Electrolyte Effects in Electrocatalytic Kinetics† DOI
Xiaoyu Li, Zhiming Zhang, Xinxin Zhuang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(24), P. 3533 - 3552

Published: Nov. 1, 2024

Comprehensive Summary Tuning electrolyte properties is a widely recognized strategy to enhance activity and selectivity in electrocatalysis, drawing increasing attention this domain. Despite extensive experimental theoretical studies, debates persist about how various components influence electrocatalytic reactions. We offer concise review focusing on current discussions, especially the contentious roles of cations. This article further examines different factors affect interfacial solvent structure, particularly hydrogen‐bonding network, delves into microscopic kinetics electron proton‐coupled transfer. also discuss overarching solvents from kinetic modeling perspective, aiming develop robust correlation between structure reactivity. Lastly, we summarize ongoing research challenges suggest potential directions for future studies effects electrocatalysis. Key Scientists In 1956, Marcus theory was developed describe mechanism outer‐sphere transfer (OS‐ET). 1992, Nocera et al. directly measured (PCET) first time, their subsequent 1995 investigated proton motion (ET) kinetics. 1999 2000, Hammes‐schiffer multistate continuum multiple charge reactions deduced rate expressions nonadiabatic PCET solution, laying foundation analysis electrochemical processes. 2006, Saveant verified concerted (CPET) oxidation phenols coupled with intramolecular amine‐driven (PT). Their work 2008 reported pH‐dependent pathways phenols. Electrolyte electrocatalysis have gained emphasis recent years. 2009, Markovic's pioneering proposed non‐covalent interactions hydrated alkaline cations adsorbed OH species oxygen reduction reaction (ORR)/hydrogen (HOR). 2011, Markovic significantly enhanced hydrogen evolution (HER) solution by improving water dissociation, which assumed dominate sluggish HER such media. comparation, Yan applied binding energy (HBE) 2015 explain HER/HOR activity. Cations play significant role regulating carbon dioxide (CO 2 RR). 2016 2017, Karen Chan introduced electric field generated solvated cation CO2RR. Conversely, 2021, Koper suggested that short‐range electrostatic partially desolvated metal CO stabilized promoted RR. Recent researches combined exploration electrical double layer (EDL) 2019, Huang Hamiltonian model quantitatively understand two meticulous Shao‐Horn's group analyzed reorganization impacts bonds donors acceptors tunneling kinetics, respectively. transport process were researched 2022, Hu Chen cation‐induced distribution bonding network connectivity played essential transport, separately.

Language: Английский

Interfacial Hydrogen-Bond Network Regulation Tuned Water Dissociation Enables Selective Chlorination of Alkenes DOI
Junwei Yao, Chuanqi Cheng, Yongmeng Wu

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 8024 - 8031

Published: Feb. 20, 2025

Electrocatalytically selective chlorination of olefins in Cl--containing solutions is a sustainable method for synthesizing chlorohydrin/vicinal dichloride; however, controlling the selectivity challenging. Here, aqueous/dimethyl carbonate (DMC) hybrid electrolytes with different H2O/DMC ratios are designed to modulate ·OH formation increase corresponding selectivities. The combined results in/ex situ spectroscopies and molecular dynamics simulations reveal origin high selectivity. TFSI- shields transportation free H2O provide moderate synthesis chlorohydrin. DMC reconstructs hydrogen bonds minimize interaction between them anode, matching requirements vicinal dichloride production. Thus, these not only achieve selectivities 80% 76% chlorohydrin dichloride, respectively, but also enable other isolated yields up 74%. This work provides facile strategy regulate anodic via rational electrolyte design.

Language: Английский

Citations

1
Investigating the Electric Double-Layer Structures between a Pt Electrode and Water/Acetonitrile Hybrid Electrolytes DOI
Boqiang Chen, Milan S. Wijesinghe,

Alexis Grimaud

et al.

