Characterizing the Solvent‐Induced Inversion of Colloidal Aggregation During Electrophoretic Deposition

Abstract Electrophoretic deposition (EPD) of colloidal particles is a practical system for the study of crystallization and related physical phenomena. The aggregation is driven by the electroosmotic flow fields and induced dipole moments generated by the polarization of the electrode‐particle‐electrolyte interface. Here, the electrochemical control of aggregation and repulsion in the electrophoretic deposition of colloidal microspheres is reported. The nature of the observed transition depended on the composition of the solvent, switching from electrode‐driven aggregation in water to electrical field‐driven repulsion in ethanol for otherwise identical systems of colloidal microspheres. This work uses optical microscopy‐derived particles and a recently developed particle insertion method approach to extract model‐free, effective interparticle potentials to describe the ensemble behavior of the particles as a function of the solvent and electrode potential at the electrode interface. This approach can be used to understand the phase behavior of these systems based on the observable particle positions rather than a detailed understanding of the electrode‐electrolyte microphysics. This approach enables simple predictability of the static and dynamic behaviors of functional colloid‐electrode interfaces

Inhibition of Tafel Kinetics for Electrolytic Hydrogen Evolution on Isolated Micron Scale Electrocatalysts on Semiconductor Interfaces

Semiconductor–liquid junctions are ubiquitous in photoelectrochemical approaches to artificial photosynthesis. By analogy with the antennae and reaction centers in natural photosynthetic complexes, separating the light-absorbing semiconductor and electrocatalysts can improve catalytic efficiency. A catalytic layer can also impair the photovoltage-generating energetics of the electrode without appropriate microscopic organization of catalytically active area on the surface. Here, we have developed a method using high-speed X-ray phase contrast imaging to study <i>in situ</i> electrolytic bubble growth on semiconductor electrodes fabricated with isolated, micron-scale platinum electrocatalysts. X-rays are a nonperturbative probe by which gas evolution dynamics can be studied under conditions relevant to solar fuels applications. The self-limited growth of a bubble residing on the isolated electrocatalyst was measured by tracking the evolution of the gas–liquid boundary. Contrary to observations on macroscopic electrodes, bubble evolution on isolated, microscopic Pt pads on Si electrodes was insensitive to increasing overpotential. The persistence of the bubble causes mass transport limitations and inhibits the expected Tafel-like kinetics. The observed scaling of catalytic current densities with pad size implies that electrolysis is occurring predominantly on the perimeter of the active area

Quaternary core–shell oxynitride nanowire photoanode containing a hole-extraction gradient for photoelectrochemical water oxidation

A nanowire photoanode SrTaO2N, a semiconductor suitable for overall water-splitting with a band gap of 2.3 eV, was coated with functional overlayers to yield a core–shell structure while maintaining its one-dimensional morphology. The nanowires were grown hydrothermally on tantalum, and the perovskite-related oxynitride structure was obtained by nitridation. Three functional overlayers have been deposited on the nanowires to enhance the efficiency of photoelectrochemical (PEC) water oxidation. The deposition of TiOx protects the oxynitride from photocorrosion and suppresses charge-carrier recombination at the surface. Ni­(OH)x acts a hole-storage layer and decreases the dark-current contribution. This leads to a significantly improved extraction of photogenerated holes to the electrode–electrolyte surface. The photocurrents can be increased by the deposition of a cobalt phosphate (CoPi) layer as a cocatalyst. The heterojunction nanowire photoanode generates a current density of 0.27 mA cm–2 at 1.23 V vs the reversible hydrogen electrode (RHE) under simulated sunlight (AM 1.5G). Simultaneously, the dark-current contribution, a common problem for oxynitride photoanodes grown on metallic substrates, is almost completely minimized. This is the first report of a quaternary oxynitride nanowire photoanode in core–shell geometry containing functional overlayers for synergetic hole extraction and an electrocatalyst