Article
Nanoscience & Nanotechnology
Yuanfeng Gao, Qingyu Xue, Jiayuan Li, Mingkai Zhang, Yuanyuan Ma, Yongquan Qu
Summary: Coupling acid-electrolyte proton exchange membrane fuel cells with cathodic hydrogenation shows potential in energy and chemical industry. The use of phytate coordination on Cu surface enhances the kinetic of proton adsorption/activation and hydrogenation activity. This work provides a promising approach to integrate electricity generation and chemical production.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Chemistry, Multidisciplinary
Biswajit Mondal, Soumitra Dinda, Neeta Karjule, Sanjit Mondal, Alagar Raja Kottaichamy, Michael Volokh, Menny Shalom
Summary: Electrolysis of water is a sustainable method to produce clean hydrogen, but it requires a high applied potential due to the pH-dependency of the hydrogen and oxygen evolution reactions. By combining proton-coupled electron transfer and single-electron transfer processes, we have achieved hydrogen production from water at low cell potentials by pH adjustment.
Review
Chemistry, Physical
Marko M. Melander
Summary: The unique feature of electrochemistry lies in the ability to control reaction thermodynamics and kinetics by applying electrode potential. Recent research has focused on incorporating and controlling electrode potential in first principles calculations within the grand canonical ensemble (GCE), aiming to provide a detailed understanding of complex phenomena in electrochemical reactions.
CURRENT OPINION IN ELECTROCHEMISTRY
(2021)
Article
Chemistry, Multidisciplinary
Yusuke Yoneda, S. Jimena Mora, James Shee, Brian L. Wadsworth, Eric A. Arsenault, Diptarka Hait, Gerdenis Kodis, Devens Gust, Gary F. Moore, Ana L. Moore, Martin Head-Gordon, Thomas A. Moore, Graham R. Fleming
Summary: This study investigates the photoinduced PCET dynamics of a biomimetic model system using various spectroscopic techniques and computational methods, providing insights into the complex dynamics and synergistic motions involved in the process. Specifically, the evolution of the 2DEV line shape, sensitive to the mixing of vibronic states, is interpreted through accurate computational modeling of the charge separated state, revealing a gradual change in electron density distribution associated with a dihedral twist occurring on a 120 fs time scale.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Shujiao Yang, Jinxiu Han, Wei Zhang
Summary: This article introduces the importance of proton-coupled electron transfer (PCET) in energy conversion and water splitting, and prospects the future development of PCET in reaction mechanisms and electrocatalyst design.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Electrochemistry
Tatsushi Nakayama, Bunji Uno
Summary: In this study, the reactivity of 1,2-, 1,3-, and 1,4-dihydroxynaphthalenes towards electrogenerated superoxide radical anion was investigated. The results showed that proton-coupled electron transfer reaction played an important role in scavenging the superoxide radical anion. The position of the quinone moiety mediated the reactivity. Additionally, a subsequent electron transfer between molecular dioxygen and product-naphthoquinone-radicals was observed, which regenerated the superoxide radical anion.
ELECTROCHIMICA ACTA
(2022)
Review
Materials Science, Multidisciplinary
Xiaobin Liao, Ruihu Lu, Lixue Xia, Qian Liu, Huan Wang, Kristin Zhao, Zhaoyang Wang, Yan Zhao
Summary: This article discusses the potential of producing fuels and high-value chemicals through electrochemical conversion processes and highlights the importance of catalysts in advanced energy conversion technologies. It also explores the progress of Density Functional Theory (DFT) as a computational tool and the key descriptors and analysis tools for evaluating electrocatalytic performances.
ENERGY & ENVIRONMENTAL MATERIALS
(2022)
Article
Chemistry, Physical
Sergey Doronin, Yury A. Budkov, Daniil M. Itkis
Summary: Based on the quantum-mechanical theory of electron transfer, a parameter was proposed to describe the electrochemical activity of doped graphenes, calculated using density of states and local density of state values obtained from density functional theory calculations, as well as reorganization energies of the redox system. The study showed that the proposed activity parameter correlates well with calculated ET rate constants, and the influence of doped elements on graphene activity follows a certain order in the oxygen reduction reaction.
