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. 2020 Mar 24;5(13):7392–7398. doi: 10.1021/acsomega.9b04419

High-Performance Metal–Organic Framework-Templated Sorbent for Selective Eu(III) Capture

Yun-Long Hou †,*, Yingxue Diao ‡, Qiangqiang Jia †, Lizhuang Chen †,*
PMCID: PMC7144142  PMID: 32280880

Abstract

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A stable porous sorbent M1 was achieved through the specific transformation of flexible thioalkyl groups and metal cluster sites in a zirconium MOF (metal–organic framework; Zr-L) template. The target polymer combines sulfoxide/sulfone and phosphoric acid in a single framework, which was fully characterized by 1H-NMR, PXRD, IR, and elemental analysis. When employed as the heavy metal adsorbent, M1 exhibit a remarkable Eu(III) sorption behavior, achieving both high chemical affinity (Kd = 105) and sorption capacity (the maximum Eu(III) sorption capacity reached 220 mg g–1 at pH = 4.0 and T = 298 K calculated from the Langmuir model). Recyclability and selectivity test of M1 further prove that the sorbent is highly stable and effective for europium enrichment in the aqueous solution. This work takes focus on the introduction of multifunctional groups into a single polymeric framework in a feasible and environmentally friendly way and highlights the sorption efficiency for europium removal from the aqueous solution.

1. Introduction

Given the increasing importance of environmental remediation during chemical production and process optimization, it is highly worthwhile to synthesize sorbents for the heavy metal removal from polluted water sources and industrial wastes. Eu(III) represents one of the rarest (0.000106%) rare-earth elements in earth and is widely applied in the manufacture of WLED, fluorescent glass, drug discovery, and quantum data storage.1,2 Furthermore, investigation of Eu(III) sorption behavior help to predict the effectiveness of sorbents for trivalent lanthanide [ln(III)] and actinide [An(III)] radionuclides, which are chemical homologues of Eu(III).3−5 A rapidly growing number of porous polymeric sorbents (such as carbon, porous silica, chalcogels, grapheme oxides, etc.) have been synthesized, and specific efforts have been made on the functionalization of inorganic metal sites or organic components for the removal of toxic heavy metal or radionuclides from polluted sources.6−9 Recently, research studies on the application of water-stable MOFs for the heavy metal removal (such as Hg, U, As, etc.) have also been studied.10−17 Unfortunately, low sorption capacity, poor selectivity, and a complicated preparation process significantly diminish the practical utility for the aforementioned materials. The ideal Eu(III) sorbent must combine porous structure, highly accessible binding sites, and an environmentally friendly synthetic methodology.

In an effort to handle those challenges, we here apply MOFs as precursor candidates for targeting the efficient materials for heavy metal removal in a simple wet treatment way. The reasons for employing the metal–organic framework (MOF) template include the following: first, porosity and rich components of MOFs open up the opportunity for the facile introduction of accessible multifunctional sites through one-pot reactions or versatile postsynthetic strategies.18−24 Second, controllable particle size and morphology of MOFs (such as metal/ligand ratio,25 modulator,26,27 crystallization process,28 etc.) allow tailoring of the properties of the sorbent. Additionally, Zr-MOFs, such as the isoreticular UiO-66 family, are known to contain inherent “missing linker defects”,29−31 which afford a responsible means of enhancing the sorption capacity of the final materials. Based on above advantages, a Zr-L MOF, L = 4-[2-[3,6,8-tris[2-(4-carboxyphenyl)-ethynyl]-pyren-1-yl]ethynyl]-benzoic acid), with predesigned thioalkyl side chains and open missing linker sties was employed as the precursor template in this report (Figure 1). We succeed in the introduction of dual functional species in a single framework through a stepwise treatment of the aqueous solutions of H2O2 and H3PO4 under mild conditions and the efficient capture of europium [Eu(III)] from water. To the best of our knowledge, this is the first example of a selective europium uptake by achieving stable MOF-templated sorbent.

Figure 1.

Figure 1

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Synthetic scheme and representative views of the polymeric M1. (a) One unit cell of Zr-MOF with the Zr coordination polyhedra shown in purple. (b) Polymeric structure of M1 with missing linker metal sites capped by phosphoric acids. (c) Molecular structure of the sorbent.

