The direct detection of metal nanoparticles is of high importance. Here we investigate inherent electrochemistry of silver nanoparticles of sizes 10, 40, 80 and 107 nm by means of cyclic voltammetry.Keywords: Silver nanoparticles, Size dependant electrochemical behavior DOI: 10.1002/elan.201100690 There is a high demand for facile direct detection of metallic nanoparticles (NPs) arising from various areas such as biosensing [1][2][3], water quality assessment [4] or toxicity studies [5,6]. Electrochemistry is a facile method for direct determination of a wide range of metal nanoparticles, for example gold [7,8], platinum [9], silver [10][11][12] or molybdenum [13]. The detailed investigation whether different sizes of the metal nanoparticles exhibit different electrochemical properties were carried out frequently, predominantly for Au, Pt and Ag nanoparticles. The electrochemical detection of metal nanoparticles can be carried in two formats: immobilizing the nanoparticles on the electrode surfaces [7,8,12,13] or direct detection of nanoparticles hitting the surface of the electrode [10,11]. Here we investigate the electrochemical behavior of silver nanoparticles of sizes 10-107 nm, following our previous study of size dependant response of Au NPs (2-50 nm) [8] and also Comptons previous study of size dependency of voltammetry of Ag NPs [14][15][16][17][18]. Comptons group demonstrated theoretically and experimentally that stripping potential of Ag NPs depends on the size of the particles [14]. We confine ourselves to the traditional method of immobilization of particular sized nanoparticles on the surface of the electrodes. We also purposely did not used electrochemically generated Ag NPs [19] as such generation of NPs leads to wide size distribution but rather commercially available Ag NPs with narrow size distribution.We studied the influence of the size of the silver nanoparticles upon their electrochemical behavior in 50 mM phosphate buffer (pH 7.4) using cyclic voltammetry. There is apparent feature of electrochemical dissolution (stripping) of silver nanoparticles on the electrode surface, at~+ 440 mV and reduction of the generated silver ions in the oxidative part of cycle from the solution at+ 100 mV. As it can be seen from the voltammograms, the behavior of various silver nanoparticles significantly differs, depending on the size of the nanoparticles. First observation one can make is that 10 and 40 nm Ag NPs exhibit two oxidative peaks, denoted as Ox 1 and Ox 2. While Ox 2 peak potential is cycle number independent and it is practically identical for both 10 and 40 nm Ag NPs (of 443 mV for 10 nm Ag NPs; and of 445 mV for 40 nm Ag NPs), the potential of the first oxidation peak (Ox 1) changes with consecutive scans, reflecting the fact that every cycle there is the reduction of the electrogenerated Ag + ions which results into the nucleation of silver nanostructures at GC and Ag NPs surfaces (note that during oxidation step not all silver is dissolved). Figure 2 shows that potential Ox 1 decr...