Construction and Characterization of Ru(II)Tris(bipyridine)‐Based Silica Thin Film Electrochemiluminescent Sensors

Abstract

Ru(II) tris-bipyridine based ECL sensors were produced by embedding the complex inside silica glass thin films deposited via a sol-gel dipping procedure on K-glass conducing substrates. Films were prepared starting from a prehydrolyzed ethanolic solution of Si(OC 2 H 5 ) 4 and Ru(bpy) 3 Cl 2 . Transparent, crack-free and homogeneous reddish silica layers, having a thickness of 200 AE 20 nm, were obtained. The films, either deposited at room temperature or thermally annealed at 100, 200 and 300 8C for 30 h, were structurally and chemically characterized. Ru(bpy) 3 Cl 2 thermal stability was previously checked by thermogravimetric analysis (TGA). The films were investigated by X-Ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS) and UV-vis spectroscopy. XPS in-depth profiles revealed a homogeneous distribution of the ruthenium complex inside the silica thin layers. SIMS data suggested that the embedded Ru(bpy) 3 Cl 2 did not react with oxygen inside the oxygen-rich silica matrix to give Ru-O bonds. Electrochemical and ECL characterization of the thin film electrodes were made by means of cyclic voltammetry (CV) and controlled potential step experiments. The ECL sensor showed a diffusive redox behavior of the Ru(bpy) 3 2 /Ru(bpy) 3 3 system. Light emission produced from the reaction between oxalic acid and the electrogenerated Ru(bpy) 3 3 was larger and stable when thermally treated electrodes were used after a suitable hydration period. The 300 8C treated sample was the best performing sensor both in terms of low complex leakage and sensitivity. Calibration plots relative to oxalic acid were obtained both in stationary and in flowing solutions in the concentration range 2 Â 10 À6 À 3 Â 10 À4 M. A linear behavior appeared in the former case, while in the latter a slight curvature was evident as a consequence of a finite diffusion time of the analyte inside the thin film. The signal repeatability, obtained by multiple 100 mL of 10 À5 M oxalic acid injections in flowing solutions, was better than 4%. The obtained detection limit (computed as three times the standard deviation of the base-line noise) was 10 À6 M as oxalic acid.

Electrochemiluminescent Systems as Devices and Sensors

“…262,[280][281][282][283][284] Silica sol-gel materials provide some advantages over organic polymers such as the ease with which they can be prepared, modified, and doped with various reagents. Particularly, silica sol-gel films are stable upon continuous electrochemical oxidation or upon drying the gels in a high humidity environment.…”

Developments and Applications of Electrogenerated Chemiluminescence Sensors Based on Micro- and Nanomaterials

“…Thus, it can be immobilized onto an electrode surface and reused in a thin-film sensor platform [4]. A [Ru(bpy) 3 ] 2+ -containing thin-film sensor produces less heavy metal waste, requires a less complicated pumping system, and reduces costs compared with a solution-based sensing method [5]. Nafion is an effective ion exchanger for [Ru(bpy) 3 ] 2+ and has been used for [Ru(bpy) 3 ] 2+ immobilization [6].…”

Highly sensitive electrogenerated chemiluminescence produced at in Eastman-AQ55D-carbon nanotube composite film electrode

“…However, because of their instability in positively biased potential and desorption in organic solvent, these methods can not be applied widely [6]. Another method is the immobilization of RuðbpyÞ 2þ 3 in sol-gel [7], for example RuðbpyÞ 2þ 3 was immobilized in titania sol-gel membranes [8], silica thin films [9], or PSS-silica-Triton X-100 composite films [10]. But RuðbpyÞ 2þ 3 is likely to leak out of the film due to the porous structure of the sol-gel.…”