2. Results and Discussions

2.1. Preparation and Characterization

The sulfur-modified linker was used to build a parent framework Zr-L with a NU1100-like ftw (4,12-connected net) topology (Figure 1), which features a high surface area and inherent missing linker sites on the Zr6O4(OH)4 clusters, as described in the literature.32 Crystalline samples of Zr-L were prepared from ZrOCl2·8H2O and the sulfur-modified tetratopic ligand (H4L; Figure S1) in the presence of benzoic acid (ligand: Zr = 1: 2) in N,N′-diethylformamide (DEF) at 120 °C (see the Experimental Section for details). The composition of the activated sample features Zr6O4(OH)8(H2O)4(L)2(H2O)7 based on elemental and thermogravimetric (TG) analyses (Figure S2), indicating that one-third of the linkers are missing, and the Zr6O4(OH)4 cluster is on average 8-connected, as reported in our previous work.33 The PXRD pattern of the as-made Zr-L powder solid confirmed the topology and crystallinity of the MOF structure (Figure S3).32

Benefitting from the high water stability of the parent framework, the chemical transformation reaction was carried out in water, which represents both environmentally friendly and energy-saving traits. Thioether side chains in the Zr-L can be readily oxidized into sulfoxide/sulfone groups by 3% hydrogen peroxide aqueous solution (see the Experimental Section for details) based on analyses of FT-IR spectra (Figure 2) and 1H-NMR of the digested solid sample (Figure S1). The overall structural integrity before and after oxidation was confirmed by the unchanged PXRD patterns (Figure S3). At the first consideration, the sample was conducted in a low concentration of 0.09% H2O2 acetonitrile solution; a new vibration peak at 1032 cm–1 (labeled with black dots) associated to the sulfoxide group appeared in the FT-IR spectrum (see Figure 2a,b). Representative vibration peaks at 1135 and 1296 cm–1 (labeled with black stars) corresponding to sulfone groups (see Figure 2c) appeared when the sample was treated by 3% of hydrogen peroxide aqueous solution for 24 h. 1H-NMR analysis of the digested sample indicates the different chemical shifts of the methyl hydrogen of sulfoxide and sulfone where the mol ratio of sulfoxide and sulfone groups was calculated to be about 2:1 (see Figure S1).

Figure 2.

Figure 2

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IR spectra of (a) an as-made sample of Zr-L, (b) a sample of Zr-L after being treated with 0.09% H2O2 of acetonitrile solution, (c) a sample of Zr-L after being treated with 3% H2O2 aqueous solution, and (d) a sample of M1 after the treatment of H3PO4 solution.

The missing linker sites of Zr6O4(OH)4 clusters are known to bind well to organophosphorus species, phosphonates, vanadates, arsenates, etc.10−17 Based on these precedents, we propose that the missing linker-induced terminal Zr-OH sites in Zr-L can be suitable targets for binding with phosphoric groups. The introduction of phosphoric acid into the porous parent framework was conducted in the diluted (0.02%) phosphoric acid aqueous solution (the mol ratio of Zr-L:H3PO4 = 1:10). After the reaction solution was allowed to stay at room temperature for 8 h, the final product M1 was obtained as a red yellow powder and characterized by FT-IR (Figure 2), TG analyses (Figure S2), SEM (Figure 3), and elemental analyses (see the Experimental Section for details). Representative vibration peaks at 1706, 1230, and 1035 cm–1 (labeled with a black crosshatch) were associated to the P–OH, P=O and P–O groups, respectively, from the IR spectra (Figure 2d). TG analyses of M1 and as-made Zr-L indicate that there were 30 and 16% residual weight left at 950°, respectively (Figure S2). This result clearly identified the formation of phosphorus species, reaching a weight percentage of about 14% in M1. Elemental analyses on the sample M1 found [C (34.48%), H (4.36%), N (0.18%)]; a fitting formula can be determined to be Zr6O4(OH)4(H2PO4)8L(H4L)(H2O)28 (mw 5820), which gives a calculated profile as [C (34.67%), H (4.36%)]. The loading weight percentage of phosphoric acid calculated from elemental analysis was 13.4%, corresponding to eight phosphoric acids per Zr6 node, which is consistent with TG analysis. This high loading percentage indicates that eight available missing linker sites were filled by the phosphoric species, leading to the protonation of the ligand, which was trapped in the host. SEM images (Figure 3) revealed that the cubic structure of the MOF template was largely retained, regardless of the acid treatment, while PXRD studies (see Figure S3d) confirmed that the materials were amorphous after the acid intercalation reaction. These results confirm that P(V)-OH groups successfully bind to the Zr6O4(OH)4 cluster node of Zr-L; the proposed Zr–O–P binding motifs are illustrated in Figure S4.13

Figure 3.