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 1779 - 1786

Published: Feb. 12, 2025

Controlling the reactivity of water at electrocatalytic interfaces is a critical challenge in many reactions. Its can be adjusted by altering composition hybrid aqueous/organic electrolytes. To advance this approach, it essential to understand how structure electrode/hybrid electrolyte interface depends upon electrode potential. This understanding largely lacking. Herein, using surface-enhanced infrared absorption spectroscopy (SEIRAS), we probed formed between Pt and acetonitrile/water mixtures containing 0.1 M LiClO4 or (butyl4N)ClO4. In presence Li+ with decreasing potential, crystalline LiOH deposits on electrolytes low content (∼1% weight) due solubility salt acetonitrile, blocking active sites hydrogen evolution reaction (HER). butyl4N+, surface becomes more hydrophobic Notably, butyl4N+ ions form an irreversibly physisorbed adlayer solely high content. Despite formation adlayer, remains for HER.

Language: Английский

Citations

0
Molecular Origin of Nanoscale Anion Ordering of LiTFSI Electrolytes Revealed through SAXS/WAXS and Molecular Dynamics Simulations DOI

Lucas Trojanowski,

Xingyi Lyu, Shao-Chun Lee

et al.

ACS Energy Letters, Journal Year: 2025, Volume and Issue: unknown, P. 696 - 702

Published: Jan. 8, 2025

Recent developments in "water-in-salt" electrolytes have precipitated a renewed effort to study imide-based electrolytes. While previous small-/wide-angle X-ray scattering (SAXS/WAXS) studies attributed the emergence of low-Q peak SAXS profile aqueous LiTFSI nanometer-scale anion clustering, molecular-level understanding root these clusters remains unclear. In this study, we combined molecular dynamics simulations and SAXS/WAXS solvation structures acetonitrile, methanol, water. We concluded that hydrogen bonding water MeOH stabilizes clusters, while nonpolar methyl groups on methanol acetonitrile interrupt nanoscale ordering TFSI anions. This causes exhibit two peaks exhibits only single below Q = 1 Å–1. These findings shed light underlying origins which may help design next generation electrolyte chemistries.

Language: Английский

Citations

0
Electrolyte Effects in Electrocatalytic Kinetics† DOI
Xiaoyu Li, Zhiming Zhang, Xinxin Zhuang

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(24), P. 3533 - 3552

Published: Nov. 1, 2024

Comprehensive Summary Tuning electrolyte properties is a widely recognized strategy to enhance activity and selectivity in electrocatalysis, drawing increasing attention this domain. Despite extensive experimental theoretical studies, debates persist about how various components influence electrocatalytic reactions. We offer concise review focusing on current discussions, especially the contentious roles of cations. This article further examines different factors affect interfacial solvent structure, particularly hydrogen‐bonding network, delves into microscopic kinetics electron proton‐coupled transfer. also discuss overarching solvents from kinetic modeling perspective, aiming develop robust correlation between structure reactivity. Lastly, we summarize ongoing research challenges suggest potential directions for future studies effects electrocatalysis. Key Scientists In 1956, Marcus theory was developed describe mechanism outer‐sphere transfer (OS‐ET). 1992, Nocera et al. directly measured (PCET) first time, their subsequent 1995 investigated proton motion (ET) kinetics. 1999 2000, Hammes‐schiffer multistate continuum multiple charge reactions deduced rate expressions nonadiabatic PCET solution, laying foundation analysis electrochemical processes. 2006, Saveant verified concerted (CPET) oxidation phenols coupled with intramolecular amine‐driven (PT). Their work 2008 reported pH‐dependent pathways phenols. Electrolyte electrocatalysis have gained emphasis recent years. 2009, Markovic's pioneering proposed non‐covalent interactions hydrated alkaline cations adsorbed OH species oxygen reduction reaction (ORR)/hydrogen (HOR). 2011, Markovic significantly enhanced hydrogen evolution (HER) solution by improving water dissociation, which assumed dominate sluggish HER such media. comparation, Yan applied binding energy (HBE) 2015 explain HER/HOR activity. Cations play significant role regulating carbon dioxide (CO 2 RR). 2016 2017, Karen Chan introduced electric field generated solvated cation CO2RR. Conversely, 2021, Koper suggested that short‐range electrostatic partially desolvated metal CO stabilized promoted RR. Recent researches combined exploration electrical double layer (EDL) 2019, Huang Hamiltonian model quantitatively understand two meticulous Shao‐Horn's group analyzed reorganization impacts bonds donors acceptors tunneling kinetics, respectively. transport process were researched 2022, Hu Chen cation‐induced distribution bonding network connectivity played essential transport, separately.

Language: Английский

Citations

0