Synthesis of bimetallic organic framework material M/Fe-MOF (M: Ni, Cu, Mn) and testing to remove toxic dyes in water environment

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In this study, the combination of Fe(III) and Ni(II), Cu(II), or Mn(II) metal salts bound to organic bridges were synthesized based on thermal method solvent in the presence of DMF. The structural properties of the materials were analyzed based on modern physicochemical methods (XRD, FT-IR, SEM, and BET).

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Nội dung Text: Synthesis of bimetallic organic framework material M/Fe-MOF (M: Ni, Cu, Mn) and testing to remove toxic dyes in water environment

Chuyên san Phát triển Khoa học và Công nghệ số 8 (4), 2022 Synthesis of bimetallic organic framework material M/Fe-MOF (M: Ni, Cu, Mn) and testing to remove toxic dyes in water environment Thi Kim Ngan Tran1,2,*, Cao Phuong Khanh Phan3, Thi Cam Quyen Ngo1,2, Ngoc Bich Hoang1,2, Le Dang Truong1,2, Thi Kim Oanh Nguyen1,2 1 Institute of Applied Technology and Sustainable Development, Nguyen Tat Thanh University, Ho Chi Minh City 700000, Vietnam 2 Faculty of Food and Environmental Engineering, Nguyen Tat Thanh University, Ho Chi Minh City 700000, Vietnam 3 Faculty of Chemical Engineering, Ho Chi Minh City University of Technology, Ho Chi Minh City, Vietnam; khanh.phan_stayfresh@hcmut.edu.vn * Corresponding author: nganttk@ntt.edu.vn ARTICLE INFO ABSTRACT The treatment and removal of toxic dyes in the aquatic environment are considered an urgent issue today. In addition to the development of traditional materials, a new material, a bimetallic organic framework, has received the attention of many researchers because of its outstanding properties and potential in high porosity and high porosity applications. surface rich in functional groups. On the basis of the above practices, Fe-MOF-based metallic materials modified with Ni, Cu, and Mn were synthesized by the solvothermal method. Evaluation of the materials from XRD, SEM, FT-IR diffraction measurements, and BET surface area measurements. From there, draw conclusions and evaluate the possibility of successful synthesis in the fabrication of new MOF materials. The adsorption capacity of the materials was preliminarily evaluated through the adsorption process of organic dyes. The results of structural characterization showed that the modification with metal ions did not change the original crystal structure of the material as well as the partial replacement of the second metal ion in the Keywords: lattice node. The material after a modification has a large bimetallic organic framework, specific surface charge, and at the same time increases the ability solvothermal, adsorption, to remove dyes from the aqueous medium. The successful study organic dyes of the topic will be the basis for the diversification of methods and materials to treat environmental pollution. 1. Introduction Metal-organic framework materials (MOFs) are made up of metal or metal oxides and are connected by polyorganic organic ligands to form a lattice, leaving large voids inside, which is a lattice. multi-dimensional, nano-sized space with surface areas that can reach over 6000 m2/g (Furukawa et al., 2010). Different from other porous solid materials such as activated carbon, zeolites, with stable structure, high porosity and large specific surface area, MOFs are currently attracting the attention of scientists around the world. as well as in water because of their superior and selective adsorption capacity (Burrows, 2011; Chen et al., 2020; Dhakshinamoorthy et al., 2016). It is difficult to predict the final structure of MOFs products 65
