Cation-Induced Interfacial Hydrophobic Microenvironment Promotes the C–C Coupling in Electrochemical CO₂ Reduction

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5532 - 5542

Published: Feb. 16, 2024

The electrochemical carbon dioxide reduction reaction (CO2RR) toward C2 products is a promising way for the clean energy economy. Modulating structure of electric double layer (EDL), especially interfacial water and cation type, useful strategy to promote C–C coupling, but atomic understanding lags far behind experimental observations. Herein, we investigate combined effect alkali metal cations on coupling at Cu(100) electrode/electrolyte interface using ab initio molecular dynamics (AIMD) simulations with constrained MD slow-growth approach. We observe linear correlation between water-adsorbate stabilization effect, which manifests as hydrogen bonds, corresponding alleviation in free energy. role larger cation, compared smaller (e.g., K+ vs Li+), lies its ability approach through desolvation coordinates *CO+*CO moiety, partially substituting hydrogen-bonding stabilizing water. Although this only results marginal barrier it creates local hydrophobic environment scarcity bonds owing great ionic radius, impeding surrounding oxygen adsorbed *CO. This skillfully circumvents further hydrogenation *CO C1 pathway, serving predominant factor facilitates coupling. study unveils comprehensive mechanism cation–water–adsorbate interactions that can facilitate optimization electrolyte EDL efficient CO2RR.

Language: Английский

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Electric Double Layer Effects in Electrocatalysis: Insights from Ab Initio Simulation and Hierarchical Continuum Modeling

JACS Au, Journal Year: 2023, Volume and Issue: 3(10), P. 2640 - 2659

Published: Sept. 18, 2023

Structures of the electric double layer (EDL) at electrocatalytic interfaces, which are modulated by material properties, electrolyte characteristics (e.g., pH, types and concentrations ions), electrode potential, play crucial roles in reaction kinetics. Understanding EDL effects electrocatalysis has attracted substantial research interest recent years. However, intrinsic relationships between specific structures kinetics remain poorly understood, especially on atomic scale. In this Perspective, we briefly review advances deciphering mainly hydrogen oxygen through a multiscale approach, spanning from atomistic scale simulated ab initio methods to macroscale hierarchical approach. We highlight importance resolving local environment, bond network, understanding effects. Finally, some remaining challenges outlined, an outlook for future developments these exciting frontiers is provided.

Language: Английский

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Molecular understanding of the critical role of alkali metal cations in initiating CO2 electroreduction on Cu(100) surface

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 19, 2024

Abstract Molecular understanding of the solid–liquid interface is challenging but essential to elucidate role environment on kinetics electrochemical reactions. Alkali metal cations (M + ), as a vital component at interface, are found be necessary for initiation carbon dioxide reduction reaction (CO 2 RR) coinage metals, and activity selectivity CO RR could further enhanced with cation changing from Li Cs , while underlying mechanisms not well understood. Herein, using ab initio molecular dynamics simulations explicit solvation sampling methods, we systematically investigate M in Cu surface. A monotonically decreasing activation barrier obtained which attributed different coordination abilities *CO . Furthermore, show that competing hydrogen evolution must considered simultaneously understand crucial alkali surfaces, where H repelled constrained by Our results provide significant insights into design environments highlight importance explicitly including reactions theoretical RR.

Language: Английский

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Mechanistic Insights into Surfactant-Modulated Electrode–Electrolyte Interface for Steering H₂O₂ Electrosynthesis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7575 - 7583

Published: March 11, 2024

Electrocatalytic reactions taking place at the electrified electrode–electrolyte interface involve processes of proton-coupled electron transfer. Interfacial protons are delivered to electrode surface via a H2O-dominated hydrogen-bond network. Less efforts made regulate interfacial proton transfer from perspective Here, we present quaternary ammonium salt cationic surfactants as electrolyte additives for enhancing H2O2 selectivity oxygen reduction reaction (ORR). Through in situ vibrational spectroscopy and molecular dynamics calculation, it is revealed that irreversibly adsorbed on response given bias potential range, leading weakening This decreases kinetics, particularly high potentials, thus suppressing 4-electron ORR pathway achieving highly selective 2-electron toward H2O2. These results highlight opportunity steering H2O-involved electrochemical modulating

Language: Английский

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Scalable decarboxylative trifluoromethylation by ion-shielding heterogeneous photoelectrocatalysis

Science, Journal Year: 2024, Volume and Issue: 384(6696), P. 670 - 676

Published: May 9, 2024

Electrochemistry offers a sustainable synthesis route to value-added fine chemicals but is often constrained by competing electron transfer between the electrode and redox-sensitive functionalities distinct from target site. Here, we describe an ion-shielding heterogeneous photoelectrocatalysis strategy impose mass-transfer limitations that invert thermodynamically determined order of transfer. This showcased enable decarboxylative trifluoromethylation sensitive (hetero)arenes using trifluoroacetate, inexpensive yet relatively inert trifluoromethyl group (CF

Language: Английский

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Addressing the Carbonate Issue: Electrocatalysts for Acidic CO₂ Reduction Reaction

Advanced Materials, Journal Year: 2024, Volume and Issue: unknown

Published: May 9, 2024

Abstract Electrochemical CO 2 reduction reaction (CO RR) powered by renewable energy provides a promising route to conversion and utilization. However, the widely used neutral/alkaline electrolyte consumes large amount of produce (bi)carbonate byproducts, leading significant challenges at device level, thereby impeding further deployment this reaction. Conducting RR in acidic electrolytes offers solution address “carbonate issue”; however, it presents inherent difficulties due competitive hydrogen evolution reaction, necessitating concerted efforts toward advanced catalyst electrode designs achieve high selectivity activity. This review encompasses recent developments RR, from mechanism elucidation design engineering. begins discussing mechanistic understanding pathway, laying foundation for RR. Subsequently, an in‐depth analysis advancements catalysts is provided, highlighting heterogeneous catalysts, surface immobilized molecular enhancement. Furthermore, progress made device‐level applications summarized, aiming develop high‐performance systems. Finally, existing future directions are outlined, emphasizing need improved selectivity, activity, stability, scalability.

Language: Английский

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Effects of Ionic Interferents on Electrocatalytic Nitrate Reduction: Mechanistic Insight

Environmental Science & Technology, Journal Year: 2024, Volume and Issue: 58(29), P. 12823 - 12845

Published: July 2, 2024

Nitrate, a prevalent water pollutant, poses substantial public health concerns and environmental risks. Electrochemical reduction of nitrate (eNO

Language: Английский

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Enhanced Electrochemical CO₂ Reduction to Formate over Phosphate‐Modified In: Water Activation and Active Site Tuning

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(27)

Published: April 26, 2024

Electrochemical CO

Language: Английский

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Accelerating the Reaction Kinetics of CO₂ Reduction to Multi‐Carbon Products by Synergistic Effect between Cation and Aprotic Solvent on Copper Electrodes

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(9)

Published: Jan. 3, 2024

Improving the selectivity of electrochemical CO

Language: Английский

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Rational design of local microenvironment for electrocatalytic water splitting

Inorganic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4080 - 4106

Published: Jan. 1, 2024

This summary describes the effects of wettability, local pH, interfacial water structure, and electrolyte composition on interface reactant compositions, key intermediate adsorption, reaction kinetics.

Language: Английский

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