Nonidealities in CO Electroreduction Mechanisms Revealed by Automation-Assisted Kinetic Analysis.

In electrocatalysis, mechanistic analysis of reaction rate data often relies on the linearization of relatively simple rate equations; this is the basis for typical Tafel and reactant order dependence analyses. However, for more complex reaction phenomena, such as surface coverage effects or mixed control, these common linearization strategies will yield incomplete or uninterpretable results. Cohesive kinetic analysis, which is often used in thermocatalysis and involves quantitative model fitting for data collected over a wide range of reaction conditions, requires more data but also provides a more robust strategy for interrogating reaction mechanisms.

Water molecules mute the dependence of the double-layer potential profile on ionic strength.

We present the results of molecular dynamics simulations of a nanoscale electrochemical cell. The simulations include an aqueous electrolyte solution with varying ionic strength (, concentrations ranging from 0-4 M) between a pair of metallic electrodes held at constant potential difference. We analyze these simulations by computing the electrostatic potential profile of the electric double-layer region and find it to be nearly independent of ionic concentration, in stark contrast to the predictions of standard continuum-based theories.

Bayesian data analysis reveals no preference for cardinal Tafel slopes in CO reduction electrocatalysis.

The Tafel slope is a key parameter often quoted to characterize the efficacy of an electrochemical catalyst. In this paper, we develop a Bayesian data analysis approach to estimate the Tafel slope from experimentally-measured current-voltage data. Our approach obviates the human intervention required by current literature practice for Tafel estimation, and provides robust, distributional uncertainty estimates.

Understanding attenuated solvent reorganization energies near electrode interfaces.

In this manuscript, we examine the role of image charge effects on the electrostatic potential fluctuations experienced by ionic species in the vicinity of an electrode surface. We combine simulation and theory to quantify these fluctuations and how they vary with distance from the electrode surface. We observe that the potential distribution narrows significantly for species within a few electrolyte screening lengths of the electrode.

Influence of three-dimensional nanoparticle branching on the Young's modulus of nanocomposites: Effect of interface orientation.

With the availability of nanoparticles with controlled size and shape, there has been renewed interest in the mechanical properties of polymer/nanoparticle blends. Despite the large number of theoretical studies, the effect of branching for nanofillers tens of nanometers in size on the elastic stiffness of these composite materials has received limited attention. Here, we examine the Young's modulus of nanocomposites based on a common block copolymer (BCP) blended with linear nanorods and nanoscale tetrapod Quantum Dots (tQDs), in electrospun fibers and thin films.