{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T14:04:13Z","timestamp":1790863453429,"version":"4.1.0"},"reference-count":50,"publisher":"American Chemical Society (ACS)","issue":"39","license":[{"start":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T00:00:00Z","timestamp":1789516800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T00:00:00Z","timestamp":1789516800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T00:00:00Z","timestamp":1789516800000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22502205"],"award-info":[{"award-number":["22502205"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22622304"],"award-info":[{"award-number":["22622304"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,1]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The reactivity of interfacial water at metal electrodes plays a decisive role in governing proton-coupled electrocatalytic kinetics, yet a quantitative understanding of how electrolyte cations modulate this reactivity remains elusive. Herein, metadynamics-biased ab initio molecular dynamics (AIMD) simulations reveal that the regulation of water activity on the Cu(111) surface by potassium ion (K+) is intrinsically governed by enthalpy\u2013entropy synergy. Thermodynamic decomposition reveals that the interfacial electric field dominates the enthalpic contribution, whereas hydrogen-bonded network disordering governs the entropic gain. Theoretically calculated infrared spectra and statistical distributions of hydrogen-bond configurations of interfacial water molecules further support a cation-induced transition from rigid, hydrogen-bond confined interfacial water to a more flexible and disordered water environment. These findings establish an atomistic thermodynamic picture of cation-regulated water activation and provide a conceptual basis for enthalpy\u2013entropy synergistic control in proton-coupled electrocatalysis.<\/jats:p>","DOI":"10.1021\/acs.jpclett.6c02786","type":"journal-article","created":{"date-parts":[[2026,9,16]],"date-time":"2026-09-16T08:02:12Z","timestamp":1789545732000},"page":"11286-11294","source":"Crossref","is-referenced-by-count":0,"title":["Enthalpy\u2013Entropy\nSynergy Governs Cation-Mediated\nInterfacial Water Activation on Cu(111)"],"prefix":"10.1021","volume":"17","author":[{"ORCID":"https:\/\/orcid.org\/0009-0007-0586-1714","authenticated-orcid":true,"given":"Jiabao","family":"Zhu","sequence":"first","affiliation":[{"name":"East China Normal University , , , ,","place":["Shanghai, China, 200062"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shiwei","family":"Chen","sequence":"additional","affiliation":[{"name":"Tsinghua University , , ,","place":["Beijing, China, 100084"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shuo","family":"Wang","sequence":"additional","affiliation":[{"name":"Dalian Institute of Chemical Physics, Chinese Academy of Sciences Dalian , , ,","place":["Dalian, China, 116023"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7678-0360","authenticated-orcid":true,"given":"Jinrong","family":"Yang","sequence":"additional","affiliation":[{"name":"East China Normal University , , , ,","place":["Shanghai, China, 200062"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,16]]},"reference":[{"key":"2026100109091697800_cit1","doi-asserted-by":"publisher","first-page":"81","DOI":"10.1038\/s41586-021-04068-z","article-title":"In situ\nRaman spectroscopy reveals the structure and dissociation\nof interfacial water","volume":"600","author":"Wang","year":"2021","journal-title":"Nature"},{"key":"2026100109091697800_cit2","doi-asserted-by":"publisher","DOI":"10.1126\/science.aad4998","article-title":"Combining\ntheory and experiment in\nelectrocatalysis: Insights into materials design","volume":"355","author":"Seh","year":"2017","journal-title":"Science"},{"key":"2026100109091697800_cit3","doi-asserted-by":"publisher","first-page":"315","DOI":"10.1126\/science.abo0823","article-title":"Visualizing