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Herein, we report a novel Bi\u2010Bi\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    CO\n                    <jats:sub>3<\/jats:sub>\n                    heterojunction electrocatalyst (Bi\u2010BOC\u2010OLA) constructed via an oleylamine\u2010assisted strategy and disclose a new self\u2010release\u2010replenishing Mars\u2010van Krevelen\u2010type mechanism that alleviates this constraint. Oleylamine\u2010induced expansion of [Bi\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>2+<\/jats:sup>\n                    layers enables the Bi\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    CO\n                    <jats:sub>3<\/jats:sub>\n                    lattice in Bi\u2010BOC\u2010OLA to function as an in situ carbon reservoir that continuously supplies carbon\u2013oxygen intermediates to active Bi centers. External CO\n                    <jats:sub>2<\/jats:sub>\n                    replenishes lattice vacancies, creating an energy\u2010efficient cycle that reduces reliance on gaseous CO\n                    <jats:sub>2<\/jats:sub>\n                    transport. Consequently, Bi\u2010BOC\u2010OLA achieves a formate Faradaic efficiency of 97%, a record partial current density of \u22121.4\u00a0A\u00a0cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    and stable operation for 160\u00a0h at \u2212400\u00a0mA\u00a0cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    . This work reveals how dynamic lattice participation in Bi\u2010Bi\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    CO\n                    <jats:sub>3<\/jats:sub>\n                    heterojunctions enables high\u2010rate CO\n                    <jats:sub>2<\/jats:sub>\n                    \u2010to\u2010formate conversion and provides a new mechanistic basis for the design of Bi\u2010based CO\n                    <jats:sub>2<\/jats:sub>\n                    RR catalysts.\n                  <\/jats:p>","DOI":"10.1002\/anie.2971119","type":"journal-article","created":{"date-parts":[[2026,9,23]],"date-time":"2026-09-23T08:44:08Z","timestamp":1790153048000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Oleylamine\u2010Assisted Construction of Bi\u2010Bi\n                    <sub>2<\/sub>\n                    O\n                    <sub>2<\/sub>\n                    CO\n                    <sub>3<\/sub>\n                    Heterojunction With a Self\u2010Release\u2010Replenishing Mars\u2010van Krevelen\u2010Type Mechanism for Efficient CO\n                    <sub>2<\/sub>\n                    Electroreduction"],"prefix":"10.1002","author":[{"given":"Jiarui","family":"Zhang","sequence":"first","affiliation":[{"name":"Xi'an Key Laboratory of Functional Organic Porous Materials School of Chemistry and Chemical Engineering Northwestern Polytechnical University  Xi'an P. 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