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Jan 31, 2018 - p-Arsanilic acid (p-ASA) is an emerging organoarsenic pollutant comprising both inorganic and organic moieties. For the efficient remov...
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Article Cite This: Environ. Sci. Technol. 2018, 52, 3466−3475

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Enhanced Adsorption of p‑Arsanilic Acid from Water by AmineModified UiO-67 as Examined Using Extended X‑ray Absorption Fine Structure, X‑ray Photoelectron Spectroscopy, and Density Functional Theory Calculations Chen Tian,†,§ Jian Zhao,‡,§ Xinwen Ou,† Jieting Wan,† Yuepeng Cai,∥ Zhang Lin,*,† Zhi Dang,† and Baoshan Xing⊥ †

School of Environment and Energy, Key Laboratory of Pollution Control and Ecosystem Restoration in Industry Clusters (Ministry of Education), Guangdong Engineering and Technology Research Center for Environmental Nanomaterials, South China University of Technology, Guangzhou 510006, China ‡ College of Environmental Science and Engineering, Key Laboratory of Marine Environmental Science and Ecology (Ministry of Education), Ocean University of China, Qingdao 266100, China ∥ School of Chemistry and Environment, South China Normal University, Guangzhou 510006, China ⊥ Stockbridge School of Agriculture, University of Massachusetts, Amherst, Massachusetts 01003, United States S Supporting Information *

ABSTRACT: p-Arsanilic acid (p-ASA) is an emerging organoarsenic pollutant comprising both inorganic and organic moieties. For the efficient removal of p-ASA, adsorbents with high adsorption affinity are urgently needed. Herein, amine-modified UiO-67 (UiO-67-NH2) metal−organic frameworks (MOFs) were synthesized, and their adsorption affinities toward p-ASA were 2 times higher than that of the pristine UiO-67. Extended X-ray absorption fine structure (EXAFS), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculation results revealed adsorption through a combination of As−O−Zr coordination, hydrogen bonding, and π−π stacking, among which As−O−Zr coordination was the dominant force. Amine groups played a significant role in enhancing the adsorption affinity through strengthening the As−O−Zr coordination and π−π stacking, as well as forming new adsorption sites via hydrogen bonding. UiO-67-NH2s could remove pASA at low concentrations ( 0.99) implied the adsorption of p-ASA on the tested MOFs was controlled by chemical interactions. The increased adsorption rates (k2) of UiO-67NH2s relative to the pristine UiO-67 implied the enhancement of chemisorption between p-ASA and the amine-modified MOFs. Moreover, in comparison with other porous MOFs (such as meso-ZIF-8 in ref 13), substantially enhanced adsorption rates were observed for UiO-67 and UiO-67NH2s, which was possibly due to the stronger chemisorption between UiO-67s and p-ASA molecules. Adsorption Isotherms. Adsorption isotherms of UiO-67, UiO-67-NH2(1), and UiO-67-NH2(2) toward p-ASA are shown in Figure 2b. All isotherms fitted well with Langmuir and Freundlich33,34 models (Table S4), but the R2 values of

source. Spectra were recorded at a pass energy of 160 eV for survey scans and 40 eV for high-resolution scans. Highresolution scans were carried out in an energy range of 295− 280 eV for C 1s and 405−395 eV for N 1s XPS spectra. Computational Calculation. DFT calculations were performed using the Vienna ab initio simulation package (VASP).29 The Perdew−Burke−Ernzerhof (PBE) functional and the potential projector augmented wave (PAW) pseudopotentials were used for all the calculations. The plane-wave cutoff energy was set to 500 eV, which has been previously tested and shown to be appropriate for UIO-67. Scalar relativistic effects were incorporated into the effective core potentials via explicit mass-velocity and Darwin corrections. Detailed calculation methods are provided in Section S1.



