No abstract

Control over the bubble growth rates forming on the electrodes of water-splitting cells or chemical reactors is critical with respect to the attainment of higher energy efficiencies within these devices. This study focuses on the diffusion-driven growth dynamics of a succession of H bubbles generated at a flat silicon electrode substrate. Controlled nucleation is achieved by means of a single nucleation site consisting of a hydrophobic micropit etched within a micrometer-sized pillar. In our experimental configuration of constant-current electrolysis, we identify gas depletion from (i) previous bubbles in the succession, (ii) unwanted bubbles forming on the sidewalls, and (iii) the mere presence of the circular cavity where the electrode is being held. The impact of these effects on bubble growth is discussed with support from numerical simulations. The time evolution of the dimensionless bubble growth coefficient, which is a measure of the overall growth rate of a particular bubble, of electrolysis-generated bubbles is compared to that of CO bubbles growing on a similar surface in the presence of a supersaturated solution of carbonated water. For electrolytic bubbles and under the range of current densities considered here (5-15 A/m), it is observed that H bubble successions at large gas-evolving substrates first experience a stagnation regime, followed by a fast increase in the growth coefficient before a steady state is reached. This clearly contradicts the common assumption that constant current densities must yield time-invariant growth rates. Conversely, for the case of CO bubbles, the growth coefficient successively decreases for every subsequent bubble as a result of the persistent depletion of dissolved CO.

Nanobubble nucleation is a problem that affects efficiency in electrocatalytic reactions since those bubbles can block the surface of the catalytic sites. In this article, we focus on the nucleation rate of O2 nanobubbles resulting from the electrooxidation of H2O2 at Pt disk nanoelectrodes. Bubbles form almost instantaneously when a critical peak current, inbp, is applied, but for lower currents, bubble nucleation is a stochastic process in which the nucleation (induction) time, tind, dramatically decreases as the applied current approaches inbp, a consequence of the local supersaturation level, ζ, increasing at high currents. Here, by applying different currents below inbp, nanobubbles take some time to nucleate and block the surface of the Pt electrode at which the reaction occurs, providing a means to measure the stochastic tind. We study in detail the different conditions in which nanobubbles appear, concluding that the electrode surface needs to be preconditioned to achieve reproducible results. We also measure the activation energy for bubble nucleation, Ea, which varies in the range from (6 to 30)kT, and assuming a spherically cap-shaped nanobubble nucleus, we determine the footprint diameter L = 8–15 nm, the contact angle to the electrode surface θ = 135–155°, and the number of O2 molecules contained in the nucleus (50 to 900 molecules).

When a gas bubble grows by diffusion in a gas-liquid solution, it affects the distribution of gas in its surroundings. If the density of the solution is sensitive to the local amount of dissolved gas, there is the potential for the onset of natural convection, which will affect the bubble growth rate. The experimental study of the successive quasi-static growth of many bubbles from the same nucleation site described in this paper illustrates some consequences of this effect. The enhanced growth due to convection causes a local depletion of dissolved gas in the neighbourhood of each bubble beyond that due to pure diffusion. The quantitative data of sequential bubble growth provided in the paper show that the radius-versus-time curves of subsequent bubbles differ from each other due to this phenomenon. A simplified model accounting for the local depletion is able to collapse the experimental curves and to predict the progressively increasing bubble detachment times.