Abstract
In this work, the new class of porous materials MIL-100(Cr) was synthetized using a solvent-free methodology to evaluate the removal of the pharmaceutical contaminants Paracetamol, Ibuprofen, Metformin, or Carbamazepine from aqueous sources. This adsorbent was characterized by thermogravimetric analysis, Fourier transform infrared spectroscopy with attenuated total reflectance, Raman spectroscopy, nitrogen adsorption-desorption, and X-ray photoelectron spectroscopy. The characterization technique results indicated that the synthesized MIL-100(Cr) has a non-uniform structure of different sizes as well as a low crystallinity structure and is thermally stable up to ~ 300 °C with a surface negatively charged in the assay pH range and the presence of two types of cavities, pentagonal and hexagonal, with sizes of 1.10 nm and 1.49 nm. The results of adsorption demonstrated higher values of Carbamazepine, Paracetamol, and Ibuprofen on MIL-100(Cr) with values of 21 mg L−1, 20 mg L−1, and 17 mg L−1, respectively, while in the case of Metformin, a lower value of 12 mg L−1 was observed. The differences in the adsorption values were explained by different interactions between the pharmaceutical compounds and the MIL-100(Cr), such as π–π and electrostatic interactions and hydrogen bonds. Despite the low crystallinity observed in MIL-100(Cr), due to synthesis solvent-free methodologies used, this material maintains the structural and physicochemical characteristics required to be utilized as an adsorbent of pharmaceutical contaminants from aqueous solutions.
Similar content being viewed by others
Data Availability
All data generated or analyzed during this study are included in this published article.
References
Ahmed, M. J. (2017). Adsorption of non-steroidal anti-inflammatory drugs from aqueous solution using activated carbons: Review. Journal of Environmental Management, 190, 274–282. https://doi.org/10.1016/j.jenvman.2016.12.073
Akiyama, G., Matsuda, R., Sato, H., & Kitagawa, S. (2014). Catalytic Glucose Isomerization by Porous Coordination Polymers with Open Metal Sites. Chemistry – An Asian Journal, 9, 2772–2777. https://doi.org/10.1002/asia.201402119
Baeza, P., Aballay, P., Matus, C., Camú, E., Fernanda Ramirez, M., Eyzaguirre, J., & Ojeda, J. (2019). Degradation of Paracetamol Adsorbed on Inorganic Supports Under UV Irradiation. Water, Air, & Soil Pollution, 230(2), 34. https://doi.org/10.1007/s11270-019-4095-z
Baeza, P., Astudillo, C., Diaz, M., Matus, C., Ramírez, M. F., Aguila, G., & Ojeda, J. (2020). Effect of the Incorporation of Ni in the Adsorption Capacity of Paracetamol (N-Acetyl-P-Aminophenol) on MIL-101(Cr). Water, Air, & Soil Pollution, 231(5), 245. https://doi.org/10.1007/s11270-020-04584-0
Benhmid, A., Edbey, K., Bukhzam, A., Alhowari, H., Mekhemer, G. A. H., & Zaki, M. I. (2018). Surface acidity of the supported molybdenum oxide catalysts probed by potentiometric titration of n-butylamine. International Research Journal of Pure and Applied Chemistry, 16, 1–7. https://doi.org/10.9734/IRJPAC/2018/41667
Chaukura, N., Mamba, B. B., & Mishra, S. B. (2017). Porous materials for the sorption of emerging organic pollutants from aqueous systems: The case for conjugated microporous polymers. Journal of Water Process Engineering, 16, 223–232. https://doi.org/10.1016/j.jwpe.2017.02.001
Chen, M. L., Zhou, S. Y., Xu, Z., Ding, L., & Cheng, Y. H. (2019). Metal-Organic Frameworks of MIL-100(Fe, Cr) and MIL-101(Cr) for Aromatic Amines Adsorption from Aqueous Solutions. Molecules., 24. https://doi.org/10.3390/molecules24203718
