多级电位调控非对称杂化纳米通道的离子整流性质研究

By learning from the asymmetric structure and smart responsive function of biological ion channels,the fabrication of responsive asymmetric artificial nanochannels demonstrates crucial research significance for developing new energy convertor,rectifier and sensor. Nowadays, several kinds of artificial asymmetric nanochannels that could respond to the external stimuli have been fabricated sucessfully. However, there is no report on the potential-responsive artificial asymmetric nanochannels.Our proposal focuses on the fabrication of polypyrrole/Al2O3 (organic/inorganic) and Prussian blue/Al2O3(organic/inorganic) asymmetric hybrid nanochannels by the combination of ion sputtering and electrochemical deposition technology, realizing the ion rectification effect. The redox reaction of electroresponsive molecules of polypyrrole and prussian blue under different potentials will change the distribution of surface charges in hybrid nanochannels, which may play significant role on the ion rectification effect of hybrid nanochannaels. We will investigate the effect of the length of electroresponsive molecules, the pore diameter, the charge polarity and the concentration of electrolyte on the ion rectification of hybrid nanochannels. Particularly, the regulation effect of multi-level-potential on the ion rectification of hybrid nanochannels and their reversibility will be investigated in detail.Finally, we will use Possion-Nernst-Plank equation to calculate the current-voltage curves of hybrid nanochannels based on a model of single hybrid cylindrical nanochannels to elucidate the potential-regulation mechanism.

模拟生物离子通道的非对称结构和智能响应功能来构筑外场响应的人工非对称纳米通道体系对于发展新型的能量转换器、整流器与传感器具有重要的研究意义。目前，多种外场响应的人工非对称纳米通道已经被研究，但电位响应的人工非对称纳米通道尚未报道。本项目结合离子溅射与电化学沉积技术制备具有非对称结构的聚吡咯/氧化铝（有机/无机）和普鲁士蓝/氧化铝(无机/无机)两种杂化纳米通道，研究其离子整流效应。利用聚吡咯或普鲁士蓝两种电响应分子在不同电位下发生氧化还原反应所导致的表面电荷变化，实现杂化纳米通道离子整流效应的多级电位响应。本项目将详细研究电响应分子沉积长度、杂化纳米通道孔径、表面电荷以及电解质浓度对杂化纳米通道离子整流效应影响。研究多个外加电位对杂化纳米通道离子整流效应的调控效应及其可逆性。最后，以单个圆柱形杂化纳米通道为模型，利用泊松-能斯特-普朗克方程计算出离子整流曲线，验证多级电位响应的机理。

构筑生物离子通道模拟的具有电位响应特征的杂化纳米通道对于发展新型的能量转换器、整流器与离子开关具有重要的研究意义。本项目制备了聚吡咯/阳极氧化铝杂化纳米通道，研究了其离子整流性质。利用聚吡咯分子在不同电位下发生氧化还原反应所导致的表面电荷变化，实现了杂化纳米通道离子整流效应的多级电位响应。详细研究了聚吡咯沉积长度、纳米通道几何参数对杂化纳米通道离子整流效应的影响。电调控的离子整流效应表现出优秀的可逆性。利用泊松-能斯特-普朗克方程计算出离子整流曲线，验证了多级电位响应的机理。同时，项目制备了聚吡咯/金网杂化纳米通道以及蒙脱土/表面活性剂杂化层状纳米通道，研究了其电位响应的离子传输性质。初步开展了人工纳米通道在盐差转换以及离子开关领域应用的研究。在国际期刊上以通讯作者发表SCI 论文12 篇，包括Adv. Mater. 1篇，Nano Energy 1篇，Nano Res. 1篇，Chem. Commun. 2篇， Chem. Eur. J. 1篇，J. Phys. Chem. C 1篇，Sci. Rep. 1篇，Energy Technol. 1篇， RSC Adv. 2篇, 《化学学报》1篇。参加国内外学术会议7次。申请国家专利6 项，其中授权3项。培养研究生7名。