Highly porous electrode designs are often employed for photoelectrochemical energy conversion applications. “Inverse opal” structures generate high surface area electrodes to enhance light absorption in semiconductors with short carrier collection lengths, effectively increasing the optical depth of ultrathin film photoelectrodes. Here, the fabrication of hierarchically structured, “host–guest” photoelectrodes based on selective atomic layer deposition of ZnO in composite polystyrene–SiO2 nanosphere films is described. Nanostructured scaffolds for ultrathin film photoanodes are prepared with a facile, continuously tunable solution‐phase synthesis. The characteristic length scales for absorption, carrier collection, and mass transport can be independently engineered into the electrode by choosing appropriate colloidal components for the composite scaffold. 20 nm ZnO photoanode layers based on the “host–guest” architecture exhibit roughly 500 times the photocurrent generated on an equivalent planar electrode and a 430% increase over a photoanode structured by a scaffold comprised of a close‐packed assembly of identical SiO2 nanospheres. This results from an improved balance of reactant mass transport and the locus of light absorption throughout the electrode. This approach offers a facile route for preparing strategically nanostructured photoelectrodes based on strategies developed from more complex fabrication techniques.
Electrokinetic flow provides a mechanism for a variety of fluid pumping schemes. The design and characterization of an electrochemically driven pump that utilizes porous carbon electrodes, iodide/triiodide redox electrolytes, and Nafion membranes is described. Fluid pumping by the cell is reversible and controlled by the cell current. Chronopotentiometry experiments indicate that the total available fluid that can be pumped in a single electrolysis without gas evolution is determined solely by the initial concentration of electrolyte and the applied current. The magnitude of the fluid flow at a given current is determined by the nature of the cation in the electrolyte and by the water absorption properties of the Nafion membrane. For 1 M aqueous electrolytes, pumping rates ranging from 1 to 14 microL/min were obtained for current densities of 10-30 mA/cm2 of membrane area. Molar volume changes for the I3-/I- redox couple and for the alkali cation migration contribute little to the observed volumetric flow rates; the magnitude of the flow is dominated by the migration-induced flow of water.
Electrolysis of ͑dimethylformamide͒ ͑DMF͒ solutions containing tetraalkylammonium iodide salts and dissolved iodine in a two-compartment cell separated by a Nafion membrane results in transfer of solution volume between the two compartments. The pumping process was reversible and the rate, which ranged from 20 to 50 L/min, was controlled by the cell current. The volume of solution pumped was significantly greater than what is predicted from the apparent molar volumes of the species involved in the electrolysis and from the charge passed. The additional volume is attributed to migration-assisted solvent flow across the membrane separator. Comparison of pumping results for a series of Nafion materials indicated that the solvent flow was related to the number of solvent molecules per ion-exchange site in the membrane. Pumping occurred with and against small external pressures up to 0.1 atm. Analysis of apparent molar ionic volumes indicates that the electrode reaction, I 3 Ϫ ϩ 2e Ϫ ϭ 3I Ϫ , contributes little to the observed volume change. Instead, the pumping is associated almost entirely with the apparent molar ionic volume of tetraalkylammonium ions and migration-assisted flow of DMF.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.