{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,9,25]],"date-time":"2026-09-25T21:39:37Z","timestamp":1790372377388,"version":"4.1.0"},"reference-count":37,"publisher":"American Chemical Society (ACS)","issue":"34","license":[{"start":{"date-parts":[[2026,8,24]],"date-time":"2026-08-24T00:00:00Z","timestamp":1787529600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-029"},{"start":{"date-parts":[[2026,8,24]],"date-time":"2026-08-24T00:00:00Z","timestamp":1787529600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-037"},{"start":{"date-parts":[[2026,8,24]],"date-time":"2026-08-24T00:00:00Z","timestamp":1787529600000},"content-version":"stm-asf","delay-in-days":0,"URL":"https:\/\/doi.org\/10.15223\/policy-045"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22271147"],"award-info":[{"award-number":["22271147"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22401144"],"award-info":[{"award-number":["22401144"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22471123"],"award-info":[{"award-number":["22471123"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003245","name":"Ministerie van Onderwijs, Cultuur en Wetenschap","doi-asserted-by":"publisher","award":["1420578"],"award-info":[{"award-number":["1420578"]}],"id":[{"id":"10.13039\/501100003245","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100012166","name":"National Key Research and Development Program of China","doi-asserted-by":"publisher","award":["2025YFA151110"],"award-info":[{"award-number":["2025YFA151110"]}],"id":[{"id":"10.13039\/501100012166","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,9,2]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Nitroarene electroreduction typically terminates at anilines, limiting access to partially reduced N\u2013O intermediates for nitrogen-scaffold synthesis. Here we redirect nitroarene electroreduction through a hydroxylamine-mediated pathway for nitrogen-scaffold synthesis. Mechanistic studies identify a phenylhydroxylamine-derived isoxazolium intermediate that undergoes N\u2013O bond cleavage to form amides or indoles. Guided by the mechanistic insight, a molybdenum catalyst was developed to decouple nitroarene reduction from N\u2013O-intermediate over-reduction, creating a productive window for intermediate accumulation and trapping. This strategy tolerates a wide range of nitroarenes and 1,3-dicarbonyl partners, providing modular access to diverse nitrogen-containing scaffolds. In a membrane\u2013electrode assembly, the platform achieved 81% Faradaic efficiency at 100 mA cm\u20132 with an ultralow cell voltage of merely 0.83 V, operated stably for 144 h, and was scaled to 10 A in a 100 cm2 device with gram-per-hour output. This work establishes nitroarene electroreduction as a platform for controllable N\u2013O-intermediate-based synthesis, expanding the use of nitroarenes beyond their conventional role as aniline precursors.<\/jats:p>","DOI":"10.1021\/jacs.6c11800","type":"journal-article","created":{"date-parts":[[2026,8,30]],"date-time":"2026-08-30T17:54:16Z","timestamp":1788112456000},"page":"37203-37212","source":"Crossref","is-referenced-by-count":1,"title":["Redirecting Nitroarene\nElectroreduction toward Nitrogen-Scaffold\nSynthesis"],"prefix":"10.1021","volume":"148","author":[{"ORCID":"https:\/\/orcid.org\/0009-0000-1930-9065","authenticated-orcid":true,"given":"Leitao","family":"Xu","sequence":"first","affiliation":[{"name":"Nanjing University , , ,","place":["Nanjing, China, 210023"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bowei","family":"Yuan","sequence":"additional","affiliation":[{"name":"Radboud University , , Heyendaalseweg 135 , ,","place":["Nijmegen, Netherlands, 6525 