Sulfonic-functionalized MIL-100-Fe MOF for the removal of diclofenac from water

In this work, a novel adsorbent (MIL-100-Fe-AMSA), for the removal of the nonsteroidal anti-inflammatory drug sodium diclofenac (DCF), was prepared by grafting aminomethanesulfonic acid to the open iron sites in a porous MIL-100-Fe MOF obtained by a green microwave-assisted synthesis.

Microporous and Mesoporous Materials 348 (2023) 112398 Contents lists available at ScienceDirect Microporous and Mesoporous Materials journal homepage: www.elsevier.com/locate/micromeso Sulfonic-functionalized MIL-100-Fe MOF for the removal of diclofenac from water ´nchez , Gemma Turnes Palomino **, Carlos Palomino Cabello * Neus Crespí Sa Department of Chemistry, University of the Balearic Islands, Palma de Mallorca, E-07122, Spain A R T I C L E I N F O A B S T R A C T Keywords: Sulfonic-grafted metal-organic frameworks 3D printing Functional devices Removal of pollutants Diclofenac In this work, a novel adsorbent (MIL-100-Fe-AMSA), for the removal of the nonsteroidal anti-inflammatory drug sodium diclofenac (DCF), was prepared by grafting aminomethanesulfonic acid to the open iron sites in a porous MIL-100-Fe MOF obtained by a green microwave-assisted synthesis The obtained materials were characterized by XRD, N2 adsorption-desorption, FTIR spectroscopy of adsorbed CO, electron microscopy and EDS spectros­ copy MIL-100-Fe-AMSA showed fast adsorption kinetics and an excellent maximum adsorption capacity of 476 mg/g Synergistic effect of H-bonding, between the electronegative ionized –SO3H groups of MIL-100-Fe-AMSA and –NH group of DCF, and π− π interactions between the aromatic rings that are present in both MOF and pollutant, is probably the main mechanism of adsorption In addition, the developed functionalized-MOF showed excellent reusability for at least five consecutive adsorption-desorption cycles, demonstrating its stability and potential for the removal of DCF For practical applications, the prepared MIL-100-Fe-AMSA was incorporated into a 3D printed column for flow-through solid-phase extraction of pharmaceuticals pollutants before HPLC determination The functional device showed excellent performance for the preconcentration and further detection and quantification of ketoprofen and DCF pollutants Introduction Water is one of the most important natural resources for life on our planet [1] Nowadays, the rapid progress of modern industry and pop­ ulation growth have led to the contamination of water with a variety of different organic pollutants, this having become a major global problem [2,3] Particularly, pharmaceutical compounds, such as antibiotics, anti-inflammatory drugs, analgesics, and hormones, and their metabo­ lites have attracted attention due to their potential harmful effects to human health and ecosystems [4,5] The inadvertently release of these compounds into the environment and their ineffective removal by wastewater treatment plants (WWWTPs) have led to their detection in different water resources, including drinking water [6–8] Therefore, a lot of research is being carried out on the elimination of pharmaceuticals from water Various strategies have been explored to remove pharmaceuticals from water bodies, such as chlorination [9], biodegradation [10], pho­ tocatalysis [11], coagulation-flocculation [12] or advanced oxidation processes (AOPs) [13] However, these methodologies are limited due to their high energy consumption, low effectiveness and the generation of residual byproducts that can also be toxic Adsorption by porous mate­ rials is considered one of the cheapest, simplest, most efficient and competitive methods for pharmaceuticals removal [14–16] Common adsorbents include carbonaceous materials [17,18], zeolites [19,20], and mesoporous silica [21,22] However, most of these solids have shortcomings such as low extraction capacity and poor adsorption selectivity, and therefore, there is a need to develop novel porous ma­ terials with high adsorption efficiency Recently, metal-organic frameworks (MOFs), a relatively new family of materials that are built up from the union of organic ligands and metal centers, have shown high potential in the adsorption removal of phar­ maceuticals from water due to their unique characteristics, such as simple synthesis, large surface area, tunable pore size and presence of metal active sites [23–27] Compared to conventional adsorbents, many MOFs exhibit superior extraction performance thanks to their ability of establishing different and multiple interactions with organic pollutants, including electrostatic interactions, acid-base interactions, H-bonding and π-π stacking [28–30] In this context, it has been reported that the * Corresponding author ** Corresponding author E-mail addresses: g.turnes@uib.es (G Turnes Palomino), carlos.palomino@uib.es (C Palomino Cabello) https://doi.org/10.1016/j.micromeso.2022.112398 Received October 2022; Received in revised form December 2022; Accepted December 2022 Available online December 2022 1387-1811/© 2022 The Authors Published by Elsevier Inc This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/bync-nd/4.0/) N Crespí S´ anchez et al Microporous and Mesoporous Materials 348 (2023) 112398 incorporation of functional groups in MOFs, through functionalization of the organic linker or the inorganic building blocks, is key to favoring and strengthening