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Its development is limited by sluggish intermediate hydrogenation and severe hydrogen evolution reaction (HER). Herein, we develop topology\u2010engineered isomeric polyoxometalate (POM)\u2010confined bimetallic metal\u2010organic framework (MOF) electrocatalysts (NH\n                    <jats:sub>2<\/jats:sub>\n                    \u2010MIL\u201053, \u201088, \u2010101). Flexible NH\n                    <jats:sub>2<\/jats:sub>\n                    \u2010MIL\u201088(FeNi) enables tight encapsulation of [PW\n                    <jats:sub>12<\/jats:sub>\n                    O\n                    <jats:sub>40<\/jats:sub>\n                    ]\n                    <jats:sup>3\u2212<\/jats:sup>\n                    (PW\n                    <jats:sub>12<\/jats:sub>\n                    ) clusters via the \u201cbreathing effect\u201d, yielding PW\n                    <jats:sub>12<\/jats:sub>\n                    @NH\n                    <jats:sub>2<\/jats:sub>\n                    \u2010MIL\u201088(FeNi) with synergistically modulated electronic distribution and proton transfer. Combined experimental and theoretical studies reveal that confined PW\n                    <jats:sub>12<\/jats:sub>\n                    induces electronic redistribution over Fe\/Ni centers, concurrently strengthening NO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    adsorption on Fe and accelerating *NO\n                    <jats:sub>2<\/jats:sub>\n                    hydrogenation on Ni. Beyond electronic effects, PW\n                    <jats:sub>12<\/jats:sub>\n                    loosens the rigid hydration layer and forms conjugated acid\u2010base pairs with MOF amino groups, promoting proton diffusion, boosting *NO\n                    <jats:sub>2<\/jats:sub>\n                    hydrogenation, and suppressing HER. Thus, PW\n                    <jats:sub>12<\/jats:sub>\n                    @NH\n                    <jats:sub>2<\/jats:sub>\n                    \u2010MIL\u201088(FeNi) achieves an NH\n                    <jats:sub>3<\/jats:sub>\n                    yield rate of 20.1\u00a0mg h\n                    <jats:sup>\u22121<\/jats:sup>\n                    mg\n                    <jats:sub>cat.<\/jats:sub>\n                    <jats:sup>\u22121<\/jats:sup>\n                    with a Faradaic efficiency of 98.6% under neutral electrolytes. When used as a cathode in rechargeable Zn\u2212nitrate batteries, it delivers a peak power density of 13.2\u00a0mW cm\n                    <jats:sup>\u22122<\/jats:sup>\n                    . This study establishes a generalizable paradigm for engineering interfacial proton transport and electronic properties\n                    <jats:italic>via<\/jats:italic>\n                    POM confinement in MOFs.\n                  <\/jats:p>","DOI":"10.1002\/anie.6487495","type":"journal-article","created":{"date-parts":[[2026,6,22]],"date-time":"2026-06-22T14:03:11Z","timestamp":1782136991000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Breathing Bimetallic MOF Confined Polyoxometalates for Hydration Layer Loosening and Electronic Redistribution Toward Efficient Nitrate Electroreduction and Zn\u2212Nitrate Batteries"],"prefix":"10.1002","volume":"65","author":[{"given":"Qiushuang","family":"Jiang","sequence":"first","affiliation":[{"name":"School of Materials Science and Chemical Engineering Harbin University of Science and Technology  Harbin P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5418-9182","authenticated-orcid":false,"given":"Xinming","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Materials Science and Chemical Engineering Harbin University of Science and Technology  Harbin P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chao","family":"Wang","sequence":"additional","affiliation":[{"name":"College of Materials Science and Chemical Engineering Harbin Engineering University  Harbin P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shengji","family":"Tian","sequence":"additional","affiliation":[{"name":"MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage School of Chemistry and Chemical Engineering Harbin Institute of Technology  Harbin P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Nan","family":"Zhao","sequence":"additional","affiliation":[{"name":"School of Materials Science and Chemical Engineering Harbin University of Science and Technology  Harbin P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0405-8352","authenticated-orcid":false,"given":"Haijun","family":"Pang","sequence":"additional","affiliation":[{"name":"School of Materials Science and Chemical Engineering Harbin University of Science and Technology  Harbin P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0964-1037","authenticated-orcid":false,"given":"Chade","family":"Lv","sequence":"additional","affiliation":[{"name":"MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage School of Chemistry and Chemical Engineering Harbin Institute of Technology  Harbin P. R. 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