Eigen\/Zundel\ncations and their interconversion in monolayer water on metal surfaces","volume":"377","author":"Tian","year":"2022","journal-title":"Science"},{"key":"2026100109091697800_cit4","doi-asserted-by":"publisher","first-page":"430","DOI":"10.1126\/science.ads1466","article-title":"Polyoxometalated\nmetal-organic framework superstructure for stable water oxidation","volume":"388","author":"Yue","year":"2025","journal-title":"Science"},{"key":"2026100109091697800_cit5","doi-asserted-by":"publisher","first-page":"959","DOI":"10.1038\/s41586-023-06060-1","article-title":"Continuous\ncarbon capture in an electrochemical solid-electrolyte reactor","volume":"618","author":"Zhu","year":"2023","journal-title":"Nature"},{"key":"2026100109091697800_cit6","doi-asserted-by":"publisher","first-page":"550","DOI":"10.1038\/nmat3313","article-title":"Trends in activity for the water\nelectrolyser reactions\non 3d M(Ni,Co,Fe,Mn) hydr(oxy)oxide catalysts","volume":"11","author":"Subbaraman","year":"2012","journal-title":"Nat. Mater."},{"key":"2026100109091697800_cit7","doi-asserted-by":"publisher","first-page":"668","DOI":"10.1038\/s41586-025-09364-6","article-title":"Acidic oxygen\nreduction by single-atom Fe catalysts on curved supports","volume":"664","author":"Zhao","year":"2025","journal-title":"Nature"},{"key":"2026100109091697800_cit8","doi-asserted-by":"publisher","first-page":"60","DOI":"10.1038\/s41560-018-0292-z","article-title":"In situ\nRaman spectroscopic\nevidence for oxygen reduction reaction intermediates at platinum single-crystal\nsurfaces","volume":"4","author":"Dong","year":"2019","journal-title":"Nat. Energy"},{"key":"2026100109091697800_cit9","doi-asserted-by":"publisher","first-page":"466","DOI":"10.1038\/nchem.330","article-title":"The role of non-covalent interactions in electrocatalytic\nfuel-cell reactions on platinum","volume":"1","author":"Strmcnik","year":"2009","journal-title":"Nat. Chem."},{"key":"2026100109091697800_cit10","doi-asserted-by":"publisher","DOI":"10.1126\/science.adn9388","article-title":"Hydrogenation\nof CO2 for sustainable\nfuel and chemical production","volume":"387","author":"Ye","year":"2025","journal-title":"Science"},{"key":"2026100109091697800_cit11","doi-asserted-by":"publisher","first-page":"643","DOI":"10.1126\/science.1209786","article-title":"Ionic Liquid\u2013Mediated Selective\nConversion of CO2 to CO at Low Overpotentials","volume":"334","author":"Rosen","year":"2011","journal-title":"Science"},{"key":"2026100109091697800_cit12","doi-asserted-by":"publisher","first-page":"783","DOI":"10.1126\/science.aas9100","article-title":"CO2 electroreduction\nto ethylene via hydroxide-mediated copper catalysis at an abrupt interface","volume":"360","author":"Dinh","year":"2018","journal-title":"Science"},{"key":"2026100109091697800_cit13","doi-asserted-by":"publisher","first-page":"433","DOI":"10.1038\/s44160-025-00941-1","article-title":"Copper\u2013palladium hydride interfaces promote electrochemical\nammonia synthesis","volume":"5","author":"Fu","year":"2026","journal-title":"Nat. Synth."},{"key":"2026100109091697800_cit14","doi-asserted-by":"publisher","first-page":"328","DOI":"10.1038\/s41929-025-01315-8","article-title":"Electrochemical oxidation\nof nitric\noxide to concentrated nitric acid with carbon-based catalysts at near-ambient\nconditions","volume":"8","author":"Xia","year":"2025","journal-title":"Nat. Catal."},{"key":"2026100109091697800_cit15","doi-asserted-by":"publisher","first-page":"402","DOI":"10.1038\/s41929-023-00951-2","article-title":"Ultralow overpotential\nnitrate reduction to ammonia via a three-step\nrelay mechanism","volume":"6","author":"Han","year":"2023","journal-title":"Nat. Catal."},{"key":"2026100109091697800_cit16","doi-asserted-by":"publisher","first-page":"148","DOI":"10.1016\/S1872-2067(21)63821-4","article-title":"The possible implications\nof magnetic field effect on understanding\nthe reactant of water splitting","volume":"43","author":"Wei","year":"2022","journal-title":"Chin. J. Catal."