Chuyên san Phát triển Khoa học và Công nghệ số 8 (4), 2022 due to the mobility of different types of covalent bonds and different organic bridges with metals (Dhakshinamoorthy et al., 2016). In addition, with outstanding properties, bimetallic MOFs with adjustable components and structures have provided outstanding performance in many applications including catalysis, gas adsorption, energy conversion, storage, and luminescence sensors (Guo et al., 2020; Jia et al., 2013; Li et al., 2020; Ngan Tran et al., 2022; Q. Wang et al., 2019). Furthermore, bimetallic MOFs can be used as precursors to synthesize a variety of nanostructured materials such as metal compounds, MOF composites, and carbon composites (Y. Wu et al., 2021). Specifically, Qiangshun et al (2020) synthesized bimetallic materials of Ni-doped Fe-BDC to improve the specific surface area and pore volume and reduce surface zeta potential to increase adsorption capacity. for both MB and MO dyes (Q. Wu et al., 2021). The potential of the bimetallic catalyst FexCu1-x (BDC) in antibiotic treatment is demonstrated by the removal of 100% of sulfamethoxazole (SMX) within 120 min, which is higher than the SMX removal efficiency compared with Fe-BDC monometallic (Tang & Wang, 2020). In 2022, author Ngan et al. research group used the solvent heat method to synthesize M/Fe-MOF bimetallic materials (M: Co, Mg, and Cu) and evaluated the photoactivity. catalyzed in the degradation reaction of organic pigment rhodamine B (RhB) under visible light (Ngan Tran et al., 2022). Hong-Tham et al. (2021) removed Rhodamine B (RhB) dye under visible light by NH2-MIL-125 (Ti) bimetallic heterogeneous photocatalysts with the ratio Mn+/Ti4+ (Mn+: Ni2+, Co2+, and Fe3+) (Thi et al., 2021). Gu et al. (2018) have shown that changing the Fe:Mg molar ratio can lead to the alteration of structural features related to the length/diameter ratio and single-cell parameters. and the surface area increased from 57 m2.g-1 (Fe-MIL-88B) to 360 m2.g-1 (Fe/Mg- MIL-88B) (Gu et al., 2019). Therefore, in this study, the combination of Fe(III) and Ni(II), Cu(II), or Mn(II) metal salts bound to organic bridges were synthesized based on thermal method solvent in the presence of DMF. The structural properties of the materials were analyzed based on modern physicochemical methods (XRD, FT-IR, SEM, and BET). From there, the bimetallic material was preliminarily evaluated for the adsorption of organic dyes. 2. Materials and methods 2.1. Chemicals This Iron (III) chloride hexahydrate (FeCl3.6H2O), Copper(II) nitrate trihydrate (Cu(NO3)2.3H2O), Nikel nitrate hexahydrate (Ni(NO3)2.6H2O), Manganese Chloride (MnCl2.6H2O) are obtained from Xilong – China. N,N-Dimethylmethanamide ((CH3)2NCHO) from Macron-Fisher, Methylene Blue (C37H27N3Na2O9S3) from Sigma-Aldrich. All chemicals were used without further purification. 2.2. Synthesis of bimetallic materials M/Fe-MOF M/Fe-MOF bimetallic materials (M: Ni, Cu, and Mn) were synthesized based on previous research by (Ding et al., 2021) with correction. The reaction process occurs in a hydrothermal vessel (Teflon), a mixture of metal salts combined with organic ligands in the presence of DMF solvent, performed based on the solvent heat method. Specifically, a mixture of 10 mmol FeCl3.6H2O, Co(NO3)2.6H2O, and 5 mmol 1,4 benzenedicarboxylic acid dissolved in 60 mL of DMF for 30 minutes at room temperature. The homogenized mixture was placed 66
