Electrochemiluminescence at 3D Printed Titanium Electrodes

Abstract

The fabrication and electrochemical properties of a 3D printed titanium electrode array are described. The array comprises 25 round cylinders (0.015 cm radius, 0.3 cm high) that are evenly separated on a 0.48 × 0.48 cm square porous base (total geometric area of 1.32 cm2). The electrochemically active surface area consists of fused titanium particles and exhibits a large roughness factor ≈17. In acidic, oxygenated solution, the available potential window is from ~-0.3 to +1.2 V. The voltammetric response of ferrocyanide is quasi-reversible arising from slow heterogeneous electron transfer due to the presence of a native/oxidatively formed oxide. Unlike other metal electrodes, both [Ru(bpy)3]1+ and [Ru(bpy)3]3+ can be created in aqueous solutions which enables electrochemiluminescence to be generated by an annihilation mechanism. Depositing a thin gold layer significantly increases the standard heterogeneous electron transfer rate constant, ko, by a factor of ~80 to a value of 8.0 ± 0.4 × 10−3 cm s−1 and the voltammetry of ferrocyanide becomes reversible. The titanium and gold coated arrays generate electrochemiluminescence using tri-propyl amine as a co-reactant. However, the intensity of the gold-coated array is between 30 (high scan rate) and 100-fold (slow scan rates) higher at the gold coated arrays. Moreover, while the voltammetry of the luminophore is dominated by semi-infinite linear diffusion, the ECL response is significantly influenced by radial diffusion to the individual microcylinders of the array.

Electrochemiluminescence Systems for the Detection of Biomarkers: Strategical and Technological Advances

“…Simple and straightforward screen-printing methods will need to be developed in order to allow for the one-step manufacturing of ECL systems. Recently, 3D-printed ECL platforms were introduced for titanium and pyrolytic graphite sheets [ 17 , 97 , 98 ], the technology of which can allow rapid prototyping and a one-step fabrication process with a high repeatability and reproducibility. Although 3D printing still has its limitations, such as poor resolution and multi-material printing as well as the flexibility in the applications of printing materials with different characteristics, it may eventually facilitate the large-scale production of ECL systems if the technology advances sufficiently.…”