A Gauss's law analysis of redox active adsorbates on semiconductor electrodes: The charging and faradaic currents are not independent.

A detailed framework for modeling and interpreting the data in totality from a cyclic voltammetric measurement of adsorbed redox monolayers on semiconductor electrodes has been developed. A three-layer model consisting of the semiconductor space-charge layer, a surface layer, and an electrolyte layer is presented that articulates the interplay between electrostatic, thermodynamic, and kinetic factors in the electrochemistry of a redox adsorbate on a semiconductor. Expressions are derived that describe the charging and faradaic current densities individually, and an algorithm is demonstrated that allows for the calculation of the total current density in a cyclic voltammetry measurement as a function of changes in the physical properties of the system (e.

A Description of the Faradaic Current in Cyclic Voltammetry of Adsorbed Redox Species on Semiconductor Electrodes.

A framework for interpreting the cyclic voltammetric responses from adsorbed redox monolayers on semiconductor electrodes has been developed. Expressions that describe quantitatively how the rates of the forward and back charge-transfer reactions impact the faradaic current density are presented. The primary insight is an explicit connection between the potential drops across the semiconductor space charge, surface, and electrolyte diffuse layers and the potential dependence of the reaction kinetics.

Beyond the Laviron Method: A New Mathematical Treatment for Analyzing the Faradaic Current in Reversible, Quasi-Reversible, and Irreversible Cyclic Voltammetry of Adsorbed Redox Species.

A new algorithm that describes the faradaic current for elementary redox reactions in the cyclic voltammetric responses of persistently adsorbed species on metal electrodes at any scan rate is presented. This work does not assume electrochemical reversibility and instead demonstrates a set of equations that encapsulate how the forward and back charge-transfer rate constants influence the data as a function of the experimental time scale. The method presented here is compared against other approaches that rely on either finite-difference calculations or that require numerical approximation of improper integrals (i.

The chain of chirality transfer in tellurium nanocrystals.

Despite persistent and extensive observations of crystals with chiral shapes, the mechanisms underlying their formation are not well understood. Although past studies suggest that chiral shapes can form because of crystallization in the presence of chiral additives, or because of an intrinsic tendency that stems from the crystal structure, there are many cases in which these explanations are not suitable or have not been tested. Here, an investigation of model tellurium nanocrystals provides insights into the chain of chirality transfer between crystal structure and shape.

Direct Visualization of Trimerized States in 1T^{'}-TaTe_{2}.

Transition-metal dichalcogenides containing tellurium anions show remarkable charge-lattice modulated structures and prominent interlayer character. Using cryogenic scanning transmission electron microscopy (STEM), we map the atomic-scale structures of the high temperature (HT) and low temperature (LT) modulated phases in 1T^{'}-TaTe_{2}. At HT, we directly show in-plane metal distortions which form trimerized clusters and staggered, three-layer stacking.