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However, in HA-containing water matrices for practical photocatalytic treatment (e.g., surface waters or wastewater effluents), HA is conventionally regarded as a persistent inhibitor; its rapid quenching of reactive species dominates the process, while the beneficial 3HA* pathway remains restricted by spin-forbidden singlet-to-triplet conversion. Herein, a heavy-atom-effect-driven molecular assembly with a bismuth catalyst was designed to overcome the spin-forbidden barrier limiting 3HA* formation. This strategy converted HA into an in situ promoter and increased antibiotic degradation by 4.24-fold. The catalyst formed a close-contact electron donor\u2013acceptor (EDA) complex with HA, through which the bismuth heavy-atom effect enhanced spin\u2013orbit coupling in attached HA, accelerated intersystem crossing, and raised 3HA* steady-state concentration by 12.1-fold. Explainable machine learning and multidimensional spectroscopy further revealed the molecular selectivity of this enhanced pathway, showing that higher-molecular-weight HA components rich in oxygenated groups and conjugated aromatic skeletons preferentially participated in the Bi3\u2013P-enhanced photochemical process and were transformed into smaller products. The mechanism was validated in real water matrices, indicating that heavy-atom-enabled intersystem crossing can be leveraged to improve photocatalytic tolerance to organic backgrounds and guide photochemical design for water treatment.<\/jats:p>","DOI":"10.1021\/acs.est.6c05691","type":"journal-article","created":{"date-parts":[[2026,9,2]],"date-time":"2026-09-02T06:00:52Z","timestamp":1788328852000},"page":"25824-25835","source":"Crossref","is-referenced-by-count":0,"title":["Unveiling the Promoting\nMechanism of Humic Acid in\nPhotocatalysis via Bismuth Heavy-Atom Effect"],"prefix":"10.1021","volume":"60","author":[{"given":"Yansong","family":"Liu","sequence":"first","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jingjing","family":"Jiang","sequence":"additional","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Hongyu","family":"Liu","sequence":"additional","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jiage","family":"Li","sequence":"additional","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yanan","family":"Zhang","sequence":"additional","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yunhe","family":"Gong","sequence":"additional","affiliation":[{"name":"Northeast Normal University , , ,","place":["Changchun, Jilin, China, 130117"]},{"name":"Jilin Jianzhu University , , ,","place":["Changchun, China, 130118"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yutong","family":"Xie","sequence":"additional","affiliation":[{"name":"Jilin Provincial Key Laboratory of Municipal Wastewater Treatment, Changchun Institute of Technology, Changchun , ,","place":["Jilin, China, 130012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Bowen","family":"Zhao","sequence":"additional","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Di","family":"Sun","sequence":"additional","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhenhao","family":"Zhao","sequence":"additional","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Mingxin","family":"Huo","sequence":"additional","affiliation":[{"name":"Northeast Normal University , , ,","place":["Changchun, Jilin, China, 130117"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5072-9033","authenticated-orcid":true,"given":"Dandan","family":"Zhou","sequence":"additional","affiliation":[{"name":"Northeast Normal University , , ,","place":["Changchun, Jilin, China, 130117"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7103-3438","authenticated-orcid":true,"given":"Shuangshi","family":"Dong","sequence":"additional","affiliation":[{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]},{"name":"Jilin University , , ,","place":["Changchun, Jilin, China, 130021"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,28]]},"reference":[{"key":"2026091511121222800_cit1","doi-asserted-by":"publisher","first-page":"123179","DOI":"10.1016\/j.watres.2025.123179","article-title":"How far do\nwe still need to go with antibiotics in aquatic environments? 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Technol."},{"issue":"1","key":"2026091511121222800_cit36","doi-asserted-by":"publisher","first-page":"1503","DOI":"10.1021\/acs.est.5c13359","article-title":"Ca2+-mediated humic acid clusters: The key to unraveling\nneutral pollutant rejection in nanofiltration","volume":"60","author":"Zhang","year":"2026","journal-title":"Environ. Sci. 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Mater."},{"issue":"7","key":"2026091511121222800_cit43","doi-asserted-by":"publisher","first-page":"236A","DOI":"10.1366\/0003702001950454","article-title":"Generalized\ntwo-dimensional correlation spectroscopy","volume":"54","author":"Noda","year":"2000","journal-title":"Appl.\nSpectrosc."},{"issue":"1","key":"2026091511121222800_cit44","doi-asserted-by":"publisher","first-page":"5314","DOI":"10.1038\/s41467-024-49605-2","article-title":"Nanoconfinement steers nonradical pathway transition\nin single atom Fenton-like catalysis for improving oxidant utilization","volume":"15","author":"Meng","year":"2024","journal-title":"Nat. Commun."},{"issue":"8","key":"2026091511121222800_cit45","doi-asserted-by":"publisher","first-page":"4019","DOI":"10.1021\/acs.est.3c10703","article-title":"New insights into the role of humic acid in\npermanganate\noxidation of diclofenac: A novel electron transfer mechanism","volume":"58","author":"Zhou","year":"2024","journal-title":"Environ. Sci. 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