Xiuting Li

Single Nanoparticle Voltammetry: Contact Modulation of the Mediated Current

The cyclic voltammetric responses of individual palladium-coated carbon nanotubes are reported. Upon impact-from the solution phase-with the electrified interface, the nanoparticles act as individual nanoelectrodes catalyzing the hydrogen-oxidation reaction. At high overpotentials the current is shown to reach a quasi-steady-state diffusion limit, allowing determination of the tube length. The electrochemical response of the individual nanotubes also reveals the system to be modulated by the electrical contact between the electrode and carbon nanotube. This modulation presents itself as fluctuations in the recorded Faradaic current.

Quantifying Single-Carbon Nanotube–Electrode Contact via the Nanoimpact Method

A new methodology is developed to enable the measurement of the resistance across individual carbon nanotube-electrode contacts. Carbon nanotubes (CNTs) are suspended in the solution phase and occasionally contact the electrified interface, some of which bridge a micron-sized gap between two microbands of an interdigitated gold electrode. A potential difference is applied between the contacts and the magnitude of the current increase after the arrival of the CNT gives a measure of the resistance associated with the single CNT-gold contact. These experiments reveal the presence of a high contact resistance (∼50 MΩ), which significantly dominates the charge-transfer process. Further measurements on ensembles of CNTs made using a dilute layer of CNTs affixed to the interdigitated electrode surface and measured in the absence of solvent showed responses consistent with the same high value of contact resistance.

Narrow Band Gap Lead Sulfide Hole Transport Layers for Quantum Dot Photovoltaics

The band structure of colloidal quantum dot (CQD) bilayer heterojunction solar cells is optimized using a combination of ligand modification and QD band gap control. Solar cells with power conversion efficiencies of up to 9.33 ± 0.50% are demonstrated by aligning the absorber and hole transport layers (HTL). Key to achieving high efficiencies is optimizing the relative position of both the valence band and Fermi energy at the CQD bilayer interface. By comparing different band gap CQDs with different ligands, we find that a smaller band gap CQD HTL in combination with a more p-type-inducing CQD ligand is found to enhance hole extraction and hence device performance. We postulate that the efficiency improvements observed are largely due to the synergistic effects of narrower band gap QDs, causing an upshift of valence band position due to 1,2-ethanedithiol (EDT) ligands and a lowering of the Fermi level due to oxidation.

Improving Formate and Methanol Fuels: Catalytic Activity of Single Pd Coated Carbon Nanotubes

The oxidations of formate and methanol on nitrogen-doped carbon nanotubes decorated with palladium nanoparticles were studied at both the single-nanotube and ensemble levels. Significant voltammetric differences were seen. Pd oxide formation as a competitive reaction with formate or methanol oxidation is significantly inhibited at high overpotentials under the high mass transport conditions associated with single-particle materials in comparison with that seen with ensembles, where slower diffusion prevails. Higher electro-oxidation efficiency for the organic fuels is achieved.

Improving Single-Carbon-Nanotube–Electrode Contacts Using Molecular Electronics

We report the use of an electroactive species, acetaminophen, to modify the electrical connection between a carbon nanotube (CNT) and an electrode. By applying a potential across two electrodes, some of the CNTs in solution occasionally contact the electrified interface and bridge between two electrodes. By observing a single CNT contact between two microbands of an interdigitated Au electrode in the presence and absence of acetaminophen, the role of the molecular species at the electronic junction is revealed. As compared with the pure CNT, the current magnitude of the acetaminophen-modified CNTs significantly increases with the applied potentials, indicating that the molecule species improves the junction properties probably via redox shuttling.

New Insights into Fundamental Electron Transfer from Single Nanoparticle Voltammetry

The reductive redox behavior of oxygen in aqueous acid solution leading first to adsorbed superoxide species at single palladium coated multiwalled carbon nanotubes (of length ca. 5 μm and width 130 nm) is reported. The small dimensions of the electroactive surface create conditions of high mass-transport permitting the resolution of electrode kinetic effects. In combination with new theoretical models, it is shown that the physical location of the formed product within the double layer of the electrode profoundly influences the observed electron transfer kinetics. This generically important result gives new physical insights into the modeling of the many electrochemical processes involving adsorbed intermediates.

Ultra-small Palladium Nanoparticle Decorated Carbon Nanotubes: Conductivity and Reactivity

Carbon nanotubes decorated with ultra-small metal nanoparticles are of great value in catalysis. We report that individual multiwalled carbon nanotubes decorated with ultra-small palladium nanoparticles can be detected by using the nano-impacts method. The high conductivity and reactivity of each decorated carbon nanotube is directly evidenced; this is achieved through studying the proton-reduction reaction for the underpotential deposition of hydrogen onto the nanoparticles decorated on the carbon nanotube walls. The reductive spikes from current amplification are analyzed to estimate the approximate length of the decorated carbon nanotubes, revealing that the decorated carbon nanotubes are electroactive along its entire length of several micrometers.

Aqueous Voltammetry in the Near Absence of Electrolyte

In order to minimize the incidence of the CO2 hydrolysis and conduct aqueous electrochemistry in the virtual absence of electrolyte, a novel methodology is developed to achieve the near minimum conductivity (≈60 nS cm-1 ) for an aqueous solution through in situ deionization with ion exchange resin beads. Aqueous electrochemistry studying the oxidations of platinum, ferrocenemethanol, and hydrogen (H2 ) were conducted in the near complete absence of trace ionic species at a platinum microelectrode (d=10 μm). Both surface and solution phase electrochemical reactions were clearly observed, indicating that under these conditions there is a sufficiently compressed double layer for an interfacial electron transfer to be driven and the iR effects are significantly smaller than theoretically expected.

Nitrite-Enhanced Charge Transfer to and from Single Polyaniline Nanotubes

As Liu et al. reported previously (Appl. Mater. Today 2017, 7, 239-245), the charge transfer to partially oxidized polyaniline (PANI) nanotubes in electrochemical reactions is heavily limited due to the non-conductivity of the reduction/oxidation products. In this paper, the doping level of individual PANI nanotubes was substantially enhanced using nitrite as an electron acceptor in sulfuric acid aqueous solution as recorded by the nano-impact method. The charge transferred to one single tube during reduction process is close to the theoretical value of 170±112 pC per tube (assuming 2-electron reduction for the PANI tubes studied), while the charge during PANI oxidation is dramatically decreased. Reaction processes are proposed based on the oxidative properties of nitrite in acid solution. UV-visible spectroscopy analysis further confirms an oxidation-reduction reaction between PANI and nitrite. In contrast the electrochemical reaction of ensembles (21 μg cm-1 ) of PANI tubes on glassy carbon electrodes simply show limited electrocatalytic activity.