How to Assess and Predict Electrical Double Layer Properties. Implications for Electrocatalysis

Chemical Reviews, Год журнала: 2024, Номер 124(22), С. 12391 - 12462

Опубликована: Ноя. 11, 2024

The electrical double layer (EDL) plays a central role in electrochemical energy systems, impacting charge transfer mechanisms and reaction rates. fundamental importance of the EDL interfacial electrochemistry has motivated researchers to develop theoretical experimental approaches assess properties. In this contribution, we review recent progress evaluating characteristics such as double-layer capacitance, highlighting some discrepancies between theory experiment discussing strategies for their reconciliation. We further discuss merits challenges various techniques having important implications aqueous electrocatalysis. A strong emphasis is placed on substantial impact electrode composition structure electrolyte chemistry addition, effects temperature pressure compare solid-liquid interfaces solid-solid interfaces.

Язык: Английский

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Unravelling the structure-activity relationship of porous binary metal-based electrocatalysts for green hydrogen evolution reaction

Coordination Chemistry Reviews, Год журнала: 2024, Номер 523, С. 216238 - 216238

Опубликована: Окт. 11, 2024

Язык: Английский

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The Effect of the Tetraalkylammonium Cation in the Electrochemical CO₂ Reduction Reaction on Copper Electrode

ACS Catalysis, Год журнала: 2024, Номер 14(17), С. 12928 - 12939

Опубликована: Авг. 14, 2024

Aprotic organic solvents such as acetonitrile offer a potential solution to promote electrochemical CO2 reduction over the competing hydrogen evolution reaction. Tetraalkylammonium cations (TAA+) are widely used supporting electrolytes in media due their high solubility and conductivity. The alkyl chain length of TAA+ is known influence electron transfer processes systems by adsorption TAA+, causing modifications double layer. In this work, we elucidate cation on mechanism selectivity CO2RR reaction under controlled dry wet conditions copper cathodes. We find that hydrophobic hydration character cation, which can be tuned length, has an effect product distribution, altering pathway. Under conditions, smaller (TEA+) preferentially oxalate production via dimerization CO2·– intermediate, whereas formate favored presence water protonation Larger (TBA+ > TPA+ TEA+) favor generation CO regardless content. situ FTIR analysis showed TBA+ able stabilize adsorbed more effectively than TEA+, explaining why larger generate higher proportion CO. Our findings also suggest concentrations suppress evolution, particularly with cations, highlighting role size shell.

Язык: Английский

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Dielectric profile at the Pt(111)/water interface

The Journal of Chemical Physics, Год журнала: 2025, Номер 162(2)

Опубликована: Янв. 8, 2025

The dielectric constant, although a simplified concept when considering atomic scales, enters many mean-field, electrochemical interface models and constant potential as an important parameter. Here, we use ab initio machine-learned molecular dynamics to scrutinize the behavior of electronic contribution ɛr(z) function distance z from Pt(111) surface. We show that resulting profile can largely be explained sum metallic response density-scaled water at interface. A slight enhancement close surface by elongated, strongly polarizable orbitals induced metal/water bonding. In spite this enhancement, our results suggest presence region with very low (where orientational does not kick in yet), even for contact hydrophilic interfaces. This will restrict double layer capacitance relatively values potentials where saturation play role yet. finding has implications on possible interpretations capacitances, dependence electric fields ion size, kinetics.

