{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,9]],"date-time":"2026-10-09T10:01:18Z","timestamp":1791540078688,"version":"4.3.4"},"reference-count":40,"publisher":"Wiley","issue":"35","license":[{"start":{"date-parts":[[2025,7,7]],"date-time":"2025-07-07T00:00:00Z","timestamp":1751846400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100012166","name":"National Key Research and Development Program of China","doi-asserted-by":"publisher","award":["2022YFA1503104"],"award-info":[{"award-number":["2022YFA1503104"]}],"id":[{"id":"10.13039\/501100012166","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100007129","name":"Natural Science Foundation of Shandong Province","doi-asserted-by":"publisher","award":["2022HWYQ\u2010009"],"award-info":[{"award-number":["2022HWYQ\u2010009"]}],"id":[{"id":"10.13039\/501100007129","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":[[2025,8,25]]},"abstract":"Abstract<\/jats:title>\n \n Traditional urea synthesis via the Bosch\u2013Meiser process suffers from high energy consumption and greenhouse gas emissions. Electrocatalytic urea production from carbon dioxide (CO\n 2<\/jats:sub>\n ) and nitrate (NO\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n ) under ambient conditions offers a sustainable alternative, yet challenges persist due to variable NO\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n concentrations and competing side reactions. Herein, we propose porphyrin metal\u2010organic framework (PMOF) and Cu\u2010porphyrin MOF (Cu\u2010PMOF) catalysts for NO\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n concentration\u2010adaptive urea synthesis. Density functional theory (DFT) calculations reveal that PMOF weakly adsorbs *NO\n 2<\/jats:sub>\n via hydrogen bonding, favoring its coupling with *CO\n 2<\/jats:sub>\n , while Cu\u2010PMOF strongly binds *NO\n 2<\/jats:sub>\n at Cu sites, facilitating spontaneous *NO\/*CO coupling to form *OCNO intermediates under dilute NO\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n conditions. Experimentally, PMOF achieves a urea yield of 28.6\u00a0\u00b5mol h\n \u22121<\/jats:sup>\n \u00a0mg\n cat<\/jats:sub>\n \u22121<\/jats:sup>\n and a Faradaic efficiency (FE) of 23.1% in 0.1\u00a0M NO\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n , whereas Cu\u2010PMOF outperforms in 0.05\u00a0M NO\n 3<\/jats:sub>\n \u2212<\/jats:sup>\n with a yield of 25.5\u00a0\u00b5mol h\n \u22121<\/jats:sup>\n mg\n cat<\/jats:sub>\n \u22121<\/jats:sup>\n and FE of 52.7%. In situ spectroscopy and mechanistic study confirm distinct pathways: PMOF relies on stepwise coupling of *HNO\n 2<\/jats:sub>\n with *CO\n 2<\/jats:sub>\n , while Cu\u2010PMOF enables consecutive *NO\u2010*CO coupling. This work highlights adaptive electrocatalyst design for efficient C\u2010N coupling, advancing sustainable urea synthesis.\n <\/jats:p>","DOI":"10.1002\/anie.202513441","type":"journal-article","created":{"date-parts":[[2025,7,1]],"date-time":"2025-07-01T22:05:06Z","timestamp":1751407506000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":33,"title":["Concentration\u2010Adaptive Electrocatalytic Urea Synthesis From CO\n 2<\/sub>\n and Nitrate via Porphyrin and Metalloporphyrin MOFs"],"prefix":"10.1002","volume":"64","author":[{"given":"Yi","family":"Tan","sequence":"first","affiliation":[{"name":"Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering Shandong University Qingdao 266237 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaokang","family":"Chen","sequence":"additional","affiliation":[{"name":"Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering Shandong University Qingdao 266237 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jian","family":"Yuan","sequence":"additional","affiliation":[{"name":"Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering Shandong University Qingdao 266237 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Guan","family":"Sheng","sequence":"additional","affiliation":[{"name":"Department of Applied Physics The Hong Kong Polytechnic University Hong Kong China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Wei\u2010Qiao","family":"Deng","sequence":"additional","affiliation":[{"name":"Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering Shandong University Qingdao 266237 China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9464-2033","authenticated-orcid":false,"given":"Hao","family":"Wu","sequence":"additional","affiliation":[{"name":"Institute of Frontier Chemistry, School of Chemistry and Chemical Engineering Shandong University Qingdao 266237 