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The reaction proceeds with hydrogen abstraction from methane followed by the formation of surface methoxy species, which is reduced to methanol. We compare the reaction energetics for C\u2212H dissociation in the presence and absence of surface defect, but find no discernible impact of O\u2010vacancy on methane oxidation. In comparison, hydroxyl produced as a result of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> or H<jats:sub>2<\/jats:sub>O photo\u2010decomposition dramatically reduces the barrier for CH<jats:sub>3<\/jats:sub>\u2010H bond cleavage. The reaction proceeds further by the reduction of surface methoxy group and is the rate\u2010limiting step for methanol formation. Additionally, we find that methyl can also react with water to form methanol with a considerably lower barrier, suggesting an active involvement of water for methanol formation. We also study the role of water as a co\u2010catalyst and observe significant reduction in barriers, facilitated by alternate pathway for proton transfer. The reaction pathways presented provide valuable insights into the mechanism of methane oxidation in the presence of H<jats:sub>2<\/jats:sub>O<jats:sub>2<\/jats:sub> as oxidant and demonstrate the rate\u2010enhancing role of water for these steps.<\/jats:p>","DOI":"10.1002\/cphc.202400708","type":"journal-article","created":{"date-parts":[[2024,11,1]],"date-time":"2024-11-01T01:11:02Z","timestamp":1730423462000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["Role of H<sub>2<\/sub>O<sub>2<\/sub> as Oxidant and H<sub>2<\/sub>O as Co\u2010Catalyst Over Anatase\u2010TiO<sub>2<\/sub>(101) for Conversion of Methane to Methanol"],"prefix":"10.1002","volume":"26","author":[{"given":"Kanishka","family":"Charakhwal","sequence":"first","affiliation":[{"name":"Department of Chemical Engineering Indian Institute of Technology Kanpur  Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8581-4780","authenticated-orcid":false,"given":"Vishal","family":"Agarwal","sequence":"additional","affiliation":[{"name":"Department of Chemical Engineering Indian Institute of Technology Kanpur  Uttar Pradesh 208016 India"},{"name":"Department of Sustainable Energy Engineering Indian Institute of Technology Kanpur  Uttar Pradesh 208016 India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2024,11,29]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1177\/014459879501300102"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.scs.2020.102242"},{"key":"e_1_2_8_3_1","doi-asserted-by":"crossref","unstructured":"W. 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