Figure 3

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SEM images of an as-made sample of (a) Zr-L and (b) a sample of polymeric M1.

After the oxidation and phosphoric acid treatment, the sulfoxide/sulfone alkyl groups embedded in the host net tend to form a hydrophilic Eu(III) nanotrap, which works cooperatively with the excellent binders of cluster nodes “capped” with free phosphoric acids. The best Eu(III) sorption capacity and recyclability of the porous sorbent can be realized by easily accessible binding sites, good chemical stability, and high metal sorption affinity of the water-stable MOF-based material after the two-step transformation.

2.2. Europium Adsorption

The Eu(III) removal ability of M1 was first investigated in various pH values as it can significantly influence the adsorbent structure and adsorption capability in the practical wastewater treatment. The pH effect on the Eu(III) adsorption capacity of M1 was estimated in a pH range from 2 to 7 (see Figure S5 for details). It was found that the M1 adsorbent work effectively and accomplished more than 30 mg/g removal performance across a range of pH value from 3 to 7 when the initial Eu(III) concentration was 54.0 ppm. The best Eu(III) uptake efficiency was achieved at pH 4 where 50 mg of Eu(III) can be captured by a per gram adsorbent. The significantly decreased uptake capacity at a lower pH value (pH <3) may be due to the competing electrostatic interaction between proton and S=O, P–O– sites, as is observed by other materials.34,35 This adsorption behavior indicates the effectiveness of the M1 adsorbent for the Eu(III) uptake from acidic solution.

The M1 sorbent’s affinity for Eu(III) ions was also assessed by the distribution coefficient (Kd) measurement. The Kd value represents an important aspect of any sorbent’s performance metrics of metal ion adsorption.36 For this, a solid crystalline sample of the M1 sorbent was shaken with a Eu(III) solutions (initial Eu concentrations, 35.0 ppm) at pH = 4 and room temperature for 30 h; the residual Eu(III) was found to be 0.11 ppm by ICP-OES analysis of the supernatant (see also the Experimental Section).The Kd is defined as

2.2. 1

where Ci is the initial metal ion concentration, Cf is the final equilibrium metal ion concentration, V is the volume of the treated solution (mL), and m is the mass of sorbent used (g). The Kd value of M1 was measured to be 1.58 × 105 mL g–1, which ranks among the top with reported porous MOF-based sorbents for heavy metal removal.10,11,13

The sorption behavior of Eu(III) on M1 was investigated by adsorption kinetics of M1 in EuCl3 aqueous solution (5.4 ppm), as shown in Figure 4. It was observed that fast kinetics can be attained within the first half hour, and the equilibrium was reached after 220–250 min. The pseudo-second-order kinetic model was also used to fit the sorption data, obtaining a high correlation coefficient (R2 ≥ 0.9995).

Figure 4.

Figure 4

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Kinetics investigation of M1. (a) Eu(III) sorption kinetics of M1. (b) Adsorption curve of Eu(III) versus contact time in aqueous solution using M1. The inset shows the pseudo-second-order kinetic plot for the adsorption (Eu(III) concentration, 5.4 ppm.).

The Eu(III) uptake performance of M1 was also studied by adsorption isotherms (at pH of 4 and T = 298 K; see Figure 5 and the Experimental Section for details). The equilibrium adsorption isotherm data was fitted well with both the Langmuir and Freundlich model, yielding a high correlation coefficient (R2 ≥ 0.997) (see Figure 5). This indicates that the Eu sorption behavior on the M1 is predominantly a monolayer with a slight multilayer coverage, which proves that Eu is sorbed both on the surface and in the inner matrix of the material. The Langmuir equations are defined as

2.2. 2

where qe is the amount adsorbed at equilibrium (mg g–1), Ce is the equilibrium concentration (mg L–1), qmax is the maximum adsorption capacity (mg g–1). The maximum adsorption capacity (qmax) for Eu(III) was calculated to be 220 mg g–1, according to the Langmuir fitting model. This remarkable adsorption capacity stands out in many recently reported materials for Eu(III) adsorption such as TiO2,3,37 clay minerals,5 activated carbon,39 graphene oxide-based sorbents,35 and other composites.40−44 Comparison of Eu(III) maximum adsorption capacity (qmax) of M1 and other adsorbents is briefly concluded in Table 1.

