Electrochemically-induced deposition of amine-functionalized silica films on gold electrodes and application to Cu(II) detection in (hydro)alcoholic medium

Well-adherent amine-functionalized porous silica films have been deposited on gold electrodes by combining the self-assembly technology, the sot-gel process, and the electrochemical modulation of pH at the electrode/solution interface. A partial self-assembled monolayer of mercaptopropyl-trimethoxysilane (MPTMS) was first formed on disposable gold electrodes from recordable CDs (Au-CDtrodes). The so pretreated MPTMS-Au-CDtrodes were immersed in a stable sot solution (pH 3) containing (3-aminopropyl)-triethoxysilane (APTES) and tetraethoxysilane (TEOS). Polycondensation of the APTES and TEOS precursors was then achieved by applying a negative potential for a given period of time to generate a local pH increase at the electrode/solution interface and promote the deposition of the amine functionalized silica film adhering well to the electrode surface owing to the MPTMS monolayer acting somewhat as a "molecular glue". Various parameters affecting the electrodeposition process have been studied and the film permeability to redox probes in solution was characterized by cyclic voltammetry. The amine-functionalized silica film electrodes were then applied to the preconcentration of copper(II) species prior to their electrochemical detection by anodic stripping differential pulse voltammetry. Getting high sensitivity has however required the application of an electrochemical pre-activation step as the majority of the organo-functional groups were in the form of ammonium moieties (because the film was prepared from an acidic sot). This was achieved by applying a sufficiently negative potential to the electrode surface to reduce protons and increase consequently the amine-to-ammonium ratio within the film and, thus, the efficiency of the precocentration process. The resulting device was then optimized for copper(II) determination in hydroalcoholic medium, giving rise to a linear response in the 0.1 - 10 mu M concentration range.