Dynamic Coordinated Geminal-atom Catalyst for Highly Efficient Photo-Fenton Reactions

Dynamic Coordinated Geminal-atom Catalyst for Highly Efficient Photo-Fenton Reactions | 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 Dynamic Coordinated Geminal-atom Catalyst for Highly Efficient Photo-Fenton Reactions Kun Qi, Yucheng Qiao, Su Zhan, Qiuchen He, Yang Zhang, Jiangpeng Li, and 5 more This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-5780372/v1 This work is licensed under a CC BY 4.0 License Status: Posted Version 1 posted You are reading this latest preprint version Abstract Understanding and leveraging non-reactive species in natural environments to modulate the active centers of geminal-atom catalysts (GACs) is crucial for enhancing their catalytic performance. In this study, we present a two-coordinated geminal Cu atomic catalyst and, for the first time, uncover the mechanism by which dynamic metal second coordination shell and non-reactive species boost its photo-Fenton activity. This breakthrough enables the efficient removal of pollutants such as marine microorganisms, oils, and microplastics. Through experimental studies, operando X-ray absorption spectroscopy, and theoretical analyses, we demonstrate that the dynamic coordination environment promotes synergistic dual-atom interactions, and the second coordination shell influences the significant orbital overlap between the central metal and the delocalized ligand orbitals, enabling direct electron transfer. Additionally, the dynamic coordination of GACs induces a local spin transition, which lowers the reaction barrier through spin-crossover at the active site. This, in turn, reduces the spin-flip barrier for forming the singlet-state *OOH and OH-, thereby accelerating spin non-conservation reactions. The interactions between CO32- ions and adjacent Cu sites significantly alter the electronic structure of the catalytic centers. These modifications enhance charge transfer kinetics, leading to a remarkable 17-fold increase in hydroxyl radical production. This innovative approach—utilizing non-reactive species to amplify the photo-Fenton activity of Cu GACs—offers a constructive solution for environmental remediation in complex matrices and provides valuable guidance for designing high-performance catalysts tailored to challenging environmental conditions. Physical sciences/Materials science/Materials for energy and catalysis Physical sciences/Chemistry/Catalysis Earth and environmental sciences/Ocean sciences/Marine chemistry Single-atom Catalyst Geminal-atom Photo-Fenton Reaction Marine Pollution Management Dynamic Coordinated Full Text Additional Declarations There is NO Competing Interest. Supplementary Files SI07012025.pdf Supplementary Information Cite Share Download PDF Status: Posted 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. 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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-5780372","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Article","associatedPublications":[],"authors":[{"id":404764749,"identity":"5f8a0b3b-aa1d-4bce-bf20-ba2f8b24270e","order_by":0,"name":"Kun 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