Disentangling Multiple pH-Dependent Factors on the Hydrogen Evolution Reaction at Au(111) DOI Creative Commons

Er-Fei Zhen,

Bing-Yu Liu,

Mengke Zhang

et al.

Precision Chemistry, Journal Year: 2025, Volume and Issue: 3(3), P. 135 - 148

Published: Jan. 8, 2025

Understanding how the electrolyte pH affects electrocatalytic activity is a topic of crucial importance in large variety systems. However, unraveling origin effects complicated often by fact that both reaction driving forces and reactant concentrations electric double layer (EDL) change simultaneously with value. Herein, we employ hydrogen evolution (HER) at Au(111)-aqueous solution interfaces as model system to disentangle different pH-dependent factors. In 0.1 M NaOH, HER current density Au(111) potential range −0.4 V < ERHE 0 up 60 times smaller than HClO4. A proper consideration local conditions within EDL developed. After correcting for effects, rate constant only weakly pH-dependent. Our analysis unambiguously reveals observed are mainly due reorganization free energy, which depends on electrostatic EDL. Possible origins temperature dependence activation energy electron transfer coefficients discussed. This work suggests factors influencing intrinsic kinetics easier understand after corrections effects.

Language: Английский

Local reaction environment in electrocatalysis DOI
Chaojie Chen, Huanyu Jin, Pengtang Wang

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(4), P. 2022 - 2055

Published: Jan. 1, 2024

Beyond conventional electrocatalyst engineering, recent studies have unveiled the effectiveness of manipulating local reaction environment in enhancing performance electrocatalytic reactions. The general principles and strategies environmental engineering for different processes been extensively investigated. This review provides a critical appraisal advancements aiming to comprehensively assess this emerging field. It presents interactions among surface structure, ions distribution electric field relation environment. Useful protocols such as interfacial reactant concentration, mass transport rate, adsorption/desorption behaviors, binding energy are in-depth discussed toward modifying Meanwhile, electrode physical structures cell configurations viable optimization methods environments. In combination with

Language: Английский

Citations

81
Electric Double Layer Effects in Electrocatalysis: Insights from Ab Initio Simulation and Hierarchical Continuum Modeling DOI Creative Commons
Peng Li,

Yuzhou Jiao,

Jun Huang

et al.

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

Citations

57
Hierarchical Interconnected NiMoN with Large Specific Surface Area and High Mechanical Strength for Efficient and Stable Alkaline Water/Seawater Hydrogen Evolution DOI Creative Commons
Minghui Ning, Yu Wang, Libo Wu

et al.

Nano-Micro Letters, Journal Year: 2023, Volume and Issue: 15(1)

Published: June 19, 2023

NiMo-based nanostructures are among the most active hydrogen evolution reaction (HER) catalysts under an alkaline environment due to their strong water dissociation ability. However, these vulnerable destructive effects of H2 production, especially at industry-standard current densities. Therefore, developing a strategy improve mechanical strength while maintaining or even further increasing activity nanocatalysts is great interest both research and industrial communities. Here, hierarchical interconnected NiMoN (HW-NiMoN-2h) with nanorod-nanowire morphology was synthesized based on rational combination hydrothermal bath processes. HW-NiMoN-2h found exhibit excellent HER accomodation abundant sites its morphology, in which nanowires connect free-standing nanorods, concurrently strengthening structural stability withstand production 1 A cm-2. Seawater attractive feedstock for electrolysis since generation desalination can be addressed simultaneously single process. The performance seawater suggests that presence Na+ ions interferes reation kinetics, thus lowering slightly. benefiting from characteristics, deliver outstanding cm-2 130 mV overpotential over 70 h M KOH seawater.

Language: Английский

Citations

51
Modeling Single‐Atom Catalysis DOI Creative Commons
Giovanni Di Liberto, Gianfranco Pacchioni

Advanced Materials, Journal Year: 2023, Volume and Issue: 35(46)

Published: Sept. 25, 2023

Electronic structure calculations represent an essential complement of experiments to characterize single-atom catalysts (SACs), consisting isolated metal atoms stabilized on a support, but also predict new catalysts. However, simulating SACs with quantum chemistry approaches is not as simple often assumed. In this work, the factors that reliable simulation activity are examined. The Perspective focuses importance precise atomistic characterization active site, since even small changes in atom's surroundings can result large reactivity. dynamical behavior and stability under working conditions, well adopting appropriate methods solve Schrödinger equation for quantitative evaluation reaction energies addressed. relevance model adopted. For electrocatalysis must include effects solvent, presence electrolytes, pH, external potential. Finally, it discussed how similarities between coordination compounds may intermediates usually observed electrodes. When these aspects adequately considered, predictive power electronic quite limited.