these interactions, thus improving the adsorption of pharmaceuticals [31,32] For example, Hasan et al [33] synthesized MIL-101 functionalized with acidic (-SO3H) and basic (-NH2) groups, by grafting them to the coordinatively unsaturated Cr3+ centers of the MOF, and used the functionalized MOFs to extract naproxen and clofi­ bric acid In the case of the adsorption of naproxen and clofibric acid over the amino-functionalized MIL-101 was 1.17 and 1.10 times higher than that of the bare MIL-101, respectively, due to the acid-base inter­ action between the basic adsorbent and the acidic adsorbates A similar approach was used by Song et al [34] to prepare MIL-101 MOFs with different number of –OH groups for the extraction of five pharmaceu­ ticals and personal care products The MIL-101 material with the highest concentration of –OH groups, MIL-101-(OH)3, showed a maximum adsorption capacity of 80 and 156 mg/g for the ketoprofen and nap­ roxen, respectively, which was attributed to H-bonding between the adsorbent (H-donor) and the pollutants (H-acceptors) On the other hand, using 2-sulfoterephthalic acid monosodium salt as a linker, MIL-101-SO3H material with high surface area (1760 m2/g) has been obtained and tested in the extraction of three fluoroquinolone antibi­ otics [35] Thanks to the electrostatic interaction between the ionized sulfonic acid groups and positive charged segment of fluoroquinolone molecules, very high adsorption capacities between 408 and 426 mg/g were obtained Very recently, it has also been reported the functionali­ zation of UiO-66-(COOH)2 with copper and iron and their use as sor­ bents for the removal of the nonsteroidal anti-inflammatory drug diclofenac sodium [36] Due to H-bonding and metal-π interactions, UiO-66-(COOFe)2 showed the maximum adsorption capacity followed by UiO-66-(COOCu)2 and UiO-66-(COOH)2 One of the most important limitations for the removal of pollutants from water by MOFs is their recovery after extraction, since it includes tedious and incomplete filtration and centrifugation steps In order to facilitate the post-extraction procedure, and thus enhance the applica­ bility of MOFs as sorbents, different strategies have been developed, including the preparation of MOFs with magnetic properties or their immobilization on robust supports [37,38] Through this last approach, promising functional materials for the extraction of organic pollutants have been obtained, such as MIL-125(Ti)-chitosan membranes [39], ZIF-8/polyacrylonitrile fibers [40], polydopamine/Zr-MOF foams [41], and MIL-101(Cr)/chitosan composite beads [42], among others In this context, recently, additive manufacturing (3D printing) has emerged as a powerful tool for the preparation of novel functional 3D printed de­ vices for the removal of pollutants from water [43–45] In this work, we report the preparation of a novel adsorbent by grafting aminomethane sulfonic acid (AMSA) to coordinatively unsat­ urated iron sites of MIL-100-Fe, an iron-benzenetricarboxylate MOF characterized by its low cost, great porosity and water stability, that was prepared in 10 by microwave-assisted method The developed sulfonic-functionalized MIL-100-Fe was used for the removal of diclo­ fenac, the non-steroidal anti-inflammatory drug that presents the most important acute toxic effects on biota The kinetics, maximum adsorp­ tion capacity, reusability and the influence of the pH of the extraction medium were studied After batch experiments, the functionalized MIL100 material was immobilized in a 3D column by a simple and fast coating method and used for the extraction and preconcentration of two pharmaceutical compounds ACROS Organics Diclofenac sodium salt (DCF, ≥98.0%), poly­ vinylidene difluoride (PVDF, MW ~ 180,000), ketoprofen (≥98%) and sodium hydroxide (NaOH, ≥97.0%) were obtained from Aldrich Iron (III) chloride hexahydrate (FeCl3⋅6H2O, >97%) was acquired from Panreac Ultrapure water (18.2 MΩ cm) was obtained from a Milli-Q water generator 2.2 Synthesis of MIL-100-Fe Iron-based MIL-100 was synthesized using a rapid microwaveassisted method by adapting a procedure described in a previous report [46] Typically, 2.43 g of FeCl3⋅6H2O were dissolved in 30 mL of water After that, 0.84 g of 1,3,5-benzenetricarboxylic acid were added under constant stirring The resulting mixture was introduced to a Teflon vessel and heated at 403 K for 10 in a microwave oven The obtained light brown solid was separated by centrifugation and washed three times with water and ethanol Finally, the product was treated with 150 mL of ethanol at 373 K for 24 h 2.3 Synthesis of sulfonic-functionalized MIL-100 (MIL-100-Fe-AMSA) MIL-100-Fe was functionalized following an adaptation of the experimental procedure reported by Hasan et al [33] Before func­ tionalization, 0.5 g of MOF were activated at 453 K for 12 h in a round bottom flask with continuous circulation of N2 to generate coor­ dinatively unsaturated sites (CUSs) After activation, MIL-100-Fe was suspended in 50 mL of ethanol, and mmol of AMSA was added The mixture was stirred under reflux overnight The obtained solid was filtered, washed with ethanol and then dried at room temperature 2.4 Fabrication of 3D printed column The design of the 3D printed column with integrated packing based on interconnected cubes was carried out using the software Rhinoceros 5.0 SR11 32 (McNeel & Associates, USA) This