AJ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhuqian","family":"Cai","sequence":"additional","affiliation":[{"name":"Nanjing University , , ,","place":["Nanjing, China, 210023"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bo","family":"Wang","sequence":"additional","affiliation":[{"name":"Jiangnan University , , , ,","place":["Wuxi, Jiangsu, China, 214122"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bowen","family":"Gao","sequence":"additional","affiliation":[{"name":"Zhejiang University , , ,","place":["Hangzhou, China, 310027"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5486-6916","authenticated-orcid":true,"given":"Aleksandr Y.","family":"Pereverzev","sequence":"additional","affiliation":[{"name":"Radboud University , , Heyendaalseweg 135 , ,","place":["Nijmegen, Netherlands, 6525 AJ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yi","family":"Zhu","sequence":"additional","affiliation":[{"name":"Jiangnan University , , , ,","place":["Wuxi, Jiangsu, China, 214122"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Chao","family":"Qian","sequence":"additional","affiliation":[{"name":"Zhejiang University , , ,","place":["Hangzhou, China, 310027"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jana","family":"Roithova\u0301","sequence":"additional","affiliation":[{"name":"Radboud University , , Heyendaalseweg 135 , ,","place":["Nijmegen, Netherlands, 6525 AJ"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8700-7621","authenticated-orcid":true,"given":"Yi","family":"Wang","sequence":"additional","affiliation":[{"name":"Nanjing University , , ,","place":["Nanjing, China, 210023"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,24]]},"reference":[{"issue":"4","key":"2026090312072409800_cit1","doi-asserted-by":"publisher","first-page":"2550","DOI":"10.1021\/acs.chemrev.8b00372","article-title":"Iron Catalysis in Reduction and Hydrometalation Reactions","volume":"119","author":"Wei","year":"2019","journal-title":"Chem. Rev."},{"issue":"8","key":"2026090312072409800_cit2","doi-asserted-by":"publisher","first-page":"564","DOI":"10.1038\/s41570-021-00289-y","article-title":"Highlights and challenges\nin the selective reduction\nof carbon dioxide to methanol","volume":"5","author":"Navarro-Jae\u0301n","year":"2021","journal-title":"Nat. Rev. Chem."},{"issue":"12","key":"2026090312072409800_cit3","doi-asserted-by":"publisher","first-page":"6720","DOI":"10.1039\/D1CS00116G","article-title":"Nitrate electroreduction:\nmechanism insight, in situ characterization, performance evaluation,\nand challenges","volume":"50","author":"Wang","year":"2021","journal-title":"Chem. Soc. Rev."},{"issue":"7","key":"2026090312072409800_cit4","doi-asserted-by":"publisher","first-page":"518","DOI":"10.1038\/s41570-024-00608-z","article-title":"Counterintuitive chemoselectivity\nin the reduction\nof carbonyl compounds","volume":"8","author":"Iwasaki","year":"2024","journal-title":"Nat. Rev. Chem."},{"issue":"12","key":"2026090312072409800_cit5","doi-asserted-by":"publisher","first-page":"2025","DOI":"10.1038\/s41557-024-01624-8","article-title":"Gold-catalysed amine\nsynthesis by reductive hydroamination of alkynes with nitroarenes","volume":"16","author":"Zhou","year":"2024","journal-title":"Nat. Chem."},{"issue":"3","key":"2026090312072409800_cit6","doi-asserted-by":"publisher","first-page":"573","DOI":"10.1038\/s41557-025-02018-0","article-title":"Direct enantioselective\nC(sp3)\u2013H coupling of N-alkyl anilines via metallaphotoredox\ncatalysis","volume":"18","author":"Zu","year":"2026","journal-title":"Nat. Chem."},{"issue":"2","key":"2026090312072409800_cit7","doi-asserted-by":"publisher","first-page":"285","DOI":"10.1093\/nsr\/nwz146","article-title":"Potential-tuned selective\nelectrosynthesis of azoxy-, azo- and amino-aromatics over a CoP nanosheet\ncathode","volume":"7","author":"Chong","year":"2020","journal-title":"Natl. Sci. Rev."