Selective Nitrogen Reduction Reaction on Single-Atom Centers of Molybdenum-Based MXenes by Pulsing the Electrochemical Potential DOI
Divya Singh, Samad Razzaq,

Shohreh Faridi

et al.

Published: Jan. 1, 2025

Electrocatalytic reduction of dinitrogen is a promising route for sustainable production ammonia, although the selectivity challenge competing nitrogen (NRR) and hydrogen evolution reactions in aqueous electrolytes has not yet been solved. Single-atom catalysts (SACs) offer hope bridging this gap because they exhibit unique electronic structure reactivity catalytic transformations compared to conventional bulk materials. In addition, potential pulse experiments have shown that promote formation kinetically unfavorable products by efficiently modulating electrolyte at solid-liquid interface. So far, combination SACs NRR mutually exclusive, since are likely be degraded during anodic due metal dissolution. Using density functional theory calculations grand canonical framework, we demonstrate present communication molybdenum-based MXenes able overcome limitation: traditional SACs, form single-atom centers pulse, their SAC-like allows directed ammonia instead gaseous cathodic pulse. Our study paves way development high-performance materials with in-situ formed sites enable advances selective under applied bias.

Language: Английский

Computational chemistry for water-splitting electrocatalysis DOI
Licheng Miao, Wenqi Jia, Xuejie Cao

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(6), P. 2771 - 2807

Published: Jan. 1, 2024

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

Language: Английский

Citations

53
Combining First-Principles Kinetics and Experimental Data to Establish Guidelines for Product Selectivity in Electrochemical CO2 Reduction DOI
Georg Kastlunger, Hendrik H. Heenen, Nitish Govindarajan

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(7), P. 5062 - 5072

Published: March 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.

Language: Английский

Citations

43
Data driven computational design of stable oxygen evolution catalysts by DFT and machine learning: Promising electrocatalysts DOI
Hwanyeol Park, Yunseok Kim, Seulwon Choi

et al.

Journal of Energy Chemistry, Journal Year: 2024, Volume and Issue: 91, P. 645 - 655

Published: Jan. 17, 2024

Language: Английский

Citations

19
Four Generations of Volcano Plots for the Oxygen Evolution Reaction: Beyond Proton-Coupled Electron Transfer Steps? DOI Creative Commons
Kai S. Exner

Accounts of Chemical Research, Journal Year: 2024, Volume and Issue: 57(9), P. 1336 - 1345

Published: April 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.

Language: Английский

Citations

16
First-principles and machine-learning approaches for interpreting and predicting the properties of MXenes DOI Creative Commons
José D. Gouveia, Tiago L. P. Galvão, Kais Iben Nassar

et al.

npj 2D Materials and Applications, Journal Year: 2025, Volume and Issue: 9(1)

Published: Feb. 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.

Language: Английский

Citations

3
On the mechanistic complexity of oxygen evolution: potential-dependent switching of the mechanism at the volcano apex DOI Creative Commons
Kai S. Exner

Materials Horizons, Journal Year: 2023, Volume and Issue: 10(6), P. 2086 - 2095

Published: Jan. 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.

Language: Английский

Citations

29
Degree of span control to determine the impact of different mechanisms and limiting steps: Oxygen evolution reaction over Co3O4(001) as a case study DOI Creative Commons
Kapil Dhaka, Kai S. Exner

Journal of Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 115970 - 115970

Published: Jan. 1, 2025

Language: Английский

Citations

1
Understanding Free-Energy Landscapes in Electrocatalysis: A Case Study on Nitrate Reduction over Au(111) DOI Creative Commons
Ebrahim Tayyebi, Kai S. Exner

ACS electrochemistry., Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 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.

Language: Английский

Citations

1
Selectivity Control in the Nitrogen Reduction Reaction over Mo2C MXene by a Nitrogen-Rich Environment DOI Creative Commons
Divya Singh, Samad Razzaq, Ebrahim Tayyebi

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 5589 - 5600

Published: March 21, 2025

Language: Английский

Citations

1
Gas-phase errors in computational electrocatalysis: a review DOI Creative Commons
Ricardo Urrego‐Ortiz, Santiago Builes, Francesc Illas

et al.

EES Catalysis, Journal Year: 2023, Volume and Issue: 2(1), P. 157 - 179

Published: Sept. 29, 2023

In this review we show how DFT gas-phase errors affect computational models of electrocatalytic reactions.

Language: Английский

Citations

22