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However, their efficiency is fundamentally constrained by kinetic mismatch between sluggish transmembrane electron injection and uncoupled proton flux required for bioenergetic transduction. This uncoupling restricts the regeneration of adenosine triphosphate (ATP) and reduced nicotinamide adenine dinucleotide (NADH), the dual cofactors essential for driving carbon fixation pathways. Here, we introduce a proton enrichment strategy utilizing protonated manganese\u2010doped carbon dots (HMnCDs) that function simultaneously as reversible proton buffers and photoelectron donors. HMnCDs localize to the periplasm of\n                    <jats:italic>Cupriavidus necato<\/jats:italic>\n                    r H16, where their labile protons reinforce the transmembrane proton gradient driving ATP synthase. Concurrently, cytoplasmic HMnCDs facilitate proton\u2010coupled electron transfer, accelerating NADH photoregeneration. The concerted management of proton and electron fluxes decouples ATP generation from respiratory NADH oxidation, creating a synergistic cofactor supply even under electron transport chain inhibition. Consequently, the biohybrid achieves light\u2010driven autotrophic growth and poly(3\u2010hydroxybutyrate) biosynthesis from CO\n                    <jats:sub>2<\/jats:sub>\n                    , attaining a record quantum efficiency of 20.8%. Multi\u2010omics analyses reveal global metabolic reprogramming, including upregulated carbon fixation pathways and adaptive modulation of energy homeostasis under the proton\u2010enriched microenvironment. This work establishes proton enrichment as a generalizable design principle for coupling photochemistry with cellular bioenergetics.\n                  <\/jats:p>","DOI":"10.1002\/anie.8155133","type":"journal-article","created":{"date-parts":[[2026,6,9]],"date-time":"2026-06-09T11:55:41Z","timestamp":1781006141000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Intracellular Proton Enrichment Drives Unified Dual\u2010Cofactor Regeneration for Biohybrid CO\n                    <sub>2<\/sub>\n                    Fixation"],"prefix":"10.1002","volume":"65","author":[{"given":"Xianghai","family":"Bian","sequence":"first","affiliation":[{"name":"College of Chemical and Biological Engineering Key Laboratory of Biomass Chemical Engineering of Ministry of Education Zhejiang University  Hangzhou 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