Self-cleaning properties of a silica/silver nanoparticles/titania sandwich sensor

One of the main challenges faced during electroanalysis of complex matrices is represented by fouling and passivation of the electrode surface, especially in the fields of biomedical and environmental trace analysis [1], where sophisticated and highly engineered sensors have to be used in order to increase sensitivity and lower detection limits. These sensors can not be cleaned by conventional mechanical or electrochemical procedures, since these methods could affect the integrity of the active layer. In order to overcome these problems, the production of highly engineered reliable and reusable devices, designed ad hoc for specific applications, which could be simply cleaned by irradiation with UV light, would be an interesting step beyond the current state of the art. In this context, a three-layered transparent electrode, in which silver nanoparticles are embedded between a bottom silica and a top titania layer [2, 3] was designed, prepared and characterized. The device structure is meant to confer multifunctional properties for a complex biomedical challenge: the detection and quantification of catecholamine neurotransmitters. The key role of each component of the device was thoroughly investigated to demonstrate the robustness and efficiency of the final sensor. In particular, the size distribution of silver nanoparticles, the device architecture and surface homogeneity were inspected by electron microscopy. The cleaning overlayer was made of the active polymorph of titanium dioxide (anatase), as confirmed by X-ray diffraction and by model contaminants photodegradation measurements. Electrochemical techniques (cyclic voltammetry and electrochemical impedance spectroscopy) revealed that an highly ordered distribution of silver nanoparticles is the active core of the device, allowing easier electron transfer and better quantification of the analytes even in the presence of conventional interferents, e.g. ascorbic acid and uric acid in human fluids. The high photoactivity of titania top layer allowed total recovery of the device performance in terms of sensitivity after a fast (less than 20 min) UV cleaning step, affordable with different UV-A sources. This self-cleaning property, combined with a remarkable resistance against ageing, allows to employ the sensor also in on-field and remote applications. References [1] C. M. Welch and R. G. Compton, Anal. Bioanal. Chem. 2006, 384, 601–619. [2] G. Maino, D. Meroni, V. Pifferi, L. Falciola, G. Soliveri, G. Cappelletti, S. Ardizzone, J. Nanoparticle Res. 2013, 15, 2087. [3] G. Soliveri, V. Pifferi, G. Panzarasa, S. Ardizzone, G. Cappelletti, D. Meroni, K. Sparnacci, L. Falciola, Analyst 2015, 140, 1486.