Chen, X., Chen, X., Cai, S., Chen, J., Xu, W., Jia, H., & Chen, J. (2018). Catalytic combustion of toluene over mesoporous Cr2O3-supported platinum catalysts prepared by in situ pyrolysis of MOFs. Journal of Chemical Engineering, 334, 768–779. https://doi.org/10.1016/j.cej.2017.10.091
Coimbra, R. N., Escapa, C., & Otero, M. (2018). Adsorption Separation of Analgesic Pharmaceuticals from Ultrapure and Waste Water: Batch Studies Using a Polymeric Resin and an Activated Carbon. Polymers., 10, 958. https://doi.org/10.3390/polym10090958
Cychosz, K. A., & Matzger, A. J. (2010). Water Stability of Microporous Coordination Polymers and the Adsorption of Pharmaceuticals from Water. Langmuir., 26(22), 17198–17202. https://doi.org/10.1021/la103234u
De Andrade, J. R., Oliveira, M. F., Da Silva, M., & Vieira, M. (2018). Adsorption of pharmaceuticals from water and wastewater using nonconventional low-cost materials: A review. Industrial and Engineering Chemistry Research, 57(9), 3103–3127. https://doi.org/10.1021/acs.iecr.7b05137
Ebele, A. J., Abou-Elwafa Abdallah, M., & Harrad, S. (2017). Pharmaceuticals and personal care products (PPCPs) in the freshwater aquatic environment. Emerging Contaminants, 3(1), 1–16. https://doi.org/10.1016/j.emcon.2016.12.004
El-Kemary, M., Sobhy, S., El-Daly, S., & Abdel-Shafi, A. (2011). Inclusion of Paracetamol into β-cyclodextrin nanocavities in solution and in the solid state. Spectrochimica Acta. Part A, Molecular and Biomolecular Spectroscopy, 79(5), 1904–1908. https://doi.org/10.1016/j.saa.2011.05.084
Fallah, Z., Zare, E. N., Ghomi, M., Ahmadijokani, F., Amini, M., Tajbakhsh, M., & Varma, R. S. (2021). Toxicity and remediation of pharmaceuticals and pesticides using metal oxides and carbon nanomaterials. Chemosphere., 275, 130055. https://doi.org/10.1016/j.chemosphere.2021.130055
Férey, G., Serre, C., Mellot-Draznieks, C., Millange, F., Surblé, S., Dutour, J., & Margiolaki, I. (2004). A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction. Angewandte Chemie International Edition, 43, 6296–6301. https://doi.org/10.1002/anie.200460592
Furukawa, S., Reboul, J., Diring, S., Sumida, K., & Kitagawa, S. (2014). Structuring of metal–organic frameworks at the mesoscopic/macroscopic scale. Chemical Society Reviews, 43(16), 5700–5734. https://doi.org/10.1039/C4CS00106K
Gadipelly, C., Pérez-González, A., Yadav, G. D., Ortiz, I., Ibáñez, R., Rathod, V. K., & Marathe, K. V. (2014). Pharmaceutical Industry Wastewater: Review of the Technologies for Water Treatment and Reuse. Industrial and Engineering Chemistry Research, 53(29), 11571–11592. https://doi.org/10.1021/ie501210j
García Márquez, A., Demessence, A., Platero-Prats, A. E., Heurtaux, D., Horcajada, P., Serre, C., Chang, J. S., Férey, G., De la Peña-O’Shea, V. A., Boissière, C., Grosso, D., & Sanchez, C. (2012). Green Microwave Synthesis of MIL-100(Al, Cr, Fe) Nanoparticles for Thin-Film Elaboration. European Journal of Inorganic Chemistry, 5165–5174. https://doi.org/10.1002/ejic.201200710
García-Medina, S., Galar-Martínez, M., Gómez-Oliván, L. M., Torres-Bezaury, R. M., Islas-Flores, H., & Gasca-Pérez, E. (2020). The relationship between cyto-genotoxic damage and oxidative stress produced by emerging pollutants on a bioindicator organism (Allium cepa): The carbamazepine case. Chemosphere., 253, 126675. https://doi.org/10.1016/j.chemosphere.2020.126675
Hall, J. N., & Bollini, P. (2020). Metal–Organic Framework MIL-100 Catalyzed Acetalization of Benzaldehyde with Methanol: Lewis or Brønsted Acid Catalysis? ACS Catalysis, 10(6), 3750–3763. https://doi.org/10.1021/acscatal.0c00399
Hasan, Z., & Jhung, S. H. (2015). Removal of hazardous organics from water using metal-organic frameworks (MOFs): Plausible mechanisms for selective adsorptions. Journal of Hazardous Materials, 283, 329–339. https://doi.org/10.1016/j.jhazmat.2014.09.046
