Performance Enhancement of Electrocatalytic Hydrogen Evolution through Coalescence-Induced Bubble Dynamics.

The evolution of electrogenerated gas bubbles during water electrolysis can significantly hamper the overall process efficiency. Promoting the departure of electrochemically generated bubbles during (water) electrolysis is therefore beneficial. For a single bubble, a departure from the electrode surface occurs when buoyancy wins over the downward-acting forces (e.g., contact, Marangoni, and electric forces). In this work, the dynamics of a pair of H2 bubbles produced during the hydrogen evolution reaction in 0.5 M H2SO4 using a dual platinum microelectrode system is systematically studied by varying the electrode distance and the cathodic potential. By combining high-speed imaging and electrochemical analysis, we demonstrate the importance of bubble-bubble interactions in the departure process. We show that bubble coalescence may lead to substantially earlier bubble departure as compared to buoyancy effects alone, resulting in considerably higher reaction rates at a constant potential. However, due to continued mass input and conservation of momentum, repeated coalescence events with bubbles close to the electrode may drive departed bubbles back to the surface beyond a critical current, which increases with the electrode spacing. The latter leads to the resumption of bubble growth near the electrode surface, followed by buoyancy-driven departure. While less favorable at small electrode spacing, this configuration proves to be very beneficial at larger separations, increasing the mean current up to 2.4 times compared to a single electrode under the conditions explored in this study.

Solutal Marangoni effect determines bubble dynamics during electrocatalytic hydrogen evolution.

Understanding and manipulating gas bubble evolution during electrochemical water splitting is a crucial strategy for optimizing the electrode/electrolyte/gas bubble interface. Here gas bubble dynamics are investigated during the hydrogen evolution reaction on a well-defined platinum microelectrode by varying the electrolyte composition. We find that the microbubble coalescence efficiency follows the Hofmeister series of anions in the electrolyte. This dependency yields very different types of H2 gas bubble evolution in different electrolytes, ranging from periodic detachment of a single H2 gas bubble in sulfuric acid to aperiodic detachment of small H2 gas bubbles in perchloric acid. Our results indicate that the solutal Marangoni convection, induced by the anion concentration gradient developing during the reaction, plays a critical role at practical current density conditions. The resulting Marangoni force on the H2 gas bubble and the bubble departure diameter therefore depend on how surface tension varies with concentration for different electrolytes. This insight provides new avenues for controlling bubble dynamics during electrochemical gas bubble formation.

In situ measurements of void fractions and bubble size distributions in bubble curtains.

We report the development of a novel measurement system designed to measure bubble properties in bubble curtains (i.e. planar bubble plumes) in situ alongside acoustical measurements. Our approach is based on electrical, contact-based needle sensors in combination with an optical system. The latter is used for calibration and validation purposes. Correcting for the insensitive distance of the needle tips yields very good agreement between the two approaches in terms of the local void fraction and bubble size distributions. Finally, the system is employed to study bubble plumes evolving from three different hose types. All hoses display consistent self-similar behaviour with spreading rates increasing with increasing gas flow. The spreading is further found to be significantly higher when the bubble plumes originated from a porous hose compared to the two other hose types featuring either discrete holes or nozzle elements.

Fabrication of freestanding Pt nanowires for use as thermal anemometry probes in turbulence measurements.

We report a robust fabrication method for patterning freestanding Pt nanowires for use as thermal anemometry probes for small-scale turbulence measurements. Using e-beam lithography, high aspect ratio Pt nanowires (~300 nm width, ~70 µm length, ~100 nm thickness) were patterned on the surface of oxidized silicon (Si) wafers. Combining wet etching processes with dry etching processes, these Pt nanowires were successfully released, rendering them freestanding between two silicon dioxide (SiO2) beams supported on Si cantilevers. Moreover, the unique design of the bridge holding the device allowed gentle release of the device without damaging the Pt nanowires. The total fabrication time was minimized by restricting the use of e-beam lithography to the patterning of the Pt nanowires, while standard photolithography was employed for other parts of the devices. We demonstrate that the fabricated sensors are suitable for turbulence measurements when operated in constant-current mode. A robust calibration between the output voltage and the fluid velocity was established over the velocity range from 0.5 to 5 m s-1 in a SF6 atmosphere at a pressure of 2 bar and a temperature of 21 °C. The sensing signal from the nanowires showed negligible drift over a period of several hours. Moreover, we confirmed that the nanowires can withstand high dynamic pressures by testing them in air at room temperature for velocities up to 55 m s-1.

