Herein we provide a generic framework for use in the acquisition and analysis of the electrochemical responses of individual nanoparticles, summarising aspects that must be considered to avoid mis-interpretation of data. Specifically, we threefold highlight the importance of the nanoparticle shape, the effect of the nanoparticle diffusion coefficient on the probability of it being observed and the influence of the used measurement bandwidth. Using the oxidation of silver nanoparticles as a model system, it is evidenced that when all of the above have been accounted for, the experimental data is consistent with being associated with the complete oxidation of the nanoparticles (50 nm diameter). The duration of many single nanoparticle events are found to be ca. milliseconds in duration over a range of experiments. Consequently, the insight that the use of lower frequency filtered data yields a more accurate description of the charge passed during a nano-event is likely widely applicable to this class of experiment; thus we report a generic methodology. Conversely, information regarding the dynamics of the nano redox event is obscured when using such lower frequency measurements; hence, both data sets are complementary and are required to provide full insight into the behaviour of the reactions at the nanoscale.

In this study, we have determined the electrical properties of amine-and thiol-terminated poly(p-phenylene) molecular wires bound either between two gold electrode contacts (Au/Au) or between a gold contact and a graphene electrode (Au/ graphene). These different junctions were studied using a scanning tunneling microscopy (STM) and a noncontact method for forming the molecular bridges (the I(s) technique, where I = current and s = distance). We show that for these molecular targets, junctions formed with Au/Au electrodes have higher conductance than those formed with Au/graphene electrodes. The measured conductance decays exponentially with an increase in the number of phenyl rings, giving a decay constant that is similar for amine-and thiolterminated molecular junctions with the Au/graphene system. This work reveals that poly(p-phenylene) chains present similar electronic properties when coupled to either gold or graphene electrodes, independently of whether the anchoring group is amine or thiol(ate), and that the transport properties are essentially dominated by the intrinsic molecular properties.

Superoxide produced at silver electrode in seawater.

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