Hidayat, D., Lestari, W. W., Dendy, D., Khoerunnisa, F., Handayani, M., Sanjaya, E. H., & Gunawan, T. (2023). Adsorption Studies of Anionic and Cationic Dyes on MIL-100(Cr) Synthesized Using Facile and Green Mechanochemical Method. Journal of Inorganic and Organometallic Polymers, 33, 1548–1561. https://doi.org/10.1007/s10904-023-02569-0
Izadi, P., Izadi, P., Salem, R., Papry, S. A., Magdouli, S., Pulicharla, R., & Brar, S. K. (2020). Non-steroidal anti-inflammatory drugs in the environment: Where were we and how far we have come? Environmental Pollution, 267, 115370. https://doi.org/10.1016/j.envpol.2020.115370
Jones, O. A., Voulvoulis, N., & Lester, J. N. (2002). Aquatic environmental assessment of the top 25 English prescription pharmaceuticals. Water Research, 36(20), 5013–5022. https://doi.org/10.1016/s0043-1354(02)00227-0
Jun, J. W., Tong, M., Jung, B. K., Hasan, Z., Zhong, C., & Jhung, S. H. (2015). Effect of central metal ions of analogous metal-organic frameworks on adsorption of organoarsenic compounds from water: plausible mechanism of adsorption and water purification. Chem., 21(1), 347–354. https://doi.org/10.1002/chem.201404658
Kar, P., Shukla, K., Jain, P., Sathiyan, G., & Gupta, R. K. (2021). Semiconductor based photocatalysts for detoxification of emerging pharmaceutical pollutants from aquatic systems: A critical review. Nano Materials Science, 3(1), 25–46. https://doi.org/10.1016/j.nanoms.2020.11.001
Karimi-Maleh, H., Ayati, A., Davoodi, R., Tanhaei, B., Karimi, F., Malekmohammadi, S., & Sillanpää, M. (2021). Recent advances in using of chitosan-based adsorbents for removal of pharmaceutical contaminants: A review. Journal of Cleaner Production, 291, 125880. https://doi.org/10.1016/j.jclepro.2021.125880
Khan, N. A., & Jhung, S. H. (2017). Adsorptive removal and separation of chemicals with metal-organic frameworks: Contribution of π-complexation. Journal of Hazardous Materials, 325, 198–213. https://doi.org/10.1016/j.jhazmat.2016.11.070
Kholdeeva, O. A., Skobelev, I. Y., Ivanchikova, I. D., Kovalenko, K. A., Fedin, V. P., & Sorokin, A. B. (2014). Hydrocarbon oxidation over Fe- and Cr-containing metal-organic frameworks MIL-100 and MIL-101–a comparative study. Catalysis Today, 238, 54–61. https://doi.org/10.1016/j.cattod.2014.01.010
Li, W. (2019). Metal–organic framework membranes: Production, modification, and applications. Progress in Materials Science, 100, 21–63. https://doi.org/10.1016/j.pmatsci.2018.09.00
Liu, B., Yang, F., Zou, Y., & Peng, Y. (2014). Adsorption of Phenol and p-Nitrophenol from Aqueous Solutions on Metal–Organic Frameworks: Effect of Hydrogen Bonding. Journal of Chemical & Engineering Data, 59(5), 1476–1482. https://doi.org/10.1021/je4010239
Liu, S., Zhang, Y., Han, Y., Feng, G., Gao, F., Wang, H., & Qiu, P. (2017). Selective Ethylene Oligomerization with Chromium-Based Metal–Organic Framework MIL-100 Evacuated under Different Temperatures. Organometallics., 36(3), 632–638. https://doi.org/10.1021/acs.organomet.6b00834
Long, P., Wu, H., Zhao, Q., Wang, Y., Dong, J., & Li, J. (2011). Solvent effect on the synthesis of MIL-96(Cr) and MIL-100(Cr). Microporous and Mesoporous Materials, 142(2-3), 489–493. https://doi.org/10.1016/j.micromeso.2010.12.036
Maes, M., Trekels, M., Boulhout, M., Schouteden, S., Vermoortele, F., Alaerts, L., Heurtaux, D., Seo, Y. K., Hwang, Y. K., Chang, J. S., Beurroies, I., Denoyel, R., Temst, K., Vantomme, A., Horcajada, P., Serre, C., & De Vos, D. E. (2011). Selective removal of N‐heterocyclic aromatic contaminants from fuels by Lewis acidic metal–organic frameworks. Angewandte Chemie, International Edition, 50, 4210–4214. https://doi.org/10.1002/anie.201100050
