Elsevier

Chemical Engineering Journal

Volume 320, 15 July 2017, Pages 427-435
Chemical Engineering Journal

Ligand field effect for Dysprosium(III) and Lutetium(III) adsorption and EXAFS coordination with novel composite nanomaterials

https://doi.org/10.1016/j.cej.2017.03.075Get rights and content

Highlights

  • Hybrid donor functionalized alumina-silica based nanomaterial was fabricated.

  • Ligand field effect was effective for specific lanthanide ions separation.

  • Nanomaterials was selective to Dy(III) or Lu(III) in presence of divers common ions.

Abstract

The separation of lanthanide (Ln(III)) elements from various waste materials is a significant issue facing developed countries. However, the chemical behaviour of Ln(III) are very similar and complex, and it is an important to understand clearly to optimize the separation processes under various conditions based on the ion-selective ligands and ligand field effect for specific Ln(III) separation with semi-cavity and high flexibility for competitiveness of industries and continuous economic growth. The study developed the hybrid Lewis base ligand functionalized alumina-silica based composite nanomaterials for heavier Ln(III) of Dy(III) and Ly(III) separation and recovery. The alumina-silica fabrication, intra-series separation, solution acidity, ion-selective and coordination mechanism by EXAFS were carried out systematically. The Dy(III) and Lu(III) adsorption was high in acidic region as the high pH area is avoided due to the hydroxyl precipitation. The adsorption data were fitted well with the Langmuir adsorption model for the both elements and the calculated maximum adsorption capacity was 125.44 and 129.77 mg/g for Dy(III) and Lu(III) ions, respectively. The ion selectivity was also performed in the presence of divers ions and Dy(III) or Lu(IIII) ions was preferentially adsorbed in a competitive environment. In the coordination mechanism by EXAFS, the Dy(III) and Lu(III) ions were strongly coordinated with the O and N atoms of the hybrid Lewis base ligand in the composite nanomaterial. Moreover, adsorption–elution cyclic results demonstrated that Dy(III) and Lu(III) ions adsorbed composite nanomaterial could be effectively desorbed HNO3 acid, and the regenerated nanomaterial was able to repeated use without significant deterioration in its original performances. All these characteristics make the nanomaterial an ideal solid-phase materials for effective Dy(III) and Lu(III) ions adsorption in complicated matrix samples.

Introduction

Rare earth metals have been widely used in all major applications in metallurgy, electronics, ceramics, optical, medical, magnets, chemical, and nuclear technologies due to their specific physical and chemical properties. For example, Dysprosium (Dy(III)) has used in magnetic alloys and ferrites for microwave purposes. In addition, Dy(III) has numerous applications in nuclear and metallurgical industries. Also the Dy(III) along with special steel is used to make nuclear reactor control rods. Moreover, in combination with vanadium and other rare earth, Dy(III) has been used in making laser materials [1], [2]. Similarly, Lutetium (Lu(III)) is one of the heavy lanthanide (Ln(III)) elements with significant uses in the production of color televisions, energy-saving lamps and glasses [3]. However, the individual Ln(III) separation from each other is very difficult due to their similar chemical properties. On the other hand, the decrease in ionic radius with atomic number within the Ln(III) implied the predictable chemical differences from lanthanum through Lu(III) [4]. Therefore, there is room to separate the specific Ln(III) considering to the complexation ability at optimum condition. Then the fast, simple, and accurate Ln(III) separation with specific complexation mechanism is very important.

Several methods are used for separation of rare earth metals such as liquid extraction, sedimentation, oxidation, ion exchange and adsorption. Liquid extraction is the common method used for the separation and recovery of metal ions from aqueous solutions [5], [6], [7], [8]. However, solid phase extraction/adsorption is replacing liquid extraction due to the absence of emulsion, great enrichment ratio, flexibility, short process, automated analytical techniques, safety and minimal costs [9], [10]. Diverse adsorption materials such as organic chelate resin, silica and silica gel, alumina, titania, and molecular-imprinted polymers have been used as adsorbents for solid phase extraction [6], [11], [12], [13], [14], [15]. In this connection, much of the research in selecting adsorbents in solid phase extraction/adsorption based on molecular embedded materials [16], [17], [18] is used for metal ions separation. From this stand point, nanomaterials can be used as suitable materials for this purpose due to their high surface area, specific pore size and pore volumes [1], [19], [20]. In this connection, diverse metal ions are separated with using different ligands group containing functionalized nanomaterials [21], [22], [23], [24], [25]. However, the Ln(III) has special interaction with N- and O-donor ligands based on the hard-soft acid-bases theory [26], [27], [28].

