Gas Evolution in Water Electrolysis.

Gas bubbles generated by the hydrogen evolution reaction and oxygen evolution reaction during water electrolysis influence the energy conversion efficiency of hydrogen production. Here, we survey what is known about the interaction of gas bubbles and electrode surfaces and the influence of gas evolution on practicable devices used for water electrolysis. We outline the physical processes occurring during the life cycle of a bubble, summarize techniques used to characterize gas evolution phenomena in situ and in practical device environments, and discuss ways that electrodes can be tailored to facilitate gas removal at high current densities.

Understanding ion-transfer reactions in silver electrodissolution and electrodeposition from first-principles calculations and experiments.

The electrified aqueous/metal interface is critical in controlling the performance of energy conversion and storage devices, but an atomistic understanding of even basic interfacial electrochemical reactions challenges both experiment and computation. We report a combined simulation and experimental study of (reversible) ion-transfer reactions involved in anodic Ag corrosion/deposition, a model system for interfacial electrochemical processes generating or consuming ions. With the explicit modeling of the electrode potential and a hybrid implicit-explicit solvation model, the density functional theory calculations produce free energy curves predicting thermodynamics, kinetics, partial charge profiles, and reaction trajectories.

Reliable reporting of Faradaic efficiencies for electrocatalysis research.

Electrocatalysis research is accelerated by measurements of reaction kinetics via electrical signals. When competing electrochemical reactions are present, the burden of proof is on the experimenter to connect these electrical signals to the assumed reaction of interest. Here, we highlight measurements of Faradaic efficiency to support claims of electrocatalyst activity, selectivity, and stability.

Solvent-controlled ion-coupled charge transport in microporous metal chalcogenides.

Interactions between ions and itinerant charges govern electronic processes ranging from the redox chemistry of molecules to the conductivity of organic semiconductors, but remain an open frontier in the study of microporous materials. These interactions may strongly influence the electronic behavior of microporous materials that confine ions and charges to length scales comparable to proton-coupled electron transfer. Yet despite mounting evidence that both solvent and electrolyte influence charge transport through ion-charge interactions in metal-organic frameworks, fundamental microscopic insights are only just beginning to emerge.

Reinvigorating electrochemistry education.

Electrochemistry is an established discipline with modern frontiers spanning energy conversion and storage, neuroscience, and organic synthesis. In spite of the expanding opportunities for academic and industrial electrochemists, particularly in the growing energy-storage sector, rigorous training of electrochemists is generally lacking at academic institutions in the United States. In this perspective, we highlight the core concepts of electrochemistry and discuss ways in which it has been historically taught.

Primary Corrosion Processes for Polymer-Embedded Free-Standing or Substrate-Supported Silicon Microwire Arrays in Aqueous Alkaline Electrolytes.

Solar fuel devices have shown promise as a sustainable source of chemical fuels. However, long-term stability of light absorbing materials remains a substantial barrier to practical devices. Herein, multiple corrosion pathways in 1 M KOH(aq) have been defined for TiO-protected Si microwire arrays in a polymer membrane either attached to a substrate or free-standing.

High Broadband Light Transmission for Solar Fuels Production Using Dielectric Optical Waveguides in TiO Nanocone Arrays.

We describe the fabrication and use of arrays of TiO nanocones to yield high optical transmission into semiconductor photoelectrodes covered with high surface loadings of light-absorbing electrocatalysts. Covering over 50% of the surface of a light absorber with an array of high-refractive-index TiO nanocones imparted antireflective behavior (<5% reflectance) to the surface and allowed >85% transmission of broadband light to the underlying Si, even when thick metal contacts or opaque catalyst coatings were deposited on areas of the light-facing surface that were not directly beneath a nanocone. Three-dimensional full-field electromagnetic simulations for the 400-1100 nm spectral range showed that incident broadband illumination couples to multiple waveguide modes in the TiO nanocones, reducing interactions of the light with the metal layer.

Spontaneous Formation of >90% Optically Transmissive, Electrochemically Active CoP Films for Photoelectrochemical Hydrogen Evolution.

Earth-abundant catalysts for the hydrogen-evolution reaction require increased mass loadings, relative to Pt films, to achieve comparable activity and stability in acidic electrolytes. We report herein that spontaneous nanostructuring of opaque, electrodeposited CoP films, 40-120 nm in thickness, leads to transparent electrocatalyst films that exhibit up to 90% optical transmission in the visible spectrum. The photocurrent density under simulated sunlight at a representative np-Si(100)/CoP photocathode increases by 200% after exposure to 0.

Surface-Initiated Ring-Opening Metathesis Polymerization of Dicyclopentadiene from the Vapor Phase.

Surface-attached polydicyclopentadiene (pDCPD) films were prepared on gold and silicon substrates via surface-initiated ring-opening metathesis polymerization (SI-ROMP) of dicyclopentadiene (DCPD). The films were grown utilizing monomer in both the vapor phase and the solution phase with the former process exhibiting rapid kinetics, producing ∼400-nm-thick pDCPD films in less than 1 min of polymerization. No significant differences in thickness were observed for films grown from monomer in the vapor phase with the different isomers (exo and endo) of DCPD.