Development of novel nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric
© Bondar et al.; licensee Springer. 2014
Received: 13 December 2013
Accepted: 19 March 2014
Published: 13 April 2014
A nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric was synthesized for selective removal of Cs ions from contaminated waters by a two-stage synthesis: radiation-induced graft polymerization of acrylic acid monomer onto the nonwoven polypropylene fabric surface with subsequent in situ formation of potassium nickel hexacyanoferrate (KNiHCF) nanoparticles within the grafted chains. Data of scanning electron microscopy, X-ray diffraction, and Fourier transform infrared spectroscopy confirmed the formation of KNiHCF homogeneous phase on the fabric surface, which consisted of crystalline cubic-shaped nanoparticles (70 to 100 nm). The efficiency of the synthesized adsorbent for removal of cesium ions was evaluated under various experimental conditions. It has demonstrated a rapid adsorption process, high adsorption capacity over a wide pH range, and selectivity in Cs ion removal from model solutions with high concentration of sodium ions.
KeywordsNanocomposite adsorbent Potassium nickel hexacyanoferrate(II) Nanoparticles Polypropylene fabric Radiation grafting Selective adsorption Cesium
The selective removal of 137Cs ions from liquid radioactive waste and their quantitative determination in the environment have a great importance in recent years. Insoluble divalent transition metal hexacyanoferrates(II) are very effective inorganic adsorbents for cesium ions . Because they possess a high selectivity for Cs binding in the presence of alkaline earth and alkali metal ions, several attempts have been made to use hexacyanoferrates (HCFs) for the treatment of liquid radioactive waste with high salt content [2, 3].
However, HCFs are usually synthesized as fine or ultrafine grains which are difficult for practical applications due to their low mechanical stability and tendency to become colloidal in aqueous solution. In order to improve their mechanical properties, deposition of insoluble hexacyanoferrates on various solid supports has been suggested as a possible solution. Different composite adsorbents were fabricated by loading nanosized HCFs onto the surface or inside of pores of inert solid supports such as silica gels , zeolites , zirconium and titanium hydroxides , different organic ion exchangers [7, 8], etc.
Fibrous natural and synthetic polymers with ion exchange groups are promising host solid support for the synthesis of composite adsorbent with nanosized HCFs. Such composite adsorbent is expected to combine the unique properties of nanoscaled HCF particles (high specific surface, high speed of chemical reactions, selectivity) and technological properties of fibrous polymer matrix (flexibility, chemical stability, high specific surface, low hydraulic permeability, and ease utilization in dynamic sorption regimes).
Among various hexacyanoferrates, one of the most promising cesium-selective reagents is potassium nickel hexacyanoferrate (KNiHFC), which displays high chemical resistance in acid and alkaline solutions, mechanical stability, and thermal stability [2, 9]. Polypropylene (PP) fibers and nonwoven fabrics are very attractive support in preparing nanocomposite adsorbents because of the low cost, good mechanical strength, chemical and thermal resistance of the PP base, and highly developed specific surface of the fibrous structure.
In this study we propose a novel nanocomposite adsorbent based on a KNiHCF-loaded polypropylene fabric for Cs, which was prepared by the radiation-induced graft polymerization of acrylic acid monomer onto the surface of nonwoven polypropylene fabric, followed by in situ formation of KNiHCF nanoparticles within the grafted polyacrylic acid chains. The synthesized adsorbent was used for the removal of Cs ions from the model solutions in batch mode, and the influence of contact time, pH, and presence of sodium ions on the adsorption process was investigated.
Nonwoven material made of polypropylene fibers, available from Saehan Filter Co., Ltd. (Cheongju, South Korea), with an average thickness of 1 mm was used for the synthesis of the nanocomposite adsorbent. Analytical grade NiCl2 · 6H2O (Duksan Pure Chemicals Co., Ltd., Ansan-si, South Korea) and K4[Fe(CN)6] 3H2O (Sigma-Aldrich, St. Louis, MO, USA) were used to prepare experimental solutions, respectively.
Nonradioactive CsCl (Dae Jung Chemicals & Metals Co., Ltd., Shiheung City, South Korea) was used as a surrogate for 137Cs because of its identical chemical characteristics. All working solutions were prepared using deionized water; pH was adjusted with a suitable quantity of NaOH and HCl, monitored with a digital pH meter. All experiments were carried out at ambient temperature.
