Synthesis and characterization of defective UiO-66 for efficient co-immobilization of arsenate and fluoride from single/binary solutions☆
Graphical abstract
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)
- et al.
Excellent catalytic activity and water resistance of UiO-66-supported highly dispersed Pd nanoparticles for toluene catalytic oxidation
Appl. Catal. B Environ.
(2020) - et al.
Effect of Pd loading on ZrO2 support resulting from pyrolysis of UiO-66: application to CO oxidation
J. Colloid Interface Sci.
(2020) - et al.
A facile synthesis for uniform tablet-like TiO2/C derived from Materials of Institut Lavoisier-125(Ti) (MIL-125(Ti)) and their enhanced visible light-driven photodegradation of tetracycline
J. Colloid Interface Sci.
(2020) - et al.
Synergistic effects of octahedral TiO2-MIL-101(Cr) with two heterojunctions for enhancing visible-light photocatalytic degradation of liquid tetracycline and gaseous toluene
J. Colloid Interface Sci.
(2020) - et al.
Metal–organic frameworks as multifunctional solid catalysts
Trends in Chemistry
(2020) - et al.
Direct epitaxial synthesis of magnetic Fe3O4@UiO-66 composite for efficient removal of arsenate from water
Microporous Mesoporous Mater.
(2019) - et al.
Manganese-cerium composite oxide pyrolyzed from metal organic framework supporting palladium nanoparticles for efficient toluene oxidation
J. Colloid Interface Sci.
(2021) - et al.
Adsorptive removal of arsenic from aqueous solution by zeolitic imidazolate framework-8 (ZIF-8) nanoparticles
Colloid. Surface. Physicochem. Eng. Aspect.
(2015) - et al.
Dual-functional sites for selective adsorption of mercury and arsenic ions in [SnS4]4-/MgFe-LDH from wastewater
J. Hazard Mater.
(2021) - et al.
Possible treatments for arsenic removal in Latin American waters for human consumption
Environ. Pollut.
(2010)
Lanthanides based metal organic frameworks for luminescence sensing of toxic metal ions
J. Solid State Chem.
One-pot synthesis of layered double hydroxide hollow nanospheres with ultrafast removal efficiency for heavy metal ions and organic contaminants
Chemosphere
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.
XANES and EXAFS investigation of uranium incorporation on nZVI in the presence of phosphate
Chemosphere
Modulated synthesis of zirconium-metal organic framework (Zr-MOF) for hydrogen storage applications
Int. J. Hydrogen Energy
Effective toluene adsorption over defective UiO-66-NH2: an experimental and computational exploration
J. Mol. Liq.
Facile chemical synthesis and novel application of zinc oxysulfide nanomaterial for instant and superior adsorption of arsenic from water
J. Clean. Prod.
Selective removal of arsenic in water: a critical review
Environ. Pollut.
Modulated synthesis of Zr-fumarate MOF
Microporous Mesoporous Mater.
Insights to perfluorooctanoic acid adsorption micro-mechanism over Fe-based metal organic frameworks: combining computational calculation with response surface methodology
J. Hazard Mater.
Chitosan functionalized iron nanosheet for enhanced removal of As(III) and Sb(III): synergistic effect and mechanism
Chem. Eng. J.
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.
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
Adsorption/desorption kinetics and breakthrough of gaseous toluene for modified microporous-mesoporous UiO-66 metal organic framework
J. Hazard Mater.
Enhanced adsorption performance of gaseous toluene on defective UiO-66 metal organic framework: equilibrium and kinetic studies
J. Hazard Mater.
Highly efficient Mn2O3 catalysts derived from Mn-MOFs for toluene oxidation: the influence of MOFs precursors
Molecular Catalysis
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.
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This paper has been recommended for acceptance by Jörg Rinklebe.