Article
Chemistry, Physical
Jakub Kocak, Eli Kraisler, Axel Schild
Summary: When a molecule dissociates, the Kohn-Sham (KS) and Pauli potentials form step structures, critical for describing dissociation and charge-transfer processes. The exact electron factorization (EEF) provides an explanation for these steps, showing they are a result of spatial electron entanglement and charge transfer. Additionally, two methods to reproduce the potentials during dissociation are proposed, offering insights into the encoding of many-electron effects in a one-electron theory.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2021)
Article
Agriculture, Multidisciplinary
Tatsushi Nakayama, Bunji Uno
Summary: The reactivity of trans-resveratrol and related compounds towards the electrogenerated superoxide radical anion (O2·-) was investigated using electrochemistry and spectroscopy. The results showed that trans-resveratrol scavenged O2·- through proton-coupled electron transfer (PCET) via three phenolic hydroxy groups (OH) on the stilbene moiety. Comparative analyses confirmed the reaction of trans-resveratrol towards O2·- using related compounds. The coplanarity of the two phenolic rings in the stilbene moiety linked by an ethylene bridge was found to be essential for successful O2·- scavenging.
JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY
(2023)
Article
Chemistry, Applied
Xueqing Gao, Xiaomeng Liu, Shujiao Yang, Wei Zhang, Haiping Lin, Rui Cao
Summary: This study reports a biology-inspired hybrid electrocatalyst that mimics the functions in natural photosynthesis, demonstrating outstanding performance in the oxygen evolution reaction. The catalyst achieves efficient oxygen evolution by constructing specialized channels for proton and electron transfer.
CHINESE JOURNAL OF CATALYSIS
(2022)
Article
Chemistry, Physical
Yuefei Zhang, Jiemin Wei, Tianyun Liu, Zheng Zhong, Zijiang Luo, Wenjun Xiao, Bing Lv, Xun Zhou, Xuefei Liu
Summary: The graphene-based Van der Waals heterostructures demonstrate great potential for the next generation of photoelectronic nanodevices. ZnSe is found to be a direct semiconductor with high electron mobility and the potential to achieve Schottky to Ohmic contact transformation. Furthermore, under light irradiation, hydrogen and oxygen evolution reactions can occur spontaneously in both acidic and alkaline media. Introducing 3d transition metal atoms significantly reduces the overpotential for the HER process of ZnSe monolayer.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Physical
Shenzhen Xu, Emily A. Carter
Summary: Research has shown that CO2 photoelectroreduction on GaP electrodes can efficiently produce methanol through the hydride transfer (HT) mechanism. However, HT may induce hydrogen evolution as a side reaction, leading to reduced selectivity.
Article
Chemistry, Multidisciplinary
Clorice R. Reinhardt, Elvira R. Sayfutyarova, Jiayun Zhong, Sharon Hammes-Schiffer
Summary: Ribonucleotide reductase (RNR) is an essential enzyme in DNA synthesis, with the active form of E. coli Ia RNR consisting of two subunits, alpha and beta, involved in a series of proton-coupled electron transfer (PCET) reactions. Quantum mechanical/molecular mechanical simulations suggest thermodynamically favored forward radical transfer in the pre-turnover state and backward radical transfer in the post-turnover state between Y731 and Y730. The simulations also propose that E623 plays a key role in influencing the directionality of PCET and predict the impact of mutation of E623 on catalysis.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Chemistry, Multidisciplinary
Niklas von Wolff, Marc Robert
Summary: Electron serves as the ultimate redox reagent for building and reshaping molecular structures. Understanding and controlling the parameters involved in dissociative electron transfer (DET) reactivity and its coupling with proton transfer are crucial for enhancing selectivity, kinetics, and energy efficiency in molecular chemistry. Various applications, such as photoredox catalysis, CO2 reduction, and alcohol oxidation, highlight the broad range of processes encompassed by DET pathways and demonstrate the importance of studying the driving force-rate relationships for future developments in energy efficient catalytic schemes in redox organic chemistry.
Article
Chemistry, Physical
Ville Korpelin, Marko M. Melander, Karoliina Honkala
Summary: Enhancing the reducibility of irreducible oxides using single metal atoms can increase their catalytic activity and thermal stability. Detailed analysis of the mechanism of single atom-induced reducibility shows that the interaction between metal atoms and oxides plays a crucial role in enhancing the reducibility.
JOURNAL OF PHYSICAL CHEMISTRY C
(2022)
Article
Chemistry, Physical
Anand M. Verma, Laura Laverdure, Marko M. Melander, Karoliina Honkala
Summary: The study investigates the electrocatalytic oxidation of glycerol using gold catalysts under different pH conditions. The findings suggest that activity and selectivity are influenced by the presence of surface-bound hydroxyl groups, with higher activity observed under alkaline conditions and lower selectivity under acidic conditions.
Article
Chemistry, Physical
Tongwei Wu, Marko M. Melander, Karoliina Honkala
Summary: This study unveils the mechanism, thermodynamics, and kinetics determining the HER/NRR efficiency on the state-of-the-art NRR electrocatalyst, Ru-N-4. The results show that NRR intermediates suppress HER through coadsorption on the catalyst, and the selectivity is determined by the initial step forming *NNH or *H. This provides crucial insights into the complex NRR/HER competition and suggests ways to improve NRR selectivity.
