Synthesis and characterization of defective UiO-66 for efficient co-immobilization of arsenate and fluoride from single/binary solutions

https://doi.org/10.1016/j.envpol.2021.116841Get rights and content

Highlights

  • A simple mediator-free defective UiO-66-fum MOFs were synthesized.

  • La-fum MOF has higher adsorption densities, stablity than Ce- and Zr-fum MOFs.

  • Arsenate ions complexed with MOFs through a monodentate formation.

  • This MOFs could be used several times with zero-dissolution behavior.

Abstract

Here, we aimed to synthesize UiO-66 architected fumaric acid mediated lanthanum (La-fum), zirconium (Zr-fum), and cerium (Ce-fum) metal-organic frameworks (MOFs) for co-immobilizations of both arsenate and fluoride from both single and binary systems. The crystalline behavior of Zr-fum MOF was the lowest compared to the other two forms, due to the fact that it required a modulator support as the nucleus growth nature of zirconium moiety is different. The Langmuir maximum adsorption densities of arsenate (fluoride) were 2.689 (4.240), 1.666 (2.255), and 2.174 (4.155) mmol/g for La-fum, Zr-fum, and Ce-fum, respectively and these adsorption densities were found to have record-high values compared with the existing materials in the literature. The arsenate and fluoride adsorption on the MOF materials were confirmed by XPS, PXRD and FTIR studies. The arsenate adsorption mechanism on La-fum and Ce-fum through monodentate complexation confirmed using the distinguished K-edge shell distance in EXAFS studies. The arsenate and fluoride-sorbed materials were recycled using 0.01 M HNO3 and were further utilized for six consecutive cycles for both arsenate and fluoride adsorption indicated the feasibility of the materials. This kind of facile and easy solvothermal synthesized MOFs could pave a way towards the removal of toxins in a practical wastewater as these have superior adsorption properties, stability and reusability.

Introduction

Co-immobilization of arsenate and fluoride from water using porous solid materials is important for avoiding severe health effects. According to the WHO (World Health Organization), in drinking water, the maximum permissible limits of both arsenate and fluoride concentrations are 10 μg/L and 1.5 mg/L, respectively (1996; Litter et al., 2010; Weerasundara et al., 2021). Among many methods reported in the literature, adsorption is found to be cheap, easy operable, and highly efficient for the adsorption of toxic ions from waters. So far, many microporous oxides such as layered double hydroxide (LDH) (Koilraj et al., 2017b; Li et al., 2021; Mubarak et al., 2018), metal oxyhydroxides (Prabhu et al., 2017; Uppal et al., 2019), carbon-based materials (Koilraj et al., 2017a), and polymer/biopolymer based composites (Zeng et al., 2020) were routinely utilized to adsorb arsenate and fluoride from water. The new class of coordination polymers namely, metal-organic frameworks (MOFs), assembled by organic moiety as linker and the metal ions center of the bridge (Dhakshinamoorthy et al., 2018). The combination of both metal center and the organic linker is considered as inorganic secondary building units (SBUs) held together in the resulting MOF architecture (Furukawa et al., 2013). The MOFs materials have unique advantages, such as controllable pore size, low density, high surface area, and has widely used in many fields, for example, adsorption (Shi et al., 2020; Yang et al., 2020; Zhang et al., 2019d), photocatalysis (Chen et al., 2020a, 2020b; Zhang et al., 2021) and catalysis (Bi et al., 2020a, 2020b; Dhakshinamoorthy et al., 2019, 2020; Hyok Ri et al., 2021; Xie et al., 2017; Zhang et al., 2020).