Chuyên san Phát triển Khoa học và Công nghệ số 8 (4), 2022 into a Teflon tube covered with stainless steel and heated to 150ºC for 15 h. The solid material samples were recovered by centrifugation at 6000 rpm for 10 minutes and further cleaned with DMF and ethanol solvents. The final material sample was dried at 120°C overnight. 2.3. Characteristics The materials were evaluated for structural characterization through methods such as X-ray diffraction (XRD) which were analyzed on the D8 Advance Bruker instrument (Germany) using CuK𝛼 radiation at a 2θ scanning angle from 10 to 35º. Infrared spectroscopy method FT-IR was measured on Nicolet 6700 - Thermo Fisher Scientific device (USA) to identify organic compounds and study the structure. SEM electron microscopy images were recorded on a machine S4800 of JEOL (Japan). The N2 adsorption-desorption isotherms determine the capillary characteristics as well as the specific surface area of the materials studied on Micromeritics 2020 (USA). Analytical methods were performed at Vietnam Institute of Science and Technology, No. 18 Hoang Quoc Viet, Cau Giay, Hanoi. 2.4. Methylene Blue dye adsorption process The adsorption capacity of modified material samples was evaluated based on the ability to remove MB pigment in an aqueous solution. The experimental process was carried out in a pH 2 - 12 environment, an amount of material 0.002 - 0.03 g/L was added to erlenmeyer containing 50 mL of dye solution at an initial concentration of 30 - 300 mg/L. After the specified time (10–240 min) 4 mL of the solution was removed and centrifuged (6000 rpm, 5 min) to remove solids. The dye concentration was determined by the UV-Vis method on a Thermo apparatus at 664 nm. 3. Result and discussion 3.1. Characterizations The crystal structure of the bimetallic material M/Fe-MOF was determined based on the XRD method, the crystallinity is shown in spectrogram Figure 1 a. In general, the modified samples all show peaks that are almost similar to those of the original Fe-MOF, showing that bimetallic modified materials have been successfully synthesized based on Fe-MOF. The shift of some peaks to lower and higher angles is mainly due to the ionic radii of different metals. The Fe-MOF data show high intensities at 12.58º and 18.9º, respectively, for the high intensities of MnFe-MOFs (11.09º and 21.58º), CuFe-MOFs (10.35º and 16.5º) and NiFe-MOFs (11.75º and 18.98º). The slight difference in peak positions and intensities of the XRD patterns of the other frames is due to the different equivalences of the Fe-MOF framework when Fe3+ is partially substituted by another metal ion (C. Wu et al., 2021). The bonds in the samples of CuFe-MOF, NiFe-MOF, and MnFe-MOF materials were analyzed based on the schematic diagram in Figure 1 b. The results show that the modified materials all have peaks that are nearly the same and similar to the characteristic peaks of the original Fe-MOF. The peak oscillation 3700 - 3000 cm-1 is the oscillation of the O-H bond of the water molecules adsorbed on the surface of the material. The 1598 - 1373 cm-1 adsorption peaks characterize the symmetric and asymmetric vibrations of the carboxylic group of the BDC organic bridge bound to the central metal and have shifted to a lower wavelength than compared with Fe-MOF. The C-H bond vibrations of the benzene rings are characterized by 67
Chuyên san Phát triển Khoa học và Công nghệ số 8 (4), 2022 peaks of 753 – 749 cm-1. Characteristic for the Fe-O bond at the peaks 554 – 527 cm-1. In addition, the peak appearance of 2945 cm-1 at weak intensity indicates that the DMF has not been completely eliminated in the pores. The change in intensity and position of the peaks may be due to a partial change of Fe3+ metal ion by a second metal ion in the lattice framework (Z. Wang et al., 2021). Figure 1. XRD(a) and FT-IR (b) diagram of bimetallic Fe MOF Figure 2 shows that the second metal present in the lattice leads to a change in the grain size, morphology, or grain distribution