P. Troosters, T. Opsomer, K. Van Hecke, K. Verguts, F. Reniers, K. Van Hoecke, P. Zsabka, T. Cardinaels and W. Dehaen
{"title":"合成btrzphen4醇的新途径:用于选择性剥离镅的亲水性2,9-双三唑-1,10-菲罗啉配体","authors":"P. Troosters, T. Opsomer, K. Van Hecke, K. Verguts, F. Reniers, K. Van Hoecke, P. Zsabka, T. Cardinaels and W. Dehaen","doi":"10.1039/D4DT03399J","DOIUrl":null,"url":null,"abstract":"<p >Selectively separating Am(<small>III</small>) from nuclear waste streams is an extremely challenging task due to the presence of the trivalent lanthanides and Cm(<small>III</small>). 1,10-Phenanthroline ligands decorated with 1,2,4-triazines or 1,2,3-triazoles have emerged as promising extractants for achieving such separation. In this article, a new robust synthetic pathway towards the hydrophilic, CHON compliant bistriazoylphenanthroline ligand BTrzPhen-tetraol is reported. BTrzPhen-tetraol was synthesised both as the hydrochloride and as a free base with overall yields of 66% and 48%, respectively. The ligand demonstrated excellent solubility and stability in dilute nitric acid solutions, with no observable decomposition after three days in 0.5 mol L<small><sup>−1</sup></small> HNO<small><sub>3</sub></small> at 50 °C. Additionally, it exhibited rapid stripping kinetics for Am(<small>III</small>) and Eu(<small>III</small>). Liquid–liquid extraction experiments conducted with BTrzPhen-tetraol, TODGA, and radiotracers of Am(<small>III</small>), Cm(<small>III</small>), and Eu(<small>III</small>) yielded maximum Eu(<small>III</small>)/Am(<small>III</small>) and Cm(<small>III</small>)/Am(<small>III</small>) separation factors of 84 and 2.4, respectively, at 0.26 mol L<small><sup>−1</sup></small> HNO<small><sub>3</sub></small>. Notably, the separation factors achieved with BTrzPhen-tetraol are comparable to those of existing systems. While only a minor influence of the BTrzPhen concentration on the distribution ratios of Am and Cm was observed under the given conditions, these results highlight the effectiveness of hydrophilic BTrzPhen ligands for selective americium stripping and encourage further optimisation to enhance performance.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 11","pages":" 4697-4705"},"PeriodicalIF":3.3000,"publicationDate":"2025-02-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d4dt03399j?page=search","citationCount":"0","resultStr":"{\"title\":\"New synthetic pathway towards BTrzPhen-tetraol: a hydrophilic 2,9-bis-triazolyl-1,10-phenanthroline ligand for selective americium stripping†\",\"authors\":\"P. Troosters, T. Opsomer, K. Van Hecke, K. Verguts, F. Reniers, K. Van Hoecke, P. Zsabka, T. Cardinaels and W. Dehaen\",\"doi\":\"10.1039/D4DT03399J\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Selectively separating Am(<small>III</small>) from nuclear waste streams is an extremely challenging task due to the presence of the trivalent lanthanides and Cm(<small>III</small>). 1,10-Phenanthroline ligands decorated with 1,2,4-triazines or 1,2,3-triazoles have emerged as promising extractants for achieving such separation. In this article, a new robust synthetic pathway towards the hydrophilic, CHON compliant bistriazoylphenanthroline ligand BTrzPhen-tetraol is reported. BTrzPhen-tetraol was synthesised both as the hydrochloride and as a free base with overall yields of 66% and 48%, respectively. The ligand demonstrated excellent solubility and stability in dilute nitric acid solutions, with no observable decomposition after three days in 0.5 mol L<small><sup>−1</sup></small> HNO<small><sub>3</sub></small> at 50 °C. Additionally, it exhibited rapid stripping kinetics for Am(<small>III</small>) and Eu(<small>III</small>). Liquid–liquid extraction experiments conducted with BTrzPhen-tetraol, TODGA, and radiotracers of Am(<small>III</small>), Cm(<small>III</small>), and Eu(<small>III</small>) yielded maximum Eu(<small>III</small>)/Am(<small>III</small>) and Cm(<small>III</small>)/Am(<small>III</small>) separation factors of 84 and 2.4, respectively, at 0.26 mol L<small><sup>−1</sup></small> HNO<small><sub>3</sub></small>. Notably, the separation factors achieved with BTrzPhen-tetraol are comparable to those of existing systems. While only a minor influence of the BTrzPhen concentration on the distribution ratios of Am and Cm was observed under the given conditions, these results highlight the effectiveness of hydrophilic BTrzPhen ligands for selective americium stripping and encourage further optimisation to enhance performance.</p>\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":\" 11\",\"pages\":\" 4697-4705\"},\"PeriodicalIF\":3.3000,\"publicationDate\":\"2025-02-19\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.rsc.org/en/content/articlepdf/2025/dt/d4dt03399j?page=search\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt03399j\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d4dt03399j","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
New synthetic pathway towards BTrzPhen-tetraol: a hydrophilic 2,9-bis-triazolyl-1,10-phenanthroline ligand for selective americium stripping†
Selectively separating Am(III) from nuclear waste streams is an extremely challenging task due to the presence of the trivalent lanthanides and Cm(III). 1,10-Phenanthroline ligands decorated with 1,2,4-triazines or 1,2,3-triazoles have emerged as promising extractants for achieving such separation. In this article, a new robust synthetic pathway towards the hydrophilic, CHON compliant bistriazoylphenanthroline ligand BTrzPhen-tetraol is reported. BTrzPhen-tetraol was synthesised both as the hydrochloride and as a free base with overall yields of 66% and 48%, respectively. The ligand demonstrated excellent solubility and stability in dilute nitric acid solutions, with no observable decomposition after three days in 0.5 mol L−1 HNO3 at 50 °C. Additionally, it exhibited rapid stripping kinetics for Am(III) and Eu(III). Liquid–liquid extraction experiments conducted with BTrzPhen-tetraol, TODGA, and radiotracers of Am(III), Cm(III), and Eu(III) yielded maximum Eu(III)/Am(III) and Cm(III)/Am(III) separation factors of 84 and 2.4, respectively, at 0.26 mol L−1 HNO3. Notably, the separation factors achieved with BTrzPhen-tetraol are comparable to those of existing systems. While only a minor influence of the BTrzPhen concentration on the distribution ratios of Am and Cm was observed under the given conditions, these results highlight the effectiveness of hydrophilic BTrzPhen ligands for selective americium stripping and encourage further optimisation to enhance performance.
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.