{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,27]],"date-time":"2026-10-27T03:25:32Z","timestamp":1793071532676,"version":"4.5.0"},"reference-count":54,"publisher":"National Academy of Sciences","issue":"3","license":[{"start":{"date-parts":[[2023,1,10]],"date-time":"2023-01-10T00:00:00Z","timestamp":1673308800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by-nc-nd\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["52000176"],"award-info":[{"award-number":["52000176"]}],"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":["91851204"],"award-info":[{"award-number":["91851204"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["www.pnas.org"],"crossmark-restriction":true},"short-container-title":["Proc. Natl. Acad. Sci. U.S.A."],"published-print":{"date-parts":[[2023,1,17]]},"abstract":"<jats:p>\n                    The electrolysis of nitrate reduction to ammonia (NRA) is promising for obtaining value-added chemicals and mitigating environmental concerns. Recently, catalysts with high-performance ammonia synthesis from nitrate has been achieved under alkaline or acidic conditions. However, NRA in neutral solution still suffers from the low yield rate and selectivity of ammonia due to the low binding affinity and nucleophilicity of NO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    . Here, we confirmed that the in-situ-generated Fe(II) ions existed as specifically adsorbed cations in the inner Helmholtz plane (IHP) with a low redox potential. Inspired by this, a strategy (Fe-IHP strategy) was proposed to enhance NRA activity by tuning the affinity of the electrode\u2013electrolyte interface. The specifically adsorbed Fe(II) ions [SA-Fe(II)] greatly alleviated the electrostatic repulsion around the interfaceresulting in a 10-fold lower in the adsorption-free energy of NO\n                    <jats:sub>3<\/jats:sub>\n                    <jats:sup>\u2212<\/jats:sup>\n                    when compared to the case without SA-Fe(II). Meanwhile, the modulated interface accelerated the kinetic mass transfer process by 25 folds compared to the control. Under neutral conditions, a Faraday efficiency of 99.6%, a selectivity of 99%, and an extremely high NH\n                    <jats:sub>3<\/jats:sub>\n                    yield rate of 485.8 mmol h\n                    <jats:sup>\u22121<\/jats:sup>\n                    g\n                    <jats:sup>\u22121<\/jats:sup>\n                    <jats:sub>FeOOH<\/jats:sub>\n                    were achieved. Theoretical calculations and in-situ Raman spectroscopy confirmed the electron-rich state of the SA-Fe(II) donated to\n                    <jats:italic>p<\/jats:italic>\n                    orbitals of N atom and favored the hydrogenation of *NO to *NOH for promoting the formation of high-selectivity ammonia. In sum, these findings complement the textbook on the specific adsorption of cations and provide insights into the design of low-cost NRA catalysts with efficient ammonia synthesis.\n                  <\/jats:p>","DOI":"10.1073\/pnas.2209979120","type":"journal-article","created":{"date-parts":[[2023,1,10]],"date-time":"2023-01-10T13:38:30Z","timestamp":1673357910000},"update-policy":"https:\/\/doi.org\/10.1073\/pnas.cm10313","source":"Crossref","is-referenced-by-count":110,"title":["Specifically adsorbed ferrous ions modulate interfacial affinity for high-rate ammonia electrosynthesis from nitrate in neutral media"],"prefix":"10.1073","volume":"120","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0697-7029","authenticated-orcid":false,"given":"Chunlei","family":"Liu","sequence":"first","affiliation":[{"name":"Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Gong","family":"Zhang","sequence":"additional","affiliation":[{"name":"Center for Water and Ecology, State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9559-2496","authenticated-orcid":false,"given":"Wei","family":"Zhang","sequence":"additional","affiliation":[{"name":"Center for Water and Ecology, State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8853-4204","authenticated-orcid":false,"given":"Zhenao","family":"Gu","sequence":"additional","affiliation":[{"name":"Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7227-8157","authenticated-orcid":false,"given":"Guibing","family":"Zhu","sequence":"additional","affiliation":[{"name":"Key Laboratory of Drinking Water Science and Technology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"341","published-online":{"date-parts":[[2023,1,10]]},"reference":[{"key":"e_1_3_4_1_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-019-0280-0"},{"key":"e_1_3_4_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1CS00116G"},{"key":"e_1_3_4_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201915992"},{"key":"e_1_3_4_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.watres.2020.115539"},{"key":"e_1_3_4_5_2","doi-asserted-by":"crossref","unstructured":"Z. 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