Passivating Lattice Oxygen in ZnO Nanocrystals to Reduce its Interactions with the Key Intermediates for a Selective Photocatalytic Methane Oxidation to Methanol

IF 16.1 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Ruimin Lan, Zhuofeng Hu, Haoran Liu, Kui Shen, Hui Wang, Tingting Hou, Yingwei Li
{"title":"Passivating Lattice Oxygen in ZnO Nanocrystals to Reduce its Interactions with the Key Intermediates for a Selective Photocatalytic Methane Oxidation to Methanol","authors":"Ruimin Lan, Zhuofeng Hu, Haoran Liu, Kui Shen, Hui Wang, Tingting Hou, Yingwei Li","doi":"10.1002/anie.202425186","DOIUrl":null,"url":null,"abstract":"An inevitable overoxidation process is considered as one of the most challenging problems in the direct conversion of methane (CH4) to methanol (CH3OH), which is limited by the uncontrollable cracking of key intermediates. Herein, we have successfully constructed a photocatalyst, the Fe-doped ZnO hollow polyhedron (Fe/ZnOHP), for the highly selective photoconversion of CH4 to CH3OH under mild conditions. In-situ experiments and density functional theory calculations confirmed that the introduction of Fe was able to decrease the energy level of the O 2p orbital, which passivated the activity of lattice oxygen in ZnO nanocrystals. This passivation effect greatly weakened the interaction between *CH3 and lattice oxygen, thus facilitating the conversion of *CH3O to *CH3 intermediate rather than the direct desorption of *CH3O. As a result, Fe/ZnOHP exhibited excellent CH3OH generation rate (ca. 1009 μmol gcat−1 h-1) and selectivity (ca. 96%) in the photocatalytic conversion of CH4 at room temperature and low pressure.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.1000,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1002/anie.202425186","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

An inevitable overoxidation process is considered as one of the most challenging problems in the direct conversion of methane (CH4) to methanol (CH3OH), which is limited by the uncontrollable cracking of key intermediates. Herein, we have successfully constructed a photocatalyst, the Fe-doped ZnO hollow polyhedron (Fe/ZnOHP), for the highly selective photoconversion of CH4 to CH3OH under mild conditions. In-situ experiments and density functional theory calculations confirmed that the introduction of Fe was able to decrease the energy level of the O 2p orbital, which passivated the activity of lattice oxygen in ZnO nanocrystals. This passivation effect greatly weakened the interaction between *CH3 and lattice oxygen, thus facilitating the conversion of *CH3O to *CH3 intermediate rather than the direct desorption of *CH3O. As a result, Fe/ZnOHP exhibited excellent CH3OH generation rate (ca. 1009 μmol gcat−1 h-1) and selectivity (ca. 96%) in the photocatalytic conversion of CH4 at room temperature and low pressure.
钝化氧化锌纳米晶体中的点阵氧以减少其与选择性光催化甲烷氧化制甲醇的关键中间体的相互作用
在甲烷(CH4)直接转化为甲醇(CH3OH)的过程中,不可避免的过氧化过程被认为是最具挑战性的问题之一,这一过程受到关键中间体不可控裂解的限制。在此,我们成功构建了一种光催化剂,Fe掺杂ZnO空心多面体(Fe/ZnOHP),用于在温和条件下高选择性地将CH4光转化为CH3OH。原位实验和密度泛函理论计算证实,Fe的引入降低了ZnO纳米晶体中o2p轨道的能级,钝化了晶格氧的活性。这种钝化效应大大削弱了*CH3与晶格氧之间的相互作用,从而有利于* ch30转化为*CH3中间体,而不是直接解吸* ch30。结果表明,Fe/ZnOHP在常温低压下光催化转化CH4时,CH3OH的生成速率(约1009 μmol gcat−1 h-1)和选择性(约96%)优异。
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
26.60
自引率
6.60%
发文量
3549
审稿时长
1.5 months
期刊介绍: Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
×
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:481959085
Book学术官方微信