Novel diamide covalent organic polymers (COPs) for arresting actinides U(VI), Pu(IV) and Am(III) from highly acidic nuclear stream

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL Separation and Purification Technology Pub Date : 2025-02-21 DOI:10.1016/j.seppur.2025.132181

Prashant Yevale , Shiny S. Kumar , Pooja Agarkar , Gauravi Yashwantrao , Anjali Tripathi , Purav Badani , Ankita Rao , Satyajit Saha

{"title":"Novel diamide covalent organic polymers (COPs) for arresting actinides U(VI), Pu(IV) and Am(III) from highly acidic nuclear stream","authors":"Prashant Yevale , Shiny S. Kumar , Pooja Agarkar , Gauravi Yashwantrao , Anjali Tripathi , Purav Badani , Ankita Rao , Satyajit Saha","doi":"10.1016/j.seppur.2025.132181","DOIUrl":null,"url":null,"abstract":"<div><div>Targeted towards the hitherto unaddressed challenge of actinide capture under harsh radiochemical conditions (nitric acid molarity ≥2 M, gamma radiation field 500 kGy), novel diamide covalent organic polymers (COPs) were successfully synthesized and characterized. The completely incinerable <strong>1,3</strong> and <strong>1,4-Diamide COP</strong>s were endowed with exceptional radiochemical stability, high surface area (>1400 m<sup>2</sup> g<sup>−1</sup>) and remarkable sorption capacity for the actinides viz. U(VI), Pu(IV) and Am(III). Batch sorption studies with Am(III), Pu(IV) and U(VI) from nitric acid medium revealed higher uptake with <strong>1,3</strong> over <strong>1,4-Diamide COP</strong>, in general. Distribution co-efficient, k<sub>D</sub> was found to enhance with nitric acid molarity, attaining saturation after 4 M. Sorption was found to follow pseudo second order kinetics, Langmuir adsorption isotherm and was enthalpy driven. <strong>1,3-Diamide COP</strong>s yielded high sorption capacity for U(VI), Pu(IV) and Am(III) (368.8, 452.3 and 189.3 mg g<sup>−1</sup> respectively), from 4 M nitric acid medium. Actinide removal was >90 % from simulated nuclear streams. Mode of complexation of COPs with uranyl was probed experimentally by X-ray Photoelectron Spectroscopy and Fourier transform Infrared Spectroscopy. Additional insights for optimized ligand and metal–ligand binding geometries were obtained by theoretical modelling.</div></div>","PeriodicalId":427,"journal":{"name":"Separation and Purification Technology","volume":"363 ","pages":"Article 132181"},"PeriodicalIF":9.0000,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Separation and Purification Technology","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1383586625007786","RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}

引用次数: 0

Abstract

Targeted towards the hitherto unaddressed challenge of actinide capture under harsh radiochemical conditions (nitric acid molarity ≥2 M, gamma radiation field 500 kGy), novel diamide covalent organic polymers (COPs) were successfully synthesized and characterized. The completely incinerable 1,3 and 1,4-Diamide COPs were endowed with exceptional radiochemical stability, high surface area (>1400 m² g⁻¹) and remarkable sorption capacity for the actinides viz. U(VI), Pu(IV) and Am(III). Batch sorption studies with Am(III), Pu(IV) and U(VI) from nitric acid medium revealed higher uptake with 1,3 over 1,4-Diamide COP, in general. Distribution co-efficient, k_D was found to enhance with nitric acid molarity, attaining saturation after 4 M. Sorption was found to follow pseudo second order kinetics, Langmuir adsorption isotherm and was enthalpy driven. 1,3-Diamide COPs yielded high sorption capacity for U(VI), Pu(IV) and Am(III) (368.8, 452.3 and 189.3 mg g⁻¹ respectively), from 4 M nitric acid medium. Actinide removal was >90 % from simulated nuclear streams. Mode of complexation of COPs with uranyl was probed experimentally by X-ray Photoelectron Spectroscopy and Fourier transform Infrared Spectroscopy. Additional insights for optimized ligand and metal–ligand binding geometries were obtained by theoretical modelling.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

新型二酰胺共价有机聚合物 (COP)，用于从高酸性核气流中捕获锕系元素 U(VI)、Pu(IV) 和 Am(III)

针对锕系元素在恶劣放射化学条件下（硝酸摩尔浓度≥2 M， γ辐射场500 kGy）捕获的难题，成功合成并表征了新型二胺共价有机聚合物（cop）。完全可焚烧的1,3和1,4-二胺类cop具有优异的放射化学稳定性、高表面积（>1400 m2 g−1）和对锕系元素U（VI）、Pu（IV）和Am（III）的吸附能力。用Am（III）、Pu（IV）和U（VI）从硝酸介质中进行的批量吸附研究表明，通常1,3比1,4-二胺COP吸收率更高。kD分布系数随硝酸摩尔浓度的增加而增加，在4 M后达到饱和。吸附遵循拟二级动力学，Langmuir吸附等温线，并由焓驱动。1,3-二胺类COPs对4 M硝酸介质中U（VI）、Pu（IV）和Am（III）的吸附量分别为368.8、452.3和189.3 mg g−1。模拟核流的锕系元素去除率为>；90 %。利用x射线光电子能谱和傅里叶变换红外光谱对COPs与铀酰的络合模式进行了实验研究。通过理论建模获得了优化配体和金属配体结合几何形状的其他见解。

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分钟内获得全文去求助

来源期刊

Separation and Purification Technology 工程技术-工程：化工

CiteScore

14.00

自引率

12.80%

发文量

2347

审稿时长

43 days

期刊介绍： Separation and Purification Technology is a premier journal committed to sharing innovative methods for separation and purification in chemical and environmental engineering, encompassing both homogeneous solutions and heterogeneous mixtures. Our scope includes the separation and/or purification of liquids, vapors, and gases, as well as carbon capture and separation techniques. However, it's important to note that methods solely intended for analytical purposes are not within the scope of the journal. Additionally, disciplines such as soil science, polymer science, and metallurgy fall outside the purview of Separation and Purification Technology. Join us in advancing the field of separation and purification methods for sustainable solutions in chemical and environmental engineering.