Mao, Y., Qi, H., Ye, G., Han, L., Zhou, W., Xu, W., & Sun, Y. (2019). Green and time-saving synthesis of MIL-100(Cr) and its catalytic performance. Microporous and Mesoporous Materials, 274, 70–75. https://doi.org/10.1016/j.micromeso.2018.07.026
Moreno-Castilla, C. (2004). Adsorption of organic molecules from aqueous solutions on carbon materials. Carbon., 42, 83–94. https://doi.org/10.1016/j.carbon.2003.09.022
Mouchaham, G., Wang, S., & Serre, C. (2018). The Stability of Metal–Organic Frameworks. In H. García & S. Navalón (Eds.), Metal-Organic Frameworks (First ed., pp. 1–28). Publisher. https://doi.org/10.1002/9783527809097.ch1
Muñoz-Senmache, J. C., Cruz-Tato, P. E., Nicolau, E., & Hernández-Maldonado, A. J. (2022). Confined space synthesis of chromium–based metal–organic frameworks in activated carbon: Synergistic effect on the adsorption of contaminants of emerging concern from water. Journal of Environmental Chemical Engineering, 10(2), 107282. https://doi.org/10.1016/j.jece.2022.107282
Natarajan, R., Saikia, K., Ponnusamy, S. K., Rathankumar, A. K., Rajendran, D. S., Venkataraman, S., & Vaidyanathan, V. K. (2022). Understanding the factors affecting adsorption of pharmaceuticals on different adsorbents – A critical literature update. Chemosphere., 287, 131958. https://doi.org/10.1016/j.chemosphere.2021.131958
Nghiem, L. D., & Hawkes, S. (2007). Effects of membrane fouling on the nanofiltration of pharmaceutically active compounds (PhACs): Mechanisms and role of membrane pore size. Separation and Purification Technology, 57(1), 176–184. https://doi.org/10.1016/j.seppur.2007.04.002
Pereira, A., Silva, L., Laranjeiro, C., Lino, C., & Pena, A. (2020). Selected Pharmaceuticals in Different Aquatic Compartments: Part I-Source, Fate and Occurrence. Molecules., 25, 1026. https://doi.org/10.3390/molecules25051026
Pusceddu, F. H., Guimarães, M. M., Lopes, L. O., Souza, L. S., Cortez, F. S., Pereira, C. D. S., & Cesar, A. (2022). Biological effects of the antihypertensive losartan under different ocean acidification scenarios. Environmental Pollution, 292, 118329. https://doi.org/10.1016/j.envpol.2021.118329
Qin, F. X., Jia, S. Y., Liu, Y., Li, H. Y., & Wu, S. H. (2015). Adsorptive removal of bisphenol A from aqueous solution using metal-organic frameworks. Desalination and Water Treatment, 54(1), 93–102. https://doi.org/10.1080/19443994.2014.883331
Rastogi, A., Tiwari, M. K., Ghangrekar, M. M. 2021.A review on environmental occurrence, toxicity and microbial degradation of Non-Steroidal Anti-Inflammatory Drugs (NSAIDs). Journal of Environmental Management 300, 113694. https://doi.org/10.1016/j.jenvman.2021.113694.
Rebitski, E. P., Aranda, P., Darder, M., Carraro, R., & Ruiz-Hitzky, E. (2018). Intercalation of metformin in montmorillonite. Dalton Transactions, 47. https://doi.org/10.1039/C7DT04197G
Ren, J., Ledwaba, M., Musyoka, N. M., Langmi, H. W., Mathe, M., Liao, S., & Pang, W. (2017). Structural defects in metal–organic frameworks (MOFs): Formation, detection and control towards practices of interests. Coordination Chemistry Reviews, 349, 169–197. https://doi.org/10.1016/j.ccr.2017.08.017
Seo, P. W., Ahmed, I., & Jhung, S. H. (2016). Adsorptive removal of pharmaceuticals and personal care products from water with functionalized metal-organic frameworks: remarkable adsorbents with hydrogen-bonding abilities. Scientific Reports, 6, 34462. https://doi.org/10.1038/srep34462
Serre, C., Millange, F., Thouvenot, C., Noguès, M., Marsolier, G., Louër, D., & Férey, G. (2002). Very Large Breathing Effect in the First Nanoporous Chromium(III)-Based Solids: MIL-53 or CrIII(OH)·{O2C−C6H4−CO2}·{HO2C−C6H4−CO2H}x·H2Oy. Journal of the American Chemical Society, 124(45), 13519–13526. https://doi.org/10.1021/ja0276974
