Concepts Relevant for the Kinetic Analysis of Reversible Reaction Systems DOI
Neil K. Razdan, Ting Lin, Aditya Bhan

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(6), P. 2950 - 3006

Published: Feb. 21, 2023

The net rate of a reversible chemical reaction is the difference between unidirectional rates traversal along forward and reverse paths. In multistep sequence, trajectories, in general, are not microscopic one another; rather, each route comprised distinct rate-controlling steps, intermediates, transition states. Consequently, traditional descriptors (e.g., orders) do reflect intrinsic kinetic information but instead conflate contributions determined by (i) occurrence forward/reverse reactions (i.e., kinetics) (ii) reversibility nonequilibrium thermodynamics). This review aims to provide comprehensive resource analytical conceptual tools which deconvolute kinetics thermodynamics disambiguate trajectories precisely identify rate- reversibility-controlling molecular species steps systems. extrication mechanistic from bidirectional accomplished through equation-based formalisms De Donder relations) grounded principles interpreted context theories developed past 25 years. aggregate mathematical detailed herein general thermochemical electrochemical encapsulates diverse body scientific literature encompassing physics, thermodynamics, kinetics, catalysis, modeling.

Language: Английский

Water electrolysis DOI
Arthur J. Shih, Mariana C. O. Monteiro, Federico Dattila

et al.

Nature Reviews Methods Primers, Journal Year: 2022, Volume and Issue: 2(1)

Published: Oct. 27, 2022

Language: Английский

Citations

247
Theoretical Advances in Understanding and Designing the Active Sites for Hydrogen Evolution Reaction DOI
Fang Sun, Qing Tang, De‐en Jiang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(14), P. 8404 - 8433

Published: June 30, 2022

As a fundamental step of water splitting and stepping stone toward exploring other multielectron transfer processes, the electrocatalytic hydrogen evolution reaction (HER) is an ideal model for both understanding electrocatalyst design. Here, we review fundamentals recent developments theoretical insights into HER, covering mechanistic aspects, key activity descriptors, local environment considerations, advances beyond computational electrode. Although it experimentally challenging to explore active sites mechanisms in process, show great potential identifying mechanisms. In this Review, especially focus depth on revealing designing HER. Major challenges ahead will also be discussed at end Review.

Language: Английский

Citations

149
TURBOMOLE: Today and Tomorrow DOI Creative Commons
Yannick J. Franzke, Christof Holzer, Josefine H. Andersen

et al.

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(20), P. 6859 - 6890

Published: June 29, 2023

TURBOMOLE is a highly optimized software suite for large-scale quantum-chemical and materials science simulations of molecules, clusters, extended systems, periodic solids. uses Gaussian basis sets has been designed with robust fast applications in mind, ranging from homogeneous heterogeneous catalysis to inorganic organic chemistry various types spectroscopy, light-matter interactions, biochemistry. This Perspective briefly surveys TURBOMOLE's functionality highlights recent developments that have taken place between 2020 2023, comprising new electronic structure methods molecules solids, previously unavailable molecular properties, embedding, dynamics approaches. Select features under development are reviewed illustrate the continuous growth program suite, including nuclear orbital methods, Hartree-Fock-based adiabatic connection models, simplified time-dependent density functional theory, relativistic effects magnetic multiscale modeling optical properties.

Language: Английский

Citations

128
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

89
Different distributions of multi-carbon products in CO2 and CO electroreduction under practical reaction conditions DOI
Jung Yoon Kim,

C.H. Sellers,

Shaoyun Hao

et al.