device was 3D printed vertically with stand with 1016 layers at a resolution of 0.500 mm using the SLA technique In order to remove unreacted monomers, the 3D printed column was washed with 2-propanol and then dried at room temperature Finally, the UV post-curing was carried out for h at 365 nm 2.5 Immobilization of MIL-100-Fe-AMSA in 3D printed column MIL-100-Fe-AMSA/3D column was prepared by an easy coating method using a concentrated ink [47] Basically, 150 mg of MIL-100-Fe-AMSA were dispersed in mL of acetone through sonication for 30 Then, the dispersion was mixed with g of PVDF solution (7.5 wt% in DMF), and the resulting mixture was sonicated for another 30 min, and subsequently concentrated by acetone evaporation using gentle nitrogen flow The obtained dispersion was pumped through the 3D printed column and, after removing the excess of dispersion using a nitrogen stream, the 3D device was introduced in an oven at 333 K to eliminate DMF 2.6 Characterization Nitrogen adsorption-desorption isotherms were acquired at 77 K by using a TriStar II (Micromeritics) gas adsorption instrument The sam­ ples were previously activated at 423 K for 15 h Data were analysed using the Brunauer-Emmett-Teller model (BET) to obtain the specific surface area and the two-dimensional non-local density functional the­ ory model (2D-NLDFT) to determine the pore size distribution The Xray diffraction (XRD) patterns were obtained using CuKα radiation on a Bruker D8 Advance diffractometer The morphology and elemental distribution of the prepared materials were studied by using a scanning electron microscope (SEM) Hitachi S–3400 N, equipped with a Bruker Experimental section 2.1 Chemicals Hydrochloric acid (HCl, 37.0%), methanol (≥99.8%), N,Ndimethylformamide (DMF, 99.5%) and acetone (≥99.8%) were ac­ quired from Scharlau 1,3,5-benzenetricarboxylic acid (H3BTC, >98%) and aminomethanesulfonic acid (AMSA, 97%) were obtained from N Crespí S´ anchez et al Microporous and Mesoporous Materials 348 (2023) 112398 AXS Xflash 4010 energy-dispersive X-ray spectroscopy (EDS) system, and transmission electron microscope (TEM) ThermoScientific Talos F200i operated at 200 kV Fourier transform infrared (FTIR) spectra were acquired using a Bruker 80v spectrometer equipped with an MCT cryodetector For IR experiments, thin self-supported wafers of the MOF samples were prepared and outgassed in a dynamic vacuum at 453 K for h After this activation treatment, carbon monoxide was dosed into the cell to study the open metal centers Zeta potential was measured by employing a Zetasizer Nano ZS90 (Malvern) A Formlabs Form 3D Printer and clear photoactive resin composed of methacrylate mono­ mers/oligomers and initiator (Formlabs Clear V4 (FLGPCL04)) were used for device fabrication For post-curing the 3D printed devices, an Upland CL-1000 ultraviolet crosslinker with a 365 nm UV lamp was used Results and discussion compared to the solvothermal method [50] Then, using a simple pro­ cedure, sulfonic-functionalized MIL-100 MOF (MIL-100-Fe-AMSA) was obtained by grafting aminomethanesulfonic acid onto the coor­ dinatively unsaturated iron sites of MIL-100 Fig 1a shows the X-ray diffraction patterns of MIL-100-Fe before and after functionalization Both diffractograms show good crystallinity and matched well with those previously reported [51], indicating that the grafting process did not alter the structure of MIL-100-Fe The textural properties of the materials were investigated by N2 adsorption-desorption measurements As shown in Fig 1b, the N2 iso­ therms of the prepared MIL-100-Fe and MIL-100-Fe-AMSA are a com­ bination of type I and IV isotherms with a significant N2 uptake at lower P/P0 values, suggesting that the obtained materials were mainly microporous Both materials exhibit a multimodal distribution with pores centered at around 10, 15 and 20 Å (inset of Fig 1b) The BET specific surface and total pore volume of the MIL-100-Fe material were 1245 m2/g and 0.77 cm3/g, respectively, which are comparable to those reported in the literature [52] In the case of MIL-100-Fe-AMSA, the values of surface area and the total pore volume decreased to 845 m2/g and 0.50 cm3/g, respectively, what could be attributed to the partial occupation of the pores of MIL-100-Fe by the aminomethanesulfonic acid molecules Similar results have been described in the literature for the functionalization of uncoordinated metal centers of MOFs with organic molecules [33,34] The prepared materials were characterized by FTIR spectroscopy (Fig S1) The FTIR spectrum of the MIL-100-Fe shows bands at 1629, 1452, 1380, 760 and 711 cm− 1, which match well with those of MIL100-Fe MOF previously reported by other authors [53,54] The band at 1629 cm− is attributed to C–O stretching vibration of carboxylic groups, while the bands at 1452 and 1380 cm− can be assigned to the symmetric and asymmetric vibration of the OCO group, respectively The last two peaks at 760 and 711 cm− corresponds to the C–H vi­ brations of benzene ring The MIL-100-Fe-AMSA sample exhibits addi­ tional absorption bands at 1223 and 1152 cm− 1, which are assigned to – S– – O asymmetric and symmetric stretching modes, respectively, the O– and at 1041 that comes from the stretching mode of S–O [55,56], con­ firming the incorporation of the sulfonic groups in the grafted sample The functionalization of MIL-100-Fe was also checked by