Variants of Surface Charges and Capacitances in Electrocatalysis: Insights from Density-Potential Functional Theory Embedded with an Implicit Chemisorption Model DOI Creative Commons
Jun Huang, Fabiola Domínguez-Flores, Marko Melander

et al.

PRX Energy, Journal Year: 2024, Volume and Issue: 3(4)

Published: Nov. 15, 2024

Prevalent electrolyte effects across a wide range of electrocatalytic reactions underscore the general importance local reaction conditions in electrical double layer (EDL). Compared to traditional EDLs, siblings feature partially charged chemisorbates that could blur our long-held views surface charge densities and differential capacitances—two interrelated quantities shaping crucial conditions. Herein, five variants density three capacitance presence are defined compared. A semiclassical model EDLs is developed for quantitative analysis differences interrelationships between these capacitances. It revealed potential- concentration-dependent net on dramatically changes Specifically, free decrease as electrode potential becomes more positive, implying . The relationship total analyzed with aid concept electrosorption valency. By linking valency absence chemisorbates, we explain concentration dependence former. conceptual presented this work has important implications experimental characterization first-principles-based atomistic simulations electrocatalysis EDL effects. Particularly, disclose hidden yet potentially disadvantage widely employed simulation models fix coverage chemisorbates. Proposing self-consistent implicit an expedient remedy disadvantage, contributes realistic modeling EDLs. Published by American Physical Society 2024

Language: Английский

Structured solvent on a split electron tail: A semiclassical theory of electrified metal-solution interfaces DOI Creative Commons

M. Zhang,

Yanxia Chen, Michael Eikerling

et al.

Physical Review Applied, Journal Year: 2025, Volume and Issue: 23(2)

Published: Feb. 4, 2025

We develop a comprehensive semiclassical continuum theory of electronic response and structured solvents at electrified metal-solution interfaces. The approach combines an orbital-free density-functional electrons on the metal side with statistical field electrolyte solution within grand canonical framework. resulting potential entire electrical double layer (EDL) is hybrid functional particle density, including classical particles, electric potential, solvent polarization, referred to as density-potential-polarization (DPPFT). DPPFT captures major atomistic phenomena EDL, electron spillover, spatially damped oscillations in polarization extending toward bulk solution, layered structure ions. Based DPPFT, EDL model for Ag(110)-KPF6 aqueous interface parameterized using experimental data double-layer capacitance (). calibrated employed study influence electronic, ion, properties structure. profiles different crystal faces various solutions are rationalized by coherently. reveal that intensified ion layering enhances zero charge narrowed ionic peaks profile. Contrary models, allows coions have appreciable densities near surface, their magnitudes depending local correlation strength between ions solvent. All all, presented framework provides holistic computationally efficient atomistic-level modeling EDLs under constant-potential conditions. Published American Physical Society 2025

Language: Английский

Citations

1
Insights into electron tunneling and confinement effects in electrochemical double layers using the jellium model DOI

Patiman Abudu,

Yitao He

Electrochimica Acta, Journal Year: 2025, Volume and Issue: unknown, P. 145998 - 145998

Published: March 1, 2025

Language: Английский

Citations

0
Electrocatalytic Transformations of C2 and C3 Hydrocarbons: Bridging from the Past to the Future DOI
Ashutosh Bhadouria, Ashmita Biswas, Brian M. Tackett

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 6296 - 6314

Published: April 3, 2025

Language: Английский

Citations

0
Variants of Surface Charges and Capacitances in Electrocatalysis: Insights from Density-Potential Functional Theory Embedded with an Implicit Chemisorption Model DOI Creative Commons
Jun Huang, Fabiola Domínguez-Flores, Marko Melander

et al.

PRX Energy, Journal Year: 2024, Volume and Issue: 3(4)

Published: Nov. 15, 2024

Prevalent electrolyte effects across a wide range of electrocatalytic reactions underscore the general importance local reaction conditions in electrical double layer (EDL). Compared to traditional EDLs, siblings feature partially charged chemisorbates that could blur our long-held views surface charge densities and differential capacitances—two interrelated quantities shaping crucial conditions. Herein, five variants density three capacitance presence are defined compared. A semiclassical model EDLs is developed for quantitative analysis differences interrelationships between these capacitances. It revealed potential- concentration-dependent net on dramatically changes Specifically, free decrease as electrode potential becomes more positive, implying . The relationship total analyzed with aid concept electrosorption valency. By linking valency absence chemisorbates, we explain concentration dependence former. conceptual presented this work has important implications experimental characterization first-principles-based atomistic simulations electrocatalysis EDL effects. Particularly, disclose hidden yet potentially disadvantage widely employed simulation models fix coverage chemisorbates. Proposing self-consistent implicit an expedient remedy disadvantage, contributes realistic modeling EDLs. Published by American Physical Society 2024

Language: Английский

Citations

1