Язык: Английский

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Computational Modeling of Electrocatalysts for CO₂ Reduction: Probing the Role of Primary, Secondary, and Outer Coordination Spheres

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 27, 2025

ConspectusIn the search for efficient and selective electrocatalysts capable of converting greenhouse gases to value-added products, enzymes found in naturally existing bacteria provide basis most approaches toward electrocatalyst design. Ni,Fe-carbon monoxide dehydrogenase (Ni,Fe-CODH) is one such enzyme, with a nickel-iron-sulfur cluster named C-cluster, where CO2 binds converted CO at high rates near thermodynamic potential. In this Account, we divide enzyme's catalytic contributions into three categories based on location function. We also discuss how computational techniques crucial insight implementing these findings homogeneous reduction electrocatalysis design principles. The binding sites (e.g., Ni "unique" Fe ion) along ligands that support it iron-sulfur cluster) form primary coordination sphere. This replicated molecular via metal center ligand framework substrate binds. sphere has direct impact electronic configuration catalyst. By computationally modeling series Co complexes bipyridyl-N-heterocyclic carbene frameworks varying degrees planarity, were able closely examine controls product distribution between H2 catalysts. secondary (SCS) Ni,Fe-CODH contains residues proximal active site pocket hydrogen-bonding stabilizations necessary reaction proceed. Enhancing SCS when synthesizing new catalysts involves substituting functional groups onto interaction substrate. To analyze endless possible substitutions, are ideal deciphering intricacies substituent effects, as demonstrated an array imidazolium-functionalized Mn Re bipyridyl tricarbonyl complexes. examining electrostatic interactions ligand, substrate, proton source lowered activation energy barriers, determined best pinpoint additions. outer comprises remaining parts Ni,Fe-CODH, elaborate protein matrix, solvent interactions, remote metalloclusters. challenge elucidating replicating role vast matrix understandably led localized focus spheres. However, certain portions Ni,Fe-CODH's expansive scaffold suggested be catalytically relevant despite considerable distance from site. Closer studies relatively overlooked areas nature's exceptionally proficient may continually improve upon protocols. Mechanistic analysis cobalt phthalocyanines (CoPc) immobilized carbon nanotubes (CoPc/CNT) reveals microenvironment effects unlock CoPc molecule's previously inaccessible intrinsic ability convert MeOH. Our research suggests incorporating spheres holistic approach vital advancing viability mitigating climate disruption. Computational methods allow us transition states determine minimize key barriers.

Язык: Английский

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Effects of Electrolyte Cations on the Oxygen Evolution Reaction

Current Opinion in Electrochemistry, Год журнала: 2025, Номер unknown, С. 101697 - 101697

Опубликована: Апрель 1, 2025

Язык: Английский

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Unveiling Double Layer Effects in Electrocatalytic CO₂ Reduction

The Journal of Physical Chemistry C, Год журнала: 2025, Номер unknown

Опубликована: Май 2, 2025

Язык: Английский

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The role of Anions and Additives in Electrochemical CO2 Reduction

Current Opinion in Electrochemistry, Год журнала: 2025, Номер unknown, С. 101707 - 101707

Опубликована: Май 1, 2025

Язык: Английский

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The ion effect on electrocatalytic oxidation reactions

Journal of Materials Chemistry A, Год журнала: 2024, Номер 12(47), С. 32548 - 32565

Опубликована: Янв. 1, 2024

The ion effect on anodic reactions manifests three major forms: (1) regulate the adsorption energy through non-covalent interactions, (2) mass transfer behavior, and (3) interfacial pH by controlling proton transfer.

Язык: Английский

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Hydration-Shell Solvation and Screening Govern Alkali Cation Concentrations at Electrochemical Interfaces

The Journal of Physical Chemistry C, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 25, 2024

Knowledge of the concentration alkali cations in an electrochemical double layer is essential for interpreting and leveraging cation effects electrocatalysis. We systematically study profiles four (Li+, Na+, K+, Cs+) at a Ag(111)-aqueous interface. Using classical molecular dynamics, potential mean force (PMF) approaching metal surface was computed decomposed into contributions from solvent surface. find that hydration shell deformations contribute importantly to free energy near electrode. Cations with larger ionic radii looser shells experience less solvation loss short-range Coulombic screening, which enable them adsorb more strongly negatively charged (Cs+ > K+ Na+ Li+). compute non-Faradaic electrosorption valency interfacial capacitance show these experimentally relevant quantities encode relative adsorbed different sizes, but not spatial positions layer.

Язык: Английский

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