{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T15:23:23Z","timestamp":1791991403933,"version":"4.4.0"},"reference-count":106,"publisher":"Wiley","issue":"43","license":[{"start":{"date-parts":[[2025,7,14]],"date-time":"2025-07-14T00:00:00Z","timestamp":1752451200000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2025,8]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Transition metal\u2010anchored nitrogen\u2010doped graphene single\u2010atom catalysts (SACs) represent an emerging class of catalysts that combine the advantages of both homogeneous and heterogeneous catalysis. To prevent demetallation and ensure catalyst stability, sufficiently strong bonds between the transition metal and the support are essential. We have quantum chemically analyzed the trend in bonding interaction between period 4 transition metals (TM\u00a0=\u00a0Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn) and the four\u2010nitrogen\u2010doped graphene support. We find that the metal\u2013support interactions strengthen from Ti to Ni but weaken from Ni to Zn. Activation strain and Kohn\u2010Sham molecular orbital (KS\u2010MO) analyses reveal that this trend stems from changes in the interaction between the metal's 3<jats:italic>d<\/jats:italic><jats:sub>xy<\/jats:sub> atomic orbital and the nitrogen lone pair orbitals of the support. As we move along period 4, the bonding mechanism changes from an increasingly more stabilizing HOMO\u2013LUMO interaction (TM\u00a0=\u00a0Ti\u2010Ni), due to the higher effective nuclear charge of the metal, to a less favorable HOMO\u2013SOMO (TM\u00a0=\u00a0Cu) and unfavorable HOMO\u2013HOMO (TM\u00a0=\u00a0Zn) interaction, as a result of the filling of the metal's 3<jats:italic>d<\/jats:italic><jats:sub>xy<\/jats:sub> atomic orbital. This results in the observed strengthening, followed by weakening, of the metal\u2013support interaction. These insights could guide the rational design of future single\u2010atom catalysts.<\/jats:p>","DOI":"10.1002\/chem.202501654","type":"journal-article","created":{"date-parts":[[2025,7,3]],"date-time":"2025-07-03T04:03:16Z","timestamp":1751515396000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":9,"title":["The Nature and Stability of Transition Metal\u2010Anchored Nitrogen\u2010Doped Graphene Single\u2010Atom Catalysts"],"prefix":"10.1002","volume":"31","author":[{"ORCID":"https:\/\/orcid.org\/0009-0006-8721-5128","authenticated-orcid":false,"given":"Angelina N.","family":"van Dam","sequence":"first","affiliation":[{"name":"Department of Theoretical Chemistry Amsterdam Institute of Molecular and Life Sciences (AIMMS) Vrije Universiteit Amsterdam  De Boelelaan 1108 Amsterdam 1081 HZ The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2100-6837","authenticated-orcid":false,"given":"Pascal","family":"Vermeeren","sequence":"additional","affiliation":[{"name":"Department of Theoretical Chemistry Amsterdam Institute of Molecular and Life Sciences (AIMMS) Vrije Universiteit Amsterdam  De Boelelaan 1108 Amsterdam 1081 HZ The Netherlands"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,7,14]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1021\/ar300361m"},{"key":"e_1_2_8_1_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-018-0090-9"},{"key":"e_1_2_8_1_3","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c00576"},{"key":"e_1_2_8_1_4","doi-asserted-by":"publisher","DOI":"10.1016\/j.cclet.2022.107959"},{"key":"e_1_2_8_1_5","doi-asserted-by":"publisher","DOI":"10.1007\/s41918-019-00050-6"},{"key":"e_1_2_8_1_6","doi-asserted-by":"publisher","DOI":"10.1002\/adma.201801995"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9TA11715F"},{"key":"e_1_2_8_2_2","doi-asserted-by":"publisher","DOI":"10.1039\/C6CS00136J"},{"key":"e_1_2_8_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/ange.201906079"},{"key":"e_1_2_8_2_4","doi-asserted-by":"publisher","DOI":"10.1007\/s12598-021-01904-z"},{"key":"e_1_2_8_2_5","doi-asserted-by":"publisher","DOI":"10.1007\/s41918-022-00142-w"},{"key":"e_1_2_8_2_6","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.201800465"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202200611"},{"key":"e_1_2_8_3_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.9b01944"},{"key":"e_1_2_8_3_3","doi-asserted-by":"publisher","DOI":"10.1016\/j.physe.2021.114975"},{"key":"e_1_2_8_3_4","doi-asserted-by":"publisher","DOI":"10.1002\/advs.202001069"},{"key":"e_1_2_8_3_5","doi-asserted-by":"publisher","DOI":"10.1021\/accountsmr.1c00016"},{"key":"e_1_2_8_3_6","doi-asserted-by":"publisher","DOI":"10.1039\/D4CP04212C"},{"key":"e_1_2_8_3_7","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.2c05992"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.4c03232"},{"key":"e_1_2_8_4_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr900295b"},{"key":"e_1_2_8_4_3","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.9b00238"},{"key":"e_1_2_8_4_4","first-page":"120","volume":"2","author":"Yang