Recently, hybrid donor ligands are received much attention for specific Ln(III) separation due to their complexation ability and coordination mechanism [28], [29]. In this study, N- and O- donor ligand containing N-methyl-N-phenyl-1,10-phenanthroline-2-carboxamide (MePhPTA) (Scheme 1) was used for Ln(III) intra-series separation after successful immobilization onto the alumina-silica composite nanomaterials. In the structure of MePhPTA, two N-atoms in phenanthroline and one O- atom in amide carbonyl are arranged for stable complex formation with the Ln(III). As the MePhPTA ligand is flexible, the most Ln(III) ions can be accommodated within this inner coordination sphere. The different radii of Ln(III) cause their different properties, such as charge densities and hydration energy. Their hydration energy ranges from 3370 to 3760 kJ/mol from Ce(III) to Lu(III) ions [30], [31]. Hence, the only way to design an ion-selective ligands and ligand field effect for specific Ln(III) separation with semi-cavity and high flexibility. Then the carrier inorganic materials have always bear the significant influence to open the functionality of the embedded organic ligand for knowing the ligand field effect [32], [33], [34]. In this connection, we have prepared alumina-silica composite nanomaterials and then incorporated with the MePhPTA ligand to understand the ligand effect while the ligand was same. Also this is the first time approach of the corresponding author to evaluate the Ln(III) separation based on the using of alumina-silica as carrier field. After Ln(III) intra-series observation by the functionalized composite nanomaterial, Dy(III) and Lu(III) ions are specific for effective separation at optimum condition. The incorporation of aluminum into the silica gives the materials with acidic active sites. It is also noted that the acidity of these solid materials generally arises from the cationic Bronsted acid sites from the coordination of aluminum species in the alumina-silica nanomaterials [35], [36], [37]. Then the acidity of composite nanomaterial surfaces is a key factor in Ln(III) separation and coordination. The present work describes our investigations of the adsorption of Dy(III) and Lu(III) ions on the composite nanomaterial.

The metal ions complexation on the solid surface functional group has been evident by the synchrotron based extended X-ray absorption fine structure (EXAFS) methods [38], [39], [40]. The EXAFS analysis provides structural speciation with metal ions identification, coordination number and bond distance of the neighboring atoms around the metal atom [41]. The Ln(III) coordination mechanisms are evident of ligand doped silica based nanomaterials. However, specific interaction was evident with low bond distance of ytterbium probe atoms [28]. This gives an idea to investigate the Ln(III) surface interaction with N- and O-donor ligand based alumina-silica composite nanomaterials with specific focus on Dy(III) and Lu(III) complex formation during adsorption at optimum condition. Here, we present the results of Dy(III) and Lu(III) ions complex with MePhPTA ligand embedded composite nanomaterial based on the EXAFS method. Significant parameters such as incorporation ligand and alumina-silica, composite nanomaterial characterization, the Ln(III) transportation behaviour were determined systematically. It is also noted that diverse ligand embedded materials gave an advantages from the stand point of sensitivity, selectivity and coordination mechanism [42], [43], [44]. There is similar valance and ionic radii of the Ln(III) and trivalent actinides (Am(III), Cm(III), and Cf(III) [45], [46], [47], the Ln(III) separation method from the present study can be used to predict the behaviour of the actinide-series elements in the nuclear fuel processing in nuclear waste treatment.

