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Probing kinetic isotope effects (KIEs) is paramount to deciphering the elusive proton-coupled electron transfer (PCET) mechanisms in alkaline media, a long-standing enigma in electrocatalysis. Such precision, however, demands the uncompromising rigor of atomic-level-precise single-crystal electrodes and ultrapure D2O to ensure definitive results. Here, we uncover a hydrogen evolution reaction KIE that varies sharply with the surface structure: \u223c6 for Pt(100), \u223c1 for Pt(111), and intermediate values for Pt(110). Through a combination of nuclear\u2013electronic orbital density functional theory (NEO-DFT) and in situ laser-induced temperature-jump (LITJ) experiments, we propose that this disparity originates from the difference between a rigid, hexagonal H-bonded network on Pt(111) and a more disordered, flexible interfacial layer on Pt(100) that would be more sensitive to isotopic substitution, as well as from differences in H\/D adsorption sites, which would influence the effective proton transfer distances. Furthermore, measurements with stepped surfaces show that step density acts as a critical dial to tune these water environments. Finally, to bridge the knowledge gap between bulk single-crystals and practical nanoparticles, {100}-oriented Pt nanocubes and {111}-oriented Pt nanotetrahedrons reveal a facet-dependent KIE trend comparable to their single-crystal counterparts. These insights provide a transformative framework for the rational design of high-performance interfaces for green hydrogen production.<\/jats:p>","DOI":"10.1021\/jacs.6c11313","type":"journal-article","created":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T16:20:06Z","timestamp":1788452406000},"page":"44323-44338","source":"Crossref","is-referenced-by-count":0,"title":["Facet Modulation of\nInterfacial Water Structure Tunes\nElectrocatalytic Hydrogen Reaction Kinetics"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8407-2260","authenticated-orcid":true,"given":"Valentin","family":"Briega-Martos","sequence":"first","affiliation":[{"name":"Cornell University , , , ,","place":["Ithaca, New York, United States, 14853"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wenqi","family":"Li","sequence":"additional","affiliation":[{"name":"Cornell University , , , ,","place":["Ithaca, New York, United States, 14853"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2726-2716","authenticated-orcid":true,"given":"Logan E.","family":"Smith","sequence":"additional","affiliation":[{"name":"Princeton University , , , ,","place":["Princeton, New Jersey, United States, 08544"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Natalia","family":"Garci\u0301a Rey","sequence":"additional","affiliation":[{"name":"Universidad de Alicante , , Apdo. 99 , ,","place":["Alicante, Spain, E-03080"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Haichuan","family":"Zhang","sequence":"additional","affiliation":[{"name":"Cornell University , , , ,","place":["Ithaca, New York, United States, 14853"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Rafael","family":"Guzman-Soriano","sequence":"additional","affiliation":[{"name":"Cornell University , , , ,","place":["Ithaca, New York, United States, 14853"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8161-2989","authenticated-orcid":true,"given":"Ruben","family":"Rizo","sequence":"additional","affiliation":[{"name":"Universidad de Alicante , , Apdo. 99 , ,","place":["Alicante, Spain, E-03080"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4509-9716","authenticated-orcid":true,"given":"Enrique","family":"Herrero","sequence":"additional","affiliation":[{"name":"Universidad de Alicante , , Apdo. 99 , ,","place":["Alicante, Spain, E-03080"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2033-5284","authenticated-orcid":true,"given":"Victor","family":"Climent","sequence":"additional","affiliation":[{"name":"Universidad de Alicante , , Apdo. 99 , ,","place":["Alicante, Spain, E-03080"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3782-6995","authenticated-orcid":true,"given":"Sharon","family":"Hammes-Schiffer","sequence":"additional","affiliation":[{"name":"Princeton University , , , ,","place":["Princeton, New Jersey, United States, 