Searcharxiv⌕ Search
Home/Archive/arXiv

arXiv · 1107.1231

Factors controlling the energetics of the oxygen reduction reaction on the Pd-Co electro-catalysts: Insight from first principles

Sebastian Zuluaga·Sergey Stolbov
View original source ↗Read source document ↗Export metadata ↓

Abstract

We report here results of our density functional theory based computational studies of the electronic structure of the Pd-Co alloy electrocatalysts and energetics of the oxygen reduction reaction (ORR) on their surfaces. The calculations have been performed for the (111) surfaces of pure Pd, Pd0.75Co0.25 and Pd0.5Co0.5 alloys, as well as of the surface segregated Pd/Pd0.75Co0.25 alloy. We find the hybridization of dPd and dCo electronic states to be the main factor controlling the electrocatalytic properties of Pd/Pd0.75Co0.25. Namely the dPd - dCo hybridization causes low energy shift of the surface Pd d-band with respect to that for Pd(111). This shift weakens chemical bonds between the ORR intermediates and the Pd/Pd0.75Co0.25 surface, which is favorable for the reaction. Non-segregated Pd0.75Co0.25 and Pd0.5Co0.5 surfaces are found to be too reactive for ORR due to bonding of the intermediates to the surface Co atoms. Analysis of the ORR free energy diagrams, built for the Pd and Pd/Pd0.75Co0.25, shows that the co-adsorption of the ORR intermediates and water changes the ORR energetics significantly and makes ORR more favorable. We find the onset ORR potential estimated for the configurations with the O - OH and OH - OH co-adsorption to be in very good agreement with experiment. The relevance of this finding to the real reaction environment is discussed.

Explore related subjects

cond-mat.mtrl-sci

Keep this discovery

BibTeXRIS

Sebastian Zuluaga, Sergey Stolbov. 2011-07-06. Factors controlling the energetics of the oxygen reduction reaction on the Pd-Co electro-catalysts: Insight from first principles. https://doi.org/10.1063/1.3643714

Cite the original work for its findings. Save a collection to share your selection of sources.

KEEP EXPLORING

Related papers

arXiv2026

Measuring chiral phonons

Chiral phonons are quantized vibrations where the atomic motion in a solid breaks improper rotation symmetries. In many cases, chiral phonons possess angular momenta and are therefore selective to circularly polarized light. Both fundamental and applied research efforts on chiral phonons have been gaining increasing attention owing to their importance in a variety of fields including spintronics, spin-selective chemical reactions, thermal transport, quantum information processing and biosensing, where the bi-directional spin-lattice coupling enabled by chiral phonons can be harnessed in new ways, and potentially lead to new functionalities. Thus far, the studies of chiral phonons across diverse materials platforms have evolved largely independently within these fields, but the experimental techniques are often interrelated. In this perspective, we present a detailed description, as well as advantages and disadvantages of the current approaches for experimentally measuring chiral phonons in chiral and achiral materials. We conclude with a discussion of new methods for measuring chiral phonons. Ultimately, this work seeks to offer an experimental guide for systematically investigating the properties of chiral phonons in various materials systems and applications.

cond-mat.mtrl-sci↗
arXiv2026

A model of grain growth in UN integrating molecular dynamics, phase-field modeling, and uncertainty quantification

Grain growth kinetics and grain-boundary (GB) properties in uranium mononitride (UN) are investigated through an integrated multiscale framework combining molecular dynamics (MD), phase-field modeling, and surrogate-assisted uncertainty quantification. MD simulations yield GB energies for 27 symmetric tilt boundaries from 0--2000~K, which are consistent with available DFT values. The average GB energy is nearly temperature-independent below 1000~K and increases at higher temperatures. A mechanistic pore-drag model applied to the only available grain growth dataset for actinide nitrides yields a mobility reduction factor of $s \approx 0.93$--$0.99$, statistically indistinguishable from unity, confirming that pore drag is negligible under the experimental conditions. The intrinsic GB mobility is therefore extracted directly from the effective mobility, yielding $M_0 = 2.05\times10^{-15}$~m$^4$/(J$\cdot$s) and $Q_M = 0.89$~eV. Phase-field simulations conducted from 1500--2000~K confirm normal curvature-driven grain growth, with grain size distributions converging to the Hillert-like form. A surrogate-assisted global sensitivity analysis---combining principal component analysis, Gaussian process regression, and Sobol decomposition---reveals that the mobility prefactor $M_0$ dominates output variance at all times, followed by the activation energy $Q_M$, while the GB energy $\gamma$ contributes minimally. These results establish the first quantitative grain growth framework for UN and identify the reduction of uncertainty in $M_0$ and $Q_M$ as the highest-priority target for future experimental efforts.

cond-mat.mtrl-sci↗
arXiv2026

Silicon Solar Cell Design for >30% Efficiency via Singlet Fission

Singlet fission (SF) materials convert high-energy photons into multiple charge carriers, providing a route to exceed the efficiency limits of single-junction silicon solar cells without many of the complexities of multi-junction tandem designs. Following the first demonstration of an SF-enhanced silicon solar cell in 2025, there is a need to understand how SF materials can be effectively integrated into high-efficiency industrial silicon devices and translated from proof of concept to a manufacturable technology. Using coupled optical and electrical simulations, we assess the efficiency potential of several industrially relevant silicon cell architectures combined with SF materials. Interdigitated back-contact (IBC) cells offer the greatest potential for improvement due to unrestricted front-surface access and can achieve efficiencies exceeding 33%. However, performance is highly sensitive to front-surface passivation quality. Appropriate silicon design, particularly controlled surface doping and fixed interfacial charge, can mitigate recombination losses and relax passivation requirements for ultra-thin exciton-transfer layers.

cond-mat.mtrl-sci↗