Particularly, for the removal of arsenic, zirconium (Zr)-based materials were performed well in wide pH profiles. Zr-based (UiO-66) materials were highly used for environmental remediation, particularly in the field of water treatment, gas adsorption, and photocatalysis (Dhakshinamoorthy et al., 2016; Zhang et al., 2019a, 2019c). Likewise, architectured MOF materials with similar characteristics were recently developed with other metal ions for water treatment applications. Generally, lanthanide-series metals such as La3+, Ce3+, and Yu3+ possessed higher adsorption densities for the removal of toxic ions such as arsenate, fluoride, chromate and phosphate/nitrate from water due to their unique characteristics and high affinities. Prabhu et al., 2019b, Prabhu et al., 2019a and Liu et al. (2016) have developed La-BDC MOFs for arsenate and phosphate removal from water, respectively (Liu et al., 2016; Prabhu et al., 2019a). Recently, cerium-based MOFs have widely used for adsorption experiments towards the sensing of noxious ions from water (Dalapati et al., 2017). For example, Mahmoud and his group (2020) have developed AUBM (Ce-1,5-dihydroxy-2,6-napthalenedicarboxylic acid) for the effective sensing application of toxic heavy metals ions such as Pb(II), Cd(II), As(III), and Hg(II) (Mahmoud et al., 2020). A few studies were performed using Zr-MOFs for arsenic removal, but La- and Ce-based MOFs were not explored well for the adsorption of arsenic ions in single or binary solutions. Most of the MOFs have been developed using high cost and toxic molecules as organic linkers to detect a single pollutant, which does not bring any novelty of the system. Besides, the sucrose-derived carbon supported lanthanum and zirconium hydroxides and chitosan supported lanthanum and aluminum hydroxides were synthesized for the removal of toxic arsenite/fluoride adsorption from single and binary solutions. In which, the mechanism of interaction of ions and selectivity of the pollutants were not identified, and the stability of the materials was unknown Prabhu et al. (2017).

In this work, we focused to synthesize La3+, Zr4+, and Ce3+-based MOFs using -fum acid as the organic linker to form highly efficient MOF adsorbents for co-immobilization of arsenate and fluoride from single and binary solutonis. The developed materials for this study were characterized with usual spectro-analytical methods and the mechanism of adsorption of toxic arsenate and fluoride on the MOFs were analyzed by XPS, EXAFS and XANES techniques. Other operating parameters such as kinetics, isotherms and interfering anions studies were performed with duplicate and the average was taken for this study in single and binary solutions. The stability, and reusability of the adsorbents were performed to address the novelty of the materials and residual toxicity in the solution was also analyzed after adsorption of both ions in single/binary solutions.

Section snippets

Synthesis of La-fum MOF

The La-fum MOF was synthesized via a simple hydrothermal method according to our previously reported method with slight modification. Prabhu et al. (2019a) the typical synthesis of La-fum MOF was performed as follows: 743 mg of La(NO3)3∙6H2O and 232.1 mg of -fum were dissolved in 70 mL of dimethyl formamide (DMF) and stirred for 30 min, and the resulting solution was sonicated for 5 min. The solution was then transferred into a Teflon-lined stainless steel autoclave and hydrothermally treated

Characterization of the synthesized MOFs

The PXRD (RIGAKU, Akishima, Japan) patterns of synthesized defective La-fum, Zr-fum, and Ce-fum MOFs are shown in Fig. 1a, and the results were in good agreement with the previous reports in the literature. The synthesized La-fum was similar to the La-BDC (BDC = 1,4-benzenedicarboxylic acid) MOF with the UiO-66 backbone reported for arsenate adsorption and was found to be unstable at higher arsenate concentration. The La-BDC was re-precipitated as lanthanum arsenate after the adsorption of

Conclusion

In this study, three different kinds of MOFs namely, La-fum, Zr-fum, and Ce-fum with defective UiO-66 background were synthesized and utilized for the removal of toxic arsenate and fluoride ions from water in single and binary mixture solutions. The synthesized MOFs showed excellent adsorption densities towards arsenate and fluoride in both single and binary solutions on La-fum and Ce-fum over Zr-fum MOF, where the later one is not fully formed as crystalline MOF. Instead, Zr-fum formed an

Credit author statement

Subbaiah Muthu Prabhu: Writing – original draft, Writing – review & editing. Chitiphon Chuaicham: EXAFS software. Chang Min Park: Writing – review & editing. Byong-Hun Jeon: Writing – review & editing. Keiko Sasaki: Writing – original draft, Supervision, Funding acquisition.

