Micro-droplet printed ion-selective membrane sensors for in situ monitoring of marine heavy metal ions

Fast, accurate, and reliable techniques for marine toxic heavy metal ions (HMI) detection are critical for the ecological environment and human health. One of the fatal drawbacks of traditional ion selective electrochemical sensors is that the modification of electrode cannot be accurately quantified, resulting in poor repeatability of the detection electrode and large error between the multi-electrode detection results. In order to tackle this challenge, this study presents ultra-fine micro-droplet printed electrodes for the in-situ detection of Cd 2+ , a carcinogenic and toxic HMI commonly found in the ocean. The ion selective membrane casting liquid was dispersed into tiny droplets with a diameter of micron through microfluidic technology, and the microdroplets were precisely arranged on the electrode surface. As a result, the modification error of electrode was reduced to pL level (accurate to 10 pL), which greatly improved the repeatability between electrodes prepared in different batches. The results of experiments with pure electrolyte, interference ions and artificial seawater indicated that the micro-droplet printed sensors possessed excellent properties of accuracy, precision, repeatability, and anti-interference. This novel micro-droplet printed sensor has the potential to capture an accurate picture of nearshore HMI in heterogeneous environments under shock conditions.