Facile Synthesis, Characterization of Poly-2-mercapto-1,3,4-thiadiazole Nanoparticles for Rapid Removal of Mercury and Silver Ions from Aqueous Solutions

Industrial pollution by heavy metal ions such as Hg2+ and Ag+ is a universal problem owing to the toxicity of heavy metals. In this study, a novel nano-adsorbent, i.e., poly-2-mercapto-1,3,4-thiadiazole (PTT), was synthesized and used to selectively adsorb mercury and silver ions from aqueous soluti...

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Main Authors: Shaojun Huang, Chengzhang Ma, Chao Li, Chungang Min, Ping Du, Yi Xia, Chaofen Yang, Qiuling Huang
Format: Article
Language:English
Published: MDPI AG 2018-02-01
Series:Polymers
Subjects:
Online Access:http://www.mdpi.com/2073-4360/10/2/150
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spelling doaj-da8a8ed7bf9f4728892a819a8175cf0f2020-11-24T21:30:08ZengMDPI AGPolymers2073-43602018-02-0110215010.3390/polym10020150polym10020150Facile Synthesis, Characterization of Poly-2-mercapto-1,3,4-thiadiazole Nanoparticles for Rapid Removal of Mercury and Silver Ions from Aqueous SolutionsShaojun Huang0Chengzhang Ma1Chao Li2Chungang Min3Ping Du4Yi Xia5Chaofen Yang6Qiuling Huang7Research Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093, ChinaSchool of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaSchool of Materials Science and Engineering, Kunming University of Science and Technology, Kunming 650093, ChinaResearch Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093, ChinaResearch Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093, ChinaResearch Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093, ChinaResearch Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093, ChinaResearch Center for Analysis and Measurement, Kunming University of Science and Technology, Kunming 650093, ChinaIndustrial pollution by heavy metal ions such as Hg2+ and Ag+ is a universal problem owing to the toxicity of heavy metals. In this study, a novel nano-adsorbent, i.e., poly-2-mercapto-1,3,4-thiadiazole (PTT), was synthesized and used to selectively adsorb mercury and silver ions from aqueous solutions. PTT nanoparticles were synthesized via chemical oxidative dehydrogenation polymerization under mild conditions. Oxidant species, medium, monomer concentration, oxidant/monomer molar ratio, and polymerization temperature were optimized to obtain optimum yields. The molecular structure and morphology of the nanoparticles were analyzed by ultraviolet-visible (UV-Vis), Fourier transform infrared (FT-IR), matrix-assisted laser desorption/ionization/time-of-flight (MALDI/TOF) mass and X-ray photoelectron (XPS) spectroscopies, wide-angle X-ray diffraction (WAXD), theoretical calculations and transmission electron microscopy (TEM), respectively. It was found that the polymerization of 2-mercapto-1,3,4-thiodiazole occurs through head-to-tail coupling between the S(2) and C(5) positions. The PTT nanoparticles having a peculiar synergic combination of four kinds of active groups, S–, –SH, N–N, and =N– with a small particle size of 30–200 nm exhibit ultrarapid initial adsorption rates of 1500 mg(Hg)·g−1·h−1 and 5364 mg(Ag)·g−1·h−1 and high adsorption capacities of up to 186.9 mg(Hg)·g−1 and 193.1 mg(Ag)·g−1, becoming ultrafast chelate nanosorbents with high adsorption capacities. Kinetic study indicates that the adsorption of Hg2+ and Ag+ follows the pseudo-second-order model, suggesting a chemical adsorption as the rate-limiting step during the adsorption process. The Hg2+ and Ag+-loaded PTT nanoparticles could be effectively regenerated with 0.1 mol·L−1 EDTA or 1 mol·L−1 HNO3 without significantly losing their adsorption capacities even after five adsorption–desorption cycles. With these impressive properties, PTT nanoparticles are very promising materials in the fields of water-treatment and precious metals recovery.http://www.mdpi.com/2073-4360/10/2/150poly-2-mercapto-1,3,4-thiadiazolesynthesischaracterizationnanoparticlesadsorptionheavy metal ionsmercurysilver
