E. H. Ismailov, Sh. F. Tagiyeva, S. N. Osmanova, A. I. Rustamova, L. V. Huseynova
{"title":"MoOx/SiO2催化剂上氧阴离子自由基与Mo(VI)配合物及其在甲烷氧化制甲醇中的作用","authors":"E. H. Ismailov, Sh. F. Tagiyeva, S. N. Osmanova, A. I. Rustamova, L. V. Huseynova","doi":"10.1007/s11237-025-09837-9","DOIUrl":null,"url":null,"abstract":"<p>Oxygen anion radicals <span>\\({O}_{2}^{-\\cdot }\\)</span> coordinated with one Mo(VI) have been identified in MoO<sub>x</sub>/SiO<sub>2</sub> samples enriched with <sup>95</sup>Mo isotope. It is shown that unpaired electron is mainly localized on the oxygen ion (g<sub>z</sub> = 2.017, g<sub>y</sub> = 2.004, g<sub>x</sub> = 1.999; A<sub>x</sub>(<sup>95</sup>Mo) = 6.1, A<sub>y</sub>(<sup>95</sup>Mo) = 6.0, A<sub>z</sub>(<sup>95</sup>Mo)=9.1 G; ∆H<sub>x</sub> = ∆H<sub>y</sub> = 2,2 G and ∆H<sub>z</sub> = 2,6 G). Using a special freezing technique, peroxide radicals (CH<sub>3</sub>OO<sup>·</sup>), which are the products of the reaction of the methyl radical with molecular oxygen in the gas phase, have been identified. The oxidation pathways of methane to methanol with participation of the oxygen ion radicals coordinated directly by Mo(VI) are discussed.</p>","PeriodicalId":796,"journal":{"name":"Theoretical and Experimental Chemistry","volume":"60 5","pages":"351 - 356"},"PeriodicalIF":0.9000,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Oxygen Anion-Radical Complexes with Mo(VI) on MoOx/SiO2 Catalysts and Their Role in the Oxidation of Methane to Methanol\",\"authors\":\"E. H. Ismailov, Sh. F. Tagiyeva, S. N. Osmanova, A. I. Rustamova, L. V. Huseynova\",\"doi\":\"10.1007/s11237-025-09837-9\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Oxygen anion radicals <span>\\\\({O}_{2}^{-\\\\cdot }\\\\)</span> coordinated with one Mo(VI) have been identified in MoO<sub>x</sub>/SiO<sub>2</sub> samples enriched with <sup>95</sup>Mo isotope. It is shown that unpaired electron is mainly localized on the oxygen ion (g<sub>z</sub> = 2.017, g<sub>y</sub> = 2.004, g<sub>x</sub> = 1.999; A<sub>x</sub>(<sup>95</sup>Mo) = 6.1, A<sub>y</sub>(<sup>95</sup>Mo) = 6.0, A<sub>z</sub>(<sup>95</sup>Mo)=9.1 G; ∆H<sub>x</sub> = ∆H<sub>y</sub> = 2,2 G and ∆H<sub>z</sub> = 2,6 G). Using a special freezing technique, peroxide radicals (CH<sub>3</sub>OO<sup>·</sup>), which are the products of the reaction of the methyl radical with molecular oxygen in the gas phase, have been identified. The oxidation pathways of methane to methanol with participation of the oxygen ion radicals coordinated directly by Mo(VI) are discussed.</p>\",\"PeriodicalId\":796,\"journal\":{\"name\":\"Theoretical and Experimental Chemistry\",\"volume\":\"60 5\",\"pages\":\"351 - 356\"},\"PeriodicalIF\":0.9000,\"publicationDate\":\"2025-05-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Theoretical and Experimental Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1007/s11237-025-09837-9\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Theoretical and Experimental Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11237-025-09837-9","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Oxygen Anion-Radical Complexes with Mo(VI) on MoOx/SiO2 Catalysts and Their Role in the Oxidation of Methane to Methanol
Oxygen anion radicals \({O}_{2}^{-\cdot }\) coordinated with one Mo(VI) have been identified in MoOx/SiO2 samples enriched with 95Mo isotope. It is shown that unpaired electron is mainly localized on the oxygen ion (gz = 2.017, gy = 2.004, gx = 1.999; Ax(95Mo) = 6.1, Ay(95Mo) = 6.0, Az(95Mo)=9.1 G; ∆Hx = ∆Hy = 2,2 G and ∆Hz = 2,6 G). Using a special freezing technique, peroxide radicals (CH3OO·), which are the products of the reaction of the methyl radical with molecular oxygen in the gas phase, have been identified. The oxidation pathways of methane to methanol with participation of the oxygen ion radicals coordinated directly by Mo(VI) are discussed.
期刊介绍:
Theoretical and Experimental Chemistry is a journal for the rapid publication of research communications and reviews on modern problems of physical chemistry such as:
a) physicochemical bases, principles, and methods for creation of novel processes, compounds, and materials;
b) physicochemical principles of chemical process control, influence of external physical forces on chemical reactions;
c) physical nanochemistry, nanostructures and nanomaterials, functional nanomaterials, size-dependent properties of materials.