Language: Английский

Citations

49
Effects of Electrolyte Ionic Species on Electrocatalytic Reactions: Advances, Challenges, and Perspectives DOI
Xinxin Lu, Wenguang Tu, Yong Zhou

et al.

Advanced Energy Materials, Journal Year: 2023, Volume and Issue: 13(27)

Published: April 27, 2023

Abstract Electrolytes have a profound impact on the chemical environment of electrocatalysis, influencing reaction rate and selectivity products. Experimental theoretical studies extensively investigated interaction mechanisms between electrolyte ions (i.e., alkali metal cations, carbonate anions) reactants or catalyst surface in electrocatalytic reactions such as hydrogen evolution reaction, oxygen reduction water oxidation CO 2 reaction. Past demonstrated noticeable dependence electrochemical activity identity ions. However, few overviews comprehensively specifically discussed effects cations anions common reactions. In order to clarify give more insights this research area, review aims summarize highlight recent progress understanding various ionic species their influence diverse for splitting, H O production, reduction. The challenges perspectives effect electrocatalysis are also presented.

Language: Английский

Citations

47
Nanocurvature-induced field effects enable control over the activity of single-atom electrocatalysts DOI Creative Commons
B.X. Wang, Meng Wang, Ziting Fan

et al.

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

Published: Feb. 26, 2024

Tuning interfacial electric fields provides a powerful means to control electrocatalyst activity. Importantly, can modify adsorbate binding energies based on their polarizability and dipole moment, hence operate independently of scaling relations that fundamentally limit performance. However, implementation such strategy remains challenging because typical methods the field non-uniformly affects only minority active sites. Here we discover uniformly tunable modulation be achieved using model system single-atom catalysts (SACs). These consist M-N

Language: Английский

Citations

43
Transition metal incorporation: electrochemical, structure, and chemical composition effects on nickel oxyhydroxide oxygen-evolution electrocatalysts DOI Creative Commons
Raúl A. Márquez, Emma Kalokowski, Michael Espinosa

et al.

Energy & Environmental Science, Journal Year: 2024, Volume and Issue: 17(5), P. 2028 - 2045

Published: Jan. 1, 2024

Trace metal cations dissolved in alkaline electrolytes incorporate into nickel hydroxide/oxyhydroxide through situ cation exchange, creating an interstratified structure near the surface of material that impacts electrochemical performance.

Language: Английский

Citations

32
Emerging Atomistic Modeling Methods for Heterogeneous Electrocatalysis DOI

Zachary Levell,

Jiabo Le,

Saerom Yu

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8620 - 8656

Published: July 11, 2024

Heterogeneous electrocatalysis lies at the center of various technologies that could help enable a sustainable future. However, its complexity makes it challenging to accurately and efficiently model an atomic level. Here, we review emerging atomistic methods simulate electrocatalytic interface with special attention devoted components/effects have been model, such as solvation, electrolyte ions, electrode potential, reaction kinetics, pH. Additionally, relevant computational spectroscopy methods. Then, showcase several examples applying these understand design catalysts green hydrogen. We also offer experimental views on how bridge gap between theory experiments. Finally, provide some perspectives opportunities advance field.

Language: Английский

Citations

27
Ion solvation kinetics in bipolar membranes and at electrolyte–metal interfaces DOI Creative Commons
Carlos Gómez-Rodellar, José M. Gisbert-González, Francisco J. Sarabia

et al.

Nature Energy, Journal Year: 2024, Volume and Issue: 9(5), P. 548 - 558

Published: March 14, 2024

Abstract Ion (de)solvation at solid–electrolyte interfaces is pivotal for energy and chemical conversion technology, such as (electro)catalysis, batteries bipolar membranes. For example, during the electrocatalytic hydrogen evolution reaction in alkaline media, water needs to be dissociated hydroxide ions solvated—a process that not well understood. Here we study dissociation ion solvation kinetics isolation polymeric membrane electrolyte–metal interfaces. We discover bias-dependent relationships between activation entropy enthalpy, which link a dispersion of interfacial capacitance. Furthermore, our results indicate OH − kinetically slower than H + display characteristics are independent catalyst structure. attribute this universal amount excess charge needed induce electric fields alter water. Of fundamental interest, these critical enable knowledge-driven electrocatalyst design.

Language: Английский

Citations

21
Effects of Ionic Interferents on Electrocatalytic Nitrate Reduction: Mechanistic Insight DOI

Jinling Fan,

Leslie Arrazolo,

Jiaxin Du

et al.

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

Citations

19