水环境中多种形态痕量重金属高效消解和检测仿生微纳传感器研究

The project focus on major requirements of on-site rapid detection of heavy metals in water environment monitoring field, and in view of the problem of difficult to accurately measure for the heavy metals in water body because of no/organic complexing state, etc. The project presents a novel bio-inspired micro-nano sensor from the shark olfactory ultra-high sensitive micro/nano structure of biological tissue for heavy metal digestion and measurement. This sensor was micro-fabricated by MEMS/NENO technology and microfluidic technology for sample separation. The sensor integrated oxidization electrode, detection electrode, reference electrode and counter electrode. It performed the electrochemical oxidation for heavy metal digestion and Stripping voltammetry for detection. The project will solve the compatibility of fabrication process, also the assays between oxidation and measurement. Through this project research, a novel portable trance heavy metal analyzer for on-site and high-speed detection will be produced. The analyzer can measurement heavy metal as Hg/Cd/Pb/As/Cu/Zn, the sensitivity is up to 1ug/L, the detection time is less than 10min, the repeatibility is up to 90%， and the efficient of digestion is up to 90% in 5min. The analyzer can be used in the field of ocean environment monitoring, lake or river water quality measurement and secondary water supply in city. And supporting the main equipment for environment monitoring. It has important scientific research significance and practical application value.

项目面向环境水体中重金属现场快速检测的重大需求，针对重金属形式多样化（无/有机络合态等）导致的总量难以准确测定的问题，提出借鉴鲨鱼嗅觉器官超高灵敏的微纳米生物组织结构，基于微纳制造技术和微流控样本分配技术，制备具有微纳米敏感结构的高效消解电极、检测电极、参比电极和对电极的微芯片，解决多电极制备工艺兼容、电化学消解和检测方法兼容、参比电极稳定性等关键问题，研制出集成重金属电化学氧化消解和溶出伏安法检测功能的仿生微纳传感器，构建手持式痕量重金属总量分析仪，实现水体中多种形态重金属现场快速、方便灵敏的检测和分析，5min内消解效率达90%，Hg、As、Zn、Cd、Pb、Cu检测灵敏度达到1μg/L，检测时间<10min，重复性>90%，用于监测近岸海洋水产养殖水体、河流、湖泊等水源地、二次供水等水质痕量重金属污染情况，为环境水质监测提供核心传感器装备，具有重要的科研究意义和实际应用价值。

项目面向自来水、净化水、地表水和海洋环境等水体中重金属现场快速在线检测的需求，基于微纳制造技术和微流控样本分配技术，制备了具有微纳米敏感结构的高效消解电极、检测电极、参比电极和对电极的微芯片，建立微纳传感器芯片批量制备工艺流程和电化学消解和检测方法，解决多电极制备工艺兼容、电化学消解和检测方法兼容、参比电极稳定性等关键问题，研制出了集成重金属电化学氧化消解和溶出伏安法检测功能的微纳传感器，研制了便携式痕量重金属检测仪，实现了多种形态重金属现场快速、方便灵敏的检测和分析，消解效率达到90%，检测灵敏度达到1μg/L，检测时间<10min，重复性>90%。应用于实际水体（近岸海洋水产养殖水体、河流、湖泊等水源地、二次供水等）水质痕量重金属检测分析，为环境水质监测提供核心传感器装备。具体完成情况如下：.（1）设计并批量制备基于硅基单面键合的集成化传感器，该传感器采用硅基-玻璃两层结构，在玻璃基底上集成三电极，即基于纳米通道阵列的参比电极，三维金微阵列工作电极以及金对电极。并且在硅基上制备了微检测腔以及进样和出样通道。所设计的传感器不仅能够批量制备，且参比电极的稳定性良好，批量制备的传感器检测同一浓度的铅离子时的相对标准偏差(RSD)在2.21%~3.35%以内，采用方波溶出伏安法检测铅的检测限为0.82μg/L，检测线性范围为5-100μg/L；.（2）批量制备基于硅基双面键合的集成化传感器，该传感器采用玻璃-硅-玻璃的“三明治”结构，铅的检测限可达到0.13μg/L，检测线性范围为0.5-150μg/L，在检测自来水，饮用水，河湖水时，其回收率在93.3%-103.3%以内；.（3）采用BDD电极，实现了络合态重金属铅的消解与检测一体化。消解10分钟后，消解效率能够达到89.04%，消解效率良好。.（4）研制了便携式痕量重金属离子检测系统，包括检测前端设备的硬件和Android系统上应用程序的开发，对几种常见的重金属离子进行了线性度和重复性测试，并且对实际水样进行了初步测试，检测精度和检测下限已基本满足实际检测需求。