RESULTS AND DISCUSSION Characterization of the As-Prepared MOFs. The assynthesized UiO-67 and UiO-67-NH2s exhibited typical characteristic peaks of Fm3m ̅ symmetric space groups in the XRD patterns (Figure S1), consistent with the reported UiO-67 topology.30 The identical XRD peaks of UiO-67-NH2’s with the pristine UiO-67 implied that introducing −NH2 groups did not change the framework structure. FTIR spectra of UiO-67NH2’s showed C−N and N−H stretching vibrations at 1257 and 3300−3500 cm−1, respectively (Figure S2). The mole ratios of −NH2/Zr calculated from XPS data were 0.88 and 1.80 for UiO-67-NH2(1) and UiO-67-NH2(2), respectively (Table S1), which were similar to their theoretical values (1.0 for UiO-67-NH2(1) and 2.0 for UiO-67-NH2(2)). These results confirmed the successful amine modification of UiO67. The structural illustrations of UiO-67, UiO-67-NH2(1), and UiO-67-NH2(2) are shown in Figure 1. The BET surface areas of UiO-67, UiO-67-NH2(1), and UiO-67-NH2(2) were 1871, 750, and 465 m2 g−1, respectively (Figure S3 and Table S1). 3468

DOI: 10.1021/acs.est.7b05761 Environ. Sci. Technol. 2018, 52, 3466−3475

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Environmental Science & Technology

Figure 2. (a) Adsorption kinetics, (b) adsorption isotherms, and (c) surface area-normalized isotherms of p-ASA adsorbed by UiO-67, UiO-67-NH2(1), and UiO-67-NH2(2).

Figure 3. Arsenic K-edge data for p-ASA adsorbed UiO-67 and UiO67-NH2 samples: (a) filtered k3-weighted EXAFS data, (b) magnitude part of Fourier transformed R-space, and (c) real part of Fourier transformed R-space. Experimental and calculated curves are displayed as black solid lines and red open circles, respectively. Results of the k3weighted fitting are listed in Table S6.

Langmuir model were higher. Therefore, the following discussion was mainly based on Langmuir fitting results of all the MOFs. Maximum adsorption capacities (Qm) calculated from Langmuir model followed an order of UiO-67 > UiO-67NH2(1) > UiO-67-NH2(2) (Figure 2b, Table S4). However, this order changed to an opposite sequence after normalizing by the surface area (Qm/Asurf in Figure 2c), indicating higher adsorption capacities of UiO-67-NH2s than the pristine UiO-67 deducting the effect of surface area. This observation could be explained by the steric hindrance of the introduced −NH2 groups situating in the aperture of the nanopores (Figure 1 and Table S1). The entry of p-ASA (with a molecule diameter of 6.625 Å13) to the internal part of UiO-67-NH2s would be obstructed because of their narrower apertures than the pristine UiO-67. It was reported that materials with a small Qm and large affinity coefficient (KL) could have a larger value of qe when compared with materials with a large Qm and small KL, at low

pollutant concentrations.35 Therefore, considering p-ASA as a micropollutant, the KL value was more significant than Qm. As shown in Table S4, KL values of UiO-67-NH2s were much higher than that of the pristine UiO-67, and increased with increasing −NH2 content. In order to further evaluate the adsorption affinity at different p-ASA concentrations, single point sorption coefficients (K)36 based on the Langmuir fitting results were calculated when Ce = 0.03 (K0.03) and 0.3 (K0.3) mg L−1. As shown in Table S4, both K0.03 and K0.3 followed the order of UiO-67-NH2(2) > UiO-67-NH2(1) > UiO-67, indicating that UiO-67-NH2s had higher affinities toward pASA. The higher affinities made UiO-67-NH2s having higher qe compared with the pristine UiO-67 at low concentrations of pASA, as shown in the inset of Figure 2b. This is very important for the practical application of UiO-67-NH2s, considering that 3469

DOI: 10.1021/acs.est.7b05761 Environ. Sci. Technol. 2018, 52, 3466−3475

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Figure 4. Uptake of p-ASA by UiO-67, UiO-67-NH2(1), and UiO-67-NH2(2); related XPS analysis after p-ASA adsorption. (a) Uptake of p-ASA (adsorbed p-ASA/Zr6 node) by UiO-67, UiO-67-NH2(1), and UiO-67-NH2(2); XPS C 1s and N 1s spectra of UiO-67, UiO-67-NH2(1), and UiO67-NH2(2) before (b, d) and after (c, e) p-ASA adsorption.

