Postdoc Fellow, University of Utah
Electrochemical studies of single nanoparticle, single nanobubble and single molecules.
I use electrochemistry (applying and measuring current/voltage to study chemistry) to study the physical behavior of single nano-bubbles and single molecules, including DNA.
Abstract: The nucleation and dynamics of gas bubbles are of fundamental interest. Herein, we use Pt nanodisk electrodes (apparent radii from 4 to 80 nm) to investigate the nucleation of individual O2 nanobubbles generated by electrooxidation of hydrogen peroxide (H2O2). A single bubble reproducibly nucleates when the dissolved O2 concentration reaches ~0.17 M at the Pt electrode surface. This nucleation concentration is ~130 times higher than the equilibrium saturation concentration of O2 and is independent of electrode size. Moreover, in acidic H2O2 solutions (1 M HClO4), in addition to producing an O2 nanobubble through H2O2 oxidation at positive potentials, individual H2 nanobubbles can also be generated at negative potentials. Alternating generation of single O2 and H2 bubbles within the same experiment allows direct comparison of the critical concentrations for nucleation of each nanobubble without knowing the precise size/geometry of the electrode, or the exact viscosity/temperature of the solution.
Pub.: 19 May '17, Pinned: 27 Jun '17
Abstract: In this article, we address the fundamental question: "What is the critical size of a single cluster of gas molecules that grows and becomes a stable (or continuously growing) gas bubble during gas evolving reactions?" Electrochemical reactions that produce dissolved gas molecules are ubiquitous in electrochemical technologies, e.g., water electrolysis, photoelectrochemistry, chlorine production, corrosion, and often lead to the formation of gaseous bubbles. Herein, we demonstrate that electrochemical measurements of the dissolved gas concentration, at the instant prior to nucleation of an individual nanobubble of H2, N2, or O2 at a Pt nanodisk electrode, can be analyzed using classical thermodynamic relationships (Henry's law and the Young-Laplace equation - including non-ideal corrections) to provide an estimate of the size of the gas bubble nucleus that grows into a stable bubble. We further demonstrate that this critical nucleus size is independent of the radius of the Pt nanodisk employed (<100 nm radius), and weakly dependent on the nature of the gas. For example, the measured critical surface concentration of H2 of ∼0.23 M at the instant of bubble formation corresponds to a critical H2 nucleus that has a radius of ∼3.6 nm, an internal pressure of ∼350 atm, and contains ∼1700 H2 molecules. The data are consistent with stochastic fluctuations in the density of dissolved gas, at or near the Pt/solution interface, controlling the rate of bubble nucleation. We discuss the growth of the nucleus as a diffusion-limited process and how that process is affected by proximity to an electrode producing ∼10(11) gas molecules per second. Our study demonstrates the advantages of studying a single-entity, i.e., an individual nanobubble, in understanding and quantifying complex physicochemical phenomena.
Pub.: 11 Oct '16, Pinned: 27 Jun '17
Abstract: Exploring the nucleation of gas bubbles at interfaces is of fundamental interest. Herein, we report the nucleation of individual N2 nanobubbles at Pt nanodisk electrodes (6–90 nm) via the irreversible electrooxidation of hydrazine (N2H4 → N2 + 4H(+) + 4e(–)). The nucleation and growth of a stable N2 nanobubble at the Pt electrode is indicated by a sudden drop in voltammetric current, a consequence of restricted mass transport of N2H4 to the electrode surface following the liquid-to-gas phase transition. The critical surface concentration of dissolved N2 required for nanobubble nucleation, CN2,critical(s), obtained from the faradaic current at the moment just prior to bubble formation, is measured to be ∼0.11 M and is independent of the electrode radius and the bulk N2H4 concentration. Our results suggest that the size of stable gas bubble nuclei depends only on the local concentration of N2 near the electrode surface, consistent with previously reported studies of the electrogeneration of H2 nanobubbles. CN2,critical(s) is ∼160 times larger than the N2 saturation concentration at room temperature and atmospheric pressure. The residual current for N2H4 oxidation after formation of a stable N2 nanobubble at the electrode surface is proportional to the N2H4 concentration as well as the nanoelectrode radius, indicating that the dynamic equilibrium required for the existence of a stable N2 nanobubble is determined by N2H4 electrooxidation at the three phase contact line.
Pub.: 01 Sep '15, Pinned: 27 Jun '17