{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,10]],"date-time":"2026-10-10T15:54:12Z","timestamp":1791647652774,"version":"4.3.4"},"reference-count":55,"publisher":"Wiley","issue":"42","license":[{"start":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T00:00:00Z","timestamp":1785369600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T00:00:00Z","timestamp":1785369600000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["22475194"],"award-info":[{"award-number":["22475194"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100004731","name":"Natural Science Foundation of Zhejiang Province","doi-asserted-by":"publisher","award":["ZCLMS25B0402"],"award-info":[{"award-number":["ZCLMS25B0402"]}],"id":[{"id":"10.13039\/501100004731","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Angew Chem Int Ed"],"published-print":{"date-parts":[[2026,10,12]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    The selective photocatalytic reduction of carbon dioxide (CO\n                    <jats:sub>2<\/jats:sub>\n                    ) to methane (CH\n                    <jats:sub>4<\/jats:sub>\n                    ) remains a formidable challenge due to the demanding eight\u2010electron\/proton\u2010coupled reduction process. Here, we report a positional engineering strategy for tailoring the spatial distribution of single\u2010atom active sites within 1D porphyrinic covalent organic frameworks (CPOF\u201013\u2010M\n                    <jats:sub>1<\/jats:sub>\n                    \u2010M\n                    <jats:sub>2<\/jats:sub>\n                    , where M\n                    <jats:sub>1<\/jats:sub>\n                    = H\/Cu and M\n                    <jats:sub>2<\/jats:sub>\n                    = H\/Cu), enabling tunable catalytic selectivity. By selectively positioning Cu atoms at either edge\u2010 or central\u2010positioned porphyrin sites of the framework, or both, we elucidate how active\u2010site location governs charge\u2010carrier dynamics and reaction pathways. Central Cu sites favor CO formation via *CO desorption, whereas edge\u2010positioned Cu sites promote sequential hydrogenation of *CO toward CH\n                    <jats:sub>4<\/jats:sub>\n                    through multielectron transfer, achieving a CH\n                    <jats:sub>4<\/jats:sub>\n                    production rate of 31.6\u00a0\u00b5mol g\n                    <jats:sup>\u22121<\/jats:sup>\n                    h\n                    <jats:sup>\u22121<\/jats:sup>\n                    with 92.9% electron selectivity. Dual\u2010site configurations exhibited intermediate selectivity, reflecting the competing catalytic preferences of the two differently positioned active sites. These findings establish active\u2010site positional engineering as a versatile design principle for tailoring photocatalytic pathways in COF\u2010based catalysts, opening new avenues for the rational design of reticular materials for solar fuel generation.\n                  <\/jats:p>","DOI":"10.1002\/anie.2029789","type":"journal-article","created":{"date-parts":[[2026,7,30]],"date-time":"2026-07-30T16:01:31Z","timestamp":1785427291000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Positional Effects of Single\u2010Atom Active Sites in 1D Porphyrinic COFs on Photocatalytic CO\n                    <sub>2<\/sub>\n                    Reduction"],"prefix":"10.1002","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-0281-0088","authenticated-orcid":false,"given":"Yu","family":"Zhao","sequence":"first","affiliation":[{"name":"Zhejiang Engineering Laboratory For Green Syntheses and Applications of Fluorine\u2010Containing Specialty Chemicals Institute of Advanced Fluorine\u2010Containing Materials Zhejiang Normal University  Jinhua P. R. China"},{"name":"State Key Laboratory of Bioinspired Interfacial Materials Science Suzhou Institute for Advanced Research University of Science and Technology of China  Suzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiuli","family":"Ye","sequence":"additional","affiliation":[{"name":"Zhejiang Engineering Laboratory For Green Syntheses and Applications of Fluorine\u2010Containing Specialty Chemicals Institute of Advanced Fluorine\u2010Containing Materials Zhejiang Normal University  Jinhua P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Shangqing","family":"Liu","sequence":"additional","affiliation":[{"name":"Zhejiang Engineering Laboratory For Green Syntheses and Applications of Fluorine\u2010Containing Specialty Chemicals Institute of Advanced Fluorine\u2010Containing Materials Zhejiang Normal University  Jinhua P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Li","family":"Fang","sequence":"additional","affiliation":[{"name":"Zhejiang Engineering Laboratory For Green Syntheses and Applications of Fluorine\u2010Containing Specialty Chemicals Institute of Advanced Fluorine\u2010Containing Materials Zhejiang Normal University  Jinhua P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guolong","family":"Xing","sequence":"additional","affiliation":[{"name":"Zhejiang Engineering Laboratory For Green Syntheses and Applications of Fluorine\u2010Containing Specialty Chemicals Institute of Advanced Fluorine\u2010Containing Materials Zhejiang Normal University  Jinhua P. R. China"},{"name":"State Key Laboratory of Bioinspired Interfacial Materials Science Suzhou Institute for Advanced Research University of Science and Technology of China  Suzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bo","family":"Song","sequence":"additional","affiliation":[{"name":"School of Optical\u2010Electrical Computer Engineering University of Shanghai for Science and Technology  Shanghai P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0847-330X","authenticated-orcid":false,"given":"Teng","family":"Ben","sequence":"additional","affiliation":[{"name":"Zhejiang Engineering Laboratory For Green Syntheses and Applications of Fluorine\u2010Containing