Potential Dependence of Nitrate Adsorption and Dissociation across Metals and Dilute Alloys: a Grand Canonical Study

Potential Dependence of Nitrate Adsorption and Dissociation across Metals and Dilute Alloys: a Grand Canonical Study | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Article Potential Dependence of Nitrate Adsorption and Dissociation across Metals and Dilute Alloys: a Grand Canonical Study Bryan R. Goldsmith, Dean Sweeney, Bolton Tran This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-6171330/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 11 Jun, 2025 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Abstract Aqueous nitrate (NO − 3 ) can be electrocatalytically reduced to value-added or benign products. However, the impact of the electrochemical potential on key reaction steps remains poorly understood. Using explicit and analytical grand-canonical density functional theory (eGC-DFT and aGC-DFT), we investigate the potential dependence of nitrate adsorption and dissociation on pure metals and Cu-based single-atom alloys (SAAs). With aGC-DFT, we find electrosorption valencies for NO − 3 adsorption on stable/metastable SAAs (stability evaluated with eGC-DFT) and pure metals range between −0.60 eV/V to −0.80 eV/V. These values correlate with the extent of the computed partial charge transfer to the surface, which trends with the fractional d-band filling of the metal. NO* 3 dissociation exhibits weak potential dependence, with symmetry factors between −0.04 eV/V and −0.20 eV/V. For Ni 1 Cu, an experimentally studied SAA for nitrate reduction, aGC-DFT predicts potential-dependent adsorption and activation energies that can differ significantly from conventional approximations, such as the computational hydrogen electrode model. However, we demonstrate that aGC-DFT computed energies and hence these differences vary drastically with the assumed double-layer properties. Overall, this work clarifies potential dependent nitrate adsorption and dissociation trends across SAAs and pure metals, emphasizing the need to account for electrochemical conditions in mechanistic studies of nitrate reduction. Physical sciences/Chemistry/Catalysis/Heterogeneous catalysis Physical sciences/Chemistry/Theoretical chemistry/Density functional theory Full Text Additional Declarations There is NO Competing Interest. Supplementary Files nitrategcSI.pdf Supplemental Material for manuscript titled" Potential Dependence of Nitrate Adsorption and Dissociation across Metals and Dilute Alloys: a Grand Canonical Study" Cite Share Download PDF Status: Published Journal Publication published 11 Jun, 2025 Read the published version in Communications Chemistry → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. Our growing team is made up of researchers and industry professionals working together to solve the most critical problems facing scientific publishing. Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-6171330","acceptedTermsAndConditions":true,"allowDirectSubmit":false,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":428066508,"identity":"d96f69c0-a10e-4c7b-8a0f-f593ddb1e337","order_by":0,"name":"Bryan R. 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However, the impact of the electrochemical potential on key reaction steps remains poorly understood. Using explicit and analytical grand-canonical density functional theory (eGC-DFT and aGC-DFT), we investigate the potential dependence of nitrate adsorption and dissociation on pure metals and Cu-based single-atom alloys (SAAs). With aGC-DFT, we find electrosorption valencies for NO\u003csup\u003e−\u003c/sup\u003e\u003csub\u003e3 \u003c/sub\u003eadsorption on stable/metastable SAAs (stability evaluated with eGC-DFT) and pure metals range between −0.60 eV/V to −0.80 eV/V. These values correlate with the extent of the computed partial charge transfer to the surface, which trends with the fractional d-band filling of the metal. NO*\u003csub\u003e3 \u003c/sub\u003edissociation exhibits weak potential dependence, with symmetry factors between −0.04 eV/V and −0.20 eV/V. For Ni\u003csub\u003e1\u003c/sub\u003eCu, an experimentally studied SAA for nitrate reduction, aGC-DFT predicts potential-dependent adsorption and activation energies that can differ significantly from conventional approximations, such as the computational hydrogen electrode model. However, we demonstrate that aGC-DFT computed energies and hence these differences vary drastically with the assumed double-layer properties. 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