Preparation and characterization of a novel hybrid chelating material for effective adsorption of Cu(II) and Pb(II)
Graphical abstract
A novel hybrid polymer Al(OH)3-poly(acylamide-dimethyldiallylammonium chloride)-dithiocarbamate with “star-like” structure was synthesized and exhibited excellent adsorption capacities for Cu2 + and Pb2 +.
Introduction
Water pollution by heavy metal ions is an increasing concern for global public health due to their severe toxicity and bioaccumulation through food chains (Lofrano et al., 2016, Zare-Dorabei et al., 2016, Zhou et al., 2016). A variety of conventional remediation methods such as ion exchange, chelation–precipitation, membrane filtration, adsorption and reverse osmosis have been applied in the mineral processing, metal electroplating, metallurgical engineering and battery manufacturing industries (Du et al., 2016, Lakard et al., 2015, Yue et al., 2016) to remove the heavy metal ions from their waste streams (Efligenir et al., 2014, Fthenakis, 2004, Xu et al., 2017, Zhao et al., 2016). Among these technologies, chelation–precipitation has attracted great attention owing to its good performance, low cost, easy handling and extensive applicability (Huang and Keller, 2015, Liu et al., 2013a).
Chelating agents, such as dithiocarbamates (DTC), have been widely used as extractive reagents due to their strong binding abilities with heavy metal ions and excellent performance in heavy metal ion decontamination. Based on the attached DTC groups, chelating agents are identified as either micro-molecules with both single and multiple DTC groups, or macromolecules with only multiple DTC groups. In recent years, macro-molecules with multiple DTC groups integrating high chelation abilities and excellent flocculation properties have drawn increasing attention (Gao et al., 2010, Liu et al., 2013b). However, most of the linear macromolecules with DTC functional groups suffer from steric hindrance and spatial mismatches, preventing the combination of DTC and heavy metal ions in chelation processes. Consequently, the chelating floccules usually have excess negative charges, inhibiting their further growth and rapid settlement (Fu et al., 2006, Fu et al., 2007, Li et al., 2015).
Over the past few years, efforts have been made to introduce cationic units into the polymer chains by synthesizing poly(dimethyldiallylammonium chloride-co-acrylamide)-graft-triethylenetetramine-dithiocarbamate (PDTATD), to accelerate the settlement of floccules by neutralizing the excess negative charges through coagulation (Fu et al., 2007, Liu et al., 2013a). However, active adsorption sites are still unable to be fully exposed due to the steric hindrance and spatial mismatches of DTC in the linear polymers. To the best of our knowledge, no attempt has been made to introduce DTC groups into star-like polymers for effective utilization of the functional adsorption groups. In terms of molecular structure, a “star-like” structure contributes more to the bridge adsorption process compared with linear chain molecules, due to the easy accessibility of heavy metal ions to DTC groups in the outstretched polymer chains. We have synthesized a polymer Al(OH)3-polyacrylamide (Al-PAM) with “star-like” structure wherein Al(OH)3 acts as a core connecting PAM chains as arms, resulting in effective flocculation of negatively charged particles due to the charge neutralization by Al(OH)3 and easy accessibility of PAM arm chains for bridge adsorption (Alagha et al., 2013, Liu et al., 2016, Sun et al., 2008). Based on the “star-like” structure, DTC groups could be introduced into the outstretched PAM chains for ready attachment and effective utilization of functional groups, thus making it efficient for removal of heavy metal ions. In addition, the cationic unit of dimethyldiallylammonium chloride (DMDAAC) could be integrated into PAM chains through copolymerization of AM and DMDAAC to reduce the excess negative charge of the formed floccules, for rapid settlement and separation of contaminants from wastewater. Herein, we firstly synthesized Al(OH)3-poly(acrylamide-dimethyldiallylammonium chloride)-DTC (APD) to serve as an adsorbent for heavy metals in aquatic systems, followed by characterizing its adsorption capacity, kinetics, isotherms and mechanisms for Cu2 + and Pb2 + adsorption. Finally, APD was also tested in turbid heavy metal wastewater to investigate the adsorption performance for both heavy metal ions and suspended particles. The results demonstrated that APD was excellent for Cu2 + and Pb2 + decontamination.
Section snippets
Materials
Acrylamide (AM), dimethyldiallylammonium chloride (DMDAAC), diethylenetriamine (DETA) and carbon disulfide (CS2), used as constituents of APD, were purchased from Alladin. AlCl3, (NH4)2CO3, (NH4)S2O8, and NaHSO3, used in the synthesis of the adsorbent, were purchased from Xilong Chemical Co. Ltd. CuSO4 and Pb(NO3)2 used in heavy metal ion adsorption tests, as well as NaOH/HNO3 to serve as pH modifiers, were purchased from Xilong Chemical Co. Ltd. All the reagents were directly used without
APD synthesis and characterization
The synthesis of APD is schematically presented in Fig. 1. AP was synthesized by co-polymerization of AM and DMDAAC on the surface of Al(OH)3 colloids connected through ionic bonds, based on the method of Yang et al. (2004), in which the amino groups of AM units in AP reacted with HCHO to produce the intermediate through a methylolation reaction. The intermediate was further reacted with DETA through a nucleophilic reaction to obtain the final product of AP-DETA (Cummings and Shelton, 2002,
Conclusions
A novel hybrid polymer, Al(OH)3-poly(acrylamide-dimethyldiallylammonium chloride)-dithiocarbamate (APD), was synthesized and shown to exhibit excellent adsorption capacities for Cu2 + and Pb2 +. The kinetic studies showed that the adsorption of Cu2 + and Pb2 + by APD fitted well to the pseudo-second-order rate equation. Moreover, 90% of Cu2 + and 98% of Pb2 + was rapidly removed by APD from 50 mL of metal solutions with a concentration of 50 mg/L, in 30 min and 10 min respectively. The adsorption
Acknowledgments
This work was financially supported by the National Natural Science Foundation (No. 51202249), Strategic Priority Research Program of Chinese Academy of Science (No. XDA09040100) and Strategic Project of Science and Technology of Chinese Academy of Science (No. XDB05050000). The authors thank all the members at the Material Chemistry and Engineering group in the Institute of Process Engineering, CAS.
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