Decoupling the anodic and cathodic behavior in asymmetric electrochemical hydroiodic acid decomposition cell for hydrogen production in the iodine-sulfur thermochemical cycle.

The HI section of the iodine-sulfur (I-S) thermochemical cycle for hydrogen production is one of the most energy-intensive sections and with significant material handling challenges, primarily due to the azeotrope formation and the corrosive nature of the hydroiodic acid-iodine-water mixture (HIx). As an alternative, the single-step direct electrochemical decomposition of the hydroiodic acid (HI) to generate hydrogen can circumvent the challenges associated with the conventional multistep HI section in the I-S cycle. In this work, we present new insights into the electrochemical HI decomposition process by deconvoluting the contributions from the anodic and the cathodic sections in the electrochemical cell system, specifically, the redox reactions involved and the overpotential contribution of the individual sections (anolyte and catholyte) in the overall performance. The studies on the redox reactions indicate that the HIx solution output from the Bunsen reaction section should be used as the anolyte. In contrast, aqueous HI without any iodine (I2) should be used as the catholyte. In the anodic section, the oxidation proceeds with I2 as the final oxidized species at low bias potentials. Higher positive potentials result in iodate formation along with oxygen evolution. For the catholyte section, I2 and tri-iodide ion reduction precede the hydrogen evolution reaction when I2 is present along with HI. Furthermore, the potential required for hydrogen production becomes more negative with an increasing I2/HI ratio in the catholyte. Polarization studies were conducted with simultaneous deconvolution of the anodic and cathodic behavior in a two-compartment cell. Model fitting of the polarization data revealed that the anolyte section's activation overpotential is negligibly low. In contrast, the activation overpotential requirement of the catholyte section is higher and dictates the onset of hydrogen production in the cell. Furthermore, the catholyte section dominates the total overpotential losses in the cell system. Operation in the ohmic resistance-dominated zone resulted in close to 90% current efficiency for the electrochemical HI decomposition. The results highlight that the potential for process improvement lies in reducing the ohmic resistance of the anolyte section and in lowering the activation overpotential of hydrogen evolution in the catholyte section.

Dynamic Electrolyte Spreading during Meniscus-Confined Electrodeposition and Electrodissolution of Copper for Surface Patterning.

Meniscus-confined electrodeposition and electrodissolution are a facile maskless approach to generate controlled surface patterns and 3D microstructures. In these processes, the solid-liquid interfacial area confined by the meniscus dictates the zone on which the electrodeposition or the electrodissolution occurs. In this work, we show that the process of electrodeposition or electrodissolution in a meniscus-confined droplet system can lead to dynamic spreading of the meniscus, thereby changing the solid-liquid interfacial area confined by the meniscus. Our results show that the wetting dynamics depends on the applied voltage and the type of interface underneath the droplet, specifically a smooth surface with a homogeneous solid-liquid interface or a superhydrophobic surface with a heterogeneous solid-liquid and liquid-vapor interface. It is found that both electrodissolution and electrodeposition processes induced droplet spreading in the case of a smooth surface with a homogeneous interface. However, a superhydrophobic surface with a heterogeneous interface under the droplet produced nonlinear spreading during electrodissolution and spreading inhibition during electrodeposition. The underlying mechanisms resulting in the observed behavior have been explicated. The dynamic droplet spreading could modify the dimensions of the patterns formed and hence is of immense importance to the meniscus-confined electrochemical micromachining. The findings also provide fundamental insights into the spreading behavior and wetting transitions induced by electrochemical reactions.

Fabricating low-cost, robust superhydrophobic coatings with re-entrant topology for self-cleaning, corrosion inhibition, and oil-water separation.

HYPOTHESIS: The superhydrophobic surfaces with re-entrant microstructures are known to provide robust superhydrophobicity by enhancing the energy barrier for Cassie-Baxter to Wenzel transition. However, the fabrication of such structured surfaces often involves sophisticated techniques and expensive ingredients. EXPERIMENTS: Herein, a multifunctional, low-cost, and fluorine-free superhydrophobic coating with re-entrant surface topology was fabricated using fly ash (FA) and room-temperature-vulcanizing silicone. A systematic study was performed to evaluate the coating properties and durability. The robustness was evaluated as a function of particle size and inter-particle spacing. The performance in self-cleaning, corrosion inhibition and oil-water separation has been presented. FINDINGS: The synthesized coatings are substrate-versatile and demonstrate superhydrophobic behavior. The close-packed coating of re-entrant FA particles attained via vibration compaction was seen to provide high robustness. The coatings retain their superhydrophobicity after multiple cycles of tape-peeling and exposure to environmental factors including temperature, pH, and UV radiation. These coatings exhibit excellent corrosion inhibition (corrosion efficiency > 99.999%), outperforming the majority of the previously reported superhydrophobic coatings. It also displays excellent self-cleaning property and high separation efficiencies in oil-water separation (>99%). We envision that such FA-based superhydrophobic coatings can solve the issues of synthesizing cheaper, sustainable, and robust superhydrophobic surfaces while simultaneously opening new avenues for FA utilization.

Understanding the wettability of rough surfaces using simultaneous optical and electrochemical analysis of sessile droplets.

The interaction of a droplet with a solid surface is characterized by two parameters, the contact angle and the wetted area under the droplet. The Cassie-Baxter and the Wenzel modes make predictions on the interfacial area by comparing the contact angles on smooth surfaces (the intrinsic wettability) with those on rough surfaces (the apparent wettability). In these models, the actual wetted area is used as a fitting parameter. In this work, we highlight the significance of determining the actual wetted area under the droplet and the limitation of using only the contact angle to represent the wetting behavior of a surface. Our experimental studies were performed on hydrophilic carbon surfaces where a combination of optical measurements (contact angle and hysteresis) along with an electrochemical approach was employed. An electrochemical method was used to determine the true wetted area using a droplet of aqueous electrolyte on the surface. The interfacial area was then used to correlate wetting behavior to that of the model predictions. We examined the impact of electrolyte concentration and potential sweep rate in our evaluation of the wetted area. Our results show that, for a rough hydrophilic surface, the decrease in contact angles with increasing solid-liquid interfacial areas is not always valid, as generally predicted by the Wenzel and the Cassie-Baxter models.

An Alternative Approach to Evaluate the Wettability of Carbon Fiber Substrates.

The wettability of carbon fiber substrate plays an important role in a vast number of electrochemical energy production and storage technologies. Here, we report an alternative approach to evaluate the relative wettability for three substrates with the solid-liquid (S-L) interfacial area as the wettability parameter. We applied electrochemical techniques to quantify the S-L interfacial area and obtained the relative wettability on for three substrates with varying fiber morphology. This work proposes and validates a methodology to experimentally measure the substrate wettability and elucidates important aspects of the relevant wetting phenomena. Our results indicate that the wettability of carbon fiber substrate is affected by the liquid intrusion resulting from the instability of the Cassie-Baxter wetting state and that the contact angle is not dependent on the S-L interfacial area under the droplet. The present technique can be used to characterize the surface wettability of a wide range of conductive surfaces with irregular and multiscale surface roughness features.