We describe the electrochemical detection of single iridium oxide nanoparticle (IrO(x) NP) collisions on a NaBH(4)-treated Pt ultramicroelectrode (UME). We observe single NP events through the enhanced current by electrocatalytic water oxidation, when IrO(x) contacts the electrode and transiently sticks to it. The overall current transient consists of repeated current spikes that return to the background level, superimposed on a current decay, rather than the staircase response seen where an NP sticks on the UME. Here each event produces a unique current spike (or "blip"). The frequency of the spikes was directly proportional to the particle concentration, and the peak current increased with the applied potential. The observed current is very sensitive to the material and surface state of the measuring electrode; a NaBH(4)-treated Pt UME was important in obtaining reproducible results.

Collisions of several kinds of metal or metal oxide single nanoparticles (NPs) with a less catalytic electrode surface have been observed through amplification of the current by electrocatalysis. Two general types of current response, a current staircase or a current blip (or spike) are seen with particle collisions. The current responses were caused by random individual events as a function of time rather than the usual continuous current caused by an ensemble of a large number of events. The treatment of stochastic electrochemistry like single NP collisions is different from the usual model for ensemble-based electrochemical behaviour. Models for the observed responses are discussed, including simulations, and the frequency of the steps or blips investigated for several systems experimentally.

Catalytic properties of nanoparticles can be significantly enhanced by controlling nanoscale alloying and its structure. In this work, by using a facet-controlled Pt@Ni core-shell octahedron nanoparticle, we show that the nanoscale phase segregation can have directionality and be geometrically controlled to produce a Ni octahedron that is penetrated by Pt atoms along three orthogonal Cartesian axes and is coated by Pt atoms along its edges. This peculiar anisotropic diffusion of Pt core atoms along the ⟨100⟩ vertex, and then toward the ⟨110⟩ edges, is explained via the minimum strain energy for Ni-Ni pair interactions. The selective removal of the Ni-rich phase by etching then results in structurally fortified Pt-rich skeletal PtNi alloy framework nanostructures. Electrochemical evaluation of this hollow nanoframe suggests that the oxygen reduction reaction (ORR) activity is greatly improved compared to conventional Pt catalysts.

Recent experiments on the observation of collisions of single nanoparticles (NPs) with an electrode through amplification of the current by electrocatalysis are described. Systems in which the particles adhere to the electrode upon collision produce a step and staircase response, while those in which particles only interact for a short time with the electrode produce a spike or blip, with little change in the steady state current. Examples of both behaviors, e. g., Pt NPs on a Au electrode for hydrazine oxidation (staircase response) and IrOx NPs on a Pt electrode for water oxidation (blip response) are shown. Controlling the nature of the electrode surface is important in generating useful responses, for example, in the case of gold NPs on an oxidized Pt electrode for borohydride oxidation.

This study demonstrates a highly sensitive sensing scheme for the detection of low concentrations of DNA, in principle down to the single biomolecule level. The previously developed technique of electrochemical current amplification for detection of single nanoparticle (NP) collisions at an ultramicroelectrode (UME) has been employed to determine DNA. The Pt NP/Au UME/hydrazine oxidation reaction was employed, and individual NP collision events were monitored. The Pt NP was modified with a 20-base oligonucleotide with a C6 spacer thiol (detection probe), and the Au UME was modified with a 16-base oligonucleotide with a C6 spacer thiol (capture probe). The presence of a target oligonucleotide (31 base) that hybridized with both capture and detection probes brought a Pt NP on the electrode surface, where the resulting electrochemical oxidation of hydrazine resulted in a current response.

We investigated the electrochemical detection of single iridium oxide nanoparticle (IrO(x) NP) collisions at the NaBH(4)-treated Pt ultramicroelectrode (UME) in a scanning electrochemical microscope (SECM) over an insulating surface. The NP collision events were monitored by observing the electrocatalytic water oxidation reaction at potentials where it does not take place on the Pt UME. These collisions occurred stochastically, resulting in a transient response ("blip") for each collision. The frequency of the collisions is proportional to the flux of NPs to the UME tip, and thus equivalent to the SECM current. A plot of collision frequency versus distance followed the theoretical approach curve behavior for negative feedback for a high concentration of mediator, demonstrating that the collisions were diffusion-controlled and that single-particle measurements of mass transport are equivalent to ensemble ones. When the SECM was operated with a Pt substrate at the same potential as the tip, the behavior followed that expected of the shielding mode. These studies and additional ones result in a model where the IrO(x) NP collision on the Pt UME is adsorptive, with oxygen produced by the catalyzed water oxidation causing a current decay. This results in a blip current response, with the current decay diminished in the presence of the oxygen scavenger, sulfite ion. Random walk and theoretical bulk simulations agreed with the proposed mechanism of IrO(x) NP collision, adsorption, and subsequent deactivation.

Collisions of electrocatalytic platinum (Pt) single nanoparticles (NPs) with a less electrocatalytic nickel (Ni) ultramicroelectrode (UME) surface were detected by amplification of the current by electrocatalysis of NPs. Two typical types of current responses, a current staircase or blip (or spike), in single NP collision experiments were observed at a time with a new system consisting of Pt NP/Ni UME/hydrazine oxidation. The staircase current response was obtained when the collided NPs were attached to the electrode and continued to produce electrocatalytic current. On the other hand, the blip current response was believed to be obtained when the NP attached but was deactivated. The different current responses depend on the different electrocatalytic reaction mechanism, characteristics of the NP, or the electrode material. How the deactivation of the electrocatalytic process affects on the current response of NP collision was investigated using the Ni UME. The current response of a single Pt NP collision is controllable from staircase to blip by changing the applied potential. The current response of the Pt NP was observed as a staircase response with 0 V (vs Ag/AgCl) and as a blip response with 0.1 V (vs Ag/AgCl) applied to the Ni UME.

A facile one-step, eco-friendly, and cost-effective approach for the formation of copper oxide (CuO) nanowires by a green method using saponin-rich Sapindus mukorossi fruit extract (SMFE). The physio-chemical characteristics of the synthesized CuO nanowires have been characterized by X-ray Diffractometry (XRD), X-ray Photoelectron Spectroscopy (XPS), FT-IR (Fourier Transform Infrared Spectroscopy, FE-SEM (Scanning Electron Microscopy), and High-Resolution Transmission Electron Microscopy (HR-TEM). Further, the electrocatalytic activity of the CuO nanowires synthesized with SMFE has been investigated, and they have been used as dopamine (DA) sensors. Because of their unique properties, the CuO nanowires/GCE exhibited remarkable electrochemical response for the detection of DA with enhanced current response. The anodic current demonstrated that the CuO nanowires/GCE linearly detects the concentration of DA over the range of 0.1 µM to 0.105 mM of DA with a regression co-efficient of 0.9960. The obtained results illustrated that the synthesized CuO nanowires can easily stimulate the electron transfer reaction between DA and the nanowires modified electrode with the improvement of the conductivity and stability of the electrode. This remarkable electrocatalytic property of CuO nanowires makes it a unique electrochemical sensor for the detection of DA. Furthermore, the sensor is free from the interference of ascorbic acid, uric acid, and other interfering species. Moreover, the anti-interference performance also showed that the CuO nanowires/GCE could be employed for the determination of DA in real samples with good selectivity and sensitivity.