collection DOAJ
language English
format Article
sources DOAJ
author Shaojun Huang
Chengzhang Ma
Chao Li
Chungang Min
Ping Du
Yi Xia
Chaofen Yang
Qiuling Huang
spellingShingle Shaojun Huang
Chengzhang Ma
Chao Li
Chungang Min
Ping Du
Yi Xia
Chaofen Yang
Qiuling Huang
Facile Synthesis, Characterization of Poly-2-mercapto-1,3,4-thiadiazole Nanoparticles for Rapid Removal of Mercury and Silver Ions from Aqueous Solutions
Polymers
poly-2-mercapto-1,3,4-thiadiazole
synthesis
characterization
nanoparticles
adsorption
heavy metal ions
mercury
silver
author_facet Shaojun Huang
Chengzhang Ma
Chao Li
Chungang Min
Ping Du
Yi Xia
Chaofen Yang
Qiuling Huang
author_sort Shaojun Huang
title Facile Synthesis, Characterization of Poly-2-mercapto-1,3,4-thiadiazole Nanoparticles for Rapid Removal of Mercury and Silver Ions from Aqueous Solutions
title_short Facile Synthesis, Characterization of Poly-2-mercapto-1,3,4-thiadiazole Nanoparticles for Rapid Removal of Mercury and Silver Ions from Aqueous Solutions
title_full Facile Synthesis, Characterization of Poly-2-mercapto-1,3,4-thiadiazole Nanoparticles for Rapid Removal of Mercury and Silver Ions from Aqueous Solutions
title_fullStr Facile Synthesis, Characterization of Poly-2-mercapto-1,3,4-thiadiazole Nanoparticles for Rapid Removal of Mercury and Silver Ions from Aqueous Solutions
title_full_unstemmed Facile Synthesis, Characterization of Poly-2-mercapto-1,3,4-thiadiazole Nanoparticles for Rapid Removal of Mercury and Silver Ions from Aqueous Solutions
title_sort facile synthesis, characterization of poly-2-mercapto-1,3,4-thiadiazole nanoparticles for rapid removal of mercury and silver ions from aqueous solutions
publisher MDPI AG
series Polymers
issn 2073-4360
publishDate 2018-02-01
description Industrial pollution by heavy metal ions such as Hg2+ and Ag+ is a universal problem owing to the toxicity of heavy metals. In this study, a novel nano-adsorbent, i.e., poly-2-mercapto-1,3,4-thiadiazole (PTT), was synthesized and used to selectively adsorb mercury and silver ions from aqueous solutions. PTT nanoparticles were synthesized via chemical oxidative dehydrogenation polymerization under mild conditions. Oxidant species, medium, monomer concentration, oxidant/monomer molar ratio, and polymerization temperature were optimized to obtain optimum yields. The molecular structure and morphology of the nanoparticles were analyzed by ultraviolet-visible (UV-Vis), Fourier transform infrared (FT-IR), matrix-assisted laser desorption/ionization/time-of-flight (MALDI/TOF) mass and X-ray photoelectron (XPS) spectroscopies, wide-angle X-ray diffraction (WAXD), theoretical calculations and transmission electron microscopy (TEM), respectively. It was found that the polymerization of 2-mercapto-1,3,4-thiodiazole occurs through head-to-tail coupling between the S(2) and C(5) positions. The PTT nanoparticles having a peculiar synergic combination of four kinds of active groups, S–, –SH, N–N, and =N– with a small particle size of 30–200 nm exhibit ultrarapid initial adsorption rates of 1500 mg(Hg)·g−1·h−1 and 5364 mg(Ag)·g−1·h−1 and high adsorption capacities of up to 186.9 mg(Hg)·g−1 and 193.1 mg(Ag)·g−1, becoming ultrafast chelate nanosorbents with high adsorption capacities. Kinetic study indicates that the adsorption of Hg2+ and Ag+ follows the pseudo-second-order model, suggesting a chemical adsorption as the rate-limiting step during the adsorption process. The Hg2+ and Ag+-loaded PTT nanoparticles could be effectively regenerated with 0.1 mol·L−1 EDTA or 1 mol·L−1 HNO3 without significantly losing their adsorption capacities even after five adsorption–desorption cycles. With these impressive properties, PTT nanoparticles are very promising materials in the fields of water-treatment and precious metals recovery.
topic poly-2-mercapto-1,3,4-thiadiazole
synthesis
characterization
nanoparticles
adsorption
heavy metal ions
mercury
silver
url http://www.mdpi.com/2073-4360/10/2/150
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