infrared spectroscopy of adsorbed carbon monoxide at 100 K For that, after activation of the obtained materials, a saturation dose of CO was introduced into the IR cell and the corresponding spectra were regis­ tered (Fig 1c) The IR spectrum of adsorbed CO on MIL-100-Fe shows an intense IR absorption band at 2170 cm− that corresponds to the fundamental C–O stretching mode of carbon monoxide interacting (through the carbon atom) with coordinatively unsaturated iron cations of MIL-100-Fe [57,58] The IR spectrum of the MIL-100-Fe-AMSA ex­ hibits the IR absorption band at 2170 cm− 1, although much less intense, indicating a partial functionalization of the open metal sites with the sulfonic acid groups In both cases, the spectra show an additional weaker band at 2135 cm− 1, which, in agreement with the literature, is assigned to physisorbed CO [57] The incorporation of AMSA molecules into the MIL-100-Fe sample was corroborated by EDS analysis (Fig 1d), in which a band at 2.31 KeV, corresponding to S (Kα) signal, was detected To study the morphology of the obtained MOFs, they were charac­ terized by scanning electron microscopy (Fig 2a and b) and trans­ mission electron microscopy (Fig 2c and d) As can be seen in the micrographs, both materials are formed of agglomerates of particles with an average crystal size of about 400 nm and octahedral shaped morphology, indicating that both, the morphology and the particle size, remain unchanged after the functionalization process 3.1 Synthesis and characterization of MIL-100-Fe-AMSA 3.2 Extraction of diclofenac under batch conditions MIL-100-Fe precursor was prepared by a green microwave-assisted synthesis, which allowed a significant decrease in the reaction time To evaluate the adsorption capacity of the sulfonic-functionalized MIL-100-Fe material as an adsorbent, diclofenac, one of the most 2.7 Adsorption experiments in batch conditions DCF solutions with different concentrations were obtained by diluting a stock solution of DCF (1 g/L) with deionized water All the batch experiments were carried out at room temperature with mg of sample (MIL-100-Fe or MIL-100-Fe-AMSA) per ml of DCF aqueous so­ lution Adsorption isotherms experiments were conducted in a concen­ tration range of 10–700 mg/L of DCF during 24 h to ensure the equilibrium conditions The pollutant concentration after the adsorption process was determined by UV–Vis spectrophotometer (Cary 300 Bio) at 276 nm The maximum adsorption capacity was obtained using the linearized form of the Langmuir equation [48], which is commonly represented as: Ce Ce = + qe qmax qmax ⋅k where Ce is the remaining DCF concentration (mg/L) at equilibrium, qe (mg/g) is the quantity of DCF adsorbed, qmax is the maximum adsorption capacity (mg/g), and k is the Langmuir constant (L/mg) Kinetic studies were carried out with the initial DCF concentration of 100 mg/L and measuring the concentration of remaining pollutant in solution at appropriate time intervals Adsorption data was analysed with a pseudo-second-order adsorption model [49], whose linearized-integral form is expressed by the following equation: t t = + qt qe k2 ⋅q2e where qt and qe (mg/g) are the amount of DCF per unit mass of the adsorbent at time t (min) and at equilibrium, respectively, and k2 is the rate constant (g/mg min) 2.8 Flow-through extraction and preconcentration of diclofenac and ketoprofen The 3D printed device with integrated packing was connected to a multi-syringe pump equipped with and 10 mL glass syringes Syringe contained an aqueous solution of a mixture of DCF and ketoprofen (1 ppm, each), and Syringe contained methanol First, 50 mL of a solution of the pharmaceutical products were automatically circulated through the column to preconcentrate them After that, the retained compounds were eluted by running mL of methanol through the column The output liquid was analysed by HPLC for the simultaneous determination of enrichment factors of both pharmaceuticals, DCF and ketoprofen N Crespí S´ anchez et al Microporous and Mesoporous Materials 348 (2023) 112398 Fig Characterization of MIL-100-Fe and MIL-100-Fe-AMSA samples: (a) XRD patterns, (b) N2 adsorption-desorption isotherms Inset: Pore size distribution, (c) FTIR spectra of CO adsorbed at 100 K, and (d) energy dispersive X-ray spectra Fig SEM images of (a) MIL-100-Fe and (b) MIL-100-Fe-AMSA samples TEM images of (c) MIL-100-Fe and (d) MIL-100-Fe-AMSA samples common pharmaceutical pollutants found in wastewater [59], was chosen as model adsorption analyte Fig 3a shows the adsorption iso­ therms of DCF on MIL-100-Fe and MIL-100-Fe-AMSA recorded at room temperature after 24 h of adsorption Langmuir model was used to fit the experimental results (Fig 3b), obtaining, in both cases, good correlation coefficients (R2 = 0.996–0.998), which confirms that this model is suitable for describing the DCF adsorption on both MOFs samples MIL-100-Fe-AMSA has a maximum adsorption capacity of DCF of 476 mg/g, which is higher than most of the values of adsorption capacity of DCF reported in the literature (Table S1) and was significantly better than that of the MIL-100-Fe (357 mg/g), demonstrating that the incor­ poration of the sulfonic acid groups improves the adsorbent properties of the MOF The adsorption rate is an important parameter to consider when N Crespí S´ anchez et al Microporous and Mesoporous Materials 348 (2023) 112398 