08544"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0321-3792","authenticated-orcid":true,"given":"Yao","family":"Yang","sequence":"additional","affiliation":[{"name":"Cornell University , , , ,","place":["Ithaca, New York, United States, 14853"]},{"name":"Cornell University , , , ,","place":["Ithaca, New York, United States, 14853"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,9,2]]},"reference":[{"issue":"6","key":"2026102111062563900_cit1","doi-asserted-by":"publisher","first-page":"6117","DOI":"10.1021\/acs.chemrev.1c00331","article-title":"Electrocatalysis in Alkaline Media\nand Alkaline Membrane-Based Energy Technologies","volume":"122","author":"Yang","year":"2022","journal-title":"Chem. Rev."},{"issue":"5","key":"2026102111062563900_cit2","doi-asserted-by":"publisher","first-page":"518","DOI":"10.1021\/accountsmr.4c00075","article-title":"Single-Crystal Metals and Oxides as Atomically Precise Energy Materials\nPlatforms for Fundamental Electrocatalysis","volume":"5","author":"Briega-Martos","year":"2024","journal-title":"Acc. Mater. Res."},{"issue":"10","key":"2026102111062563900_cit3","doi-asserted-by":"publisher","first-page":"986","DOI":"10.1038\/s41929-025-01421-7","article-title":"Electrolyte Effects in Proton\u2013Electron\nTransfer\nReactions and Implications for Renewable Fuels and Chemicals Synthesis","volume":"8","author":"Sebastia\u0301n-Pascual","year":"2025","journal-title":"Nat. Catal."},{"key":"2026102111062563900_cit4","doi-asserted-by":"publisher","first-page":"943","DOI":"10.1039\/d5ey00161g","article-title":"Unlocking\nthe Potential: Key Roles of Interfacial Water in Electrocatalysis","volume":"3","author":"Tang","year":"2025","journal-title":"EES Catal."},{"key":"2026102111062563900_cit5","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202425590","article-title":"Water in Electrocatalysis","volume":"64","author":"Yuan","year":"2025","journal-title":"Angew. Chem., Int. 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Am. Chem. Soc."},{"issue":"4","key":"2026102111062563900_cit10","doi-asserted-by":"publisher","first-page":"487","DOI":"10.1063\/1674-0068\/cjcp2511177","article-title":"Structure of Water Molecules at Pt Electrode\/Electrolyte\nInterface Probed by Heterodyne-Detected Second Harmonic Generation","volume":"39","author":"Bai","year":"2026","journal-title":"Chin. J. Chem. Phys."},{"issue":"23","key":"2026102111062563900_cit11","doi-asserted-by":"publisher","first-page":"5988","DOI":"10.1021\/jp020785q","article-title":"Coulostatic Potential\nTransients\nInduced by Laser Heating of a Pt(111) Single-Crystal Electrode in\nAqueous Acid Solutions. Rate of Hydrogen Adsorption and Potential\nof Maximum Entropy","volume":"106","author":"Climent","year":"2002","journal-title":"J. Phys. Chem. B"},{"issue":"4","key":"2026102111062563900_cit12","doi-asserted-by":"publisher","DOI":"10.1002\/celc.202101175","article-title":"Prospects\nof Using the Laser-Induced\nTemperature Jump Techniques for Characterisation of Electrochemical\nSystems","volume":"9","author":"Ding","year":"2022","journal-title":"ChemElectroChem"},{"issue":"21","key":"2026102111062563900_cit13","doi-asserted-by":"publisher","first-page":"9290","DOI":"10.1021\/jp900792q","article-title":"Potential-Dependent\nWater Orientation\non Pt(111), Pt(100), and Pt(110), as Inferred from Laser-Pulsed Experiments.\nElectrostatic and Chemical Effects","volume":"113","author":"Garcia-Araez","year":"2009","journal-title":"J. Phys.\nChem. C"},{"issue":"4","key":"2026102111062563900_cit14","doi-asserted-by":"publisher","first-page":"17031","DOI":"10.1038\/nenergy.2017.31","article-title":"Interfacial Water Reorganization\nas a pH-Dependent Descriptor of the Hydrogen Evolution Rate on Platinum\nElectrodes","volume":"2","author":"Ledezma-Yanez","year":"2017","journal-title":"Nat. Energy"},{"issue":"1","key":"2026102111062563900_cit15","doi-asserted-by":"publisher","first-page":"613","DOI":"10.1021\/acsami.8b15003","article-title":"Effect of the Interfacial Water Structure on the Hydrogen\nEvolution Reaction on Pt(111) Modified with Different Nickel Hydroxide\nCoverages in Alkaline Media","volume":"11","author":"Sarabia","year":"2019","journal-title":"ACS Appl. Mater.