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(12), P. 1115 - 1124

Published: Dec. 20, 2023

Language: Английский

Citations

74
Electrochemical Potential-Driven Shift of Frontier Orbitals in M–N–C Single-Atom Catalysts Leading to Inverted Adsorption Energies DOI
Jincheng Liu, Feng Luo, Jun Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(46), P. 25264 - 25273

Published: Nov. 8, 2023

Electronic structure is essential to understanding the catalytic mechanism of metal single-atom catalysts (SACs), especially under electrochemical conditions. This study delves into nuanced modulation "frontier orbitals" in SACs on nitrogen-doped graphene (N-C) substrates by potentials. We observe shifts Fermi level and changes d-orbital occupation with alterations potentials, emphasizing a synergy between discretized atomic orbitals metals continuous bands N-C based environment. Using O2 CO2 as model adsorbates, we highlight direct consequences these adsorption energies, unveiling an intriguing inversion energies Co/N-C SAC negative Such insights are attributed role dxz dz2 orbitals, pivotal for stabilizing π* O2. Through this exploration, our work offers interplay electronic structures behaviors SACs, paving way enhanced catalyst design strategies processes.

Language: Английский

Citations

71
Mechanism of Cations Suppressing Proton Diffusion Kinetics for Electrocatalysis DOI
Xiaoyu Li, Tao Wang,

Yu‐Chen Cai

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(14)

Published: Feb. 10, 2023

Proton transfer is crucial for electrocatalysis. Accumulating cations at electrochemical interfaces can alter the proton rate and then tune electrocatalytic performance. However, mechanism regulating remains ambiguous. Here, we quantify cation effect on diffusion in solution by hydrogen evolution microelectrodes, revealing be suppressed more than 10 times. Different from prevalent opinions that transport slowed down modified electric field, found water structure imposes a evident kinetics. FTIR test path integral molecular dynamics simulation indicate prefers to wander within hydration shell of rather hop rapidly along wires. Low connectivity networks disrupted corrupts fast-moving bulk water. This study highlights promising way kinetics via structure.

Language: Английский

Citations

59
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

58
Key Roles of Interfacial OH− ion Distribution on Proton Coupled Electron Transfer Kinetics Toward Urea Oxidation Reaction DOI Creative Commons

Ruopeng Li,

Yaqiang Li, Peixia Yang

et al.

Small, Journal Year: 2023, Volume and Issue: 19(30)

Published: May 16, 2023

Enhancing alkaline urea oxidation reaction (UOR) activity is essential to upgrade renewable electrolysis systems. As a core step of UOR, proton-coupled electron transfer (PCET) determines the overall performance, and accelerating its kinetic remains challenge. In this work, newly raised electrocatalyst NiCoMoCuOx Hy with derived multi-metal co-doping (oxy)hydroxide species during electrochemical states reported, which ensures considerable UOR (10/500 mA cm-2 at 1.32/1.52 V vs RHE, respectively). Impressively, comprehensive studies elucidate correlation between electrode-electrolyte interfacial microenvironment electrocatalytic behavior. Specifically, featured dendritic nanostructure creates strengthened electric field distribution. This structural factor prompts local OH- enrichment in electrical double layer (EDL), so that dehydrogenative catalyst directly reinforced facilitate subsequent PCET kinetics nucleophilic urea, resulting high performance. practical utilization, -driven coupled cathodic hydrogen evolution (HER) carbon dioxide reduction (CO2 RR), harvested value-added products H2 C2 H4 , respectively. work clarifies novel mechanism improve performance through structure-induced modulation.

Language: Английский

Citations

51
Electrochemically Driven Hydrogen Atom Transfer Catalysis: A Tool for C(sp3)/Si–H Functionalization and Hydrofunctionalization of Alkenes DOI Creative Commons
Sheng Zhang, Michael Findlater

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(13), P. 8731 - 8751

Published: June 16, 2023

Electrochemically driven hydrogen atom transfer (HAT) catalysis provides a complementary approach for the transformation of redox-inactive substrates that would be inaccessible to conventional electron (ET) catalysis. Moreover, electrochemically HAT could promote organic transformations with either abstraction or donation as key step. It versatile and effective tool direct functionalization C(sp3)–H/Si–H bonds hydrofunctionalization alkenes. Despite these attractive properties, has been largely overlooked due lack understanding both catalytic mechanism how catalyst selection should occur. In this Review, we give an overview applications in The mechanistic pathways, physical properties mediators, state-of-the-art examples are described discussed.

Language: Английский

Citations

48