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Here, we develop a metal\u2010free porous boron nitride catalyst that demonstrates exceptional selectivity in the photocatalytic production of EG from methanol under mild conditions. Comprehensive experiments and calculations are conducted to thoroughly investigate the reaction mechanism, revealing that the OB\n                    <jats:sub>3<\/jats:sub>\n                    unit in the porous BN plays a critical role in the preferential activation of C\u2212H bond in methanol to form \u22c5CH\n                    <jats:sub>2<\/jats:sub>\n                    OH via a concerted proton\u2010electron transfer mechanism. More prominent energy barriers are observed for the further dehydrogenation of the \u22c5CH\n                    <jats:sub>2<\/jats:sub>\n                    OH intermediate on the OB\n                    <jats:sub>3<\/jats:sub>\n                    unit, inhibiting the formation of some other by\u2010products during the catalytic process. Additionally, a small downhill energy barrier for the coupling of \u22c5CH\n                    <jats:sub>2<\/jats:sub>\n                    OH in the OB\n                    <jats:sub>3<\/jats:sub>\n                    unit promotes the selective generation of EG. This study provides valuable insights into the underlying mechanisms and can serve as a guide for the design and optimization of photocatalysts for efficient and selective EG production under mild conditions.\n                  <\/jats:p>","DOI":"10.1002\/anie.202318236","type":"journal-article","created":{"date-parts":[[2024,2,7]],"date-time":"2024-02-07T07:04:06Z","timestamp":1707289446000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":35,"title":["Oxygen\u2010Activated Boron Nitride for Selective Photocatalytic Coupling of Methanol to Ethylene Glycol"],"prefix":"10.1002","volume":"63","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-8893-7767","authenticated-orcid":false,"given":"Jianli","family":"Liang","sequence":"first","affiliation":[{"name":"Department of Chemistry City University of Hong Kong  83 Tat Chee Avenue 999077 Kowloon Hong Kong P.\u2005R. China"},{"name":"Center of Super-Diamond and Advanced Films (COSDAF) City University of Hong Kong  83 Tat Chee Avenue 999077 Kowloon Hong Kong P.\u2005R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6106-3505","authenticated-orcid":false,"given":"Qianqian","family":"Song","sequence":"additional","affiliation":[{"name":"College of Physics and Materials Science Tianjin Normal University  300387 Tianjin P.\u2005R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-1601-2471","authenticated-orcid":false,"given":"Huabin","family":"Zhang","sequence":"additional","affiliation":[{"name":"KAUST Catalysis Center (KCC) King Abdullah University of Science and Technology (KAUST)  23955-6900 Thuwal Kingdom of Saudi Arabia"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0009-0007-5926-8879","authenticated-orcid":false,"given":"Zheyang","family":"Liu","sequence":"additional","affiliation":[{"name":"Institute for Energy Research Jiangsu University  301 Xuefu Road 212013 Zhenjiang P.\u2005R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-7693-9327","authenticated-orcid":false,"given":"Yang","family":"Li","sequence":"additional","affiliation":[{"name":"Department of Chemistry City University of Hong Kong  83 Tat Chee Avenue 999077 Kowloon Hong Kong P.\u2005R. China"},{"name":"Center of Super-Diamond and Advanced Films (COSDAF) City University of Hong Kong  83 Tat Chee Avenue 999077 Kowloon Hong Kong P.\u2005R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6589-6122","authenticated-orcid":false,"given":"Zhifeng","family":"Jiang","sequence":"additional","affiliation":[{"name":"Institute for Energy Research Jiangsu University  301 Xuefu Road 212013 Zhenjiang P.\u2005R. China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5557-4437","authenticated-orcid":false,"given":"Xiong Wen (David)","family":"Lou","sequence":"additional","affiliation":[{"name":"Department of Chemistry City University of Hong Kong  83 Tat Chee Avenue 999077 Kowloon Hong Kong P.\u2005R. 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