FTIR analysis showed the −NH and C−N vibration bands still present in UiO-67-NH2(2) after the first adsorption cycle (Figure S8), suggesting that the −NH2 moieties remained stable during the repeated adsorption process. Meanwhile, XRD results showed that the crystal structure of UiO-67 and UiO-67-NH2(2) did not change after regeneration (Figure S9). These results revealed that the UiO-67 and UiO-67-NH2(2) could be regenerated and reused for multiple times, thus confirming the practical value and application of UiO-67s as the adsorbents of p-ASA. Mechanism of p-ASA Adsorption on UiO-67-NH2s. To get insight into the adsorption mechanism of UiO-67-NH2s toward p-ASA, electrostatic interaction, As−O−Zr coordination, hydrogen bonding, and π−π interaction were taken into consideration.37 The effects of pH on the adsorption of p-ASA were studied to investigate the contribution of electrostatic interaction. Figure S10a showed that UiO-67 and UiO-67-

the concentrations of p-ASA in environment are usually very low. The comparison of adsorption capacity and affinity of the present UiO-67s with other adsorbents in the published literature is listed in Table S5. The Qm value of UiO-67 (454.54 mg g−1) was higher than most of the reported absorbents. Despite the mesoporous ZIF-8 having the highest Qm (791 mg g−1) and Qm/Asurf (0.70 mg m−2), UiO-67-NH2(2) was superior for p-ASA capture in practical applications due to its much higher adsorption capacity and affinity toward p-ASA (qe0.03 = 4.50 mg g−1 and K0.03 = 150 L g−1) than ZIF-8 (qe0.03 = 0.76 mg g−1 and K0.03 = 25.3 L g−1) at low concentrations. Reusability. The regeneration efficiency of UiO-67s is shown in Figure S7. Despite the adsorption capacities being slightly decreased after the first recycle, UiO-67 and UiO-67NH2(2) still exhibited considerable adsorption capacities after four cycles regeneration (over 85% of the original capacity). 3470

DOI: 10.1021/acs.est.7b05761 Environ. Sci. Technol. 2018, 52, 3466−3475

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It has been well-documented that Zr-based materials could efficiently capture arsenate groups due to the bidentate binuclear and monodentate mononuclear complexes forming between the Zr−OH groups and As.22,39 For the as-prepared UiO-67 and UiO-67-NH2s, these Zr−OH groups mainly originated from the defects present in Zr−O clusters.23,40 To further reveal the role of As−O−Zr coordination in p-ASA adsorption, X-ray adsorption spectroscopy of As was determined. The As−O and As−Zr shells could be obviously isolated in the k3-weighted As K-edge EXAFS spectra and the corresponding Fourier-transforms (Figure 3), indicating the formation of As−O−Zr inner-sphere complexes after adsorption. In all the samples, the As−O first-neighbor contributions were fit with 3.6−3.9 oxygen atoms at 1.69 Å (Table S6), which agreed with the DFT calculation in the previous study.39 The second-neighbor contributions were fitted with the As− Zr atom distances of 3.44, 3.41, and 3.40 Å for UiO-67, UiO67-NH2(1), and UiO-67-NH2(2), respectively (Table S6). The As−Zr distances were consistent with that in the bidentate binuclear complex obtained from the DFT calculation (see details in the “DFT Calculation” section), which was also observed in other Zr-based MOFs.41 Moreover, the As−Zr distances in UiO-67-NH2(1) and UiO-67-NH2(2) were shorter than that in UiO-67, indicating that the amine modification of UiO-67 shortened the As−Zr atom distance, and thus formed stronger inner-sphere complexes. The enhanced As−O−Zr coordination was one of the explanations for the higher adsorption affinity of UiO-67-NH2’s toward p-ASA than the pristine UiO-67. The higher coordination number (CN) of the As−Zr contribution in UiO-67-NH2s than the pristine UiO-67 (Table S6) also indicated stronger As−O−Zr coordination. Such enhancement could be ascribed to the synergistic effect of other interactions, such as π−π stacking and hydrogen bonding. Moreover, according to the Langmuir fitting results, the maximum molecule uptake of p-ASA by UiO-67 was found to be 5.3:1 (p-ASA/Zr6 in Figure 4a), which exceeded the stoichiometric p-ASA/Zr6 value calculated by As−O−Zr coordination (4:1 of p-ASA/Zr6 based on the bidentate binuclear complex forming between p-ASA and the defective UiO-67 unit). Considering the absence of −NH2 groups in UiO-67 ligands, the hydrogen bonds between the pristine UiO67 and p-ASA were perceived to be relatively weak. Thus, the higher p-ASA uptake than the stoichiometric value was possibly due to the π−π stacking. Further indication was conducted with the high resolution C 1s XPS spectra (Figure 4b,c). For UiO67s before p-ASA adsorption, three peaks were observed at 284.6, 285.9, and 288.5 eV, which belonged to the sp2 CC, C−N, and O−CO groups in the BPDC linkers.42,43 The characteristic peak of π−π* component appeared at 291.2 eV44 after adsorption, suggesting the contribution of π−π stacking for p-ASA adsorption. Meanwhile, the π−π* proportions of UiO-67-NH2(1) and UiO-67-NH2(2) were 2.11 and 7.78%, respectively, which were both higher than that of the pristine UiO-67, suggesting the enhancement of π−π interaction after the −NH2 modification. Considering the adsorption affinity of UiO-67-NH2s being higher than that of the pristine UiO-67, an additional mechanism other than As−O−Zr coordination and π−π interaction should also contribute to the adsorption by UiO67-NH2s. As mentioned above, the good fitting of the adsorption kinetic to the pseudo-second-order model suggested that the adsorption capacities of UiO-67s were determined by