},{"key":"2026100109091697800_cit17","doi-asserted-by":"publisher","first-page":"1256","DOI":"10.1126\/science.1211934","article-title":"Enhancing Hydrogen\nEvolution Activity in Water Splitting by Tailoring Li+-Ni(OH)2-Pt\nInterfaces","volume":"334","author":"Subbaraman","year":"2011","journal-title":"Science"},{"key":"2026100109091697800_cit18","doi-asserted-by":"publisher","first-page":"900","DOI":"10.1038\/s41929-022-00846-8","article-title":"Hydrogen bond network\nconnectivity in the electric\ndouble layer dominates the kinetic pH effect in hydrogen electrocatalysis\non Pt","volume":"5","author":"Li","year":"2022","journal-title":"Nat. Catal."},{"key":"2026100109091697800_cit19","doi-asserted-by":"publisher","first-page":"7834","DOI":"10.1038\/s41467-024-52131-w","article-title":"Effect of ion-specific water structures\nat metal surfaces on hydrogen production","volume":"15","author":"Tian","year":"2024","journal-title":"Nat.\nCommun."},{"key":"2026100109091697800_cit20","doi-asserted-by":"publisher","first-page":"17031","DOI":"10.1038\/nenergy.2017.31","article-title":"Interfacial water\nreorganization\nas a pH-dependent descriptor of the hydrogen evolution rate on platinum\nelectrodes","volume":"2","author":"Ledezma-Yanez","year":"2017","journal-title":"Nat. Energy"},{"key":"2026100109091697800_cit21","doi-asserted-by":"publisher","first-page":"285","DOI":"10.1039\/D2EE02836K","article-title":"Engineering\na local potassium cation concentrated microenvironment toward the\nampere-level current density hydrogen evolution reaction","volume":"16","author":"Gao","year":"2023","journal-title":"Energy Environ. Sci."},{"key":"2026100109091697800_cit22","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202218669","article-title":"Mechanism of Cations Suppressing\nProton Diffusion Kinetics for Electrocatalysis","volume":"62","author":"Li","year":"2023","journal-title":"Angew. Chem., Int. Ed."},{"key":"2026100109091697800_cit23","doi-asserted-by":"publisher","first-page":"10388","DOI":"10.1021\/jacs.5c15554","article-title":"A Bidentate\nHydrogen-Bond Molecular Vise Activates Interfacial Water for Universal\nHydrogen Electrocatalysis","volume":"148","author":"Mi","year":"2026","journal-title":"J. Am. Chem. Soc."},{"key":"2026100109091697800_cit24","doi-asserted-by":"publisher","first-page":"1161","DOI":"10.1038\/s41557-025-01859-z","article-title":"Disordered\ninterfacial H2O promotes\nelectrochemical C\u2013C coupling","volume":"17","author":"Zhang","year":"2025","journal-title":"Nat. Chem."},{"key":"2026100109091697800_cit25","doi-asserted-by":"publisher","first-page":"648","DOI":"10.1038\/s41557-025-01948-z","article-title":"Bulk water redox chemistry\nenables radical-mediated C\u2013C coupling\nin CO2 electroreduction","volume":"18","author":"Li","year":"2026","journal-title":"Nat. Chem."},{"key":"2026100109091697800_cit26","doi-asserted-by":"publisher","first-page":"5532","DOI":"10.1021\/jacs.3c13602","article-title":"Cation-Induced Interfacial\nHydrophobic Microenvironment Promotes\nthe C\u2013C Coupling in Electrochemical CO2 Reduction","volume":"146","author":"Yang","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026100109091697800_cit27","doi-asserted-by":"publisher","first-page":"21032","DOI":"10.1021\/jacs.5c05728","article-title":"Elucidating the\nActivity of Electrochemical Nitrate Reduction: High-Valent Anionic\nIntermediates as Kinetic Gatekeepers","volume":"147","author":"Qian","year":"2025","journal-title":"J. Am.\nChem. Soc."},{"key":"2026100109091697800_cit28","doi-asserted-by":"publisher","first-page":"35118","DOI":"10.1021\/jacs.5c12947","article-title":"Alkali Metal Cations Induce Pseudo-outer-sphere\nOxygen Reduction Reaction Mechanism in Electrolyte-Catalyst Synergy","volume":"147","author":"Tian","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026100109091697800_cit29","doi-asserted-by":"publisher","first-page":"25186","DOI":"10.1021\/jacs.3c07506","article-title":"How the Acidity of Water Droplets\nand Films Is Controlled by the Air\u2013Water Interface","volume":"145","author":"de la Puente","year":"2023","journal-title":"J. Am. Chem. Soc."