Article
Chemistry, Physical
Ville Korpelin, Toni Kiljunen, Marko M. Melander, Miguel A. Caro, Henrik H. Kristoffersen, Nisha Mammen, Vesa Apaja, Karoliina Honkala
Summary: This study identified commonly overlooked errors in thermostated DFT-MD simulations applied to study (electro)catalytic chemistry, highlighting the need for caution when using traditional thermostats in simulating catalytic properties or structures of interfacial systems.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Review
Chemistry, Physical
Ankit Kumar Verma, Anand Mohan Verma, Ananth Govind Rajan
Summary: This review focuses on the theoretical basis of classical and quantum confinement effects in two-dimensional (2D) electrode materials and discusses the recent experimental advances in this area. It covers topics such as ion transport, mass and electron transport mechanisms, and the impact of step edges, defects, and dopants on electron transport in 2D electrode materials. Opportunities for further research involving first-principles calculations, molecular dynamics simulations, and the development of analytical theories are also identified.
CURRENT OPINION IN ELECTROCHEMISTRY
(2022)
Review
Chemistry, Physical
Fabiola Dominguez-Flores, Marko M. Melander
Summary: In this article, we present a short review on how computational and theoretical methods can be used to understand and model the effects of electrode potential, solvent, electrolyte, and pH on electrocatalytic rates. We discuss the connections and learnings between different simulation methods and models, and identify some gaps in the current approaches.
CURRENT OPINION IN ELECTROCHEMISTRY
(2022)
Article
Electrochemistry
Marko M. Melander
Summary: Electrochemical reactions should occur in a frozen and out of equilibrium environment, but this clashes with most theoretical and simulation approaches. Non-ergodic rate theory re-analyzes these claims and finds that in most activated electrochemical reactions, the reaction environment is completely mobile and equilibrated under constant potential conditions.
ELECTROCHIMICA ACTA
(2023)
Article
Chemistry, Physical
Fabiola Dominguez-Flores, Marko M. M. Melander
Summary: This work analyzes different electrostatic corrections on canonical DFT for studying reaction thermodynamics and kinetics at electrochemical interfaces. The study shows that these corrections cannot differentiate between electrostatic, covalent, and charge-transfer interactions. The authors propose using conceptual DFT and provide guidelines for choosing appropriate electrostatic corrections to develop more general approximations.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Omar Lopez-Estrada, Nisha Mammen, Laura Laverdure, Marko M. M. Melander, Hannu Hakkinen, Karoliina Honkala
Summary: The hydrogen evolution reaction (HER) is crucial for addressing climate change. Nanomaterials, such as ligand-protected metal clusters, show promise as HER catalysts due to their atomic precision and tailored intrinsic activity. In this computational study, we investigate the effect of charge state and dopants on the catalytic activity of MAu24(SCH3)(18) clusters towards the Volmer step of HER. Our results highlight the importance of considering redox potentials, charge states, and kinetic barriers in identifying promising catalytic materials.
Article
Chemistry, Physical
Pernille D. Pedersen, Marko M. Melander, Thomas Bligaard, Tejs Vegge, Karoliina Honkala, Heine A. Hansen
Summary: This study investigated the reaction pathways of alkaline CO2RR on the edge of MoTe2 using a grand canonical ensemble DFT approach, finding that CO2RR is favored over the competing hydrogen evolution reaction.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Tomoaki Kumeda, Laura Laverdure, Karoliina Honkala, Marko M. Melander, Ken Sakaushi
Summary: This article investigates the effects of cations on the mechanism of alkaline ORR on well-defined Pt(111) surfaces. The authors find that cations determine both the active electrode surface and the competition between inner- and outer-sphere PCET steps. The transition from Pt-O to Pt-OH influenced by cations determines the ORR mechanism, activity, and selectivity, providing important insights for the design of electrochemical systems and computational catalyst screening studies.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Review
Chemistry, Physical
Tongwei Wu, Marko M. Melander, Karoliina Honkala
Summary: This review presents the latest computational advances in the electrocatalytic nitrogen reduction reaction (eNRR) in an aqueous medium, focusing on catalyst design and proton accessibility. By discussing the importance of constant potential and explicit solvent simulations, the role of the electrochemical interface, and the impact of the active center microenvironment on reaction activity and selectivity, it provides theoretical insights for the rational optimization of experimental designs.
CURRENT OPINION IN ELECTROCHEMISTRY
(2023)