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Here, we introduced\u00a0a molecular engineering strategy by assembling a functionalized molecular molybdenum complex (PyMoBr\n 3<\/jats:sub>\n PNP) on graphdiyne (GDY) through \u03c0\u2013\u03c0 interactions. The resulting interface\u2010assembled molecular electrode, PyMoBr\n 3<\/jats:sub>\n PNP\/GDY\/carbon paper (CP), catalyzed N\n 2<\/jats:sub>\n conversion to ammonia (NH\n 3<\/jats:sub>\n ) using 2,4,6\u2010trimethylpyridinium triflate ([ColH][OTf]) as the proton source. Rigorous isotopic labeling and continuous time\u2010dependent controls confirmed the genuine nature of catalytic N\n 2<\/jats:sub>\n to NH\n 3<\/jats:sub>\n turnover. Encouraged by the intrinsic N\n 2<\/jats:sub>\n reduction activity, the PyMoBr\n 3<\/jats:sub>\n PNP\/GDY\/CP cathode was further coupled with a molecular hybrid photoanode (ZnTCPP\/Al\n 2<\/jats:sub>\n O\n 3<\/jats:sub>\n \/BiVO\n 4<\/jats:sub>\n ) for photoelectrocatalytic N\n 2<\/jats:sub>\n reduction. The integrated system decreased the applied bias, achieved a turnover frequency (TOF) of 47.52\u00a0h\n \u22121<\/jats:sup>\n and a turnover number (TON) of 157.54 over 4\u00a0h for NH\n 3<\/jats:sub>\n production, representing the highest performance reported to date for molecular\u2010based electrochemical and photoelectrochemical N\n 2<\/jats:sub>\n reduction. All of these results highlight the potential of molecular engineering platforms to enhance catalyst utilization, improve reaction efficiency, and lower energy consumption for N\n 2<\/jats:sub>\n fixation.\n <\/jats:p>","DOI":"10.1002\/anie.8913465","type":"journal-article","created":{"date-parts":[[2026,9,30]],"date-time":"2026-09-30T03:35:48Z","timestamp":1790739348000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Molecular Engineering at Electrode Interface Enables Efficient Catalytic Nitrogen Reduction"],"prefix":"10.1002","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-3647-8877","authenticated-orcid":false,"given":"De\u2010Shan","family":"Zhang","sequence":"first","affiliation":[{"name":"Key Laboratory of Supramolecular Photochemistry & CAS\u2010HKU Joint Laboratory on New Materials New Cornerstone Science Laboratory Technical Institute of Physics and Chemistry The Chinese Academy of Sciences Beijing P. 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