Reference electrodes (REs) play an essential role in electrochemical measurements. REs require liquid junctions to allow for ion conductivity between the RE and the sample solution. However, a liquid junction causes unwanted ion leakage into the analyte and clogging inducing reference potential inaccuracy. In this study, we report a liquid-junction-free amperometric probe sensor with an integrated RE, based on a closed bipolar electrode (cBPE) system. The liquid junction of the RE was replaced by the cBPE, which provides electrical conductivity instead of ionic conductivity between the inner solution of the RE and the sample solution. Since the solutions were in two separate cells, undesired contamination was completely prevented. We successfully conducted voltammetric and amperometric quantitative detection of 0.1–0.5 mM ferrocenemethanol using this system. Although its uses are limited, the present probe sensor with integrated liquid-junction-free reference electrode provides a feasible alternative for amperometric electrochemical measurements.

参比电极（RE）在电化学测量中起着至关重要的作用。REs需要液接，以使RE和样品溶液之间具有离子传导性。但是，液接会导致不希望的离子泄漏到分析物中并发生堵塞，从而导致参考电位不准确。在这项研究中，我们报告了一种基于闭式双极电极（cBPE）系统的集成了RE的无液接电流型探头传感器。RE的液体连接被cBPE代替，cBPE在RE的内部溶液和样品溶液之间提供了电导率，而不是离子电导率。由于溶液位于两个单独的单元中，因此完全避免了不希望的污染。我们成功进行了0.1–0的伏安和安培定量检测。使用该系统的5 mM二茂铁甲醇。尽管其使用受到限制，但是具有集成的无液接参比电极的本探针传感器为安培电化学测量提供了可行的替代方案。