Fig DCF adsorption isotherms (a), and corresponding Langmuir plots (b) of MIL-100-Fe and MIL-100-Fe-AMSA (c) Kinetic adsorption data (c) and corresponding linear fit of pseudo-second order kinetics model (d) for the adsorption of DCF (100 mg/L) on MIL-100-Fe and MIL-100-Fe-AMSA designing adsorbents for the removal of pollutants, and can be assessed by evaluating the effect of the contact time on the adsorption Fig 3c shows the percentage of DCF adsorbed by MIL-100-Fe before and after functionalization at different time intervals As can be observed, DCF was extracted faster using the MIL-100-Fe-AMSA MOF, reaching after only min, a percentage of extraction higher than 80%, showing the remarkable fast uptake of DCF by this material The adsorption kinetic data were analysed using a pseudo-second-order kinetic model (Fig 3d) In both cases, correlation coefficients of 0.999 were obtained, indicating that the experimental data are well described by this model To gain a better understanding of the DCF adsorption efficiency of MIL-100-Fe-AMSA, the possible interactions involved during the extraction process were studied For that, since the protonation/ desprotonation of adsorbates and the surface charges of adsorbents de­ pends on the solution pH, DCF adsorption over MIL-100-Fe-AMSA was carried out in a wide pH range (4.5–10.5) As shown in Fig 4a, the extraction capacity of MIL-100-Fe-AMSA was hardly affected by the pH of the solution and only a slight decrease of 8% was observed in the adsorption capacity when the pH changes from 4.5 to 10.5 Considering the isoelectric point of MIL-100-Fe-AMSA (Fig 4b) and the pKa of DCF (4.2) [60], this decrease could be due to the electrostatic repulsion be­ tween the negatively charged surface of the MIL-100-Fe-AMSA, that becomes more negative as the pH increases, and the DCF molecules, which are negatively charged over the pH range studied However, the small variation of the DCF adsorption on MIL-100-Fe with the pH sug­ gests that the electrostatic interactions are not significant in the extraction process So the superior extraction capacity of MIL-100-Fe-AMSA can be due by the synergistic effect of H-bonding and π-π interactions As DCF has hydrogen bond donor atoms (− NH group) and the sulfonic acid group of the MIL-100-Fe-AMSA, which is ionized in the pH range studied, can act as hydrogen bond acceptor, strong inter­ molecular hydrogen bonds can be established between them [61] In order to confirm this interaction, FTIR analysis was carried out (Fig S2) The FTIR spectrum of MIL-100-Fe-AMSA after DCF adsorption shows a shift of the stretching vibration of sulfonic group, which, in agreement with the literature, proves the interaction between the sulfonic groups and DCF molecules [30,62] Accordingly, after washing and removing the adsorbed DCF, the original MIL-100-Fe-AMSA spectrum is recov­ ered On the other hand, the adsorption of DCF over MIL-101-Fe-AMSA can also be facilitated by the π− π interactions between the benzene rings of both DCF and the skeleton of MIL-100-Fe-AMSA [28,63] The sug­ gested mechanism for DCF adsorption on MIL-100-Fe-AMSA is shown in Fig To evaluate the reusability of MIL-100-Fe-AMSA in the adsorption Fig (a) Effect of pH of solution on the extraction of DCF over MIL-100-Fe-AMSA (b) Zeta potential of the MIL-100-Fe-AMSA at different pH values N Crespí S´ anchez et al Microporous and Mesoporous Materials 348 (2023) 112398 Fig Proposed adsorption mechanism for DCF removal using MIL-100-Fe-AMSA removal of the DCF, its recyclability was tested by doing five consecu­ tives adsorption-desorption cycles As can be seen in Fig 6a, after the five cycles, the extraction capacity of the material exceeded 93% in both cases, without its structure and iron content being affected (Fig 6b and Fig S3), which demonstrates the excellent recyclability of the prepared MIL-100-Fe-AMSA In addition, the leaching of iron ions into the water, after the extraction of DCF, was negligible, corroborating the stability of MIL-100-Fe-AMSA 3.3 MIL-100-Fe-AMSA/3D device for the enrichment of pharmaceuticals In order to facilitate and improve the applicability of the MIL-100-FeAMSA for pollutant extraction from water, the material was immobilized into a 3D printed device by a simple and fast coating method Basically, a MIL-100-Fe-AMSA/PVDF ink was prepared and incorporated to the 3d printed column obtaining a functional device (Fig 7) To exemplify the application of the developed MIL-100-Fe-AMSA/3D column, it was tested for the simultaneous adsorption and enrichment of DCF and ketoprofen from water Fig shows the chromatograms of standard solution of the two pharmaceutical products (1 mg/L, each) before and after solid-phase extraction with the MIL-100-Fe-AMSA/3D column It can be observed that the signals corresponding to both pol­ lutants in the direct analysis are very weak, however, after preconcen­ tration with the MIL-100-Fe-AMSA/3D column and using mL of methanol as eluent, these signals significantly increase, reaching Fig Schematic representation of the preparation of the MIL-100-Fe-AMSA/ 3D column with integrated packing based on interconnected cubes Fig (a) Recyclability of MIL-100-Fe-AMSA for the adsorption of DCF from water (b) X-ray diffraction patterns of MIL-100-Fe-AMSA before and after DCF extraction N Crespí S´ anchez et al Microporous and Mesoporous Materials 348 (2023) 112398 