{"title":"Photocatalytic Oxidative Esterification of Benzaldehyde with the Participation of Crystalline Carbon Nitride","authors":"G. V. Korzhak, T. R. Stara, S. Ya. Kuchmiy","doi":"10.1007/s11237-025-09832-0","DOIUrl":null,"url":null,"abstract":"<p>It has been established that crystalline carbon nitride obtained by heat treatment of g-C<sub>3</sub>N<sub>4</sub> in molten KCl and LiCl salts exhibits photocatalytic activity in the oxidative esterification of benzaldehyde in methanol and ethanol solutions. The reaction proceeds only in the presence of palladium ions, which are reduced with the alcohols in situ, and acid, which promote benzaldehyde acetalization. A probable mechanism of the photocatalytic process is proposed, which involves the oxidation of acetal by a superoxide ion radical, the subsequent interaction of the formed acetal radical with an oxygen molecule, the formation of a tickle organic peroxide and its fragmentation according to the Russell mechanism with the formation of benzoate.</p>","PeriodicalId":796,"journal":{"name":"Theoretical and Experimental Chemistry","volume":"60 5","pages":"307 - 314"},"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/s11237-025-09832-0","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
It has been established that crystalline carbon nitride obtained by heat treatment of g-C3N4 in molten KCl and LiCl salts exhibits photocatalytic activity in the oxidative esterification of benzaldehyde in methanol and ethanol solutions. The reaction proceeds only in the presence of palladium ions, which are reduced with the alcohols in situ, and acid, which promote benzaldehyde acetalization. A probable mechanism of the photocatalytic process is proposed, which involves the oxidation of acetal by a superoxide ion radical, the subsequent interaction of the formed acetal radical with an oxygen molecule, the formation of a tickle organic peroxide and its fragmentation according to the Russell mechanism with the formation of benzoate.
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.