Section snippets

Materials

All materials and chemicals were of analytical grade and used as purchased without further purification. Silica source of Tetramethylorthosilicate (TMOS), the triblock copolymers of poly(ethylene oxide-b-propylene oxide-b-ethylene oxide) as Pluronic F108, designated as F108 (EO141PO44EO141) and Al(NO3)3·9H2O were purchased from Sigma-Aldrich Company Ltd. USA. The Ln(III) as the nitrate derivatives were purchased from Rare Metallic Co. Ltd., Japan and other metal ions reagent were purchased from

Characterization of alumina-silica and conjugate material

The N2 adsorption–desorption isotherms with specific area, pore size and pore volumes of the sample are shown in Fig. 1(A). The isotherms are IV type with H2 shaped hysteresis loops, indicating synthesized alumina-silica pores are mesoporous material [36], [37]. The sharp capillary condensation steps were occurred at the relative pressure of 0.4–0.6, which is indicating the uniform mesoporous characteristic [33]. Also the alumina-silica has consisted of a high surface area of 379 m2/g with the

Conclusions

In this work, extensive laboratory experiments were performed for selective Dy(III) and Lu(III) ions adsorption and recovery based on ligand field effect and coordination mechanism by EXAFS using hybrid Lewis base anchored alumina-silica based composite nanomaterial. The nanomaterial clarified an excellent adsorption properties in terms of sensitivity and selectivity because of the coordination complexation with O and N donor atoms on its surface which can create intensive interaction with

Acknowledgment

This research was partially supported by the Grant-in-Aid for Research Activity Start-up (24860070) from the Japan Society for the Promotion of Science. The authors extend their appreciation to the International Scientific Partnership Program ISPP at King Saud University for funding this research work through ISPP# 87. The EXAFS experiments have been carried out with the approvals of KEK, Tsukuba (Proposal No. 2014G102). The author also wishes to thanks to the anonymous reviewers and editor for

References (58)

  • M.R. Awual

    Ring size dependent crown ether based mesoporous adsorbent for high cesium adsorption from wastewater

    Chem. Eng. J.

    (2016)
    M.R. Awual et al.

    Encapsulation of cesium from contaminated water with highly selective facial organic-inorganic mesoporous hybrid adsorbent

    Chem. Eng. J.

    (2016)
    M.R. Awual et al.

    A reliable hybrid adsorbent for efficient radioactive cesium accumulation from contaminated wastewater

    Sci. Rep.

    (2016)
  • M.R. Awual et al.

    Novel conjugate adsorbent for visual detection and removal of toxic lead(II) ions from water

    Microporous Mesoporous Mater.

    (2014)
    M.R. Awual et al.

    A sensitive ligand embedded nano-conjugate adsorbent for effective cobalt(II) ions capturing from contaminated water

    Chem. Eng. J.

    (2015)
    M.R. Awual et al.

    Colorimetric detection and removal of copper(II) ions from wastewater samples using tailor-made composite adsorbent

    Sens. Actuators, B: Chem.

    (2015)
  • K.A. Northcott et al.

    The adsorption of divalent metal cations on mesoporous silicate MCM-41

    Chem. Eng. J.

    (2010)
  • X.Q. Chen et al.

    Selective removal of chromium from different aqueous systems using magnetic MCM-41 nanosorbents

    Chem. Eng. J.

    (2011)
  • M.R. Awual et al.

    A novel ligand based dual conjugate adsorbent for cobalt(II) and copper(II) ions capturing from water

    Sens. Actuators, B: Chem.

    (2014)
    M.R. Awual et al.

    Investigation of ligand immobilized nano-composite adsorbent for efficient cerium(III) detection and recovery

    Chem. Eng. J.

    (2015)
    A. Shahat et al.

    Functional ligand anchored nanomaterial based facial adsorbent for cobalt(II) detection and removal from water samples

    Chem. Eng. J.

    (2015)
  • M.R. Awual et al.

    Trace copper(II) ions detection and removal from water using novel ligand modified composite adsorbent

    Chem. Eng. J.

    (2013)
    M.R. Awual et al.

    PH dependent Cu(II) and Pd(II) ions detection and removal from aqueous media by an efficient mesoporous adsorbent

    Chem. Eng. J.

