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Here we show iron\u2013nitrogen-doped carbon as an efficient and durable electrocatalyst for selective nitric oxide reduction into hydroxylamine. Using in operando spectroscopic techniques, the\u00a0catalytic site is identified as isolated ferrous moieties, at which the rate for hydroxylamine production increases in a super-Nernstian way upon pH decrease. Computational multiscale modelling attributes the origin of unconventional pH dependence to the redox active (non-innocent) property of NO. This makes the rate-limiting NO adsorbate state more sensitive to surface charge which varies with the pH-dependent overpotential. Guided by these fundamental insights, we achieve a Faradaic efficiency of 71% and an unprecedented production rate of 215\u2009\u03bcmol\u2009cm<jats:sup>\u22122<\/jats:sup> h<jats:sup>\u22121<\/jats:sup> at a short-circuit mode in a flow-type fuel cell without significant catalytic deactivation over 50 h operation.<\/jats:p>","DOI":"10.1038\/s41467-021-22147-7","type":"journal-article","created":{"date-parts":[[2021,3,25]],"date-time":"2021-03-25T11:06:58Z","timestamp":1616670418000},"update-policy":"https:\/\/doi.org\/10.1007\/springer_crossmark_policy","source":"Crossref","is-referenced-by-count":234,"title":["Selective electrochemical reduction of nitric oxide to hydroxylamine by atomically dispersed iron catalyst"],"prefix":"10.1038","volume":"12","author":[{"given":"Dong Hyun","family":"Kim","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7804-1406","authenticated-orcid":false,"given":"Stefan","family":"Ringe","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-0734-8475","authenticated-orcid":false,"given":"Haesol","family":"Kim","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Sejun","family":"Kim","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5574-2090","authenticated-orcid":false,"given":"Bupmo","family":"Kim","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6714-1647","authenticated-orcid":false,"given":"Geunsu","family":"Bae","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0310-6666","authenticated-orcid":false,"given":"Hyung-Suk","family":"Oh","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9836-3261","authenticated-orcid":false,"given":"Fr\u00e9d\u00e9ric","family":"Jaouen","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wooyul","family":"Kim","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8261-9381","authenticated-orcid":false,"given":"Hyungjun","family":"Kim","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2231-6116","authenticated-orcid":false,"given":"Chang Hyuck","family":"Choi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"297","published-online":{"date-parts":[[2021,3,25]]},"reference":[{"key":"22147_CR1","unstructured":"Hermann Bothe, Stuart Ferguson & Newton, W. 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