Density functional theory study on the selective oxidation of ethylene glycol to glycolic acid over Ptn (n = 4–55) clusters

IF 4.5 3区 工程技术 Q2 ENGINEERING, CHEMICAL
Shiping Wu, Yanhong Quan, Jun Ren
{"title":"Density functional theory study on the selective oxidation of ethylene glycol to glycolic acid over Ptn (n = 4–55) clusters","authors":"Shiping Wu,&nbsp;Yanhong Quan,&nbsp;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.

Ptn (n = 4-55)簇上乙二醇选择性氧化制乙醇酸的密度泛函理论研究
利用密度泛函理论计算研究了Pt4、Pt13、Pt38和Pt55簇上乙二醇选择性氧化制乙醇酸的过程。计算结果表明,乙醇酸在Pt4、Pt13和Pt38表面上优先通过OH脱氢生成HOCH2CH2O,而在Pt55表面上没有OH参与,这一过程是直接发生的。观察到的效应可能是由于OH的加入,它调节了乙二醇O原子中的电子密度,从而影响了O - h键的裂解。此外,在Pt13表面表现出最低能垒的HOCH2CH2O与HOCH2CHO之间的β-H消除限制了Ptn簇上乙醇酸的形成。这是因为Pt13团簇的d波段中心比其他团簇更接近费米能,从而提高了Pt的电子密度。这有利于HOCH2CH2O在Pt位点的吸附和HOCH2CH2O中C-H键的活化,从而获得优异的催化性能。本文对Pt粒度对乙二醇选择性氧化制乙醇酸的影响提供了理论见解。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
CiteScore
7.60
自引率
6.70%
发文量
868
审稿时长
1 months
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.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信