W.","year":"2020","journal-title":"NMS"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202009400"},{"key":"e_1_2_8_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201710599"},{"key":"e_1_2_8_5_3","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201701345"},{"key":"e_1_2_8_5_4","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.201803689"},{"key":"e_1_2_8_5_5","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202200275"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202003917"},{"key":"e_1_2_8_6_2","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201905241"},{"key":"e_1_2_8_6_3","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.8b00138"},{"key":"e_1_2_8_6_4","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c06122"},{"key":"e_1_2_8_6_5","doi-asserted-by":"publisher","DOI":"10.1039\/C6EE03446B"},{"key":"e_1_2_8_6_6","doi-asserted-by":"publisher","DOI":"10.1039\/c1cp21228a"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41565-018-0167-2"},{"key":"e_1_2_8_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.5b01223"},{"key":"e_1_2_8_7_3","doi-asserted-by":"publisher","DOI":"10.1039\/D5CC00796H"},{"key":"e_1_2_8_7_4","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.0c05100"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202405650"},{"key":"e_1_2_8_8_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202404677"},{"key":"e_1_2_8_8_3","volume":"16","author":"Yu T.","year":"2024","journal-title":"CS Appl. Mater. Interfaces"},{"key":"e_1_2_8_8_4","doi-asserted-by":"publisher","DOI":"10.1002\/cctc.202100831"},{"key":"e_1_2_8_8_5","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.1c05610"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202219227"},{"key":"e_1_2_8_9_2","doi-asserted-by":"publisher","DOI":"10.1039\/D0CS00795A"},{"key":"e_1_2_8_9_3","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2022.214493"},{"key":"e_1_2_8_9_4","doi-asserted-by":"publisher","DOI":"10.1007\/s41918-022-00169-z"},{"key":"e_1_2_8_9_5","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202418942"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-020-14984-9"},{"key":"e_1_2_8_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.0c00818"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c04801"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41524-020-00411-6"},{"key":"e_1_2_8_12_2","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-018-0094-5"},{"key":"e_1_2_8_13_1","author":"Perilli D.","year":"2025","journal-title":"Angew. Chem. Int. Ed."},{"key":"e_1_2_8_13_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.mtchem.2023.101728"},{"key":"e_1_2_8_13_3","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.2c02307"},{"key":"e_1_2_8_13_4","doi-asserted-by":"publisher","DOI":"10.1016\/j.carbon.2020.12.045"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201701486"},{"key":"e_1_2_8_14_2","doi-asserted-by":"publisher","DOI":"10.1039\/D1CC02042K"},{"key":"e_1_2_8_14_3","doi-asserted-by":"publisher","DOI":"10.1038\/s41596-019-0265-0"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct500727c"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1002\/9781118558409"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1515\/9783110660074-008"},{"key":"e_1_2_8_17_2","first-page":"1","volume-title":"Reviews in Computational Chemistry","author":"Bickelhaupt F. M.","year":"2000"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.3c07681"},{"key":"e_1_2_8_18_2","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpcc.0c04432"},{"key":"e_1_2_8_18_3","doi-asserted-by":"publisher","DOI":"10.3389\/fchem.2019.00219"},{"key":"e_1_2_8_18_4","first-page":"10","author":"Jia