Data availability Data will be made available on request Acknowledgements N Crespí acknowledges the support from the Spanish Ministerio de ´n y Ciencia (FPU pre-doctoral fellowship) Financial support Educacio ´n and Agencia Estatal from the Spanish Ministerio de Ciencia e Innovacio ´n de Investigacio (project PID2019-107604RB-I00/MCIN/AEI/ 10.13039/501100011033) is gratefully acknowledged Appendix A Supplementary data Supplementary data to this article can be found online at https://doi org/10.1016/j.micromeso.2022.112398 References [1] D.D Mara, Water, sanitation and hygiene for the health of developing nations, Publ Health 117 (2003) 452–456 [2] J.C.G Sousa, A.R Ribeiro, M.O Barbosa, M.F.R Pereira, A.M.T Silva, A review on environmental monitoring of water organic pollutants identified by EU guidelines, J Hazard Mater 344 (2018) 146–162 [3] I.Y L´ opez-Pacheco, A Silva-Nú˜ nez, C Salinas-Salazar, A Ar´ evalo-Gallegos, L A Lizarazo-Holguin, D Barcel´ o, H.M.N Igbal, R Parra-Saldívar, Anthropogenic contaminants of high concern: existence in water resources and their adverse effects, Sci Total Environ 690 (2019) 1068–1088 [4] B Petrie, R Barden, B Kasprzyk-Hordern, A review on emerging contaminants in waste waters and the environment: current knowledge, understudied areas and recommendations for future monitoring, Water Res 72 (2015) 3–27 [5] T.C Schmidt, J Field, Water analysis for emerging chemical contaminants, Anal Chem 88 (2016), 1495-1495 [6] D Barcel´ o, M Petrovic, Pharmaceuticals and personal care products (PPCPs) in the environment, Anal Bioanal Chem 387 (2007) 1141–1142 [7] P Seo, B Bhadra, I Ahmed, N.A Khan, S.H Jhung, Adsorptive removal of pharmaceuticals and personal care products from water with functionalized metalorganic frameworks: remarkable adsorbents with hydrogen-bonding abilities, Sci Rep (2016), 34462 [8] T Rasheed, M Bilal, A.A Hassa, F Nabeel, R.N Bharagava, L.F.R Ferreira, H N Tran, H.M.N Iqbal, Environmental threatening concern and efficient removal of pharmaceutically active compounds using metal-organic frameworks as adsorbents, Environ Res 185 (2020), 109436 [9] C.W Pai, D Leong, C.Y Chen, G.S Wang, Occurrences of pharmaceuticals and personal care products in the drinking water of Taiwan and their removal in conventional water treatment processes, Chemosphere 256 (2020), 12700 [10] M Martins, S Sanches, I.A.C Pereira, Anaerobic biodegradation of pharmaceutical compounds: new insights into the pharmaceutical-degrading bacteria, J Hazard Mater 357 (2018) 289–297 [11] D Awfa, M Ateia, M Fujii, M.S Johnson, C Yoshimura, Photodegradation of pharmaceuticals and personal care products in water treatment using carbonaceous-TiO2 composites: a critical review of recent literature, Water Res 142 (2018) 26–45 [12] G Kooijmana, M.K de Kreuk, C Houtman, J.B van Lier, Perspectives of coagulation/flocculation for the removal of pharmaceuticals from domestic wastewater: a critical view at experimental procedures, J Water Proc Eng 34 (2020), 101161 [13] Y Zhou, C Chen, K Guo, Z Wu, L Wang, Z Hua, J Fang, Kinetics and pathways of the degradation of PPCPs by carbonate radicals in advanced oxidation processes, Water Res 185 (2020), 116231 [14] J Akhtar, N Amin, K Shahzad, A review on removal of pharmaceuticals from water by adsorption, Desalination Water Treat 57 (2016) 12842–12860 [15] M.B Ahmed, J.L Zhou, H.H Ngo, W Guo, Adsorptive removal of antibiotics from water and wastewater: progress and challenges, Sci Total Environ 532 (2015) 112–126 [16] R Natarajan, K Saikia, S.K Ponnusamy, A.K Rathankumar, D.S Rajedran, S Venkataraman, D.B Tannani, V Arvind, T Somanna, K Banerkee, N Mohideen, V.K Vaidyanathan, Understanding the factors affecting adsorption of pharmaceuticals on different adsorbents – a critical literature uptade, Chemosphere 287 (2022), 131958 ´ [17] S Alvarez-Torrellas, A Rodríguez, G Ovejero, J García, Comparative adsorption performance of ibuprofen and tetracycline from aqueous solution by carbonaceous materials, Chem Eng J 283 (2016) 936–947 [18] H Zhao, X Liu, Z Cao, Y Zhan, X Shi, Y Yang, J Zhou, J Xu, Adsorption behaviour and mechanism of chloramphenicols, sulfonamides, and non-antibiotic pharmaceuticals on multi-walled carbon nanotubes, J Hazard Mater 310 (2016) 235–245 [19] D Smiljanic, D.B de Gennaro, F Izzo, A Langella, A Dakovic, C Germinario, G E Rottinghaus, M Spasojevic, M Mercurio, Removal of emerging contaminants Fig Chromatograms of pharmaceutical standard solutions before and after solid-phase extraction by using MIL-100-Fe-AMSA/3D column enrichment factors of 17 and for DCF and ketoprofen, respectively The obtained results demonstrate the suitability of the MIL-100-Fe-AMSA/ 3D device for the adsorption and preconcentration of pharmaceuticals pollutants from water Conclusions In this study, the use of sulfonic-functionalized MIL-100-Fe metalorganic framework (MIL-100-Fe-AMSA) as sorbent for the removal of diclofenac has been explored for the first time The MIL-100-Fe-AMSA was prepared by grafting the coordinatively unsaturated iron sites of MIL-100-Fe with aminomethanesulfonic acid, obtaining a functional adsorbent with high surface area The developed material showed fast uptake (>80% of extraction after only min), high reusability and excellent adsorption capacity of 476 mg/g, which is higher than that of the MIL-100-Fe, confirming the role of the sulfonic groups on the