Rising and Sinking in Resonance: Mass Distribution Critically Affects Buoyancy-Driven Spheres via Rotational Dynamics.

We present experimental results for spherical particles rising and settling in a still fluid. Imposing a well-controlled center of mass offset enables us to vary the rotational dynamics selectively by introducing an intrinsic rotational timescale to the problem. Results are highly sensitive even to small degrees of offset, rendering this a practically relevant parameter by itself. We further find that, for a certain ratio of the rotational to a vortex shedding timescale (capturing a Froude-type similarity), a resonance phenomenon sets in. Even though this is a rotational effect in origin, it also strongly affects translational oscillation frequency and amplitude, and most importantly, the drag coefficient. This observation equally applies to both heavy and light spheres, albeit with slightly different characteristics for which we offer an explanation. Our findings highlight the need to consider rotational parameters when trying to understand and classify path properties of rising and settling spheres.

Electrochemically Induced pH Change: Time-Resolved Confocal Fluorescence Microscopy Measurements and Comparison with Numerical Model.

Confocal fluorescence microscopy is a proven technique, which can image near-electrode pH changes. For a complete understanding of electrode processes, time-resolved measurements are required, which have not been achieved previously. Here we present the first measurements of time-resolved pH profiles with confocal fluorescence microscopy. The experimental results compare favorably with a one-dimensional reaction-diffusion model; this holds up to the point where the measurements reveal three-dimensionality in the pH distribution. Specific factors affecting the pH measurement such as attenuation of light and the role of dye migration are also discussed in detail. The method is further applied to reveal the buffer effects observed in sulfate-containing electrolytes. The work presented here is paving the way toward the use of confocal fluorescence microscopy in the measurement of 3D time-resolved pH changes in numerous electrochemical settings, for example, in the vicinity of bubbles.

Small-scale entrainment in inclined gravity currents.

We investigate the effect of buoyancy on the small-scale aspects of turbulent entrainment by performing direct numerical simulation of a gravity current and a wall jet. In both flows, we detect the turbulent/nonturbulent interface separating turbulent from irrotational ambient flow regions using a range of enstrophy iso-levels spanning many orders of magnitude. Conform to expectation, the relative enstrophy isosurface velocity v n in the viscous superlayer scales with the Kolmogorov velocity for both flow cases. We connect the integral entrainment coefficient E to the small-scale entrainment and observe excellent agreement between the two estimates throughout the viscous superlayer. The contribution of baroclinic torque to v n is negligible, and we show that the primary reason for reduced entrainment in the gravity current as compared to the wall-jet are 1) the reduction of v n relative to the integral velocity scale u T ; and 2) the reduction in the surface area of the isosurfaces.

Clustering of particles in turbulence due to phoresis.

We demonstrate that diffusiophoretic, thermophoretic, and chemotactic phenomena in turbulence lead to clustering of particles on multifractal sets that can be described using one single framework, valid when the particle size is much smaller than the smallest length scale of turbulence l_{0}. To quantify the clustering, we derive positive pair correlations and fractal dimensions that hold for scales smaller than l_{0}. For scales larger than l_{0} the pair-correlation function is predicted to show a stretched exponential decay towards 1. In the case of inhomogeneous turbulence we find that the fractal dimension depends on the direction of inhomogeneity. By performing experiments with particles in a turbulent gravity current we demonstrate clustering induced by salinity gradients in conformity to the theory. The particle size in the experiment is comparable to l_{0}, outside the strict validity region of the theory, suggesting that the theoretical predictions transfer to this practically relevant regime. This clustering mechanism may provide the key to the understanding of a multitude of processes such as formation of marine snow in the ocean and population dynamics of chemotactic bacteria.