贫氧Cu@多孔层@多胺复合材料的制备及其在生理pH下的葡萄糖无酶电化学检测研究

Glucose sensor is a highly active area of sensor research. The development of non-enzymatic glucose sensors and their application to real biological samples have risen at a considerable rate. For the Cu-based materials, the lack of CuIII/CuII redox couples restricts their electro-catalytic activity in physiology pH solution. According to the IHOAM model, the Cu+·nH2O/Cu redox couples on the surface of active Cu atoms have highly catalytic activity in electro-catalysis process. So preparation of Cu nanostructures with pure surface is important for the application of Cu-based non-enzymatic sensor to physiology pH solution. In the present project, surface oxide-less Cu nanostructures with high activity will be prepared in aqueous solution, based on the active Cu, oxide-less Cu@porous-layer@polyamine nanocomposite will be prepared to construct non-enzymatic sensor that can be applied to physiology pH solution. A porous-layer (SiO2 or TiO2) will be designed on the surface of Cu nanostructures as an oxygen permeability layer to control the oxide state of Cu atoms, ensuring the generation of Cu+ on the surface of Cu atoms. Then the oxide-less Cu@porous-layer will be encapulsated by polyamine. The polyamine layer not only can improve the anti-oxidation property in air storage, but also allow the pass of glucose molecules and molecules containing oxygen in physiology pH solution. The electro-catalytic activity of the oxide-less Cu@porous-layer@polyamine nanocomposite in physiology pH solution will be studied for non-enzymatic sensing of glucose. Method for synthesis of surface oxide-less Cu nanostructures in aqueous solution, technology for adjustment of porous-layer and polyamine layer, Cu-based non-enzymatic glucose sensor that can be applied to physiology pH solution will be designed based on this project.

将无酶传感器应用于生理条件下血糖实际样品检测是未来的研究趋势，对于Cu纳米材料来说，在生理pH下电极表面Cu(III)/Cu(II)电对的缺失使得Cu对葡萄糖的电催化氧化反应无法进行。利用表面结合度低的活性Cu原子表面的Cu+·nH2O/Cu电对有望实现Cu基无酶传感器在生理pH下对葡萄糖的检测。项目拟以高活性贫氧Cu纳米材料为基础，设计制备贫氧Cu@多孔层@多胺复合材料，构建适用于生理pH条件的新型Cu基无酶葡萄糖电化学传感器。研究方案采用水溶液法在酸性条件下合成活性贫氧Cu纳米材料，沉积SiO2或TiO2多孔层控制贫氧Cu表面在电催化应用时轻度氧化生成有效Cu+·nH2O/Cu电对，沉积多胺层满足贫氧Cu在储存时的抗氧化要求和在电催化使用时允许含氧小分子及葡萄糖分子透过的要求。以制备的贫氧Cu@多孔层@多胺复合材料构建无酶传感器，研究在近中性pH条件下对葡萄糖的检测应用。

铜基纳米材料催化剂在能源转换和环境修复方面的应用潜力，日益受到研究者的重视。充分利用铜基纳米材料本身的物理化学性质对其进行修饰改性，进而提高其催化活性具有一定的意义。项目通过结构设计、形貌控制和活性物质复合等策略，成功地构建了系列铜基复合电催化剂，催化剂在无酶检测葡萄糖、超级电容器和电催化水分解等方面表现出了优异的催化活性。设计合成了表面贫氧高活性单质Cu纳米颗粒，片状、海胆状CuO纳米材料，海胆状Co(OH)2@CuO复合结构，片状Co3O4@CuO复合结构，Cu2S-Cu(OH)2纳米管阵列等系列材料。通过小分子有机酸调节合成环境，完善了表面贫氧的高活性单质铜纳米颗粒的制备方法；通过添加诱导剂，调控晶体的生长和结合方向，获得了不同形貌的氧化铜纳米材料；同时，尝试在铜基材料表面引入钴活性中心，通过氨分子配位作用，构建铜和钴化合物间的键连关系，增强复合材料间的协同作用，获得系列铜基复合催化剂。通过对材料的结构研究，探讨了材料的形成机理。系统研究了催化剂的电催化活性，催化剂在无酶检测葡萄糖、超级电容器和电催化水分解析氢/析氧等方面表现出预期的催化活性。研究了复合材料间的协同作用与性能间的关系，探讨了催化作用机制等问题，为铜基纳米材料高效催化剂的进一步设计及开发提供了可靠的研究基础。相关研究工作已在Journal of Colloid and Interface Science、Electrochimica Acta、Materials Research Bulletin等刊物上正式发表。