China"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,7,7]]},"reference":[{"key":"e_1_2_5_1_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.202303588"},{"key":"e_1_2_5_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3EE00008G"},{"key":"e_1_2_5_3_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.esci.2022.11.002"},{"key":"e_1_2_5_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202318589"},{"key":"e_1_2_5_5_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcatb.2023.122917"},{"key":"e_1_2_5_6_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41929-023-01020-4"},{"key":"e_1_2_5_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202409697"},{"key":"e_1_2_5_8_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.202201500"},{"key":"e_1_2_5_9_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcatb.2023.122962"},{"key":"e_1_2_5_10_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.2c01956"},{"key":"e_1_2_5_11_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsnano.4c06516"},{"key":"e_1_2_5_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-024-52832-2"},{"key":"e_1_2_5_13_1","doi-asserted-by":"publisher","DOI":"10.1002\/adma.202402160"},{"key":"e_1_2_5_14_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202410938"},{"key":"e_1_2_5_15_1","doi-asserted-by":"publisher","DOI":"10.1038\/s44160-024-00603-8"},{"key":"e_1_2_5_16_1","first-page":"1748","volume":"2","author":"Liu Y.\u2010C.","year":"2025","journal-title":"Nat. Nanotechnol."},{"key":"e_1_2_5_17_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202410625"},{"key":"e_1_2_5_18_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3CC05821B"},{"key":"e_1_2_5_19_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.2c03452"},{"key":"e_1_2_5_20_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41557-020-0481-9"},{"key":"e_1_2_5_21_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2EY00038E"},{"key":"e_1_2_5_22_1","doi-asserted-by":"publisher","DOI":"10.1002\/cey2.345"},{"key":"e_1_2_5_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.4c16801"},{"key":"e_1_2_5_24_1","doi-asserted-by":"publisher","DOI":"10.1039\/D3CC00102D"},{"key":"e_1_2_5_25_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsenergylett.1c02471"},{"key":"e_1_2_5_26_1","doi-asserted-by":"publisher","DOI":"10.1002\/sus2.193"},{"key":"e_1_2_5_27_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.apcatb.2022.121618"},{"key":"e_1_2_5_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.0c04442"},{"key":"e_1_2_5_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.3c00957"},{"key":"e_1_2_5_30_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202305719"},{"key":"e_1_2_5_31_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.202302608"},{"key":"e_1_2_5_32_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202407090"},{"key":"e_1_2_5_33_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-021-26724-8"},{"key":"e_1_2_5_34_1","doi-asserted-by":"publisher","DOI":"10.1021\/acscatal.4c06348"},{"key":"e_1_2_5_35_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41893-021-00741-3"},{"key":"e_1_2_5_36_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b11446"},{"key":"e_1_2_5_37_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-023-44131-z"},{"key":"e_1_2_5_38_1","doi-asserted-by":"publisher","DOI":"10.1002\/aenm.202500872"},{"key":"e_1_2_5_39_1","doi-asserted-by":"publisher","DOI":"10.1038\/s41467-025-57708-7"},{"key":"e_1_2_5_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202402684"}],"container-title":["Angewandte Chemie International Edition"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1002\/anie.202513441","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,11,8]],"date-time":"2025-11-08T09:36:28Z","timestamp":1762594588000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1002\/anie.202513441"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2025,7,7]]},"references-count":40,"journal-issue":{"issue":"35","published-print":{"date-parts":[[2025,8,25]]}},"alternative-id":["10.1002\/anie.202513441"],"URL":"https:\/\/doi.org\/10.1002\/anie.202513441","archive":["Portico"],"relation":{},"ISSN":["1433-7851","1521-3773"],"issn-type":[{"value":"1433-7851","type":"print"},{"value":"1521-3773","type":"electronic"}],"subject":[],"published":{"date-parts":[[2025,7,7]]},"assertion":[{"value":"2025-06-19","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-07-01","order":2,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2025-07-07","order":3,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}],"article-number":"e202513441"}}