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However, its complex proton\u2010coupled electron transfer processes involve multiple competing pathways, in which the fate of key intermediates governs reaction activity and product selectivity. In this review, we provide an intermediate\u2010centered perspective on eNO\n                    <jats:sub>3<\/jats:sub>\n                    RR, covering the reaction pathways from NO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    activation to the selective synthesis of NH\n                    <jats:sub>3<\/jats:sub>\n                    , N\n                    <jats:sub>2<\/jats:sub>\n                    , and NH\n                    <jats:sub>2<\/jats:sub>\n                    OH. We then summarize current techniques for probing N\u2010containing intermediates and active hydrogen (*H). On this basis, we discuss how catalyst design and microenvironment engineering regulate key processes in eNO\n                    <jats:sub>3<\/jats:sub>\n                    RR, including intermediate adsorption, retention and desorption, N\u2500O bond cleavage, hydrogenation, and N\u2500N coupling. We also examine the emerging role of data\u2010driven approaches in optimizing eNO\n                    <jats:sub>3<\/jats:sub>\n                    RR systems. Drawing these discussions together, we distill principles for selective product synthesis. Finally, we discuss remaining challenges in achieving a deeper mechanistic understanding, regulating the interfacial microenvironment, and applying eNO\n                    <jats:sub>3<\/jats:sub>\n                    RR to real wastewater.\n                  <\/jats:p>","DOI":"10.1002\/anie.3154221","type":"journal-article","created":{"date-parts":[[2026,8,26]],"date-time":"2026-08-26T04:32:54Z","timestamp":1787718774000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Intermediate\u2010Mediated Selectivity in Electrocatalytic Nitrate Reduction for Nitrogen Product Synthesis"],"prefix":"10.1002","volume":"65","author":[{"given":"Yingying","family":"Zhou","sequence":"first","affiliation":[{"name":"Department of Mechanical Engineering The Hong Kong Polytechnic University  Hung Hom Kowloon Hong Kong SAR"},{"name":"Research Institute for Smart Energy The Hong Kong Polytechnic University  Hung Hom Kowloon Hong Kong SAR"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jie","family":"Wu","sequence":"additional","affiliation":[{"name":"Department of Mechanical Engineering The Hong Kong Polytechnic University  Hung Hom Kowloon Hong Kong SAR"},{"name":"Research Centre for Carbon\u2010Strategic Catalysis The Hong Kong Polytechnic University  Hung Hom Kowloon Hong Kong SAR"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Weisong","family":"Li","sequence":"additional","affiliation":[{"name":"Department of Mechanical Engineering The Hong Kong Polytechnic University  Hung Hom Kowloon Hong Kong SAR"},{"name":"PolyU\u2010Daya Bay Technology and Innovation Research Institute  Huizhou Guangdong P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuchen","family":"Yang","sequence":"additional","affiliation":[{"name":"Department of Mechanical Engineering The Hong Kong Polytechnic University  Hung Hom Kowloon Hong Kong SAR"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3093-7964","authenticated-orcid":false,"given":"Qing","family":"Xia","sequence":"additional","affiliation":[{"name":"Department of Mechanical Engineering The Hong Kong Polytechnic University  Hung Hom Kowloon Hong Kong SAR"},{"name":"Research Centre for Carbon\u2010Strategic Catalysis The Hong Kong Polytechnic University  Hung Hom Kowloon Hong Kong SAR"},{"name":"PolyU\u2010Daya Bay Technology and Innovation Research Institute  Huizhou Guangdong P. R. 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