},{"issue":"5","key":"2026090312072409800_cit8","doi-asserted-by":"publisher","first-page":"771","DOI":"10.1038\/s41557-023-01429-1","article-title":"Synthesis\nof polysubstituted azepanes by dearomative\nring expansion of nitroarenes","volume":"16","author":"Mykura","year":"2024","journal-title":"Nat. Chem."},{"issue":"6","key":"2026090312072409800_cit9","doi-asserted-by":"publisher","first-page":"1621","DOI":"10.1021\/cr00030a007","article-title":"Addition, Reduction, and Oxidation Reactions of Nitrosobenzene","volume":"94","author":"Zuman","year":"1994","journal-title":"Chem. Rev."},{"issue":"5908","key":"2026090312072409800_cit10","doi-asserted-by":"publisher","first-page":"1661","DOI":"10.1126\/science.1166401","article-title":"Gold-Catalyzed Synthesis of Aromatic\nAzo Compounds from Anilines and Nitroaromatics","volume":"322","author":"Grirrane","year":"2008","journal-title":"Science"},{"issue":"6162","key":"2026090312072409800_cit11","doi-asserted-by":"publisher","first-page":"1073","DOI":"10.1126\/science.1242005","article-title":"Nanoscale Fe2O3-Based Catalysts for\nSelective Hydrogenation of Nitroarenes to Anilines","volume":"342","author":"Jagadeesh","year":"2013","journal-title":"Science"},{"issue":"5","key":"2026090312072409800_cit12","doi-asserted-by":"publisher","first-page":"564","DOI":"10.1038\/nmat4555","article-title":"Interfacial electronic\neffects control the reaction selectivity of platinum catalysts","volume":"15","author":"Chen","year":"2016","journal-title":"Nat. Mater."},{"issue":"31","key":"2026090312072409800_cit13","doi-asserted-by":"publisher","first-page":"17329","DOI":"10.1021\/jacs.3c04857","article-title":"Reductive Coupling\nof Nitroarenes and HCHO for General Synthesis of Functional Ethane-1,2-diamines\nby a Cobalt Single-Atom Catalyst","volume":"145","author":"Sun","year":"2023","journal-title":"J. Am. Chem.\nSoc."},{"issue":"16","key":"2026090312072409800_cit14","doi-asserted-by":"publisher","first-page":"11289","DOI":"10.1021\/jacs.4c00547","article-title":"Multicomponent Reductive\nCoupling for Selective Access to Functional \u03b3-Lactams\nby a Single-Atom Cobalt Catalyst","volume":"146","author":"Sun","year":"2024","journal-title":"J. Am. Chem.\nSoc."},{"issue":"8","key":"2026090312072409800_cit15","doi-asserted-by":"publisher","first-page":"6572","DOI":"10.1021\/jacs.4c15284","article-title":"Reduction-Interrupted Tandem Reaction\nfor General Synthesis of Functional Amino Acids by a Heterogeneous\nCobalt Catalyst","volume":"147","author":"Hua","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"21","key":"2026090312072409800_cit16","doi-asserted-by":"publisher","first-page":"13230","DOI":"10.1021\/acs.chemrev.7b00397","article-title":"Synthetic Organic Electrochemical\nMethods Since 2000: On the Verge of a Renaissance","volume":"117","author":"Yan","year":"2017","journal-title":"Chem. Rev."},{"issue":"13","key":"2026090312072409800_cit17","doi-asserted-by":"publisher","first-page":"1872","DOI":"10.1021\/acs.accounts.3c00192","article-title":"Designed Nanomaterials for Electrocatalytic\nOrganic Hydrogenation Using Water as the Hydrogen Source","volume":"56","author":"Liu","year":"2023","journal-title":"Acc. Chem. Res."},{"issue":"4","key":"2026090312072409800_cit18","doi-asserted-by":"publisher","first-page":"277","DOI":"10.1038\/s41570-024-00589-z","article-title":"Electrochemical\nhydrogenation and oxidation of organic species involving water","volume":"8","author":"Liu","year":"2024","journal-title":"Nat. Rev. Chem."