Electrolysis Activation of Fused-Filament-Fabrication 3D-Printed Electrodes for Electrochemical and Spectroelectrochemical Analysis.

Following the expiration of the patents on fused-filament-fabrication (FFF), the availability and uses of this 3D-printing technology have exploded. Several recent reports describe how conductive composites can be used with FFF printers to generate 3D-printed electrodes (3DEs) for energy storage and electrochemical analysis. As printed materials, these electrodes have very high impedance values because of the high content of insulating thermoplastic required for FFF printers. To overcome this challenge, deposition of metals or activation with harsh chemicals has previously been employed. Here, a benign postprinting process was developed using the electrolysis of water to selectively remove the insulating thermoplastic (polylactic acid) via saponification. Optimization of the hydroxide-treatment process was found to reduce the impedance of 3DEs by 3 orders of magnitude in filaments from two manufacturers. This electrolysis-activation strategy offers a safe, accessible, and affordable means for improving the electrochemical performance of 3DEs. Here, the ability of these modified 3DEs to be used for electrochemical analysis and integrated into complex electrochemical cells is demonstrated.

Maintaining Electrochemical Performance of Flexible ITO-PET Electrodes under High Strain.

Flexible electrode materials, particularly indium tin oxide (ITO)-coated polyethylene terephthalate (PET), have attracted the attention of researchers for a wide variety of applications. However, there has been limited attention to the effects of electrode flexibility during electrochemical processes. In this research article, we studied how bending commercially available ITO-PET electrodes impacts the electrodeposition process of polyaniline (PANI). Thicker ITO layers start cracking at a normalized strain of 0.10 (bending radius of 10 mm), and cracking becomes detrimental to full deposition at a normalized strain of 0.16 or higher (bending radius of 6 mm or lower). Thinner ITO layers were evaluated as electrodes in electrochemical applications; however, the higher resistance of these electrodes prevented uniform electrodeposition of PANI. In order to overcome the issues of cracking, conductive thin films and copper tape were explored as low-cost methods for electrically bridging cracks in the electrode. While conductive thin films reduced the resistance effect, copper tape was found to fully restore the original electrochemical activity as measured by chronoamperometry and enable uniform electrodeposition at a bending radius as low as 3 mm. This strategy was then demonstrated by performing electrochromic bleaching of PANI under high-strain conditions. These studies illustrate some of the limitations of ITO-PET electrodes and strategies for overcoming these limitations for future applications that require a high degree of flexibility in a transparent electrode substrate.

3D Printed UV-Visible Cuvette Adapter for Low-Cost and Versatile Spectroscopic Experiments.

Ultraviolet-visible (UV-vis) spectroscopy represents one of the most popular analytical techniques in chemical research labs. A variety of vendors provide instruments that are suited for the analysis of liquid samples at moderate concentrations. However, to accommodate more specialized experiments, expensive accessories are required and often do not fit the specific needs of experimental scientists. In this work, we present a generalized adapter that can be 3D printed and used with existing spectrometers to enable a wide array of experiments to be performed. In the case of liquid samples, we provide a method for dramatically reducing the price of a quartz cuvette with minimal impact on performance. Through simple modification of the design, cuvettes with various path lengths can be prepared. Additionally, we illustrate the ability to turn any sample container into a working cuvette to simplify experimental protocols, prevent contamination risks, and further reduce costs. This strategy also enables gaseous and solid samples to be evaluated easily and reproducibly. Furthermore, we demonstrate how this concept can be extended to interface additional instrumentation with a commercial UV-vis spectrometer. All of the digital designs are provided under a creative commons license to enable other researchers to modify and adapt the designs for their unique experimental requirements.