Specialty Chemicals Institute of Advanced Fluorine\u2010Containing Materials Zhejiang Normal University  Jinhua P. R. China"},{"name":"State Key Laboratory of Bioinspired Interfacial Materials Science Suzhou Institute for Advanced Research University of Science and Technology of China  Suzhou P. R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2026,7,30]]},"reference":[{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202205585"},{"key":"e_1_2_8_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201207199"},{"key":"e_1_2_8_4_1","doi-asserted-by":"publisher","DOI":"10.1038\/s43586\u2010023\u201000243\u2010w"},{"key":"e_1_2_8_5_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.chemrev.8b00400"},{"key":"e_1_2_8_6_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c00101"},{"key":"e_1_2_8_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201405041"},{"key":"e_1_2_8_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202304585"},{"key":"e_1_2_8_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202311999"},{"key":"e_1_2_8_10_1","doi-asserted-by":"publisher","DOI":"10.20517\/cs.2025.24"},{"key":"e_1_2_8_11_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010023\u201041943\u2010x"},{"key":"e_1_2_8_12_1","doi-asserted-by":"publisher","DOI":"10.1002\/cssc.201801294"},{"key":"e_1_2_8_13_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.8b04250"},{"key":"e_1_2_8_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202405825"},{"key":"e_1_2_8_15_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41560\u2010019\u20100431\u20101"},{"key":"e_1_2_8_16_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c12006"},{"key":"e_1_2_8_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202209446"},{"key":"e_1_2_8_18_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.aal1585"},{"key":"e_1_2_8_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.accounts.4c00517"},{"key":"e_1_2_8_20_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202300172"},{"key":"e_1_2_8_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/C9SC03800K"},{"key":"e_1_2_8_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b09705"},{"key":"e_1_2_8_23_1","doi-asserted-by":"publisher","DOI":"10.20517\/cs.2024.34"},{"key":"e_1_2_8_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.5c11188"},{"key":"e_1_2_8_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.2c12542"},{"key":"e_1_2_8_26_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cej.2023.148301"},{"key":"e_1_2_8_27_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202307991"},{"key":"e_1_2_8_28_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201902543"},{"key":"e_1_2_8_29_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CS00183G"},{"key":"e_1_2_8_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202507002"},{"key":"e_1_2_8_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/agt2.582"},{"key":"e_1_2_8_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202504348"},{"key":"e_1_2_8_33_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202309820"},{"key":"e_1_2_8_34_1","doi-asserted-by":"publisher","DOI":"10.1002\/smll.202506081"},{"key":"e_1_2_8_35_1","doi-asserted-by":"publisher","DOI":"10.1002\/marc.202400780"},{"key":"e_1_2_8_36_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcatb.2023.122393"},{"key":"e_1_2_8_37_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c07640"},{"key":"e_1_2_8_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202415202"},{"key":"e_1_2_8_39_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202504772"},{"key":"e_1_2_8_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202409925"},{"key":"e_1_2_8_41_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202513157"},{"key":"e_1_2_8_42_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202414287"},{"key":"e_1_2_8_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/adfm.201905153"},{"key":"e_1_2_8_44_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202203062"},{"key":"e_1_2_8_45_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467\u2010024\u201052291\u20109"},{"key":"e_1_2_8_46_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202505546"},{"key":"e_1_2_8_47_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.3c00053"},{"key":"e_1_2_8_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c07047"},{"key":"e_1_2_8_49_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c06920"},{"key":"e_1_2_8_50_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c07916"},{"key":"e_1_2_8_51_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.1c08033"},{"key":"e_1_2_8_52_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jechem.2024.01.002"},{"key":"e_1_2_8_53_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsami.0c19233"},{"key":"e_1_2_8_54_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6EE00383D"},{"key":"e_1_2_8_55_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jcis.2018.12.022"},{"key":"e_1_2_8_56_1","doi-asserted-by":"publisher","DOI":"10.1021\/acssuschemeng.9b06170"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.2029789","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1002\/anie.2029789","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.2029789","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2026,10,10]],"date-time":"2026-10-10T15:47:24Z","timestamp":1791647244000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.2029789"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2026,7,30]]},"references-count":55,"journal-issue":{"issue":"42","published-print":{"date-parts":[[2026,10,12]]}},"alternative-id":["10.1002\/anie.2029789"],"URL":"https:\/\/doi.org\/10.1002\/anie.2029789","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2026,7,30]]},"assertion":[{"value":"2026-04-17","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-07-16","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2026-07-30","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e2029789"}}