},{"key":"2026100109091697800_cit30","doi-asserted-by":"publisher","first-page":"8173","DOI":"10.1039\/D6CC00436A","article-title":"Local environment neighbor sensitivity analysis: visualization\nof cation effect at liquid\u2013solid interface","volume":"62","author":"Jinnouchi","year":"2026","journal-title":"Chem. Commun."},{"key":"2026100109091697800_cit31","doi-asserted-by":"publisher","first-page":"3902","DOI":"10.1021\/ct3001848","article-title":"Structure\nand Dynamics of Liquid Water from ab Initio Molecular Dynamics-Comparison\nof BLYP, PBE, and revPBE Density Functionals with and without van\nder Waals Corrections","volume":"8","author":"Lin","year":"2012","journal-title":"J. Chem. Theory Comput."},{"key":"2026100109091697800_cit32","doi-asserted-by":"publisher","first-page":"2065","DOI":"10.1039\/C7SC04205A","article-title":"Hydrogen-bond structure dynamics\nin bulk water: insights from ab initio simulations with coupled cluster\ntheory","volume":"9","author":"Liu","year":"2018","journal-title":"Chem. Sci."},{"key":"2026100109091697800_cit33","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202209398","article-title":"Temperature\nDependent Properties\nof the Aqueous Electron","volume":"61","author":"Lan","year":"2022","journal-title":"Angew. Chem., Int.\nEd."},{"key":"2026100109091697800_cit34","doi-asserted-by":"publisher","first-page":"7299","DOI":"10.1021\/acs.jpclett.1c02001","article-title":"Linear Correlation\nbetween Water Adsorption Energies and Volta Potential\nDifferences for Metal\/water Interfaces","volume":"12","author":"Li","year":"2021","journal-title":"J. Phys.\nChem. Lett."},{"key":"2026100109091697800_cit35","doi-asserted-by":"publisher","first-page":"16958","DOI":"10.1021\/acs.jpcc.5c05310","article-title":"Cation- and Potential-Dependent Modulation\nof Hydrophobic Hydration at Electrocatalytic Interfaces","volume":"129","author":"Yang","year":"2025","journal-title":"J. Phys. Chem. C"},{"key":"2026100109091697800_cit36","doi-asserted-by":"publisher","first-page":"17461","DOI":"10.1039\/D5SC04670J","article-title":"Atomic insights into how electrolyte\nconcentration controls CO electroreduction to acetate","volume":"16","author":"Bai","year":"2025","journal-title":"Chem. Sci."},{"key":"2026100109091697800_cit37","doi-asserted-by":"publisher","first-page":"16281","DOI":"10.1021\/jacs.4c04588","article-title":"Superdiffusive Rotation of Interfacial Water on Noble Metal Surface","volume":"146","author":"Zhu","year":"2024","journal-title":"J. Am. Chem. Soc."},{"key":"2026100109091697800_cit38","doi-asserted-by":"publisher","first-page":"6608","DOI":"10.1039\/c3cp44302g","article-title":"Computing vibrational spectra from ab initio molecular\ndynamics","volume":"15","author":"Thomas","year":"2013","journal-title":"Phys. Chem. Chem. Phys."},{"key":"2026100109091697800_cit39","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.physrep.2022.11.001","article-title":"The physics\nbehind water irregularity","volume":"998","author":"Sun","year":"2023","journal-title":"Phys. Rep."},{"key":"2026100109091697800_cit40","doi-asserted-by":"publisher","first-page":"146","DOI":"10.1016\/j.molstruc.2011.07.054","article-title":"The molecular\nstructure of liquid water delivered by absorption spectroscopy in\nthe whole IR region completed with thermodynamics data","volume":"1004","author":"Mare\u0301chal","year":"2011","journal-title":"J. Mol. Struct."},{"key":"2026100109091697800_cit41","doi-asserted-by":"publisher","first-page":"5250","DOI":"10.1038\/s41467-025-60298-z","article-title":"Entropy-driven\ndifference in interfacial water reactivity between slab and nanodroplet","volume":"16","author":"Chen","year":"2025","journal-title":"Nat. Commun."