{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T01:11:06Z","timestamp":1791508266649,"version":"4.3.4"},"reference-count":40,"publisher":"Wiley","issue":"16","license":[{"start":{"date-parts":[[2025,3,13]],"date-time":"2025-03-13T00:00:00Z","timestamp":1741824000000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100001381","name":"National Research Foundation Singapore","doi-asserted-by":"publisher","award":["NRF\u2010NRFF14\u20102022\u20100003"],"award-info":[{"award-number":["NRF\u2010NRFF14\u20102022\u20100003"]}],"id":[{"id":"10.13039\/501100001381","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001348","name":"Agency for Science, Technology and Research","doi-asserted-by":"publisher","award":["U2102d2002"],"award-info":[{"award-number":["U2102d2002"]}],"id":[{"id":"10.13039\/501100001348","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["advanced.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Advanced Materials"],"published-print":{"date-parts":[[2025,4]]},"abstract":"Abstract<\/jats:title>\n \n Tuning transition metal spin states potentially offers a powerful means to control electrocatalyst activity. However, implementing such a strategy in electrochemical CO\n 2<\/jats:sub>\n reduction (CO\n 2<\/jats:sub>\n R) is challenging since rational design rules have yet to be elucidated. Here we show how the addition of P dopants to a ferromagnetic element (Fe, Co, and Ni) single\u2010atom catalyst (SAC) can shift its spin state. For instance, with Fe SAC, P dopants enable a switch from low spin state (\n d<\/jats:italic>\n x2\u2010 y2<\/jats:sub>\n 0<\/jats:sup>\n ,\n d<\/jats:italic>\n z2<\/jats:sub>\n 0<\/jats:sup>\n ,\n d<\/jats:italic>\n xz<\/jats:sub>\n 2<\/jats:sup>\n ,\n d<\/jats:italic>\n yz<\/jats:sub>\n 1<\/jats:sup>\n ,\n d<\/jats:italic>\n xy<\/jats:sub>\n 2<\/jats:sup>\n ) in Fe\u2010N\n 4<\/jats:sub>\n to high spin state (\n d<\/jats:italic>\n x2\u2010y2<\/jats:sub>\n 0<\/jats:sup>\n ,\n d<\/jats:italic>\n xz<\/jats:sub>\n 1<\/jats:sup>\n ,\n d<\/jats:italic>\n yz<\/jats:sub>\n 1<\/jats:sup>\n ,\n d<\/jats:italic>\n z2<\/jats:sub>\n 1<\/jats:sup>\n ,\n d<\/jats:italic>\n xy<\/jats:sub>\n 2<\/jats:sup>\n ) in Fe\u2010N\n 3<\/jats:sub>\n \u2010P. This is studied using a suite of characterization efforts, including X\u2010ray absorption spectroscopy (XAS), electron spin resonance (ESR) spectroscopy, and superconducting quantum interference device (SQUID) measurements. When used for CO\n 2<\/jats:sub>\n R, the SAC with Fe\u2010N\n 3<\/jats:sub>\n \u2010P active sites yields >\u00a090% Faradaic efficiency to CO over a wide potential window of \u2248530\u00a0mV and a maximum CO partial current density of \u2248600\u00a0mA cm\n \u22122<\/jats:sup>\n . Density functional theory calculations reveal that high spin state Fe\n 3+<\/jats:sup>\n exhibits enhanced electron back donation via the\n d<\/jats:italic>\n xz<\/jats:sub>\n \/\n d<\/jats:italic>\n yz<\/jats:sub>\n \u2010\u03c0* bond, which enhances\n *<\/jats:sup>\n COOH adsorption and promotes CO formation. Taken together, the results show how the SAC spin state can be intentionally tuned to boost CO\n 2<\/jats:sub>\n R performance.\n <\/jats:p>","DOI":"10.1002\/adma.202417034","type":"journal-article","created":{"date-parts":[[2025,3,13]],"date-time":"2025-03-13T04:36:46Z","timestamp":1741840606000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":90,"title":["Tuning Transition Metal 3d Spin state on Single\u2010atom Catalysts for Selective Electrochemical CO\n 2<\/sub>\n Reduction"],"prefix":"10.1002","volume":"37","author":[{"given":"Yipeng","family":"Zang","sequence":"first","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering National University of Singapore Singapore 117585 Republic of Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yan","family":"Liu","sequence":"additional","affiliation":[{"name":"School of Chemical Sciences University of Auckland Auckland 1010 New Zealand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ruihu","family":"Lu","sequence":"additional","affiliation":[{"name":"School of Chemical Sciences University of Auckland Auckland 1010 New Zealand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qin","family":"Yang","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering National University of Singapore Singapore 117585 Republic of Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bingqing","family":"Wang","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering National University of Singapore Singapore 117585 Republic of Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mingsheng","family":"Zhang","sequence":"additional","affiliation":[{"name":"Institute of Materials Research and Engineering (IMRE) Agency for Science Technology and Research (A*STAR) 2 Fusionopolis Way, Innovis #08\u201003 Singapore 138634 Republic of Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yu","family":"Mao","sequence":"additional","affiliation":[{"name":"School of Chemical Sciences University of Auckland Auckland 1010 New Zealand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Ziyun","family":"Wang","sequence":"additional","affiliation":[{"name":"School of Chemical Sciences University of Auckland Auckland 1010 New Zealand"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-7261-2098","authenticated-orcid":false,"given":"Yanwei","family":"Lum","sequence":"additional","affiliation":[{"name":"Department of Chemical and Biomolecular Engineering National University of Singapore Singapore 117585 Republic of Singapore"},{"name":"Institute of Materials Research and Engineering (IMRE) Agency for Science Technology and Research (A*STAR) 2 Fusionopolis Way, Innovis #08\u201003 Singapore 138634 Republic of Singapore"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,3,13]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00071J"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1007\/s41918-022-00140-y"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-019-0306-7"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsenergylett.0c02665"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7EE03245E"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202016219"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201903068"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-024-46175-1"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3CS00913K"},{"key":"e_1_2_9_10_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-22865-y"},{"key":"e_1_2_9_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202317022"},{"key":"e_1_2_9_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201913080"},{"key":"e_1_2_9_13_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41565-023-01407-1"},{"key":"e_1_2_9_14_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-42307-1"},{"key":"e_1_2_9_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c11088"},{"key":"e_1_2_9_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsaem.1c00269"},{"key":"e_1_2_9_17_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0009-2614(03)01287-9"},{"key":"e_1_2_9_18_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.pmatsci.2023.101089"},{"key":"e_1_2_9_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.nanolett.1c04382"},{"key":"e_1_2_9_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c07197"},{"key":"e_1_2_9_21_1","volume":"57","author":"Li S.","year":"2022","journal-title":"J. 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