Songolzadeh, M., Soleimani, M., & Takht Ravanchi, M. (2019). Evaluation of metal type in MIL-100 structure to synthesize a selective adsorbent for the basic N-compounds removal from liquid fuels. Microporous and Mesoporous Materials, 274, 54–60. https://doi.org/10.1016/j.micromeso.2018.07.032
Taoufik, N., Boumya, W., Janani, F. Z., Elhalil, A., Mahjoubi, F. Z., & Barka, N. (2020). Removal of emerging pharmaceutical pollutants: A systematic mapping study review. Journal of Environmental Chemical Engineering, 8(5), 104251. https://doi.org/10.1016/j.jece.2020.104251
Tian, M., He, X., Feng, Y., Wang, W., Chen, H., Gong, M., Liu, D., Clarke, J. L., & Van Eerde, A. (2021). Pollution by Antibiotics and Antimicrobial Resistance in LiveStock and Poultry Manure in China, and Countermeasures. Antibiotics., 10, 539. https://doi.org/10.3390/antibiotics10050539
Trung, T. K., Ramsahye, N. A., Trens, P., Tanchoux, N., Serre, C., Fajula, F., & Férey, G. (2010). Adsorption of C5–C9 hydrocarbons in microporous MOFs MIL-100(Cr) and MIL-101(Cr): A manometric study. Microporous and Mesoporous Materials, 134(1), 134–140. https://doi.org/10.1016/j.micromeso.2010.05.018
Vicenteno-Vera, A. G., Campos-Hernandez, T., Ramirez-Silva, M. T., Galano, A., & Rojas-Hernandez, A. (2010). Determination of pKa Values of Diclofenac and Ibuprofen in Aqueous Solutions by Capillary Zone Electrophoresis. ECS Transactions, 29(1), 443. https://doi.org/10.1149/1.3532340
Villaescusa, I., Fiol, N., Poch, J., Bianchi, A., & Bazzicalupi, C. (2011). Mechanism of paracetamol removal by vegetable wastes: The contribution of π–π interactions, hydrogen bonding and hydrophobic effect. Desalination., 270(1), 35–142. https://doi.org/10.1016/j.desal.2010.11.037
Vimont, A., Goupil, J. M., Lavalley, J. C., Daturi, M., Surblé, S., Serre, C., & Audebrand, N. (2006). Investigation of Acid Sites in a Zeotypic Giant Pores Chromium(III) Carboxylate. Journal of the American Chemical Society, 128(10), 3218–3227. https://doi.org/10.1021/ja056906s
Vimont, A., Leclerc, H., Maugé, F., Daturi, M., Lavalley, J. C., Surblé, S., & Férey, G. (2007). Creation of Controlled Brønsted Acidity on a Zeotypic Mesoporous Chromium (III) Carboxylate by Grafting Water and Alcohol Molecules. Journal of Physical Chemistry C, 111(1), 383–388. https://doi.org/10.1021/jp064686e
Wang, L., Zhang, F., Wang, C., Li, Y., Yang, J., Li, L., & Li, J. (2020). Ethylenediamine-functionalized metal organic frameworks MIL-100(Cr) for efficient CO2/N2O separation. Separation and Purification Technology, 235, 116219. https://doi.org/10.1016/j.seppur.2019.116219
Waring, W. S. (2016). Antidiabetic drugs. Medicine, 44(3), 138–140. https://doi.org/10.1016/j.mpmed.2015.12.011
Yang, J., Du, B., Liu, J., Krishna, R., Zhang, F., Zhou, W., & Chen, B. (2018). MIL-100Cr with open Cr sites for a record N2O capture. ChemComm., 54(100), 14061–14064. https://doi.org/10.1039/C8CC07679K
Zhu, S., Liu, Y., Liu, S., Zeng, G., Jiang, L., Tan, X., & Yang, C. (2017). Adsorption of emerging contaminant metformin using graphene oxide. Chemosphere., 179, 20–28. https://doi.org/10.1016/j.chemosphere.2017.03.071
Acknowledgements
The authors are grateful to DI 039.321/2023 VINCI-PUCV.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of Interest
The authors declare no competing interests.
Additional information
Publisher’s Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Matus, C., Baeza, P., Serrano-Lotina, A. et al. Removal of Pharmaceuticals from an Aqueous Matrix by Adsorption on Metal–Organic Framework MIL-100(Cr). Water Air Soil Pollut 234, 718 (2023). https://doi.org/10.1007/s11270-023-06736-4
Received:
Accepted:
Published:
DOI: https://doi.org/10.1007/s11270-023-06736-4