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Inspired by the proton-relay function of the hydrogen-bond network in photosystem II, we report a sustainable strategy to engineer an artificial proton-transfer pathway on CoFe layered double hydroxide (LDH) electrocatalysts using vancomycin-derived carbon dots (Van-Cdots). The Van\u2013Cdots create an extended interfacial hydrogen-bond network that actively steers the proton-coupled electron transfer (PCET) mechanism. Kinetic isotope effect measurements reveal a striking transition from a primary KIE (2.00) for pristine CoFe-LDH to a secondary KIE (\u22641.49) for the Van\u2013Cdots\/CoFe-LDH hybrid, definitively removing proton transfer from the rate-determining step. pH-dependent kinetics demonstrate a shift from a concerted PCET pathway to a non-concerted mechanism, with fractional reaction orders (0.20\u22120.58) indicative of Grotthuss-type proton hopping. Proton inventory studies provide quantitative evidence for participation of multiple protonic sites (Z = 2.508) with an exceptionally low fractionation factor (\u03c6 = 0.076), characteristic of low-barrier hydrogen bonds approaching those inferred in natural photosynthesis. Gerischer impedance spectroscopy confirms that proton-exchange kinetics outpace natural diffusion, establishing a chemical\u2013electrochemical\u2013chemical mechanism. The optimized hybrid achieves a substantially reduced Tafel slope (146 mV dec\u22121) and enhanced stability. This work establishes bio-derived carbon dots as a sustainable, integrable platform for engineering proton-relay interfaces, bridging a critical gap between synthetic electrocatalysis and nature\u2019s integrated design.<\/jats:p>","DOI":"10.1021\/acsami.6c08087","type":"journal-article","created":{"date-parts":[[2026,7,14]],"date-time":"2026-07-14T17:43:02Z","timestamp":1784050982000},"page":"40951-40963","source":"Crossref","is-referenced-by-count":0,"title":["Engineering Bio-Derived Carbon Dot Mediators for Sustainable Steering of Proton-Coupled Electron Transfer in Water Oxidation"],"prefix":"10.1021","volume":"18","author":[{"given":"Sahar","family":"Geravandi","sequence":"first","affiliation":[{"name":"Razi University , , ,","place":["Kermanshah, Iran, 6714967346"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0983-9809","authenticated-orcid":true,"given":"Foroozan","family":"Feizi","sequence":"additional","affiliation":[{"name":"Razi University , , ,","place":["Kermanshah, Iran, 6714967346"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6560-4815","authenticated-orcid":true,"given":"Mojtaba","family":"Shamsipur","sequence":"additional","affiliation":[{"name":"Razi University , , ,","place":["Kermanshah, Iran, 6714967346"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Afshin","family":"Pashabadi","sequence":"additional","affiliation":[{"name":"Razi University , , ,","place":["Kermanshah, Iran, 6714967346"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,7,14]]},"reference":[{"issue":"3","key":"2026080518081664100_cit1","doi-asserted-by":"publisher","first-page":"723","DOI":"10.1016\/j.apenergy.2009.06.034","article-title":"A survey of the electricity consumption-growth literature","volume":"87","author":"Payne","year":"2010","journal-title":"Appl. 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