To improve the reference potential stability of on-chip amperometric sensors, we propose a novel integrated Ag/AgCl reference electrode structure. This structure can refresh the saturated potassium chloride filling solution surrounding the Ag/AgCl electrode. We then designed a flow-through amperometric sensor and a multilayer microfluidic chip based on the integrated reference electrode. In order to improve the detection signal strength of the flow-through sensor, a numerical simulation model was established. The simulation results showed that a combination of (1) using a step-type detection cell structure that maintains micro-channel width while reducing micro-channel height, and (2) controlling the sample flow rate to limit the mass transfer of the sensor surface effectively, improves the detection signal strength. The step-type detection cell structure had dimensions of 200 μm × 200 μm × 100 μm (length × width × height), and the electroosmotic flow driving voltage was 120 V/cm. Finally, successful trace detection of Mg2+ and Pb2+ in the water was achieved using the amperometric sensor and microfluidic chip: detection limits were 5 μmol/L and 84 μmol/L. The preparation of an on-chip flow-through amperometric sensor with an integrated Ag/AgCl reference electrode will facilitate improved portability of microfluidic detection technology.
Keywords: amperometric detection; detection cell structure optimization; integrated Ag/AgCl reference electrode; mass transfer; microfluidic chip.