Figure 5. Optimal configurations obtained via DFT calculations of (a) As−O−Zr coordination, (b) π−π stacking, (c) and H-bonding between UiO-67-NH2(2) and p-ASA (magenta for As, cyan for Zr, red for O, blue for N, gray for C, and white for H). The interaction energy between UiO-67-NH2(2) and p-ASA was calculated to be −297.4 kJ mol−1 (As−O−Zr coordination π−π stacking, and Hbonding).

NH2s exhibited the highest adsorption capacity at pH 4.0 and then sharply decreased with the increasing pHs. The isoelectric points of the three UiO-67s were determined to be between pH 4 and 5; thus, their zeta potentials were quite low at pH 4.0 (Figure S10b). Moreover, the aqueous dissociation constants (pKa) of p-ASA molecules were 1.91, 4.13, and 9.19, respectively (Figure S11). Therefore, the arsenic group in pASA is electroneutral at pH 4.0.38 These results indicated that the electrostatic attraction was not the dominant force for the p-ASA adsorption at pH 4.0. 3471

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Figure 6. Adsorption mechanism of UiO-67-NH2 toward p-ASA.

the number of active sites on the adsorbents.32 Since the surface area of UiO-67-NH2(2) was only 60% of that of UiO-67NH2(1) (Table S1), we conclude that the active sites in UiO67-NH2(2) could also be ∼60% of those in UiO-67-NH2(1). Therefore, the adsorption capacity of UiO-67-NH2(2) should be about 60% of UiO-67-NH2(1) theoretically. However, the Langmuir fitted adsorption capacity and the molecular uptake of p-ASA/Zr6 by UiO-67-NH2(2) were calculated to be 178 mg g−1 and 2.3:1, respectively, which were much higher than 60% of the p-ASA amount adsorbed by UiO-67-NH2(1) (Table S4 and Figure 4a). This result suggested that the additional −NH2 groups provided more active sites, thus enhancing the adsorption capacity and affinity of UiO-67-NH2(2). Considering the previous discussion, hydrogen bonds between UiO-67NH2’s and p-ASA were expected to be the key role for the enhancement. XPS N 1s results provided strong evidence for the hydrogen bond formation (Figure 4d,e). Before adsorption, the symmetrical peaks locating at 399.4 eV were attributed to the free −NH245 in the BPDC linkers of UiO-67-NH2s (Figure 4d). No signals of H-bonded −NH2 were observed in the spectra. After adsorption, although no −NH2 groups existing on the pristine UiO-67 structure, the peak for free −NH2 was still observed (Figure S12), which belonged to the adsorbed pASA. Moreover, a new peak assigned to H-bonded −NH2 at 400.2 eV45 was observed in the N 1s spectra of UiO-67-NH2s after adsorption (Figure 4e), and the peak ratio increased with the amine content in UiO-67-NH2s. This result indicated that these hydrogen bonds increased the sites for p-ASA adsorption on UiO-67-NH2s. DFT Calculations. To further elucidate the roles of −NH2 groups in UiO-67-NH2s for p-ASA adsorption, the possible interaction scenarios of UiO-67 and UiO-67-NH2(2) with pASA were further investigated at the molecular level through DFT calculation. For UiO-67, it was obvious that the As−O− Zr coordination had the highest interaction energy (−181.5 kJ mol−1 in Figure S13a) and was considered to be the most favorable adsorption force. The optimal configurations of the Zr nodes and p-ASA molecules suggested the formation of