    (2014)
    A. Shahat et al.

    Large-pore diameter nano-adsorbent and its application for rapid lead(II) detection and removal from aqueous media

    Chem. Eng. J.

    (2015)
  • S.A. El-Safty et al.

    Large three-dimensional mesocage pores tailoring silica nanotubes as membrane filters: nanofiltration and permeation flux of proteins

    J. Mater. Chem.

    (2011)
    S.A. El-Safty et al.

    Optical mesosensors for monitoring and removal of ultra-trace concentration of Zn(II) and Cu(II) ions from water

    Analyst

    (2012)
    M. Naushad et al.

    Synthesis of sodium dodecyl sulfate-supported nanocomposite cation exchanger: removal and recovery of Cu2+ from synthetic, pharmaceutical and alloy samples

    J. Iran. Chem. Soc.

    (2015)
  • M.R. Awual et al.

    Functionalized novel mesoporous adsorbent for selective lead(II) ions monitoring and removal from wastewater

    Sens. Actuators, B: Chem.

    (2014)
    M.R. Awual et al.

    Ultimate selenium(IV) monitoring and removal from water using a new class of organic ligand based composite adsorbent

    J. Hazard. Mater.

    (2015)
    M. Naushad et al.

    Water purification using cost effective material prepared from agricultural waste: kinetics, isotherms and thermodynamic studies

    Clean Soil Air Water

    (2016)
  • E.P. Diamandis et al.

    Time-resolved fluorescence using a europium chelate of 4,7-bis-(chlorosulfopheny1)-1,10-phenanthroline-2,9-dicarboxylic acid (BCPDA): Labeling procedures and applications in immunoassays

    J. Immunol. Methods

    (1988)
  • R.G. Pearson

    Hard and soft acids and bases (HSAB). I. Fundamental principles

    J. Chem. Educ.

    (1968)
  • M.R. Awual et al.

    Selective lanthanide sorption and mechanism using novel hybrid Lewis base (N-methyl-N-phenyl-1,10-phenanthroline-2-carboxamide) ligand modified adsorbent

    J. Hazard. Mater.

    (2013)
  • T. Kobayashi et al.

    Effect of the introduction of amide oxygen into 1,10-phenanthroline on the extraction and complexation of trivalent lanthanide in acidic condition

    Sep. Sci. Technol.

    (2010)
  • M.R. Ganjali et al.

    Neutral N, N′-bis(2-pyridinecarboxamide)-1,2-ethane as sensing material for determination of lutetium(III) ions in biological and environmental samples

    Mater. Sci. Eng., C

    (2009)
  • N.N. Greenwood et al.

    Chemistry of the Elements

    (1984)
  • M.J. Climent et al.

    Use of mesoporous MCM-41 aluminosilicates as catalysts in the production of fine chemicals: preparation of dimethylacetals

    J. Catal.

    (1996)
  • S.A. El-Safty et al.

    Efficient adsorbents of nanoporous aluminosilicate monoliths for organic dyes from aqueous solution

    J. Colloid Interface Sci.

    (2011)
  • M.K. Mardkhe et al.

    A statistical approach to control porosity in silica-doped alumina supports

    Microporous Mesoporous Mater.

    (2015)
  • Z. Sun et al.

    Hierarchically ordered macro-/mesoporous silica monolith: tuning macropore entrance size for size-selective adsorption of proteins

    Chem. Mater.

    (2011)
  • B. Huang et al.

    Facile structure-controlled synthesis of mesoporous γ-alumina: effects of alcohols in precursor formation and calcination

    Microporous Mesoporous Mater.

    (2013)
  • Cited by (259)

    • Comparative analysis of HHV and LHV values of biocoke fuel from palm oil mill solid waste

      2024, Case Studies in Chemical and Environmental Engineering
    • Synthesis of chain-like nitrogen-doped carbon for high-performance supercapacitors

      2024, Colloids and Surfaces A: Physicochemical and Engineering Aspects
    View all citing articles on Scopus
    View full text