\nInterfaces"},{"key":"2026102111062563900_cit16","doi-asserted-by":"publisher","first-page":"669","DOI":"10.1038\/s41557-025-01934-5","article-title":"Isotope-Dependent Tafel Analysis\nProbes Proton Transfer Kinetics during Electrocatalytic Water Splitting","volume":"18","author":"Huang","year":"2026","journal-title":"Nat. Chem."},{"key":"2026102111062563900_cit17","doi-asserted-by":"publisher","first-page":"128","DOI":"10.1098\/rspa.1960.0097","article-title":"Kinetics\nof Electrolytic Hydrogen and Deuterium Evolution","volume":"256","author":"Conway","year":"1960","journal-title":"Proc. R. Soc. London, Ser. A"},{"issue":"6","key":"2026102111062563900_cit18","doi-asserted-by":"publisher","first-page":"2308","DOI":"10.1021\/acs.jpclett.0c00185","article-title":"Kinetic Isotope\nEffects Quantify pH-Sensitive Water Dynamics at the Pt Electrode Interface","volume":"11","author":"Rebollar","year":"2020","journal-title":"J. Phys. Chem. Lett."},{"issue":"2","key":"2026102111062563900_cit19","doi-asserted-by":"publisher","first-page":"271","DOI":"10.1038\/s41557-022-01084-y","article-title":"Inverse\nKinetic Isotope Effects in\nthe Oxygen Reduction Reaction at Platinum Single Crystals","volume":"15","author":"Yang","year":"2023","journal-title":"Nat. Chem."},{"issue":"5","key":"2026102111062563900_cit20","doi-asserted-by":"publisher","first-page":"1160","DOI":"10.1149\/1.2114050","article-title":"Oxygen Reduction Kinetics\nin Deuterated\nPhosphoric Acid","volume":"132","author":"Ghoneim","year":"1985","journal-title":"J. Electrochem. Soc."},{"issue":"18","key":"2026102111062563900_cit21","doi-asserted-by":"publisher","first-page":"3542","DOI":"10.1021\/acs.jpclett.6b01235","article-title":"Elucidating Proton\nInvolvement in the Rate-Determining Step for Pt\/Pd-Based and Non-Precious-Metal\nOxygen Reduction Reaction Catalysts Using the Kinetic Isotope Effect","volume":"7","author":"Tse","year":"2016","journal-title":"J. Phys. Chem. Lett."},{"issue":"6","key":"2026102111062563900_cit22","doi-asserted-by":"publisher","first-page":"469","DOI":"10.1002\/cphc.201901091","article-title":"Kinetic Isotope Effect as a Tool to Investigate the\nOxygen Reduction Reaction on Pt-based Electrocatalysts \u2013 Part\nI: High-loading Pt\/C and Pt Extended Surface","volume":"21","author":"George","year":"2020","journal-title":"ChemPhysChem"},{"key":"2026102111062563900_cit23","doi-asserted-by":"publisher","first-page":"428","DOI":"10.1039\/C9FD00032A","article-title":"Quantum Proton\nTunneling in Multi-Electron\/-Proton Transfer Electrode Processes","volume":"221","author":"Sakaushi","year":"2020","journal-title":"Faraday Discuss."},{"key":"2026102111062563900_cit24","doi-asserted-by":"publisher","first-page":"113372","DOI":"10.1016\/j.jelechem.2019.113372","article-title":"Observation\nof Kinetic Isotope Effect in Electrocatalysis with Fully Deuterated\nUltrapure Electrolytes","volume":"849","author":"Sakaushi","year":"2019","journal-title":"J. Electroanal. Chem."},{"issue":"6","key":"2026102111062563900_cit25","doi-asserted-by":"publisher","DOI":"10.1126\/sciadv.adr6465","article-title":"Cation Effects on\nCO2 Reduction Catalyzed by Single-Crystal and Polycrystalline\nGold under Well-Defined Mass Transport Conditions","volume":"11","author":"Cui","year":"2025","journal-title":"Sci. Adv."},{"issue":"22","key":"2026102111062563900_cit26","doi-asserted-by":"publisher","first-page":"224111","DOI":"10.1063\/5.0088427","article-title":"Nuclear\u2013Electronic Orbital\nApproach to Quantization of Protons in Periodic Electronic Structure\nCalculations","volume":"156","author":"Xu","year":"2022","journal-title":"J. Chem. Phys."},{"issue":"23","key":"2026102111062563900_cit27","doi-asserted-by":"publisher","first-page":"238002","DOI":"10.1103\/PhysRevLett.131.238002","article-title":"First-Principles Approach for Coupled Quantum Dynamics of Electrons\nand Protons in Heterogeneous Systems","volume":"131","author":"Xu","year":"2023","journal-title":"Phys.\nRev. Lett."},{"issue":"19","key":"2026102111062563900_cit28","doi-asserted-by":"publisher","first-page":"194109","DOI":"10.1063\/5.0230570","article-title":"Lagrangian Formulation of Nuclear\u2013Electronic\nOrbital Ehrenfest\nDynamics with Real-Time TDDFT for Extended Periodic Systems","volume":"161","author":"Xu","year":"2024","journal-title":"J. Chem. Phys."