A 3D-printed millifluidic device for triboelectricity-driven pH sensing based on ZnO nanosheets with super-Nernstian response

Abstract

This paper suggests a straightforward and rapid fabrication method applying the integration of 3D printing and triboelectric nanogenerator (TENG) technologies to realize milli/microfluidic multipurpose devices. The proposed liquid-solid TENG device is served as an energy harvester and sensor at the same time with flexibility in operation modes. Accordingly, an innovative ethylene vinyl acetate (EVA)-made millifluidic pH sensor is fabricated based on zinc oxide nanosheets as a showcase of the functional adaptability of the ubiquitous device, and its performance is analyzed and compared with contemporary electrochemical pH sensors. High crystallinity of the nanosheets with an incline to (103) orientation in parallel with high levels of oxygen vacancies provides capacity for surface charge accumulation at the nanosheet-aqueous solution interface and the ensuing ultrahigh sensitivity of the triboelectric sensor. The millichannel is optimized in terms of sensing surface area, flow rate, and hydrophobicity properties by opting for appropriate geometry, TENG operation modes, and materials. Despite the finding that quasi-single-electrode mode TENG experiences a higher response (8.12 × Nernst limit) in comparison with quasi-contact-separation configuration (4.14 × Nernst limit), the latter enjoys superior linearity, stability, repeatability, reproducibility, and reliability characteristics corresponding to R2 of 98.93%, drift rate of 13 mV/h, relative standard deviation (RSD) of 1.23% in third hysteresis loop, 2.24%, and maximum standard error of ±0.2 pH units across multiple trials, respectively, in a wide pH range of 2–13. Time- and cost-effectiveness, user-friendliness, self-powering, portability, and biocompatibility of the device could be asserted as considerable advantages to open the door for feasibly realizing the new generation of real-life and point-of-care devices.