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Conventional HMTA production relies on toxic formaldehyde (HCHO) and energy\u2010intensive Haber\u2013Bosch\u2010derived ammonia (NH\n                    <jats:sub>3<\/jats:sub>\n                    ) as feedstocks. This study demonstrates a sustainable electrocatalytic approach for the direct synthesis of HMTA via paired electrolysis, using nitrate (NO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    ) and polyethylene terephthalate (PET) waste as nitrogen and carbon sources, respectively. With iron\u2010doped nickel phosphide (Fe\u2013Ni\n                    <jats:sub>2<\/jats:sub>\n                    P) as a bifunctional catalyst, the system achieves concurrent cathodic NO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    reduction to NH\n                    <jats:sub>3<\/jats:sub>\n                    with a Faradaic efficiency of \u223c 96.0%, and anodic oxidation of PET\u2010derived ethylene glycol to electrophilic *HCHO intermediates. These resulting intermediates subsequently condense with nucleophilic NH\n                    <jats:sub>3<\/jats:sub>\n                    to form HMTA with \u223c75.2% carbon selectivity. Mechanistic studies reveal that Fe doping induces charge redistribution and upshifts the d\u2010band center, thereby facilitating the adsorption and activation of reactants and lowering the energy barrier for *HCHO intermediate formation and desorption\u2014a critical step enabling subsequent C\u2500N coupling. This work establishes a mild and sustainable electrocatalytic route for HMTA synthesis from environmental waste, underscoring the potential of paired electrolysis in valorizing waste into valuable organonitrogen chemicals.\n                  <\/jats:p>","DOI":"10.1002\/anie.9224223","type":"journal-article","created":{"date-parts":[[2026,9,29]],"date-time":"2026-09-29T05:09:06Z","timestamp":1790658546000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Sustainable Electrosynthesis of Hexamethylenetetramine via Paired Electrolysis of Nitrate and PET Waste"],"prefix":"10.1002","author":[{"given":"Jingtao","family":"Zhou","sequence":"first","affiliation":[{"name":"Key Laboratory of Photochemical Conversion and Optoelectronic Materials &amp; CAS\u2010HKU Joint Laboratory On New Materials Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P. R. China"},{"name":"University of Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiu","family":"Chen","sequence":"additional","affiliation":[{"name":"HKU\u2010CAS Joint Laboratory on New Materials &amp; Department of Chemistry The University of Hong Kong  Hong Kong SAR P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5559-8749","authenticated-orcid":false,"given":"Rui","family":"Shi","sequence":"additional","affiliation":[{"name":"Key Laboratory of Photochemical Conversion and Optoelectronic Materials &amp; CAS\u2010HKU Joint Laboratory On New Materials Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P. R. China"},{"name":"University of Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5404-3215","authenticated-orcid":false,"given":"Zhengxiao","family":"Guo","sequence":"additional","affiliation":[{"name":"HKU\u2010CAS Joint Laboratory on New Materials &amp; Department of Chemistry The University of Hong Kong  Hong Kong SAR P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9313-1290","authenticated-orcid":false,"given":"Edmund C. M.","family":"Tse","sequence":"additional","affiliation":[{"name":"HKU\u2010CAS Joint Laboratory on New Materials &amp; Department of Chemistry The University of Hong Kong  Hong Kong SAR P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0032-2600","authenticated-orcid":false,"given":"Fulai","family":"Liu","sequence":"additional","affiliation":[{"name":"Key Laboratory of Photochemical Conversion and Optoelectronic Materials &amp; CAS\u2010HKU Joint Laboratory On New Materials Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P. R. China"},{"name":"University of Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6689-8923","authenticated-orcid":false,"given":"Yong","family":"Chen","sequence":"additional","affiliation":[{"name":"Key Laboratory of Photochemical Conversion and Optoelectronic Materials &amp; CAS\u2010HKU Joint Laboratory On New Materials Technical Institute of Physics and Chemistry Chinese Academy of Sciences Beijing P. R. China"},{"name":"University of Chinese Academy of Sciences  Beijing P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,9,28]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"crossref","first-page":"647","DOI":"10.1126\/science.1226458","article-title":"Photoinduced Ullmann C\u2013N Coupling: Demonstrating the Viability of a Radical Pathway","volume":"338","author":"Creutz S. E.","year":"2012","journal-title":"Science"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CS00381C"},{"key":"e_1_2_8_4_1","doi-asserted-by":"crossref","first-page":"178","DOI":"10.1126\/science.149.3680.178","article-title":"Hexamethylenetetramine Hexahydrate: A New Type of Clathrate Hydrate","volume":"149","author":"Jeffrey G. A.","year":"1965","journal-title":"Science"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c06840"},{"key":"e_1_2_8_6_1","unstructured":"Markets R. a. 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