Effect of forced convection on the collision and interaction between nanoparticles and ultramicroelectrode

Detection of nanoparticle (NP) collision events at ultramicroelectrode (UME) has emerged as a new methodology for the investigation of single NP in recent years. Although the method was widely employed, some fundamental knowledge such as how the NP moves to and interacts with the UME remain less understood. It was generally recognized that the recorded rate of collision was determined by diffusion that should follow Fick's first law. However, significant lower collision frequency compared with that of predicted by theory were frequently reported. Experiments carried out by us suggest that the collision frequency will increase dramatically if forced convection (stir or flow injection) is applied during detection. Furthermore, the collision frequency gradually increases to a maximum and then decreases, along with the increase of the convection intensity. This phenomenon is interpreted as follows: (a) there are two steps for a freely moving NP to generate a detectable collision signal. The first step is the move of NP from bulk solution to the surface of the UME which is mass transfer limited; the second step is the landing of NP on the surface of UME which is affected by many factors and is the critical step; (b) there is a barrier that must be overcame before the contact between freely moving NP and UME. Forced convection with moderate intensity can not only increase the mass transfer rate but also help to overcome this barrier and thus enhance the collision frequency; (c) the landing of NP on the surface of UME can be suppressed by stronger convections, because NP will be swept away by hydrodynamic force.