Figure 5.

Figure 5

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(a) Eu(III) adsorption isotherms fitted with Langmuir and Freundlich models for M1 at pH of 4 and T = 298 K. (b) Langmuir plot. (c) Freundlich plot.

Table 1. Comparison of the Adsorption Capacity of M1 with Other Absorbents for Eu(III).

adsorbents capacity (mg g–1) pH temperature(K) reference
commercial titanium dioxide 5 5.5 298 (38)
titanium phosphate@graphene oxide 64 5.5 298 (34)
activated carbon 46 5.0 298 (39)
cellulose-based silica 24 6.0 298 (40)
Fe3O4@carboxymethyl cellulose 42 5.5 293 (41)
Aspergillus niger 135 6.0 297 (42)
carbonaceous nanofibers 91 4.5 298 (43)
graphene oxide nanosheets 175 6.0 298 (44)
M1 220 4.0 298 this work
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The high Kd value and remarkable maximum adsorption capacity (qmax) indicate the high affinity and sorption efficiency of the M1 framework toward Eu(III) ions. This excellent performance should partly contribute to a large number of hydrophilic sulfoxide/sulfone groups, as is clearly shown by the removal of over 36% Eu(III) when the oxidized Zr-L was employed as the sorbent in the control experiment. Furthermore, high density of the hydrophilic groups, large accessible P–OH groups capped on Zr6 nodes, and strong binding affinity was responsible for the enhanced Eu(III) removal capability. Further investigation of the structure–property relation may help to understand the Eu(III) adsorption mechanism on MOF-based materials for potential radionuclide treatment.

Considering the practical application of the trivalent radionuclide removal from industrial wastewater, the effect of competing ions and recyclability of adsorbents are important. To investigate the selective binding ability of the M1 solid for Eu(III), the experiment was performed in a multicomponent system with a mixture of M1, Eu(III), and competing cations, including Sr(II), Cs(I), Cd(II), and Zn(II) at 0.33–7.68 ppm (see Table 2), together with Ca(II) and Na(I) at 13 and 24 ppm (to mimic the higher natural occurrence of these two metals), respectively. As can be found in Table 2, over 94% of Eu(III) removal was observed and in clear contrast with a large amount of background metal ions such as Cd(II), Zn(II), Ca(II), and Na(I), which was kept in the solution. The high selectivity demonstrates the strong binding affinity of the M1 adsorbent for Eu(III). In addition, other hard metal ions of Cs(I) and Sr(II) was also removed by 61 and 29%, respectively. It further indicates the effective hard–hard interaction between hard metal ions Eu(III)/Cs(I)/Sr(II) and P–O– sites in the M1 solid. Due to the high chemical stability of M1 solid in water and acid solution, the Eu-loaded M1 can be easily reactivated by washing with the HCl (pH = 2) solution while maintaining an effective Eu(III) removal capability with >93% percentage in the three cycles (Figure 6 and the experimental details in the Experimental Section). EDX analyses of the sample after three Eu(III) sorption–desorption cycles show no Eu(III) residual, further confirming the recoverability of the sorbent (Figure S6).

Table 2. Concentrations (ppm) of Metal Ions before and after Treatment by M1.

solution Eu(III) Sr(II) Cd(II) Cs(I) Zn(II) Ca(II) Na(II)
before treatment 5.39 7.68 7.14 0.33 7.10 12.91 24.19
after treatment 0.32 5.43 5.87 0.13 5.89 11.46 21.33
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Figure 6.

Figure 6

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Recycle experiment (pH = 4.0 and T = 298 K, Ci = 54 ppm): Eu(III) removal percentage in three runs.

