Computational chemistry for water-splitting electrocatalysis

Chemical Society Reviews, Год журнала: 2024, Номер 53(6), С. 2771 - 2807

Опубликована: Янв. 1, 2024

This review presents the basics of electrochemical water electrolysis, discusses progress in computational methods, models, and descriptors, evaluates remaining challenges this field.

Язык: Английский

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Data driven computational design of stable oxygen evolution catalysts by DFT and machine learning: Promising electrocatalysts

Journal of Energy Chemistry, Год журнала: 2024, Номер 91, С. 645 - 655

Опубликована: Янв. 17, 2024

Язык: Английский

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First-principles and machine-learning approaches for interpreting and predicting the properties of MXenes

npj 2D Materials and Applications, Год журнала: 2025, Номер 9(1)

Опубликована: Фев. 1, 2025

MXenes are a versatile family of 2D inorganic materials with applications in energy storage, shielding, sensing, and catalysis. This review highlights computational studies using density functional theory machine-learning approaches to explore their structure (stacking, functionalization, doping), properties (electronic, mechanical, magnetic), application potential. Key advances challenges critically examined, offering insights into applying research transition these from the lab practical use.

Язык: Английский

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Combining First-Principles Kinetics and Experimental Data to Establish Guidelines for Product Selectivity in Electrochemical CO₂ Reduction

ACS Catalysis, Год журнала: 2023, Номер 13(7), С. 5062 - 5072

Опубликована: Март 29, 2023

The electrochemical reduction of CO2 is envisioned as one the most promising ways to close industrial carbon cycle by producing high-value chemicals and fuels using renewable electricity. Although performance electrolyzers has improved substantially in past decade, they still suffer from poor selectivity toward desired products, ethylene ethanol. This part due fact that a detailed mechanistic understanding various products lacking, although such an essential for process optimization. Herein, we perform microkinetic simulations based on constant-potential density functional theory elucidate reaction pathways electroreduction Cu(100) major multicarbon products. We find first product bifurcates oxygenates, followed acetate. Acetaldehyde direct intermediate production provide atomistic level insights role played electrode potential electrolyte pH determining ethylene, methane relate origin general trends energetics. verify results our experimental database previously reported measurements. Finally, suggest guidelines improving specific Our study paves way design efficient targeted thereby moving step closer their widespread adaptation.

Язык: Английский

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On the mechanistic complexity of oxygen evolution: potential-dependent switching of the mechanism at the volcano apex

Materials Horizons, Год журнала: 2023, Номер 10(6), С. 2086 - 2095

Опубликована: Янв. 1, 2023

The anodic four-electron oxygen evolution reaction (OER) corresponds to the limiting process in acidic or alkaline electrolyzers produce gaseous hydrogen at cathode of device. In last decade, tremendous efforts have been dedicated identification active OER materials by electronic structure calculations density functional theory approximation. Most these works rely on assumption that mononuclear mechanism, comprising *OH, *O, and *OOH intermediates, is operative under conditions, a single elementary step (most likely formation) governs kinetics. present manuscript, six different mechanisms are analyzed, potential-dependent volcano curves constructed comprehend electrocatalytic activity pathways approximation descriptor Gmax(U), measure based notion free-energy span model. While description mainly describes legs plot, corresponding electrocatalysts with low intrinsic activity, it demonstrated preferred pathway apex strong function applied electrode potential. observed mechanistic complexity including switch favored increasing overpotential sets previous investigations aiming steps into question since entire breadth was not accounted for. A prerequisite for future atomic-scale studies highly catalysts refers evaluation several so neither important features overlooked nor incorrectly determined.

Язык: Английский

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Four Generations of Volcano Plots for the Oxygen Evolution Reaction: Beyond Proton-Coupled Electron Transfer Steps?

Accounts of Chemical Research, Год журнала: 2024, Номер 57(9), С. 1336 - 1345

Опубликована: Апрель 15, 2024

ConspectusDue to its importance for electrolyzers or metal–air batteries energy conversion storage, there is huge interest in the development of high-performance materials oxygen evolution reaction (OER). Theoretical investigations have aided search active material motifs through construction volcano plots kinetically sluggish OER, which involves transfer four proton–electron pairs form a single molecule. The theory-driven approach has gained unprecedented popularity catalysis and communities, largely due simplicity, as adsorption free energies can be used approximate electrocatalytic activity by heuristic descriptors.In last two decades, binding-energy-based method witnessed renaissance with special concepts being developed incorporate missing factors into analysis. To this end, Account summarizes discusses different generations example OER. While first-generation methods relied on assessment thermodynamic information OER intermediates means scaling relations, second third strategies include overpotential kinetic effects analysis trends. Finally, fourth generation approaches allowed incorporation various mechanistic pathways methodology, thus paving path toward data- mechanistic-driven electrocatalysis.Although concept been significantly expanded recent years, further research activities are discussed challenging one main paradigms concept. date, evaluation trends relies assumption proton-coupled electron steps (CPET), even though experimental evidence sequential (SPET) steps. computational SPET solid-state electrodes ambitious, it strongly suggested comprehend their storage processes, including This achieved knowledge from homogeneous heterogeneous electrocatalysis focusing class single-atom catalysts center well defined. derived how analyze over could shape our understanding at electrified solid/liquid interfaces, crucial progress sustainable climate neutrality.

Язык: Английский

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Selectivity Control in the Nitrogen Reduction Reaction over Mo₂C MXene by a Nitrogen-Rich Environment

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 5589 - 5600

Опубликована: Март 21, 2025

Язык: Английский

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Degree of span control to determine the impact of different mechanisms and limiting steps: Oxygen evolution reaction over Co3O4(001) as a case study

Journal of Catalysis, Год журнала: 2025, Номер unknown, С. 115970 - 115970

Опубликована: Янв. 1, 2025

Язык: Английский

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Understanding Free-Energy Landscapes in Electrocatalysis: A Case Study on Nitrate Reduction over Au(111)

ACS electrochemistry., Год журнала: 2025, Номер unknown

Опубликована: Фев. 25, 2025

Free-energy landscapes are essential tools in electrocatalysis for assessing catalyst activity and selectivity of proton-coupled electron transfer steps. It is a common approach to focus on the thermodynamic part free-energy landscape refer only reaction intermediates, which turn leads results being highly dependent accuracy calculated binding energies adsorbed intermediates. Since evaluation electrocatalytic processes solid surfaces usually requires density functional theory calculations (DFT) with periodic boundary conditions, free energy reference molecules relevant binding-energy determination subject an inherent error. For this purpose, gas-phase error corrections have been introduced recent years, allow correction DFT error, based assessment formation enthalpies, by assigning double or triple bonds molecules. In contribution, we present simple unbiased errors: do not distinguish between bond order but correct all single, double, referring atomization compounds. We employ our nitrate reduction Au(111) as case study, using different levels exchange–correlation functionals generalized gradient meta-generalized approximation. shown that inclusion well solvation ion significantly affects energetics predictions descriptor-based analysis, highlighting importance correcting DFT-based gaining reliable insights into systems.

Язык: Английский

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Selective nitrogen reduction reaction on single-atom centers of molybdenum-based MXenes by pulsing the electrochemical potential

Materials Today, Год журнала: 2025, Номер unknown

Опубликована: Апрель 1, 2025

Язык: Английский

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