},{"issue":"4","key":"2026090312072409800_cit19","doi-asserted-by":"publisher","first-page":"494","DOI":"10.1038\/s41565-025-02117-6","article-title":"Tandem architectures\nfor electrochemical CO2 reduction:\nfrom coupled atomic sites to tandem electrolysers","volume":"21","author":"Filippi","year":"2026","journal-title":"Nat. Nanotechnol."},{"key":"2026090312072409800_cit20","doi-asserted-by":"publisher","DOI":"10.1093\/nsr\/nwag186","article-title":"Nanogalvanic\ncell catalysts: bridging electrochemical and thermal catalysis","volume":"13","author":"Huang","year":"2026","journal-title":"Natl. Sci. Rev."},{"issue":"1","key":"2026090312072409800_cit21","doi-asserted-by":"publisher","first-page":"5679","DOI":"10.1038\/s41467-023-41423-2","article-title":"Atomically dispersed Cu coordinated\nRh metallene arrays for simultaneously electrochemical aniline synthesis\nand biomass upgrading","volume":"14","author":"Mao","year":"2023","journal-title":"Nat. Commun."},{"issue":"12","key":"2026090312072409800_cit22","doi-asserted-by":"publisher","first-page":"10118","DOI":"10.1021\/jacs.4c14111","article-title":"In Situ Li+ Intercalation into Nanosized Chevrel Phase Mo6S8 toward\nEfficient Electrochemical Nitroarene Reduction","volume":"147","author":"Tan","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"6","key":"2026090312072409800_cit23","doi-asserted-by":"publisher","DOI":"10.1002\/cmtd.202400003","article-title":"Decoding Voltammograms\nat the Molecular Frontier: Integration\nof Voltammetry and Mass Spectrometry","volume":"4","author":"Surendran","year":"2024","journal-title":"Chem.\nMethods"},{"issue":"44","key":"2026090312072409800_cit24","doi-asserted-by":"publisher","first-page":"40440","DOI":"10.1021\/jacs.5c11990","article-title":"Primary and\nSecondary Coordination Sphere Effects in the Cobalt Complex-Catalyzed\nElectrocatalytic O2 Reduction to Water","volume":"147","author":"Bairagi","year":"2025","journal-title":"J. Am.\nChem. Soc."},{"issue":"1","key":"2026090312072409800_cit25","doi-asserted-by":"publisher","first-page":"4143","DOI":"10.1038\/s41467-026-70691-x","article-title":"Paired electrolysis enables para-C\u2013H\namination of phenols with nitroarenes and mechanistic visualization\nvia multifunctional electrochemical mass spectrometry","volume":"17","author":"Peng","year":"2026","journal-title":"Nat. Commun."},{"key":"2026090312072409800_cit26","doi-asserted-by":"publisher","first-page":"204","DOI":"10.1016\/j.ijms.2013.06.007","article-title":"Infrared spectroscopy\nof trapped molecular dications below 4K","volume":"354\u2013355","author":"Jas\u030ci\u0301k","year":"2013","journal-title":"Int.\nJ. Mass Spectrom."},{"issue":"2","key":"2026090312072409800_cit27","doi-asserted-by":"publisher","first-page":"223","DOI":"10.1021\/acs.accounts.5b00489","article-title":"Helium Tagging Infrared Photodissociation Spectroscopy\nof Reactive Ions","volume":"49","author":"Roithova\u0301","year":"2016","journal-title":"Acc. Chem. Res."},{"issue":"45","key":"2026090312072409800_cit28","doi-asserted-by":"publisher","first-page":"41390","DOI":"10.1021\/jacs.5c10757","article-title":"Understanding the Competition between\nAlcohol Formation and Dimerization during Electrochemical Reduction\nof Aromatic Carbonyl Compounds","volume":"147","author":"Eisenberg","year":"2025","journal-title":"J. Am. Chem.\nSoc."},{"issue":"41","key":"2026090312072409800_cit29","doi-asserted-by":"publisher","first-page":"37414","DOI":"10.1021\/jacs.5c11419","article-title":"Efficient,\nVersatile, and Durable Electrocatalytic Nitroaromatic-to-Arylamine\nReduction via Heteroatom-Site Hydrogen-Atom Transfer","volume":"147","author":"Ran","year":"2025","journal-title":"J. Am. Chem. Soc."