3. Conclusions

In summary, we succeed in the preparation of MOF-templated polymeric materials for the high-performance metal ion sorption. The highlight is the application in the selective Eu(III) recognition and adsorption with a remarkable efficiency in terms of Kd (1.58 × 105 mL g–1) and qmax (220 mg g–1). The excellent performance of M1 benefits from strong binding sites derived from the protonated metal clusters, hydrophilic sulfoxide/sulfone side chains, and free phosphoric acids embedded in the pore surface. Notably, the recyclability test and the effect of competing ions further confirms the advantage of M1 as an Eu(III) sorbent, rendering the potential application for the practical trivalent radionuclide treatment in the nuclear power industry. This simple wet treatment process allows rapid and scalable sorbent preparation from other commercially available MOFs (such as UiO-66, etc.) without costly carbonization, complicated ligand syntheses, or challenging activation steps.

4. Experimental Section

4.1. General Procedure

Compound H4L was prepared by our reported methods.39 Solution nuclear magnetic resonance (NMR) spectra were recorded at 298 K on Mercury VX-300 spectrometers with working frequencies of 300 and 400 MHz for 1H and 75 and 100 MHz for 13C nuclei. Chemical shifts are reported in ppm relative to the signals corresponding to the residual nondeuterated solvents with tetramethylsilane (TMS) as the internal standard. Powder X-ray diffraction data was collected in reflection mode at room temperature on an Inel Equinox 1000 X-ray diffractometer (Inel, France) equipped with a CPS 180 detector using monochromated Cu Kα (λ = 1.5406 Å) radiation. The X-ray tube operated at a voltage of 30 kV and a current of 30 mA. The CHN elemental analyses were performed with a Vario Micro CUBE CHN elemental analyzer. The quantification of the metal ions was conducted with a PerkinElmer Optima 2100 DV ICP (inductively coupled plasma) optical emission spectrometer. Thermogravimetric analyses (TGA) were carried out in a nitrogen stream using PerkinElmer thermal analysis equipment (STA 6000) with a heating rate of 5 °C min–1 with an empty Al2O3 crucible being used as the reference.

4.2. Preparation of Zr-L

Molecule H4L (L = C84H86O12S12) (100 mg, 0.067 mmol) and DEF (20 mL) solution of ZrOCl2·8H2O (38.0 mg, 0.12 mmol) and benzoic acid (1.8 g, 15 mmol, about 125 molar equivalents to ZrOCl2·8H2O) were added in a Schlenk tube. The tube was heated at 120 °C in an oven for 72 h followed by programmed cooling to room temperature over 18 h to afford a yellow powder. For elemental analysis, the ample was washed by DMF (3 × 2.0 mL) and soaked in acetonitrile (3 × 3.0 mL, replaced by fresh acetonitrile every 6 h). The resulting solid was further washed by acetone (3 × 2.0 mL), filtered, and then evacuated at 60 °C for 8 h. Elemental analysis found [C (46.93%), H (4.65%), N (0.12%)]; a fitting formula can be determined to be Zr6O4(OH)8(H2O)4(C84H86O12S12)2(H2O)7 (mw 4290), which gives a calculated profile as [C (47.03%), H (4.75%)]. The Zr-L solid sample was also characterized by TGA (see Figure S2).

4.3. Preparation of M1

An as-made sample of Zr-L (∼5.0 mg) was added to an aqueous solution of 3% H2O2 (5.0 mL). After the mixture was kept at room temperature for 24 h, the supernatant was replaced by 0.02% H3PO4 aqueous solution (5.0 mL), and the solution was kept at room temperature for 8 h. Afterward, the solid was isolated by centrifugation, washed by water (3 × 1.0 mL), and analyzed by powder X-ray diffraction. Elemental analysis found [C (34.48%), H (4.36%), N (0.18%)]; a fitting formula can be determined to be Zr6O4(OH)4(H2PO4)8L(H4L)(H2O)28 (mw 5820), which gives a calculated profile as [C (34.67%), H (4.36%)]. The M1 solid sample was also characterized by TG analysis (see Figure S2).

