{"title":"Activation of uranyl peroxides by ionizing radiation prior to uranyl carbonate formation†","authors":"Zoe C. Emory, Jay A. LaVerne and Peter C. Burns","doi":"10.1039/D4DT01841A","DOIUrl":null,"url":null,"abstract":"<p >The solid form of the uranyl peroxide cage (UPC) cluster LiU<small><sub>28</sub></small> (Li<small><sub>28</sub></small>[(UO<small><sub>2</sub></small>)<small><sub>28</sub></small>(O<small><sub>2</sub></small>)<small><sub>42</sub></small>]) was irradiated by 5 MeV He<small><sup>2+</sup></small> ions to achieve doses up to 42 MGy. An intermediate compound formed that reacts with atmospheric CO<small><sub>2</sub></small> to form uranyl carbonates. The role of water in the UPC to uranyl carbonate transformation was studied by flowing either dry or hydrated Ar over samples during He<small><sup>2+</sup></small> irradiation, and by storing samples in dry and humid environments before and after irradiation. Raman, infrared, and X-ray photoelectron spectroscopies and electrospray ionization mass spectrometry were used to characterize solid Li–U<small><sub>28</sub></small> salts before and after He<small><sup>2+</sup></small> irradiation. The highest yield of uranyl carbonates occurred when hydrated Ar gas was flowed across the sample during He<small><sup>2+</sup></small> irradiation. Electron paramagnetic resonance spectroscopy provided evidence of hydroxyl and superoxide radicals in both unirradiated and γ-irradiated Li–U<small><sub>28</sub></small>.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 42","pages":" 17169-17178"},"PeriodicalIF":3.5000,"publicationDate":"2024-09-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2024/dt/d4dt01841a?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt01841a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
The solid form of the uranyl peroxide cage (UPC) cluster LiU28 (Li28[(UO2)28(O2)42]) was irradiated by 5 MeV He2+ ions to achieve doses up to 42 MGy. An intermediate compound formed that reacts with atmospheric CO2 to form uranyl carbonates. The role of water in the UPC to uranyl carbonate transformation was studied by flowing either dry or hydrated Ar over samples during He2+ irradiation, and by storing samples in dry and humid environments before and after irradiation. Raman, infrared, and X-ray photoelectron spectroscopies and electrospray ionization mass spectrometry were used to characterize solid Li–U28 salts before and after He2+ irradiation. The highest yield of uranyl carbonates occurred when hydrated Ar gas was flowed across the sample during He2+ irradiation. Electron paramagnetic resonance spectroscopy provided evidence of hydroxyl and superoxide radicals in both unirradiated and γ-irradiated Li–U28.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.