of the materials compared with the octahedral structure of the Fe-MOF monometallic pattern. The results show that the samples of Cu/Fe-MOF, Ni/Fe−MOF, and Mn/Fe−MOF have surface morphology with large, uneven grain size, partially deformed crystals, and phenomenon clumps of particles. This phenomenon is completely consistent with previous reports, the final morphology of Fe-MOF can be influenced by the incorporation of the second metal element (Tang & Wang, 2020). The Nitrogen adsorption-desorption isotherm (BET) used to determine the capillary structure is shown in Figure 3. In comparison with the original Fe-MOF with a surface area of 32.8 m2/g and size of 7.9 nm pore, it can be seen that the doping of Cu, Mn, and Ni metals leads to significant changes. The N2 adsorption and desorption curve belong to type II (according to IUPAC classification) characteristic for the presence of micro and small capillaries. The BET-specific surface area has a difference between Fe-MOF bimetallic materials with different metal ion centers, specifically Cu/Fe-MOF (33.3 m2/g), Mn/Fe-MOF (32.3 m2) /g) and Ni/Fe-MOF (33.7 m2/g). Some previous publications showed that when adding Cu2+ metal ions, the specific surface area of MIL- 101 (Fe) increased significantly from 510.66 m2/g to 747.75 m2/g (Y. Wu et al., 2021). 68
Chuyên san Phát triển Khoa học và Công nghệ số 8 (4), 2022 Figure 2. SEM image of materials when changing the crystallinity ratio of Fe-MOF bimetallic materials Figure 3: N2 adsorption-desorption isotherm curves of M/Fe-MOF: (a) Fe-MOF, (b) NiFe- MOF, (c) CuFe-MOF, and (d) MnFe-MOF 69
Chuyên san Phát triển Khoa học và Công nghệ số 8 (4), 2022 Table 1 BET data of Fe-MOF based bimetallic samples Samples BET surface area Pore volume Pore size (nm) (m2/g) (cm3/g) Fe-MOF 32.8 0.065 7.95 NiFe-MOF 33.7 0.057 6.76 CuFe-MOF 33.3 0.179 21.58 MnFe-MOF 32.3 0.049 6.08 3.2. MB adsorption capacity of M/Fe-MOF materials (M: Ni, Mn, and Cu) Preliminary evaluation experiments on dye adsorption capacity of bimetallic samples at experimental conditions similar to bimetallic modified samples with Co2+ ions. The adsorption results are presented in Figure 4, on the same synthesis conditions, NiFe-MOF and CuFe-MOF exhibit superior adsorption capacity compared to Fe-MOF and MnFe-MOF. Specifically, the best MB adsorption capacity of CuFe-MOF (201.2 mg/g), NiFe-MOF (267.7 mg/g), and MnFe- MOF (133.1 mg/g) compared with Fe-MOF (147.8 mg/g). Based on the evaluation results of MnFe-MOF, the adsorption capacity is lower than that of Fe-MOF. However, RhB adsorbed very little despite the same cationic dye, based on this result it can be seen that the adsorption capacity depends not only on the structure of the adsorbent but also on the length of the structure. bamboo dye. This is consistent with the preliminary assessment via SEM images and specific surface area analysis of the materials. On the other hand, the dye adsorption capacity depends on the ratio between the two metals in the lattice or the central metal and the substitution metal. Yue Gug et al. (2018) studied the crystal formation of the MIL−88B(Fe) material structure by changing the ratio of Mg2+/Fe3+ and applied it to the removal of Arsenic metal present in wastewater (Gu et al., 2019). Figure 4: The dye adsorption process of M/Fe MOF (M: Mn, Cu, and Ni) 4. Conclusions Bimetallic Fe-MOF materials modified with Ni, Cu, and Mn were successfully synthesized by the solvent heat method. The structure of the materials was evaluated by modern analytical methods such as XRD, SEM, FT-IR, and isotherm of nitrogen adsorption-desorption. 70