4.4. Effect of pH Value and Kd Measurement for Eu(III) Removal by M1

A series of europium(III) chloride aqueous solution with an initial concentration of 54 ppm at pH = 2, 3, 4, 5, 6, and 7 were freshly prepared using the stock hydrogen chloride solution. The M1 sample (∼3.0 mg) was shaken with the europium sample solution (3.0 mL) at 150 rpm and room temperature for 24 h using an IKA KS 501 digital orbital shaker. Afterward, the solid was isolated by centrifugation and washed by water (3 × 1.0 mL). The Eu content in the supernatant was analyzed using ICP-OES. The M1 sample (∼8.0 mg) was shaken with the europium sample solution (35 ppm, 4.0 mL, pH = 4) at room temperature for 30 h. The Eu content in the supernatant was measured to be 0.11 ppm using ICP-OES.

4.5. Eu(III) Adsorption Kinetics of M1

The M1 sample (∼2.0 mg) was shaken with the europium sample solution (5.39 ppm, 2.0 mL, pH = 4) at room temperature for 8 h. During the adsorption, the mixture was withdrawn and filtered at intervals through a 0.22 μm membrane filter for all samples (each sample of 0.1 mL); then, each of the filtrates was diluted using water and quantified by ICP-OES to determine the remaining Eu(III) content. The experimental data were fitted with the pseudo-second-order kinetic model using the following equation

4.5.

where k2 (g mg–1 min–1) is the rate constant of the pseudo-second-order adsorption, qt (mg g–1) is the amount of Eu(III) adsorbed at time t (min), and qe (mg g–1) is the amount of Eu(III) adsorbed at equilibrium.

4.6. Eu(III) Sorption Isotherm Measurement of M1

Europium(III) chloride solutions (pH = 4) of various concentrations (100, 200, 400, 500, 600, 800, 1000, and 1200 mg L–1) were prepared and used in the following adsorption procedure. A freshly made sample of M1 (∼6.0 mg) was added into each of the EuCl3 solution (2.0 mL) in a glass vial. After the mixture was shaken at 150 rpm and room temperature for 24 h using an IKA KS 501 digital orbital shaker, the solid was separated by centrifugation and the concentration of the remaining Eu in the supernatant was determined by ICP-OES. Based on the Langmuir adsorption equation, the saturated Eu(III) adsorption capacity qmax of M1 was calculated to be 220 mg g–1 (R2 = 0.997).

4.6.

where a plot of Ce/qe to Ce (see Figure 5, inset) yields the sorption capacity qmax (mg g–1) as the reciprocal of the slope.

4.7. Test of Recyclability

In a clear glass vial, a sample of M1 (∼6.0 mg) was shaken with a freshly prepared europium solution (54 ppm, 3.0 mL) at 150 rpm and room temperature for 24 h using an IKA KS 501 digital orbital shaker. Afterward, the solid was isolated by centrifugation, washed with HCl aqueous solution (pH = 2) and water (5 × 1.0 mL), and used for the next cycle. After three runs, the recovered solid was washed with water and analyzed by powder X-ray diffraction. After these cycling steps, the Eu content in the supernatant can still be consistently reduced down to 3.5 ppm (i.e., 94% of the total Eu was removed; ICP-OES results).

4.8. Effect of Competing Ions

A mixture solution of Eu(III) (5.39 ppm) and competing cations (Sr2+, Cs+, Cd2+ , Zn2+ , Na+, and Ca2+ at 0.33–24.19 ppm; see Table 1) was shaken with the solid sample of M1 (∼3.0 mg) in a clear glass vial at 150 rpm and room temperature for 24 h using an IKA KS 501 digital orbital shaker. Afterward, the solid was isolated and the concentration of the remaining ions in the supernatant was determined by ICP-OES.

Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (grant no. 21671084), the NSF of Jiangsu Province (grant no. BK20131244), the Six Talent Peaks Project in Jiangsu Province (grant no. 2014-XCL-008), the Qing Lan Project of Jiangsu Province, the Innovation Program of Graduate Students in Jiangsu Province (grant no. KYLX16-0508), a project funded by the Priority Academic Program Development of Jiangsu Higher Education Institution, the Innovation Program for Graduate Student from Jiangsu University of Science and Technology (grant no. YCX15S-19), and the Foundation of Jiangsu Educational Committee (16KJB430011).

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.9b04419.

  • Additional physical measurements and structural analysis (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao9b04419_si_001.pdf (736.2KB, pdf)

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