},{"issue":"2","key":"2026090312072409800_cit30","doi-asserted-by":"publisher","first-page":"160","DOI":"10.1038\/s41565-022-01277-z","article-title":"Efficient electrocatalytic valorization\nof chlorinated organic water pollutant to ethylene","volume":"18","author":"Choi","year":"2023","journal-title":"Nat. Nanotechnol."},{"issue":"3","key":"2026090312072409800_cit31","doi-asserted-by":"publisher","first-page":"334","DOI":"10.1038\/s41557-024-01721-8","article-title":"Isotopic labelling\nof water reveals the hydrogen transfer route in electrochemical CO2\nreduction","volume":"17","author":"Zhang","year":"2025","journal-title":"Nat. Chem."},{"issue":"39","key":"2026090312072409800_cit32","doi-asserted-by":"publisher","first-page":"21464","DOI":"10.1002\/anie.202107510","article-title":"MnO2 Electrocatalysts\nCoordinating Alcohol Oxidation for Ultra-Durable Hydrogen and Chemical\nProductions in Acidic Solutions","volume":"60","author":"Li","year":"2021","journal-title":"Angew. Chem.,\nInt. Ed."},{"issue":"51","key":"2026090312072409800_cit33","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202213328","article-title":"Progress in Hydrogen Production Coupled with Electrochemical\nOxidation of Small Molecules","volume":"61","author":"Wang","year":"2022","journal-title":"Angew. Chem.,\nInt. Ed."},{"key":"2026090312072409800_cit34","doi-asserted-by":"publisher","first-page":"155851","DOI":"10.1016\/j.tetlet.2025.155851","article-title":"Step-wise\nflow synthesis of l-ascorbic acid from L-sorbose","volume":"174","author":"Modum","year":"2026","journal-title":"Tetrahedron Lett."},{"key":"2026090312072409800_cit35","doi-asserted-by":"publisher","first-page":"372","DOI":"10.1016\/S1872-2067(23)64446-8","article-title":"Enhanced dehydrogenation\nkinetics for ascorbic acid electrooxidation with ultra-low cell voltage\nand large current density","volume":"50","author":"Zhou","year":"2023","journal-title":"Chin. J. Catal."},{"issue":"1","key":"2026090312072409800_cit36","doi-asserted-by":"publisher","first-page":"4210","DOI":"10.1038\/s41467-023-39848-w","article-title":"Acidic\nenol electrooxidation-coupled hydrogen production with ampere-level\ncurrent density","volume":"14","author":"Chen","year":"2023","journal-title":"Nat. Commun."},{"issue":"19","key":"2026090312072409800_cit37","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202500678","article-title":"Exploiting Antisite Defects in FeWN2 Nanosheets for\nEnol Electro-oxidation Coupled with H2 Evolution at a Large Current\nDensity","volume":"64","author":"Chen","year":"2025","journal-title":"Angew. Chem., Int. Ed."}],"container-title":["Journal of the American\nChemical Society"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/pubs.acs.org\/doi\/pdf\/10.1021\/jacs.6c11800","content-type":"application\/pdf","content-version":"vor","intended-application":"unspecified"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/34\/37203\/67332207\/jacs.6c11800.pdf","content-type":"application\/pdf","content-version":"vor","intended-application":"syndication"},{"URL":"https:\/\/pubs.acs.org\/jacsat\/article-pdf\/148\/34\/37203\/67332207\/jacs.6c11800.pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,9,3]],"date-time":"2026-09-03T16:26:09Z","timestamp":1788452769000},"score":1,"resource":{"primary":{"URL":"https:\/\/pubs.acs.org\/jacsat\/article\/148\/34\/37203\/5322079\/Redirecting-Nitroarene-Electroreduction-toward"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,8,24]]},"references-count":37,"journal-issue":{"issue":"34","published-online":{"date-parts":[[2026,8,24]]},"published-print":{"date-parts":[[2026,9,2]]}},"URL":"https:\/\/doi.org\/10.1021\/jacs.6c11800","relation":{},"ISSN":["0002-7863","1520-5126"],"issn-type":[{"value":"0002-7863","type":"print"},{"value":"1520-5126","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,8,24]]}}}