},{"key":"2026100109091697800_cit42","doi-asserted-by":"publisher","first-page":"194110","DOI":"10.1063\/5.0240275","article-title":"Machine-learning\nsurrogate models for particle insertions and element substitutions","volume":"161","author":"Jinnouchi","year":"2024","journal-title":"J. Chem. Phys."},{"key":"2026100109091697800_cit43","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevLett.119.016801","article-title":"Determining Potentials\nof Zero Charge of Metal Electrodes versus the Standard Hydrogen Electrode\nfrom Density-Functional-Theory-Based Molecular Dynamics","volume":"119","author":"Le","year":"2017","journal-title":"Phys. Rev. Lett."},{"key":"2026100109091697800_cit44","doi-asserted-by":"publisher","first-page":"6448","DOI":"10.1021\/jp046022f","article-title":"Absolute and relative\nentropies from computer simulation\nwith applications to ligand binding","volume":"109","author":"Carlsson","year":"2005","journal-title":"J. Phys.\nChem. B"},{"key":"2026100109091697800_cit45","doi-asserted-by":"publisher","DOI":"10.1063\/1.4973001","article-title":"Accurate schemes\nfor calculation\nof thermodynamic properties of liquid mixtures from molecular dynamics\nsimulations","volume":"145","author":"Caro","year":"2016","journal-title":"J. Chem. Phys."},{"key":"2026100109091697800_cit46","doi-asserted-by":"publisher","first-page":"29468","DOI":"10.1021\/jacs.5c09908","article-title":"Unveiling\nthe Angstrom-Scale Interfacial Electron Spillover through the Metal\/Electrolyte\nInterface","volume":"147","author":"Yi","year":"2025","journal-title":"J. Am. Chem. Soc."},{"key":"2026100109091697800_cit47","doi-asserted-by":"publisher","DOI":"10.1063\/5.0239284","article-title":"Dielectric\nprofile at the Pt(111)\/water\ninterface","volume":"162","author":"Zhu","year":"2025","journal-title":"J. Chem. Phys."},{"key":"2026100109091697800_cit48","doi-asserted-by":"publisher","first-page":"11277","DOI":"10.1021\/jacs.7b06765","article-title":"Promoter Effects\nof Alkali Metal Cations on the Electrochemical Reduction of Carbon\nDioxide","volume":"139","author":"Resasco","year":"2017","journal-title":"J. Am. Chem. Soc."},{"key":"2026100109091697800_cit49","doi-asserted-by":"publisher","first-page":"8697","DOI":"10.1021\/ja902267b","article-title":"Dissociation of Water During Formation\nof Anodic Aluminum Oxide","volume":"131","author":"Su","year":"2009","journal-title":"J. Am. Chem. Soc."},{"key":"2026100109091697800_cit50","doi-asserted-by":"publisher","first-page":"265","DOI":"10.1021\/acs.jpclett.4c03437","article-title":"The Melamine-Driven\nSolvation Effect Promotes Oxygen\nReduction on a Platinum Catalyst: Machine Learning-Aided Free Energy\nCalculations","volume":"16","author":"Jinnouchi","year":"2025","journal-title":"J. Phys. Chem. Lett."}],"container-title":["The Journal of Physical\nChemistry Letters"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/acs.jpclett.6c02786","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article-pdf\/17\/39\/11286\/68527395\/acs.jpclett.6c02786.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article-pdf\/17\/39\/11286\/68527395\/acs.jpclett.6c02786.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,1]],"date-time":"2026-10-01T13:31:16Z","timestamp":1790861476000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jpclcd\/article\/17\/39\/11286\/5431004\/Enthalpy-Entropy-Synergy-Governs-Cation-Mediated"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,9,16]]},"references-count":50,"journal-issue":{"issue":"39","published-online":{"date-parts":[[2026,9,16]]},"published-print":{"date-parts":[[2026,10,1]]}},"URL":"https:\/\/doi.org\/10.1021\/acs.jpclett.6c02786","relation":{"has-preprint":[{"id-type":"doi","id":"10.26434\/chemrxiv.15006895\/v1","asserted-by":"object"}]},"ISSN":["1948-7185"],"issn-type":[{"value":"1948-7185","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,9,16]]}}}