{"title":"Density functional theory study on the selective oxidation of ethylene glycol to glycolic acid over Ptn (n = 4–55) clusters","authors":"Shiping Wu, Yanhong Quan, Jun Ren","doi":"10.1007/s11705-025-2585-7","DOIUrl":null,"url":null,"abstract":"<div><p>The selective oxidation of ethylene glycol to glycolic acid on the Pt<sub>4</sub>, Pt<sub>13</sub>, Pt<sub>38</sub>, and Pt<sub>55</sub> clusters was investigated by using density-functional theory calculations. The calculated results imply that glycolic acid is preferentially generated through the dehydrogenation of ethylene glycol by OH to form HOCH<sub>2</sub>CH<sub>2</sub>O on the Pt<sub>4</sub>, Pt<sub>13</sub>, and Pt<sub>38</sub> surfaces, but that this process occurs directly without OH participation on the Pt<sub>55</sub> surface. The observed effect likely arises from the addition of OH, which modulates the electron density in the O atom of ethylene glycol, thereby affecting the cleavage of the O–H bond. Furthermore, the glycolic acid formation on the Pt<sub><i>n</i></sub> clusters is limited by the <i>β</i>–H elimination of HOCH<sub>2</sub>CH<sub>2</sub>O to HOCH<sub>2</sub>CHO, which exhibits the lowest energy barrier on the Pt<sub>13</sub> surface. It is because the <i>d</i>-band center of the Pt<sub>13</sub> cluster is closer to the Fermi energy than that of other clusters, which then enhances the electronic density of Pt. This facilitates the adsorption of HOCH<sub>2</sub>CH<sub>2</sub>O at the Pt sites and the activation of the C–H bond in HOCH<sub>2</sub>CH<sub>2</sub>O and therefore results in superior catalytic performance. This paper offers theoretical insights into the influence of Pt size on the selective oxidation of ethylene glycol to glycolic acid.\n</p><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":571,"journal":{"name":"Frontiers of Chemical Science and Engineering","volume":"19 8","pages":""},"PeriodicalIF":4.5000,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Frontiers of Chemical Science and Engineering","FirstCategoryId":"5","ListUrlMain":"https://link.springer.com/article/10.1007/s11705-025-2585-7","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
引用次数: 0
Abstract
The selective oxidation of ethylene glycol to glycolic acid on the Pt4, Pt13, Pt38, and Pt55 clusters was investigated by using density-functional theory calculations. The calculated results imply that glycolic acid is preferentially generated through the dehydrogenation of ethylene glycol by OH to form HOCH2CH2O on the Pt4, Pt13, and Pt38 surfaces, but that this process occurs directly without OH participation on the Pt55 surface. The observed effect likely arises from the addition of OH, which modulates the electron density in the O atom of ethylene glycol, thereby affecting the cleavage of the O–H bond. Furthermore, the glycolic acid formation on the Ptn clusters is limited by the β–H elimination of HOCH2CH2O to HOCH2CHO, which exhibits the lowest energy barrier on the Pt13 surface. It is because the d-band center of the Pt13 cluster is closer to the Fermi energy than that of other clusters, which then enhances the electronic density of Pt. This facilitates the adsorption of HOCH2CH2O at the Pt sites and the activation of the C–H bond in HOCH2CH2O and therefore results in superior catalytic performance. This paper offers theoretical insights into the influence of Pt size on the selective oxidation of ethylene glycol to glycolic acid.
期刊介绍:
Frontiers of Chemical Science and Engineering presents the latest developments in chemical science and engineering, emphasizing emerging and multidisciplinary fields and international trends in research and development. The journal promotes communication and exchange between scientists all over the world. The contents include original reviews, research papers and short communications. Coverage includes catalysis and reaction engineering, clean energy, functional material, nanotechnology and nanoscience, biomaterials and biotechnology, particle technology and multiphase processing, separation science and technology, sustainable technologies and green processing.