{"title":"Electrodeposition behaviour of samarium in 1,3-dimethyl-2-imidazolidone solvent","authors":"Chrysanthus Andrew, Jayakumar Mani","doi":"10.1515/pac-2024-0110","DOIUrl":null,"url":null,"abstract":"The present study investigates the electrochemistry spectroscopy of Sm(III), and electrodeposition of samarium metal in neutral ligand-based ionic liquid (solvate ionic liquid). Mixture consisted of a samarium precursor (either samarium triflate or samarium nitrate hexahydrate) in the solvate ionic liquid, 1.3-dimethyl-2-imidazolidone (DMI). FT-IR analysis of Sm(III)-DMI electrolytes indicates that Sm<jats:sup>3+</jats:sup> ion coordinates with DMI through carbonyl group (C=O); the band splits into two with emergence of new peak at 1630 cm<jats:sup>−1</jats:sup> and 1649 cm<jats:sup>−1</jats:sup> for the triflate and nitrate solutions, respectively. Raman spectroscopy also confirms the solvation of Sm(III) with DMI through oxygen atom of the carbonyl group. Voltametric behaviour of Sm(III) ion indicates two-step reduction mechanism <jats:italic>via</jats:italic> Sm(III)/Sm(II) at <jats:italic>ca.</jats:italic> −2.0 V and Sm(II)/Sm(0) at <jats:italic>ca.</jats:italic> −3.0 V vs. Ag/Ag<jats:sup>+</jats:sup> for both samarium(III)-containing electrolytes. Diffusion coefficient value of Sm(III) was determined to be 2.185 × 10<jats:sup>−6</jats:sup> cm<jats:sup>2</jats:sup>/s and 2.418 × 10<jats:sup>−8</jats:sup> cm<jats:sup>2</jats:sup>/s for triflate and nitrate electrolytes, respectively. Electrodeposition of samarium was achieved through constant potential electrolysis using copper substrate as the working electrode which yielded compact deposits from triflate-DMI and non-uniform granular deposit from nitrate-DMI electrolyte. <jats:italic>Ex situ</jats:italic> X-ray photoelectron spectroscopy analysis of the as-deposited samples revealed the presence of metallic Sm (1081 eV) co-existing with its oxide form (1083 eV).","PeriodicalId":20911,"journal":{"name":"Pure and Applied Chemistry","volume":"1 1","pages":""},"PeriodicalIF":2.0000,"publicationDate":"2024-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Pure and Applied Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1515/pac-2024-0110","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The present study investigates the electrochemistry spectroscopy of Sm(III), and electrodeposition of samarium metal in neutral ligand-based ionic liquid (solvate ionic liquid). Mixture consisted of a samarium precursor (either samarium triflate or samarium nitrate hexahydrate) in the solvate ionic liquid, 1.3-dimethyl-2-imidazolidone (DMI). FT-IR analysis of Sm(III)-DMI electrolytes indicates that Sm3+ ion coordinates with DMI through carbonyl group (C=O); the band splits into two with emergence of new peak at 1630 cm−1 and 1649 cm−1 for the triflate and nitrate solutions, respectively. Raman spectroscopy also confirms the solvation of Sm(III) with DMI through oxygen atom of the carbonyl group. Voltametric behaviour of Sm(III) ion indicates two-step reduction mechanism via Sm(III)/Sm(II) at ca. −2.0 V and Sm(II)/Sm(0) at ca. −3.0 V vs. Ag/Ag+ for both samarium(III)-containing electrolytes. Diffusion coefficient value of Sm(III) was determined to be 2.185 × 10−6 cm2/s and 2.418 × 10−8 cm2/s for triflate and nitrate electrolytes, respectively. Electrodeposition of samarium was achieved through constant potential electrolysis using copper substrate as the working electrode which yielded compact deposits from triflate-DMI and non-uniform granular deposit from nitrate-DMI electrolyte. Ex situ X-ray photoelectron spectroscopy analysis of the as-deposited samples revealed the presence of metallic Sm (1081 eV) co-existing with its oxide form (1083 eV).
期刊介绍:
Pure and Applied Chemistry is the official monthly Journal of IUPAC, with responsibility for publishing works arising from those international scientific events and projects that are sponsored and undertaken by the Union. The policy is to publish highly topical and credible works at the forefront of all aspects of pure and applied chemistry, and the attendant goal is to promote widespread acceptance of the Journal as an authoritative and indispensable holding in academic and institutional libraries.