extraction process Adsorption mechanism analysis indicated that elec­ trostatic interactions between DCF and MIL-100-Fe-AMSA were not significant in the removal of DCF, and synergistic effect of H-bonding and π− π interactions was suggested to be the main mechanism for explaining the improved efficiency of the MIL-100-Fe-AMSA The ob­ tained MIL-100-Fe-AMSA was used for the preparation of a functional device (MIL-100-Fe-AMSA/3D column), which showed high efficiency for the simultaneous extraction and preconcentration of DCF and keto­ profen, making it a promising device for the analysis of low levels of emerging pollutants from water CRediT authorship contribution statement ´nchez: Writing – original draft, Visualization, Neus Crespí Sa Methodology, Investigation Gemma Turnes Palomino: Writing – re­ view & editing, Writing – original draft, Supervision, Funding acquisi­ tion Carlos Palomino Cabello: Writing – review & editing, Writing – original draft, Visualization, Supervision 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 N Crespí S´ anchez et al [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33] [34] [35] [36] [37] [38] [39] [40] [41] Microporous and Mesoporous Materials 348 (2023) 112398 [42] W Zhuo, N Zhuo, Y Lan, W Yang, Z Yang, X Li, X Zhou, Y Liu, J Shen, X Zhang, Adsorption of three selected pharmaceuticals and personal care products (PPCPs) onto MIL-101(Cr)/natural polymer composite beads, Separ Purif Technol 177 (2017) 272–280 [43] R Pei, L Fan, F Zhao, J Xiao, Y Yang, A Lai, S.F Zhou, G Zhan, 3D-Printed metal-organic frameworks within biocompatible polymers as excellent adsorbents for organic dyes removal, J Hazard Mater 384 (2020), 121418 [44] E.R Kearns, R Gillespie, D.M D’Alessandro, 3D printing of metal-organic framework composite materials for clean energy and environmental applications, J Mater Chem (2021) 27252–27270 [45] M Del Rio, M Villar, S Quesada, G.T Palomino, L Ferrer, C.P Cabello, Silverfunctionalized UiO-66 metal-organic framework-coated 3D printed device for the removal of radioactive iodine from wastewaters, Appl Mater Today 24 (2021), 101130 [46] A.G M´ arquez, A Demessence, A Platero-Prats, D Heurtaux, P Horcajada, C Serre, J Chang, G F´erey, V Pe˜ na-O’Shea, C Boissi` ere, D Grosso, C Sanchez, Green microwave synthesis of MIL-100(Al, Cr, Fe) nanoparticles for thin-film elaboration, Eur J Inorg Chem (2012) 5165–5174, 2012 [47] M.S Denny, S.M Cohen, In situ modification of metal-organic frameworks in mixed-matrix membranes, Angew Chem Int Ed 54 (2015) 9029–9032 [48] K.Y Foo, B.H Hameed, Insights into the modeling of adsorption isotherm systems, Chem Eng J 156 (2010) 2–10 [49] Y.S Ho, G McKay, Pseudo-second order model for sorption processes, Process Biochem 34 (1999) 451–465 [50] Y Fang, Z Yang, H Li, X Liu, MIL-100(Fe) and its derivatives: from synthesis to application for wastewater decontamination, Environ Sci Pollut Res 27 (2020) 4703–4724 [51] P Horcajada, S Surbl´ e, C Serre, D Hong, Y Seo, J Chang, J Gren` eche, I Margiolaki, G F´ erey, Synthesis and catalytic properties of MIL-100(Fe), an iron (III) carboxylate with large pores, Chem Commun 27 (2007) 2820–2822 [52] M.A Simon, E Anggraeni, F.E Soetaredjo, S.P Santoso, W Irawaty, T.C Thanh, S B Hartono, M Yuliana, S Ismadji, Hydrothermal synthesize of HF-free MIL-100 (Fe) for isoniazid-drug delivery, Sci Rep (2019), 16907 [53] H Lv, H Zhao, T Cao, L Qian, Y Wang, G Zhao, Efficient degradation of high concentration azo-dye wastewater by heterogeneous Fenton process with ironbased metal-organic framework, J Mol Catal Chem 400 (2015) 81–89 [54] M Nehra, N Dilbaghi, N.K Singhal, A.A Hassan, K.H Kim, S Kumar, Metal organic frameworks MIL-100(Fe) as an efficient adsorptive material for phosphate management, Environ Res 169 (2019) 229–236 [55] Y Dou, H Zhang, A Zhou, F Yang, L Shu, Y She, J.R Li, Highly efficient catalytic esterification in an -SO3H-functionalized Cr(III)-MOF, Ind Eng Chem Res 57 (2018) 8388–8395 [56] N Devarajan, P Suresh, MIL-101-SO3H metal-organic framework as a Brønsted acid catalyst in Hantzsch reaction: an efficient and sustainable methodology for one-pot synthesis of 1,4-dihydropyridine, New J Chem 43 (2019) 6806–6814 [57] H Leclerc, A Vimont, J.C Lavalley, M Daturi, A.D Wiersum, P.L Llewellyn, P Horcajada, G F´ erey, C Serre, Infrared study of the influence of reducible iron (iii) metal sites on the adsorption of CO, CO2, propane, propene and propyne in the mesoporous metal-organic framework MIL-100, Phys Chem Chem Phys 13 (2011) 11748–11756 [58] S Wuttke, P Bazin, A Vimont, C Serre, Y.K Seo, Y.K Hwang, J.S Chang, G F´erey, M Daturi, Discovering the active sites for C3 separation in MIL-100(Fe) by using operando IR spectroscopy, Chem Eur J 18 (2012) 11959–11967 [59] L Lonappan, S.K Brar, R.K Das, M Verma, R.Y Surampalli, Diclofenac and its transformation products: environmental occurrence and toxicity – a review, Environ Int 96 (2016) 127–138 [60] B.N Bhadra, P.W Seo, S.H Jhung, Adsorption of diclofenac sodium from water using oxidized activated carbon, Chem Eng J 301 (2016) 27–34 [61] J Hao, Q Zhang, P Chen, X Zheng, Y Wu, D Ma, D Wei, H Liu, G Liu, W Lv, Removal of pharmaceuticals and personal care products (PPCPs) from water and wastewater using novel sulfonic acid (− SO3H) functionalized covalent organic frameworks, Environ Sci.: Nano (2019) 3374–3387 [62] Y Peng, Y Zhang, H Huang, C Zhong, Flexibility