Electrochemiluminescence at 3D Printed Titanium Electrodes

• Published in: Frontiers in chemistry Vol. 9; p. 662810
• Main Authors: Douman, Samantha F., De Eguilaz, Miren Ruiz, Cumba, Loanda R., Beirne, Stephen, Wallace, Gordon G., Yue, Zhilian, Iwuoha, Emmanuel I., Forster, Robert J.
• Format: Journal Article
• Language: English
• Published: Frontiers Media S.A 25.05.2021
• Subjects: 3D-electrode array; annihilation and co-reactant system; Chemistry; electrochemiluminescence; heterogeneous electron transfer kinetics; voltammetry
• ISSN: 2296-2646; 2296-2646
• DOI: 10.3389/fchem.2021.662810

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 cm 2 ). 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, k o , 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.