Preparation of the KNiHCF-loaded polypropylene fabric
The composite material based on the nonwoven polypropylene fabric with chemically bound KNiHCF nanoparticles was synthesized through a two-stage experiment. At the first stage, the chemically inert polypropylene base was activated through the radiation-induced graft polymerization of acrylic acid monomer (AA) for the introduction of chemically active carboxyl groups onto the surface of PP fibers through covalent bonding between grafted polyacrylic acid (PAA) chains and PP base . Grafted fabric samples with a medium value of AA grafting degree (120% to 170% and carboxyl group density of 6.0 to 7.5 mmol/g) were taken for the experimental work. The second stage consisted of Ni2+ ion loading onto PAA chains grafted to the PP fabric (PP-g-PAA) followed by the in situ formation and stabilization of KNiHCF nanoparticles within the grafted layer. For this purpose, the PP-g-PAA fabric was immersed in 0.1 M NiCl2 solution for 12 h. After filtration, washing with distilled water, and drying at ambient temperature, the resulting PP-g-PAA (Ni) fabric was added to 2.5% solution of potassium hexacyanoferrate(II) for 24 h under gentle mixing. Finally, the KNiHCF-loaded PP fabric was separated by filtration, washed with deionized water until clear rinsing solution, and dried at 60°C for 24 h.
Characterization of the KNiHCF-loaded polypropylene fabric
The surface morphology of the original PP and KNiHCF-loaded PP fabrics was recorded by a Hitachi S-4100 field emission scanning electron microscope (SEM; Hitachi, Ltd., Tokyo, Japan) at an acceleration voltage of 15 keV. The elemental composition was performed by energy-dispersive X-ray spectroscopy (EDS). The studied samples were sputter-coated with a thin Pt layer prior to examination.
Fourier transform infrared (FT-IR) measurements were carried out using a Spectrum™ 100 FT-IR spectrometer (PerkinElmer, Waltham, MA, USA) with attenuated total reflectance (ATR) mode. Spectra were collected by cumulating 24 scans. X-ray diffraction studies were carried out on a DRON-3 diffractometer (Scientific Industrial Enterprise “Burevestnik”, St. Petersburg, Russia) using Cu-Kα radiation in the range 10° to 90° in 2θ at room temperature.
A cesium chlorite stock solution of 1,000 mg/l was diluted, as required, to obtain the desired concentration. The pH of the solution was adjusted by using dilute solutions of hydrochloric acid, or sodium hydroxide, depending on the requirement.
Adsorption experiments were carried out in batch mode under shaking by placing a dry nanocomposite fabric (0.1 g) in a series of polypropylene flasks with 20 ml of CsCl solution. Once the required time elapsed, the residual solution was filtered through a Whatman filter paper and analyzed for Cs concentration by the atomic absorption spectrophotometer model AA-8500 (Nippon Jarrell-Ash Co., Ltd., Kyoto, Japan).
where C0 and C t are the initial concentration and concentration of Cs at time t (mg/l) in the experimental solution, V is the volume of the solution (l), and W is the weight of the adsorbent (g). At the equilibrium time, Q t = Q e .
where C e is the cesium concentration at equilibrium.
All the experiments were performed in duplicate.
Results and discussion
Preparation of the KNiHCF-loaded polypropylene fabric
The nanocomposite adsorbent based on potassium nickel hexacyanoferrate-loaded polypropylene fabric was synthesized through a two-stage experiment: radiation-induced graft polymerization of acrylic acid monomer onto the nonwoven PP fabric followed by the in situ formation of KNiHCF nanoparticles within the grafted chains.
The first stage, which resulted in the synthesis of the PP fabric with grafted PAA chains with a wide spectrum of carboxylic group density, was examined previously . The first stage is a very important one due to several reasons. First, it allows the activation of the chemically inert polypropylene base through covalent bonding between grafted PAA chains of nano/micro-sized length and the PP fibers' surface. As a result of the grafting process, the PP-g-PAA fabric surface became covered with cation exchange groups, which could be loaded with any metal ions.
Second, the grafted chains loaded with Ni2+ ions serve as precursors of KNiHCF nanoparticles. The formation of KNiHCF nanoparticles occur inside of the grafted chains, and thus, these nanoparticles become attached to the fibers' surface via both physical and chemical forces. Third, the characteristics of grafted chains (density, length, chemical nature of the functional group) make it possible to control the in situ formation of inorganic nanoparticles, namely their density of distribution, size, and morphology. Therefore, it is possible to consider the grafted chains as a ‘nanoreactor’ for the nanoparticles' formation. Furthermore, they stabilize and isolate the formed nanoparticles, thus preventing their aggregation. Thus, the grafted chains can open wide opportunities for the in situ synthesis of inorganic nanoparticles with tailored morphology and size.