},{"issue":"8","key":"2026102111062563900_cit29","doi-asserted-by":"publisher","first-page":"1335","DOI":"10.1021\/acs.accounts.5c00119","article-title":"Explaining\nKinetic Isotope Effects in Proton-Coupled Electron Transfer Reactions","volume":"58","author":"Hammes-Schiffer","year":"2025","journal-title":"Acc. Chem. Res."},{"key":"2026102111062563900_cit30","doi-asserted-by":"publisher","first-page":"13054","DOI":"10.1021\/acs.jpclett.5c03144","article-title":"Isotope Effects\nfor Water at Pt(111) Computed with Nuclear-Electronic Orbital Theory","volume":"16","author":"Smith","year":"2025","journal-title":"J. Phys. Chem. Lett."},{"key":"2026102111062563900_cit31","doi-asserted-by":"publisher","first-page":"3719","DOI":"10.1039\/ft9969203719","article-title":"Hydrogen Electrochemistry\non Platinum Low-Index Single-Crystal Surfaces in Alkaline Solution","volume":"92","author":"Markovic\u0301a","year":"1996","journal-title":"J. Chem. Soc., Faraday Trans."},{"key":"2026102111062563900_cit32","doi-asserted-by":"publisher","first-page":"497","DOI":"10.1016\/j.electacta.2017.04.162","article-title":"Effect of pH and Water Structure\non the Oxygen Reduction Reaction on platinum electrodes","volume":"241","author":"Briega-Martos","year":"2017","journal-title":"Electrochim. Acta"},{"key":"2026102111062563900_cit33","doi-asserted-by":"publisher","first-page":"136620","DOI":"10.1016\/j.electacta.2020.136620","article-title":"Why the activity\nof the hydrogen oxidation reaction on platinum decreases as pH increases","volume":"354","author":"Briega-Martos","year":"2020","journal-title":"Electrochim. Acta"},{"key":"2026102111062563900_cit34","doi-asserted-by":"publisher","first-page":"138","DOI":"10.1016\/j.electacta.2015.01.069","article-title":"Towards\nthe Understanding of the Interfacial pH Scale at Pt(111) Electrodes","volume":"162","author":"Rizo","year":"2015","journal-title":"Electrochim. Acta"},{"issue":"22","key":"2026102111062563900_cit35","doi-asserted-by":"publisher","first-page":"19721","DOI":"10.1021\/acscatal.5c05622","article-title":"Cation-Dependent Interfacial Properties Determine the\nActivity of Pt(111) Electrodes in Alkaline Media","volume":"15","author":"Yu","year":"2025","journal-title":"ACS Catal."},{"key":"2026102111062563900_cit36","doi-asserted-by":"publisher","first-page":"114068","DOI":"10.1016\/j.jelechem.2020.114068","article-title":"New Insights into\nthe Pt(hkl)-Alkaline Solution Interphases from the Laser Induced Temperature\nJump Method","volume":"872","author":"Sarabia","year":"2020","journal-title":"J. Electroanal. Chem."},{"issue":"9","key":"2026102111062563900_cit37","doi-asserted-by":"publisher","first-page":"4106","DOI":"10.1063\/1.1494980","article-title":"Multiconfigurational\nNuclear-Electronic\nOrbital Approach: Incorporation of Nuclear Quantum Effects in Electronic\nStructure Calculations","volume":"117","author":"Webb","year":"2002","journal-title":"J. Chem. Phys."},{"issue":"9","key":"2026102111062563900_cit38","doi-asserted-by":"publisher","first-page":"4222","DOI":"10.1021\/acs.chemrev.9b00798","article-title":"Multicomponent Quantum Chemistry:\nIntegrating Electronic and Nuclear Quantum Effects via the Nuclear\u2013Electronic\nOrbital Method","volume":"120","author":"Pavos\u030cevic\u0301","year":"2020","journal-title":"Chem. Rev."},{"issue":"3","key":"2026102111062563900_cit39","doi-asserted-by":"publisher","first-page":"030901","DOI":"10.1063\/5.0053576","article-title":"Nuclear\u2013Electronic\nOrbital Methods: Foundations and Prospects","volume":"155","author":"Hammes-Schiffer","year":"2021","journal-title":"J. Chem. Phys."},{"issue":"12","key":"2026102111062563900_cit40","doi-asserted-by":"publisher","first-page":"5521","DOI":"10.1021\/acs.jpcc.1c10362","article-title":"OH Binding\nEnergy as a Universal Descriptor of the Potential of Zero Charge on\nTransition Metal Surfaces","volume":"126","author":"Kelly","year":"2022","journal-title":"J. Phys. Chem. C"},{"key":"2026102111062563900_cit41","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1155\/2018\/4186968","article-title":"The Adsorption\nand Diffusion Manners of Hydrogen Atoms on Pt (100), Pt (110), and\nPt (111) Surfaces","volume":"2018","author":"Vurdu","year":"2018","journal-title":"Adv. Condens. 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