Declaration of competing interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgments

Financial support was provided to KS by the Japan Society for the Promotion of Science (JSPS) through research grants JP16F16082 and to SMP (P16082) and KS (P17081) by the JSPS Postdoctoral Fellowship for Foreign Researchers. The EXAFS experiments were performed at Kyushu University Beamline (SAGA-LS/BL06) with Proposal No. 2017IK006. CMP would like to thank the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (

References (55)

  • M.E. Mahmoud et al.

    Lanthanides based metal organic frameworks for luminescence sensing of toxic metal ions

    J. Solid State Chem.

    (2020)
  • M. Mubarak et al.

    One-pot synthesis of layered double hydroxide hollow nanospheres with ultrafast removal efficiency for heavy metal ions and organic contaminants

    Chemosphere

    (2018)
  • S.M. Prabhu et al.

    Synthesis of sucrose-derived porous carbon-doped Zrx La1-xOOH materials and their superior performance for the simultaneous immobilization of arsenite and fluoride from binary systems

    Chem. Eng. J.

    (2017)
  • M. Qiu et al.

    XANES and EXAFS investigation of uranium incorporation on nZVI in the presence of phosphate

    Chemosphere

    (2018)
  • J. Ren et al.

    Modulated synthesis of zirconium-metal organic framework (Zr-MOF) for hydrogen storage applications

    Int. J. Hydrogen Energy

    (2014)
  • X. Shi et al.

    Effective toluene adsorption over defective UiO-66-NH2: an experimental and computational exploration

    J. Mol. Liq.

    (2020)
  • H. Uppal et al.

    Facile chemical synthesis and novel application of zinc oxysulfide nanomaterial for instant and superior adsorption of arsenic from water

    J. Clean. Prod.

    (2019)
  • L. Weerasundara et al.

    Selective removal of arsenic in water: a critical review

    Environ. Pollut.

    (2021)
  • G. Wißmann et al.

    Modulated synthesis of Zr-fumarate MOF

    Microporous Mesoporous Mater.

    (2012)
  • Y. Yang et al.

    Insights to perfluorooctanoic acid adsorption micro-mechanism over Fe-based metal organic frameworks: combining computational calculation with response surface methodology

    J. Hazard Mater.

    (2020)
  • J. Zeng et al.

    Chitosan functionalized iron nanosheet for enhanced removal of As(III) and Sb(III): synergistic effect and mechanism

    Chem. Eng. J.

    (2020)
  • X. Zhang et al.

    Enhanced hydrophobic UiO-66 (University of Oslo 66) metal-organic framework with high capacity and selectivity for toluene capture from high humid air

    J. Colloid Interface Sci.

    (2019)
  • X. Zhang et al.

    The preparation of defective UiO-66 metal organic framework using MOF-5 as structural modifier with high sorption capacity for gaseous toluene

    Journal of Environmental Chemical Engineering

    (2019)
  • X. Zhang et al.

    Adsorption/desorption kinetics and breakthrough of gaseous toluene for modified microporous-mesoporous UiO-66 metal organic framework

    J. Hazard Mater.

    (2019)
  • X. Zhang et al.

    Enhanced adsorption performance of gaseous toluene on defective UiO-66 metal organic framework: equilibrium and kinetic studies

    J. Hazard Mater.

    (2019)
  • X. Zhang et al.

    Highly efficient Mn2O3 catalysts derived from Mn-MOFs for toluene oxidation: the influence of MOFs precursors

    Molecular Catalysis

    (2020)
  • X. Zhang et al.

    Enhanced photocatalytic degradation of gaseous toluene and liquidus tetracycline by anatase/rutile titanium dioxide with heterophase junction derived from materials of Institut Lavoisier-125(Ti): degradation pathway and mechanism studies

    J. Colloid Interface Sci.

    (2021)
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