{"title":"新型双功能硫代亚甲基吡啶接枝聚合物树脂在酸性溶液中除汞","authors":"Nikhilesh Iyer , Ritesh Ruhela , Suvarna Saundarajan , Sanjukta Abhay Kumar , Dhruva Kumar Singh","doi":"10.1016/j.scenv.2025.100280","DOIUrl":null,"url":null,"abstract":"<div><div>This work brings forth a novel porous solid sorbent, thio-methylene-pyridine (TMP) ligand grafted polymeric resin (TMP resin), for selective mercury removal over a wide range of acidity in which the bi-functional group catered to sorption of both cationic and anionic species of Hg<sup>2 +</sup> in aqueous hydrochloric acid medium. TMP resin showed quantitative sorption of ‘Hg<sup>2+</sup>’ in high as well as low acidic solutions (chloride medium) with uptake capacity in the range of 70–80 mg Hg/g, indicating sorption of ‘Hg<sup>2+</sup>’ in both cationic and anionic form as (HgCl<sub>4</sub>)<sup>2-</sup>, hence utilizing the bi-functionality of TMP ligand. Spectroscopic investigation on metal-ligand interactions, as well as DFT calculations indicated towards two separate mechanisms, one being preference for soft-soft co-ordinate complexation at lower acidity and other being anion exchange of Hg-chloride complex by pyridinium group at higher acidity. Near complete back extraction of Hg<sup>2+</sup> from the Hg-loaded sorbent was achieved using 0.1 M thiourea solution at 0.1 M HCl. Resin was regenerated upto 5 cycles of repeated loading and elution wherein there was no appreciable change in the performance with respect to Hg<sup>2+</sup> sorption & desorption.</div></div>","PeriodicalId":101196,"journal":{"name":"Sustainable Chemistry for the Environment","volume":"11 ","pages":"Article 100280"},"PeriodicalIF":0.0000,"publicationDate":"2025-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Novel bifunctional thio-methylene-pyridine grafted polymeric resin for mercury removal from acidic solutions\",\"authors\":\"Nikhilesh Iyer , Ritesh Ruhela , Suvarna Saundarajan , Sanjukta Abhay Kumar , Dhruva Kumar Singh\",\"doi\":\"10.1016/j.scenv.2025.100280\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>This work brings forth a novel porous solid sorbent, thio-methylene-pyridine (TMP) ligand grafted polymeric resin (TMP resin), for selective mercury removal over a wide range of acidity in which the bi-functional group catered to sorption of both cationic and anionic species of Hg<sup>2 +</sup> in aqueous hydrochloric acid medium. TMP resin showed quantitative sorption of ‘Hg<sup>2+</sup>’ in high as well as low acidic solutions (chloride medium) with uptake capacity in the range of 70–80 mg Hg/g, indicating sorption of ‘Hg<sup>2+</sup>’ in both cationic and anionic form as (HgCl<sub>4</sub>)<sup>2-</sup>, hence utilizing the bi-functionality of TMP ligand. Spectroscopic investigation on metal-ligand interactions, as well as DFT calculations indicated towards two separate mechanisms, one being preference for soft-soft co-ordinate complexation at lower acidity and other being anion exchange of Hg-chloride complex by pyridinium group at higher acidity. Near complete back extraction of Hg<sup>2+</sup> from the Hg-loaded sorbent was achieved using 0.1 M thiourea solution at 0.1 M HCl. Resin was regenerated upto 5 cycles of repeated loading and elution wherein there was no appreciable change in the performance with respect to Hg<sup>2+</sup> sorption & desorption.</div></div>\",\"PeriodicalId\":101196,\"journal\":{\"name\":\"Sustainable Chemistry for the Environment\",\"volume\":\"11 \",\"pages\":\"Article 100280\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2025-08-14\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Sustainable Chemistry for the Environment\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2949839225000756\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Sustainable Chemistry for the Environment","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2949839225000756","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
摘要
这项工作提出了一种新的多孔固体吸附剂,巯基亚甲基吡啶(TMP)配体接枝聚合物树脂(TMP树脂),用于在广泛的酸度范围内选择性除汞,其中双官能团迎合了水溶液中Hg2 +的阳离子和阴离子的吸附。TMP树脂对Hg2+在高酸性和低酸性溶液(氯介质)中的定量吸附能力在70-80 mg Hg/g范围内,表明阳离子和阴离子形式的Hg2+都能以(HgCl4)2-的形式吸附,从而利用了TMP配体的双官能性。金属-配体相互作用的光谱研究以及DFT计算表明了两种不同的机制,一种是在较低酸度下倾向于软-软配位配合,另一种是在较高酸度下汞-氯配合物与吡啶基团的阴离子交换。在0.1 M硫脲溶液中,以0.1 M HCl的浓度,对Hg2+进行了近乎完全的反萃取。树脂可再生至5次重复加载和洗脱,其中在Hg2+吸附方面没有明显的变化;解吸。
Novel bifunctional thio-methylene-pyridine grafted polymeric resin for mercury removal from acidic solutions
This work brings forth a novel porous solid sorbent, thio-methylene-pyridine (TMP) ligand grafted polymeric resin (TMP resin), for selective mercury removal over a wide range of acidity in which the bi-functional group catered to sorption of both cationic and anionic species of Hg2 + in aqueous hydrochloric acid medium. TMP resin showed quantitative sorption of ‘Hg2+’ in high as well as low acidic solutions (chloride medium) with uptake capacity in the range of 70–80 mg Hg/g, indicating sorption of ‘Hg2+’ in both cationic and anionic form as (HgCl4)2-, hence utilizing the bi-functionality of TMP ligand. Spectroscopic investigation on metal-ligand interactions, as well as DFT calculations indicated towards two separate mechanisms, one being preference for soft-soft co-ordinate complexation at lower acidity and other being anion exchange of Hg-chloride complex by pyridinium group at higher acidity. Near complete back extraction of Hg2+ from the Hg-loaded sorbent was achieved using 0.1 M thiourea solution at 0.1 M HCl. Resin was regenerated upto 5 cycles of repeated loading and elution wherein there was no appreciable change in the performance with respect to Hg2+ sorption & desorption.