3D printed electrodes design and voltammetric response

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The limiting aspects in the voltammetric response of 3D printed electrodes is thoroughly investigated with numerical simulations and new 3D printed electrode designs. Severe diffusion limitations, resulting from a recessed electrode geometry, is found in a commonly used 3D printed electrode and electrochemical cell design, impeding the investigation of electron transfer kinetics at these electrodes by classical methods, such as Nicholson's, widely used on this and similarly mass transport-limited designs. A new 3D printed electrode design, an inlaid disk (non-recessed) geometry, is used to investigate the voltammetric response of printed electrodes in bulk solution, i.e., without mass transport limitations. At this condition, it is clear that the voltammetric response is limited by contact resistance, arising from the printed material low electrical conductivity. Gold modified electrodes, deliberately designed with different contact resistances, highlight the resistive behavior, with quasi-reversible voltammetric profiles. This contrasts with the common assumption of a voltammetric response limited by finite electron kinetics. Electron transfer rate constants (k0) and transfer coefficients (α) for electrodes with and without surface modifications are calculated from experimental data using a modified Butler-Volmer equation, incorporating ohmic losses. The reported k0 and α values are independent of electrode geometry or printing parameters, unlike the observable rate constant usually reported for 3D printed electrodes. By accounting for contact resistance and finite electron transfer kinetics, cathodic and anodic peak potentials and currents of voltammograms recorded with 3D printed electrodes are predicted before printing, allowing electrode designs to be optimized in the virtual space.