H.","year":"2022","journal-title":"J. Mater. Chem. A"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0245218"},{"key":"e_1_2_8_19_2","doi-asserted-by":"publisher","DOI":"10.1039\/D4CP04042B"},{"key":"e_1_2_8_19_3","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202403211"},{"key":"e_1_2_8_19_4","doi-asserted-by":"publisher","DOI":"10.1002\/ntls.20220039"},{"key":"e_1_2_8_19_5","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202004653"},{"key":"e_1_2_8_19_6","doi-asserted-by":"publisher","DOI":"10.1002\/chem.202200755"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.44.7888"},{"key":"e_1_2_8_20_2","volume-title":"104, SCM, Theoretical Chemistry","author":"BAND","year":"2023"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevA.38.3098"},{"key":"e_1_2_8_21_2","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.33.8822"},{"key":"e_1_2_8_21_3","doi-asserted-by":"publisher","DOI":"10.1063\/1.464304"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.3382344"},{"key":"e_1_2_8_22_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.21759"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1949201"},{"key":"e_1_2_8_24_1","first-page":"1142","volume":"24","author":"Lenthe E.","year":"2003","journal-title":"J. Chem. Phys."},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.466059"},{"key":"e_1_2_8_25_2","doi-asserted-by":"publisher","DOI":"10.1063\/1.467943"},{"key":"e_1_2_8_25_3","doi-asserted-by":"publisher","DOI":"10.1063\/1.478813"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/ct500172n"},{"key":"e_1_2_8_26_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.23323"},{"key":"e_1_2_8_26_3","doi-asserted-by":"publisher","DOI":"10.1088\/0022-3719\/21\/23\/012"},{"key":"e_1_2_8_26_4","doi-asserted-by":"publisher","DOI":"10.1088\/0953-8984\/3\/35\/005"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1103\/PhysRevB.86.045112"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.1056"},{"key":"e_1_2_8_28_2","doi-asserted-by":"publisher","DOI":"10.1007\/s002140050021"},{"key":"e_1_2_8_28_3","doi-asserted-by":"publisher","DOI":"10.1063\/5.0258496"},{"key":"e_1_2_8_28_4","volume-title":"104, SCM Theoretical Chemistry","author":"ADF","year":"2023"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja027925u"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1080\/0026897042000275017"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.25871"},{"key":"e_1_2_8_31_2","unstructured":"b)X.Sun T.Soini L. P.Wolters W.\u2010J.vanZeist C.Fonseca Guerra T. A.Hamlin F. M.Bickelhaupt PyFrag 2019 Vrije Universiteit Amsterdam The Netherlands."},{"key":"e_1_2_8_32_1","unstructured":"CYLview2.0; C. Y. Legault Universit\u00e9 de Sherbrooke 2020(http:\/\/www.cylview.org)."},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1021\/ic50196a034"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1139\/V09-037"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.10351"},{"key":"e_1_2_8_35_2","doi-asserted-by":"publisher","DOI":"10.1002\/jcc.27184"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp9820830"},{"key":"e_1_2_8_37_1","volume-title":"Cartesian Coordinates for \u201cThe Nature and Stability of Transition Metal\u2010Anchored Nitrogen\u2010Doped Graphene SACs\u201d","author":"Dam A. N."}],"container-title":["Chemistry \u2013 A European Journal"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/chem.202501654","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,12]],"date-time":"2025-10-12T14:14:15Z","timestamp":1760278455000},"score":1,"resource":{"primary":{"URL":"https:\/\/chemistry-europe.onlinelibrary.wiley.com\/doi\/10.1002\/chem.202501654"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,7,14]]},"references-count":106,"journal-issue":{"issue":"43","published-print":{"date-parts":[[2025,8]]}},"alternative-id":["10.1002\/chem.202501654"],"URL":"https:\/\/doi.org\/10.1002\/chem.202501654","archive":["Portico"],"relation":{},"ISSN":["0947-6539","1521-3765"],"issn-type":[{"value":"0947-6539","type":"print"},{"value":"1521-3765","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,7,14]]},"assertion":[{"value":"2025-05-08","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-07-03","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-07-14","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202501654"}}