{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,14]],"date-time":"2026-10-14T20:10:23Z","timestamp":1792008623783,"version":"4.4.0"},"reference-count":37,"publisher":"Wiley","issue":"7","license":[{"start":{"date-parts":[[2025,12,29]],"date-time":"2025-12-29T00:00:00Z","timestamp":1766966400000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"},{"start":{"date-parts":[[2025,12,29]],"date-time":"2025-12-29T00:00:00Z","timestamp":1766966400000},"content-version":"tdm","delay-in-days":0,"URL":"http:\/\/doi.wiley.com\/10.1002\/tdm_license_1.1"}],"content-domain":{"domain":["chemistry-europe.onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Chemistry A European J"],"published-print":{"date-parts":[[2026,2,16]]},"abstract":"<jats:title>ABSTRACT<\/jats:title>\n                  <jats:p>\n                    Boron oxide (B\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    ) has recently emerged as a promising metal\u2010free catalyst for the oxidative dehydrogenation (ODH) of methane, with remarkable selectivity for formaldehyde (HCHO) and carbon monoxide (CO) at 823 K. Since B\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    melts at \u223c725 K, the ODH reaction is likely to proceed in its molten state. In 2023,\n                    <jats:italic>ab\u2010initio<\/jats:italic>\n                    molecular dynamics simulations by Rousseau and co\u2010workers revealed that molten B\n                    <jats:sub>2<\/jats:sub>\n                    O\n                    <jats:sub>3<\/jats:sub>\n                    comprises of 8\u2010, 6\u2010, 4\u2010membered cyclic B\u2212O\u2212B sites and a B\u2212B site. So herein, we carried out a detailed DFT\u2010based mechanistic investigation for CH\n                    <jats:sub>4<\/jats:sub>\n                    oxidation across these structural motifs with\n                    <jats:sup>1<\/jats:sup>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    and\n                    <jats:sup>3<\/jats:sup>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    . Due to the multireference character of\n                    <jats:sup>1<\/jats:sup>\n                    O\n                    <jats:sub>2<\/jats:sub>\n                    and its associated species, CASSCF\/NEVPT2 methodology was employed. Among all motifs, the B\u2212B site exhibits superior catalytic activity toward HCHO formation (36.6\u00a0kcal mol\n                    <jats:sup>\u22121<\/jats:sup>\n                    ), while cyclic B\u2212O\u2212B sites require significantly higher activation barriers (\u223c 50 to 78\u00a0kcal mol\n                    <jats:sup>\u22121<\/jats:sup>\n                    ). Orbital analysis reveals that electron transfer in cyclic B\u2212O\u2212B sites originates from oxygen lone\u2010pair located in the ring, while at the B\u2212B site, it originates from \u03c3(B\u2212B) bond. In addition, CO formation is thermodynamically more favorable than CO\n                    <jats:sub>2<\/jats:sub>\n                    , consistent with existing experimental observations. Overall, these mechanistic insights offer a foundation for designing efficient, metal\u2010free methane oxidation catalysts.\n                  <\/jats:p>","DOI":"10.1002\/chem.202502684","type":"journal-article","created":{"date-parts":[[2025,12,29]],"date-time":"2025-12-29T13:52:51Z","timestamp":1767016371000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["B\u2212B Sites in Molten Boron Oxide are Superior to Cyclic B\u2212O\u2212B Sites for Methane Oxidation to Formaldehyde and Carbon Monoxide"],"prefix":"10.1002","volume":"32","author":[{"ORCID":"https:\/\/orcid.org\/0009-0003-5185-2422","authenticated-orcid":false,"given":"Akhilesh","family":"Sharma","sequence":"first","affiliation":[{"name":"Computational Catalysis Center Department of Chemistry Indian Institute of Technology Roorkee Roorkee 247667 Uttarakhand India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3268-9020","authenticated-orcid":false,"given":"Parveen","family":"Rawal","sequence":"additional","affiliation":[{"name":"Computational Catalysis Center Department of Chemistry Indian Institute of Technology Roorkee Roorkee 247667 Uttarakhand India"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3004-2936","authenticated-orcid":false,"given":"Puneet","family":"Gupta","sequence":"additional","affiliation":[{"name":"Computational Catalysis Center Department of Chemistry Indian Institute of Technology Roorkee Roorkee 247667 Uttarakhand India"},{"name":"Center For Sustainable Energy Indian Institute of Technology Roorkee Roorkee 247667 Uttarakhand India"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2025,12,29]]},"reference":[{"key":"e_1_2_6_2_1","author":"Chen J. 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