bidentate binuclear As−O−Zr complexes after adsorption (Figure S13a), which was consistent with the aforementioned EXAFS analysis. In addition, the relatively high adsorption energy (−40.2 kJ mol−1) of the π−π interaction between p-ASA and UiO-67 (face-centered distance, 3.8 Å, Figure S13b) indicated that the π−π stacking also played an important role in the adsorption. After amine modification, the optimal configurations between UiO-67-NH2(2) and p-ASA are shown in Figure 5. The As−O−Zr bidentate binuclear complex, π−π stacking, and hydrogen bonds were all present in the UiO-67-NH2(2) samples after adsorption. Moreover, it was obvious that the binding energies of As−O−Zr coordination and π−π interaction in UiO-67-NH2(2) were both higher than those in the pristine UiO-67, while the As−Zr atom distance and the benzene rings face-centered distance were shorter (Figures 5 and S13). These results indicated that As−O−Zr coordination and π−π stacking were enhanced after −NH2 modification. Moreover, −NH2 groups in UiO-67-NH2(2) also provided extra adsorption sites for p-ASA through hydrogen bonds with an optimal configuration of NH···O and a bonding energy of −52.4 kJ mol−1 (Figure 5c), thus further increasing the adsorption affinity. These results were in agreement with the EXAFS and XPS analyses. The interaction energies followed the order: UiO-67-NH2(2) and p-ASA > water molecule and pASA > p-ASA and p-ASA according to DFT calculation (Figures 5 and S13), suggesting that p-ASA molecules were monolayerly adsorbed on UiO-67-NH2(2) because free p-ASA molecules cannot be further adsorbed by the bound p-ASA on UiO-67-NH2(2). Overall, p-ASA would form a monolayer adsorption on the surface of UiO-67-NH2(2), under the combined interactions of As−O−Zr coordination, π−π stacking, and hydrogen bonding (Figure 6). It should be noted that amine groups on UiO-67-NH2(2) played a significant role in enhancing the adsorption affinity through forming new adsorption sites via hydrogen bonding, as well as strengthening the As−O−Zr coordination and π−π stacking. 3472

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standard for drinking water of the WHO (10 μg L−1). The adsorption results of UiO-67-NH2s in swine manure lixivium at different p-ASA concentrations are shown in Figure 7c. It can be seen that when the initial concentration of p-ASA was 5 mg L−1, a dosage of 0.15 g L−1 UiO-67-NH2(2) could decrease the arsenic concentration to 28.1 μg L−1, which satisfied the arsenic standard in surface water of China (50 μg L−1, GB3838−2002). To reduce the arsenic concentration to the same level (below 50 μg L−1), the needed dosages of graphene and activated carbon were 4 and 6.7 g L−1, respectively, which were 26.7 and 44.8 times higher than that of UiO-67-NH2(2) (Table S7). Moreover, since UiO-67 has already been studied as a watertreatment adsorbent for a period of time,16 its modification is supposed to be more simple and commercially available, compared with synthesizing a new MOF. These results suggested that the amine-modified UiO-67 was a promising candidate for removing p-ASA from natural and wastewaters.



