Statistical Treatment of Activity and Durability of Electrocatalysts with Distributed Binding Energies

Abstract

We present a statistical treatment of the catalytic activity and durability of nonhomogeneous electrocatalysts that possess distributed binding energies of reaction intermediates. The treatment is simple, generic, and amenable to analytical solutions. It is revealed that the highest overall catalytic activity is obtained with a suitable level of nonhomogeneity that is commensurate with the average property. The evolution of the binding energy distribution is described by the Fokker-Planck theory. Exponential decay of the catalytic activity is predicted theoretically and confirmed experimentally. The exponential decay shows one-or two stages, depending on the initial distribution properties. The present work represents a step toward closing the gap between ideal and practical electrocatalysts using statistical considerations.

Locating the cocktail and scaling-relation breaking effects of high-entropy alloy catalysts on the electrocatalytic volcano plot

“…However, one should note that this increase has limited value. According to more detailed work by Huang [12], the increase will stop at around 0.10-0.17 eV from the volcanic top, and then slowly depart from the volcanic top. This is because, when σ increases to a certain value, the probability density of sites around the volcanic top region will be large enough, so that it will dominate in the activity contribution; after this point, if we further increase σ, the activity-dominated sites will always be sites located around the volcanic top; at yet higher σ, the normal distribution will become be dispersed, gradually decreasing the probability density of sites around the volcanic top region, and then leading to a slow decrease in the total activity.…”

“…Second, a normal distribution function is ruled by its expected value and variance; that is, its degrees of freedoms (DOF) are only two, far fewer than the DOF of the active site of HEA. Additionally, in recent work, Huang has proved that a normal distribution will result in a simple but meaningful expression for the activity [12]. Thus, introducing a normal distribution may express those two effects in a simple way.…”

A Novel Trimetal Phosphide with Amorphous Porous Structure for the Enhanced Electrocatalysis of Oxygen Evolution Reaction

“…Electrocatalytic water splitting has always been favored by researchers due to its economic and environmentally friendly characteristics. [1][2][3] However, the sluggish kinetic process leads to high overpotential and low efficiency in its practical applications. 4,5 At present, noble metal-based electrocatalysts are considered to be very effective catalysts for OER, such as iridium and rutheniumbased composite materials.…”