{"title":"Modeling Interfacial Electric Fields and the Ethanol Oxidation Reaction at Electrode Surfaces","authors":"Yuhan Mei, Fanglin Che, Nathaniel Deskins","doi":"10.1039/d4cp02765e","DOIUrl":null,"url":null,"abstract":"The electrochemical environment present at surfaces can have a large effect on intended applications. Such environments may occur, for instance, at battery or electrocatalyst surfaces. Solvent, coadsorbates, and electrical field effects may strongly influence surface chemistry. Understanding these phenomena is an on-going area of research, especially in the realm of electrocatalysis. Herein, we modeled key steps in the ethanol oxidation reaction (EOR) over a common EOR catalyst, Rh(111), using density functional theory. We assessed how the presence of electrical fields may influence important C-C and C-H bond scission and C-O bond formation reactions with and without coadsorbed water. We found that electric fields combined with the presence of water can significantly affect surface chemistry, including adsorption and reaction energies. Our results show that C-C scission (necessary for the complete oxidation of ethanol) is most likely through CH<small><sub>x</sub></small>CO adsorbates. With no electric field or solvent present C-C scission of CHCO has the lowest reaction energy and dominates the oxidation of ethanol. But when applying strong negative fields (with or without solvent), the C-C scission of CH<small><sub>2</sub></small> CO and CHCO becomes competitive. The current work provides insights into how electric fields and water solvent affect EOR, especially when simulated using density functional theory.","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":null,"pages":null},"PeriodicalIF":2.9000,"publicationDate":"2024-10-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4cp02765e","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The electrochemical environment present at surfaces can have a large effect on intended applications. Such environments may occur, for instance, at battery or electrocatalyst surfaces. Solvent, coadsorbates, and electrical field effects may strongly influence surface chemistry. Understanding these phenomena is an on-going area of research, especially in the realm of electrocatalysis. Herein, we modeled key steps in the ethanol oxidation reaction (EOR) over a common EOR catalyst, Rh(111), using density functional theory. We assessed how the presence of electrical fields may influence important C-C and C-H bond scission and C-O bond formation reactions with and without coadsorbed water. We found that electric fields combined with the presence of water can significantly affect surface chemistry, including adsorption and reaction energies. Our results show that C-C scission (necessary for the complete oxidation of ethanol) is most likely through CHxCO adsorbates. With no electric field or solvent present C-C scission of CHCO has the lowest reaction energy and dominates the oxidation of ethanol. But when applying strong negative fields (with or without solvent), the C-C scission of CH2 CO and CHCO becomes competitive. The current work provides insights into how electric fields and water solvent affect EOR, especially when simulated using density functional theory.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.