Chuyên san Phát triển Khoa học và Công nghệ số 8 (4), 2022 The presence of the second metal in the lattice framework of Fe-MOF materials increases the ability to remove dyes in an aqueous medium through the adsorption process. The adsorption capacity of organic dyes of NiFe-MOF and CuNi-MOF was higher than that of single metal Fe- MOF, while MnFe-MOF gave lower results. Therefore, it is necessary to conduct more studies on the change of molar ratios between the bimetallic centers in order to find the best materials for the adsorption process, opening up the potential application of the material in the field of substance treatment. Toxic organic colors cause environmental pollution. ACKNOWLEDGEMENTS The study was supported by The Youth Incubator for Science and Technology Programe, man-aged by Youth Development Science and Technology Center – Ho Chi Minh Communist Youth Union and Department of Science and Technology of Ho Chi Minh City, the contract number is No. 10/2021/HĐ-KHCNT-VƯ. References Burrows, A. D. (2011). Mixed-component metal-organic frameworks (MC-MOFs): Enhancing functionality through solid solution formation and surface modifications. CrystEngComm, 13(11), 3623–3642. https://doi.org/10.1039/c0ce00568a Chen, L., Wang, H. F., Li, C., & Xu, Q. (2020). Bimetallic metal-organic frameworks and their derivatives. Chemical Science, 11(21), 5369–5403. https://doi.org/10.1039/d0sc01432j Dhakshinamoorthy, A., Asiri, A. M., & Garcia, H. (2016). Mixed-metal or mixed-linker metal organic frameworks as heterogeneous catalysts. Catalysis Science and Technology, 6(14), 5238–5261. https://doi.org/10.1039/c6cy00695g Ding, L., Zeng, M., Wang, H., & Jiang, X. B. (2021). Synthesis of MIL-101-derived bimetal– organic framework and applications for lithium-ion batteries. Journal of Materials Science: Materials in Electronics, 32(2), 1778–1786. https://doi.org/10.1007/s10854-020-04946-8 Furukawa, H., Ko, N., Go, Y. B., Aratani, N., Choi, S. B., Choi, E., Yazaydin, A. Ö., Snurr, R. Q., O’Keeffe, M., Kim, J., & Yaghi, O. M. (2010). Ultrahigh porosity in metal-organic frameworks. Science, 329(5990), 424–428. https://doi.org/10.1126/science.1192160 Gu, Y., Xie, D., Wang, Y., Qin, W., Zhang, H., Wang, G., Zhang, Y., & Zhao, H. (2019). Facile fabrication of composition-tunable Fe/Mg bimetal-organic frameworks for exceptional arsenate removal. Chemical Engineering Journal, 357, 579–588. https://doi.org/10.1016/j.cej.2018.09.174 Guo, H., Su, S., Liu, Y., Ren, X., & Guo, W. (2020). Enhanced catalytic activity of MIL-101(Fe) with coordinatively unsaturated sites for activating persulfate to degrade organic pollutants. Environmental Science and Pollution Research, 27(14), 17194–17204. https://doi.org/10.1007/s11356-020-08316-z Jia, J., Xu, F., Long, Z., Hou, X., & Sepaniak, M. J. (2013). Metal-organic framework MIL-53(Fe) for highly selective and ultrasensitive direct sensing of MeHg+. Chemical Communications, 49(41), 4670–4672. https://doi.org/10.1039/c3cc40821c Li, J., Wang, L., Liu, Y., Zeng, P., Wang, Y., & Zhang, Y. (2020). Removal of berberine from wastewater by MIL-101(Fe): Performance and mechanism. ACS Omega, 5(43), 27962– 27971. https://doi.org/10.1021/acsomega.0c03422 Ngan Tran, T. K., Ho, H. L., Nguyen, H. V., Tran, B. T., Nguyen, T. T., Thi Bui, P. Q., & Bach, L. G. (2022). Photocatalytic degradation of Rhodamine B in aqueous phase by bimetallic metal-organic framework M/Fe-MOF (M = Co, Cu, and Mg). Open Chemistry, 20(1), 52– 60. https://doi.org/10.1515/chem-2021-0110 Tang, J., & Wang, J. (2020). Iron-copper bimetallic metal-organic frameworks for efficient Fenton- like degradation of sulfamethoxazole under mild conditions. Chemosphere, 241, 125002. https://doi.org/10.1016/j.chemosphere.2019.125002 71
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