ENVIRONMENTAL IMPLICATIONS The defective UiO-67-NH2 designed on the basis of the structural features of p-ASA showed high adsorption affinity toward p-ASA. The study of adsorption mechanism indicated that the contribution of different adsorption forces followed an order of As−O−Zr coordination > π−π stacking > H-bonding. The −NH2 groups in UiO-67-NH2 played an important role for the efficient adsorption, including enhancing the As−O−Zr coordination and π−π stacking, as well as providing new adsorption sites for p-ASA adsorption through H-bonding. These synergistic interactions resulted in strong affinity of UiO67-NH2 toward p-ASA, which were beneficial for the removal of p-ASA in simulated natural water and wastewater. This study revealed the great potential of −NH2 modified UiO-67s for the removal of p-ASA in practical applications. Moreover, this work also provided a new route for increasing the adsorption affinity of adsorbents toward targeted pollutants through engineering different functional groups to achieve synergistic effects.



ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.7b05761. Materials and methods, XRD patterns, FTIR spectra, N2 isotherms, pore size distributions, pore and surface properties, TG-MS curves, temperature-dependent XRD, TGA curves, parameters of pseudo-second-order kinetic for p-ASA adsorption, fitting results of Langmuir and Freundlich models, p-ASA adsorption capacity and affinity of different types of adsorbents, reusability results, p-ASA uptake as a function of solution pH, dissociation constants, shell-by-shell fitting from EXAFS data, XPS spectra, optimal configurations (PDF)

Figure 7. p-ASA adsorption by UiO-67, UiO-67-NH2(1), and UiO-67NH2(2) in the presence of DOM or in swine manure lixiviums. (a) Effect of DOM on the removal rates of p-ASA, (b) residual arsenic concentrations (C0 = 0.5 mg L−1) in the presence of DOM, and (c) residual arsenic concentrations after adsorption in swine manure lixiviums with different initial concentrations of p-ASA. The adsorbent concentrations were kept at 0.15 g L−1 in 30 mL of solution. The mixtures were shaken at pH 4.0 ± 0.1 and 25 °C with a speed of 200 rpm for 12 h.

Adsorption Behavior of Amine-Modified UiO-67 in Simulated Natural and Wastewaters. To test if UiO-67NH2s could efficiently remove p-ASA for practical application, DOM-containing water and swine manure lixivium were used to simulate natural water and wastewater, respectively. Adsorption results indicated that at a p-ASA concentration of 0.5 mg L−1, the removal rate of UiO-67-NH2(2) was slightly decreased from 99.6 to 98.7% when the DOM concentration increased from 0 to 16 mg C L−1, which were higher than those of UiO-67 (Figure 7a). When the DOM concentration was 16 mg C L−1, the residual arsenic concentrations after adsorbed by UiO-67-NH2(1) and UiO-67-NH2(2) were 4.15 and 2.26 μg L−1, respectively (Figure 7b), which were lower than the arsenic



AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. Phone: 86-20-39380503. Fax: 8620-39380508. ORCID

Jian Zhao: 0000-0002-4971-5643 Zhang Lin: 0000-0002-6600-2055 Baoshan Xing: 0000-0003-2028-1295 3473

DOI: 10.1021/acs.est.7b05761 Environ. Sci. Technol. 2018, 52, 3466−3475

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§

C.T. and J.Z. contributed equally to the creation of this work.

Notes

The authors declare no competing financial interest.



ACKNOWLEDGMENTS This work was supported by the National Natural Science Foundation of China (grant no. 21477129), the Guangdong Innovative and Entrepreneurial Research Team Program (No. 2016ZT06N569), the China Postdoctoral Science Foundation (no. 2016M600654), and the Fundamental Research Funds for the Central Universities (no. 2017PY009 and 2017BQ054). The authors thank the beamline 4W1B (Beijing Synchrotron Radiation Facility) for providing the beam time.



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