induced high-performance MOFbased adsorbent for nitroimidazole antibiotics capture, Chem Eng J 333 (2018) 678–685 [63] A Karami, R Sabouni, M Ghommem, Experimental investigation of competitive co-adsorption of naproxen and diclofenac from water by an aluminum-based metal-organic framework, J Mol Liq 305 (2020), 112808 from water by zeolite-rich composites: a first approach aiming at diclofenac and ketoprofen, Microporous Mesoporous Mater 298 (2020), 110057 D.N Ribeiro de Sousa, S Insa, A.A Mozeto, M Petrovic, T.F Chaves, P.S Fadini, Equilibrium and kinetic studies of the adsorption of antibiotics from aqueous solutions onto powdered zeolites, Chemosphere 205 (2018) 137–146 C.E Choong, S Ibrahim, W.J Basirun, Mesoporous silica from batik sludge impregnated with aluminum hydroxide for the removal of bisphenol A and ibuprofen, J Colloid Interface Sci 541 (2019) 12–17 J.A.S Costa, R.A de Jesus, D.O Santos, J.B Neris, R.T Figueiredo, C.M Paranhos, Synthesis, functionalization, and environmental application of silica-based mesoporous materials of the M41S and SBA-n families: a review, J Environ Chem Eng (2021), 105259 E Jin, S Lee, E Kang, Y Kim, W Choe, Metal-organic frameworks as advanced adsorbents for pharmaceutical and personal care products, Coord Chem Rev 425 (2020), 213526 A Tchinsa, M.F Hossain, T Wang, Y Zhou, Removal of organic pollutants from aqueous solution using metal organic frameworks (MOFs)-based adsorbents: a review, Chemosphere 284 (2021), 131393 L Huang, R Shen, Q Shuai, Adsorptive removal of pharmaceuticals from water using metal-organic frameworks: a review, J Environ Manag 277 (2021), 111389 J Cao, Z Yang, W Xiong, Y Zhou, Y Wu, M Jia, C Zhou, Z Xu, Ultrafine metal species confined in metal-organic frameworks: fabrication, characterization and photocatalytic applications, Coord Chem Rev 439 (2021), 213924 J Cao, Z Yang, W Xiong, Y Zhou, Y Wu, M Jia, H Peng, Y Yuan, Y Xiang, C Zhou, Three-dimensional MOF-derived hierarchically porous aerogels activate peroxymonosulfate for efficient organic pollutants removal, Chem Eng J 427 (2022), 130830 Z Hasan, S.H Jhung, Removal of hazardous organics from water using metalorganic frameworks (MOFs): plausible mechanisms for selective adsorption, J Hazard Mater 283 (2015) 329–339 M Zheng, J Chen, L Zhang, Y Cheng, C Lu, Y Liu, A Singh, M Trivedi, A Kumar, J Liu, Metal organic frameworks as efficient adsorbents for drugs from water, Mater Today Commun 31 (2022), 103514 I Ahmed, Z Hasan, G Lee, H.J Lee, S.H Jhung, Contribution of hydrogen bonding to liquid-phase adsorptive removal of hazardous organics with metal-organic framework-based materials, Chem Eng J 430 (2022), 132596 D.K Yoo, B.N Bhadra, S.H Jhung, Adsorptive removal of hazardous organics from water and fuel with functionalized metal-organic frameworks: contribution of functional groups, J Hazard Mater 403 (2021), 123655 D.K Yoo, G Lee, M.M.H Mondol, H.J Lee, C.M Kim, S.H Jhung, Preparation and applications of metal-organic frameworks composed of sulfonic acid, Coord Chem Rev 474 (2023), 214868 Z Hasan, E.J Choi, S.H Jhung, Adsorption of naproxen and clofibric acid over a metal-organic framework MIL-101 functionalized with acidic and basic groups, Chem Eng J 219 (2013) 537–544 J.Y Song, S.H Jhung, Adsorption of pharmaceuticals and personal care products over metal-organic frameworks functionalized with hydroxyl groups: quantitative analyses of H-bonding in adsorption, Chem Eng J 322 (2017) 366–374 X Guo, C Kang, H Huang, Y Chang, C Zhong, Exploration of functional MOFs for efficient removal of fluoroquinolone antibiotics from water, Microporous Mesoporous Mater 286 (2019) 84–91 H.A Younes, M Taha, R Mahmoud, H.M Mahmoud, R.M Abdelhameed, High adsorption of sodium diclofenac on post-synthetic modified zirconium-based metal-organic frameworks: experimental and theoretical studies, J Colloid Interface Sci 607 (2022) 334–346 R.M Rego, G Kuriya, M.D Kurkuri, M Kigga, MOF based engineered materials in water remediation: recent trends, J Hazard Mater 403 (2021), 123605 Y Yao, C Wang, J Na, M.S.A Hossain, X Yan, H Zhang, M.A Amin, J Qi, Y Yamauchi, J Li, Small 18 (2022), 2104387 M.J Khosravi, S.M Hosseini, V Vatanpour, Performance improvement of PES membrane decorated by MIL-125(Ti)/chitosan nanocomposite for removal of organic pollutants and heavy metal, Chemosphere 290 (2022), 133335 R Zhao, X Shi, T Ma, H Rong, Z Wang, F Cui, G Zhu, C Wang, Constructing mesoporous adsorption channels and MOF-polymer interfaces in electrospun composite fibers for effective removal of emerging organic contaminants, ACS Appl Mater Interfaces 13 (2021) 755–764 J Zhao, L Xu, Y Su, H Yu, H Liu, S Qian, W Zheng, Y Zhao, Zr-MOFs loaded on polyurethane foam by polydopamine for enhanced dye adsorption, J Environ Sci 101 (2021) 177–188 ... unsaturated Cr3+ centers of the MOF, and used the functionalized MOFs to extract naproxen and clofi­ bric acid In the case of the adsorption of naproxen and clofibric acid over the amino-functionalized... from water Conclusions In this study, the use of sulfonic-functionalized MIL-100-Fe metalorganic framework (MIL-100-Fe- AMSA) as sorbent for the removal of diclofenac has been explored for the. .. UiO-66-(COOFe)2 showed the maximum adsorption capacity followed by UiO-66-(COOCu)2 and UiO-66-(COOH)2 One of the most important limitations for the removal of pollutants from water by MOFs is their