The intent of the second stage consisted in the in situ formation of KNiHCF nanoparticles on the PP fibers' surface. The second stage involved Ni ion loading onto the grafted chains and subsequent reaction of PP-g-PAA (Ni) fibers with potassium hexacyanoferrate solution.
We believe that the close position of the charged carboxyl groups through the nano/micro-sized length of grafted PAA chains as well as the close position of the neighboring chains could have created the nucleation sites of Ni nanoclusters which, by subsequent reaction with potassium hexacyanoferrate, have led to the formation of KNiHCF nanoparticles within the grafted chains.
Characterization of the KNiHCF-loaded polypropylene fabric
Results of the EDS analysis of the outer surface of the KNiHCF-loaded PP fabric
Cesium adsorption studies
The adsorption of cesium ions on potassium nickel hexacyanoferrate proceeds via stoichiometric ion exchange between the potassium and cesium ions. To investigate the efficiency of the synthesized nanocomposite KNiHCF-loaded PP fabric, the effect of contact time, pH, and sodium ion concentration on cesium ion adsorption was investigated in detail.
Effect of contact time on cesium ion adsorption
Effect of pH on cesium ion adsorption
Effect of sodium ion concentration on cesium ion adsorption
A novel composite adsorbent based on polypropylene fabric with chemically bound nanoparticles of potassium nickel hexacyanoferrate was successfully prepared by a two-stage experiment: radiation-induced graft polymerization of acrylic acid onto the surface of nonwoven polypropylene fabric followed by the in situ formation of KNiHCF nanoparticles and their stabilization on the fabric surface within the grafted chains.
SEM, FT-IR-ATR, and X-ray diffraction techniques confirmed the formation of KNiHCF as crystalline nanoparticles with a face-centered cubic structure. The cesium adsorption on the composite adsorbent based on the KNiHCF-loaded PP fabric was studied as a function of contact time, pH, and the presence of competitive sodium ions. The synthesized adsorbent demonstrated fast adsorption kinetics, high adsorption capacity over a wide pH range, and selectivity in removal of Cs ions from an alkaline solution with a high concentration of competitive sodium ions.
This work was financially supported by the State Agency of Science, Innovation and Informatics of Ukraine in 2013, which is gratefully acknowledged.
- Naushad M: Inorganic and composite ion exchange materials and their applications. Ion Exchange Lett 2009, 2: 1–14.
- Mimura H, Lehto J, Harjula R: Selective removal of cesium from simulated high-level liquid wastes by insoluble ferrocyanides. J Nucl Sci Technol 1997, 34: 607–609. 10.1080/18811248.1997.9733715View Article
- Harjula R, Lehto J, Tusa E, Paavola A: Industrial scale removal of cesium with hexacyanoferrate exchanger - process development. Nuclear Technol 1994, 107: 272–278.
- Milonjić S, Bispo I, Fedoroff M, Loos-Neskovic C, Vidal-Majdar C: Sorption of cesium on copper hexacyanoferrate/polymer/silica composites in batch and dynamic conditions. J Radioanal Nucl Chem 2002, 252: 497–501. 10.1023/A:1015846502676View Article
- Kazemian H, Zakeri H, Rabbani MS: Cs and Sr removal from solution using potassium nickel hexacyanoferrate impregnated zeolites. J Radioanal Nucl Chem 2006, 268: 231–236. 10.1007/s10967-006-0158-xView Article
- Voronina AV, Semenishchev VS: Influence of the concentrations of potassium, sodium, ammonium ions on the cesium sorption with mixed nickel potassium ferrocyanide sorbent based on hydrated titanium dioxide. Radiochemistry 2013, 55: 399–403. 10.1134/S1066362213040103View Article
- Singh IJ, Misra BM: Studies on sorption of radiocesium on copper-hexacyanoferrate-loaded resins. Sep Sci Technol 1996, 31: 1695–1706. 10.1080/01496399608000720View Article
- Valsala TP, Roy SC, Shah JG, Gabriel J, Raj K, Venugopal V: Removal of radioactive caesium from low level radioactive waste (LLW) streams using cobalt ferrocyanide impregnated organic anion exchanger. J Hazard Mater 2009, 166: 1148–1153. 10.1016/j.jhazmat.2008.12.019View Article
- Mimura H, Lehto J, Harjula R: Chemical and thermal stability of potassium nickel hexacyanoferrate (II). J Nucl Sci Technol 1997, 34: 582. 10.1080/18811248.1997.9733711View Article
- Bondar Y, Han DH: Optimization of radiation-chemical synthesis of polypropylene fibers with carboxyl groups. Rep Ukrainian Acad Sci (in Ukraine) 2012, 105–110.
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited.