析应用研究

Molybdelum disulfide nanomaterials have aroused great research interests due to their peculiar properties in recent years. But few have reported electrochemical study of monodisperse molybdelum disulfide nanoparticles in solutions. This project focuses on synthesis of highly monodisperse molybdelum disulfide nanoparticles in organic solvents with their sizes < 5 nm and study of their electrochemical properties, which is expected to develop a novel detection method based on electrochemistry of nanoparticles and interaction with detected substances. To further construct electrochemical sensors of biomacromolecules and small molecules based on molybdelum disulfide nanoparticles and achieve highly sensitive detection. The study of core@shell nanoparticles has a wide range of applications because of the unique combination of the nanoscale core and the functional shell. This project also focuses on synthesis of composite nanomaterials MoS2@Au with molybdelum disulfide nanoparticles as the core and gold nanoparticles as the shell and characterization of their optical and electrochemical properties as well as study of their application in electrocatalysis, electrochemical and optical sensors. They are expected to realize highly sensitive and specific detection for biomolecules. This project explores systematically electrochemical and optical properties as well as applications of molybdelum disulfide and its composite nanomaterials, not only which will extend their application research, but also which will found a base for synthesis of novel nanometer composite materials with specific functions. It will have the extremely theoretical significance and the research value.

一方面，纳米二硫化钼由于其独特的性质而引起了人们极大的研究兴趣。而有关单分散的纳米二硫化钼粒子在溶液中的电化学研究还未见报道。本项目拟合成在一些有机溶剂中呈高度单分散、尺寸在5纳米以下的二硫化钼粒子，研究它们在溶液中的电化学行为，探索建立基于它们的电化学、检测与其有相互作用的物质的新的电分析方法。并构筑基于纳米二硫化钼的电化学传感器，用于生物大分子和小分子的高灵敏检测。另一方面，本项目也拟合成纳米金包覆纳米二硫化钼的新的核壳型复合纳米粒子，表征它们的电化学和光学性质，应用于电催化的研究，并用于构筑电化学传感器和光化学传感器，实现对一些物质尤其是生物分子的高灵敏和特异性检测。系统地开展纳米二硫化钼及其复合材料的电化学和光学性质研究及应用，不仅拓展了这种纳米材料的应用研究，也为合成具有特定功能的新的纳米复合材料打下基础，具有十分重要的理论意义和研究价值。

纳米二硫化钼由于其独特的结构和性质而引起人们极大的研究兴趣。在本项目中，我们提出用超声和梯度离心的简单方法制备不同尺寸的纳米二硫化钼，证实了不同尺寸的二硫化钼对析氢反应和氧还原反应的尺寸效应，即尺寸越小，催化活性越高；获得了2纳米以下的、在溶剂中呈高度单分散的二硫化钼纳米粒子和层状纳米二硫化钼复合物，构筑了基于纳米二硫化钼的电化学传感器，用于生物大分子DNA和小分子过氧化氢、葡萄糖的高灵敏检测；发现了超小的二硫化钼纳米粒子对氧还原反应的电催化，构筑了二硫化钼纳米粒子支撑在金纳米粒子（尺寸不超过16 nm）上的复合膜，实现在碱性溶液中对氧还原的高效电催化；通过自组装形成共价键，将超小的二硫化钼纳米粒子固定在金电极上，改善了其对氢析出反应的电催化活性；借助电聚合的方法制备聚吡咯/多硫化钼共聚膜电沉积在玻碳电极上，实现催化析氢性能可与商品化的铂/碳催化剂相媲美。提供了一种通过研磨和电化学活化的简便方法将磷化钼表面氧化层转化为活性磷化钼，从而提高磷化钼的实际氢析出催化活性。发现硒掺杂形成的NiP1.93Se0.07显示了较好的析氢活性，提供了掺杂能改变催化剂析氢活性的新思路。合成了半胱氨酸修饰的二硫化钼纳米颗粒，有助于消除体内因辐射产生的活性氧（ROS）等自由基和修复DNA的损伤，在作为辐射防护剂方面显示了应用潜力。.本项目系统地开展了纳米二硫化钼及其复合材料在电化学传感和电催化方面的研究，不仅拓展了二硫化钼纳米粒子在电化学传感和电催化能源转化领域的应用，而且提出基于自组装和电聚合构筑高效电催化界面的新思路。对于发展高灵敏、高选择性的电分析检测新方法,以及能源转化具有重要理论意义与应用价值。