Open access peer-reviewed chapter - ONLINE FIRST
MOFs type MIL used as water removal agent.
Abstract
Currently, there are approximately 250 antibiotics registered for use in human and veterinary medicine worldwide, which, as a result of inadequate management and poor disposal of waste, among other bad practices in their management, are more common in wastewater; this situation has begun to attract more attention and be an interesting topic for the proposal of solutions. In the search for options to solve this problem, structured materials are being actively studied; one material that has received significant attention is the metal organic framework (MOF) type. The use of MOFs with various topologies and characteristics are demonstrating great effectiveness in the elimination of different types of contaminants from water, such as medications, such as anti-inflammatories, antibiotics, explosives, and heavy metals. Different antibiotics are used as models in these studies, from which it follows that the nature of the drugs that can be eliminated from effluents is very varied, which allows us to see that it can be an interesting option. Another objective pursued by these studies is to seek to establish the number of cycles in which these materials can be used to carry out the capture of drugs, as well as the type of kinetics that follow the adsorption of these materials in the MOFs.
Keywords
- MOF
- antibiotic
- water removal
- wastewater
- recyclability
- bioremediation
1. Introduction
Antibiotics are molecules with several functional groups like aromatic rings, heterocyclic, and aliphatic chains and might be conjugated with sugar fragments (type A) [1]. These compounds have been widely used in medicine, animal husbandry, and agriculture due to their low cost and potential to inhibit or eliminate the growth of pathogenic microorganisms [2]. Moreover, several reports talk about other properties of these molecules, such as antifungal, antiparasitic, antioxidant, and antitumoral agents, which results in great interest in their development and applications [3]. However, antibiotics also represent a problem for the environment because of their bad deposition and treatment after their administration. Many reports have found that the accumulation of these pharmaceutical products in water carries a lot of problems in public health because of microbial resistance to the constant exposition of people to these compounds, and this might have toxic effects on the respiratory, digestive, and reproductive systems, among others [2, 4]. Mainly, microbial resistance has increased not only to the indiscriminate use of antibiotics to treat other infections that do not have a correlation with bacteria diseases but also to the high concentration of antibiotics in ecosystems leading to multi-resistance bacteria (MRB). An example of MRB is
Therefore, this has resulted in the development of new strategies to solve this problem; one of these solutions is the obtention and synthesis of new materials that can adsorb and remove these compounds from water, one of the most important ecosystems. Metal organic frameworks (MOFs) are hybrid materials that have homogeneous porosity, great stability, high surface areas, and multidimensional structures that can capture and release substances via several stimulations. The synthesis of these materials can be driven with a wide range of metal and organic ligands that can be functionalized with carboxylates, phenolates, imidazolates, and sulfonates, among others, and their stability in water can be enhanced with the conjugation with other molecules like polietilenglicole, sugar or silices [5]. The attractive features of these materials are the highly combinatory possibilities for their synthesis and architecture; for this reason, the synthesis of selective materials that can capture and degrade or reuse the molecule adsorbed is possible.
MOFs have been used for various purposes; due to their characteristics, they have found application for gas storage, as catalysts in different types of reactions, as detectors of various types of compounds, and as drug carriers; this last application has aroused the interest for the use of these materials in the removal of drugs in bodies of water, for a few years to date, research on this topic has aroused great interest, demonstrated in the gradual increase in publications of applications of these reticular materials in water treatment.
This work addresses several examples of the applicability of MOFs as water removal agents and demonstrates that MOFs can be suitable and selective platforms for the removal of many different antibiotics found in water.
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2. MOFs used have water removal agents
2.1 Materials Institute of Lavoisier (MIL)
MILs are a class of MOFs based on linkers with benzoic di or tri-carboxylates combined with several metals like Fe, Al, Cr, Ti, etc. These MOFs are very attractive because of their water stability, high porosity, and superficial areas of up to 1000 m2. These features allow these families to be used in several applications like gas capture and capture/release of drugs. The last is one of the features that made it a great candidate to remove antibiotics from water. However, several reports have pointed out that the use of MILs as composite materials enhances their properties, allows the materials to be more selective, and increases the number of life cycles. The next table enlists several reports of MIL-based materials with great removal potential from different antibiotics (Table 1).
| MOF | Antibiotic | Experiment | Results | Ref |
|---|---|---|---|---|
| In2S3@MIL-125(Ti) | Tetracycline (TC) | Absorption of the drug on aqueous media and its photodegradation in a tetracycline solution of 100 mg/L and photodegradation in visible light | The efficiency of Aditive mass of MIL 125 (Ti diuring synthesis process, was denoted has MLS-5 in the removal of low concentrations of tetracycline is 99 and 70% at high concentrations. The amount of photodegradation with MLS-1 was 63.3% | [6] |
| MIL-101(HCl) MIL-101(HF) | Oxytetracycline (OTC) | Absorption of drug in aqueous media | The efficiency of absorption in MIL-101(HCl) was 115.34 mg/g, which was higher than other materials like ZIF-8 | [7] |
| MIL-100(Fe) MIL-101(Fe) MIL-53(Fe) | Tetracycline (TC) | Absorption of drug on aqueous media and its photodegradation | Initial concentration of 50 mg/L. The recovery was 96.6% in MIL-101(Fe), and 87% was photodegraded under visible light. | [8] |
| CuCo/MIL-101 | Tetracycline (TC) | Absorption of drug on aqueous media | Recovery of 82.9% in a solution of 100 mg/L | [9] |
| MIL-125(Ti) | Tetracycline hydrochloride (TCH) | 0.03 g of MIL-125(Ti) was added to a 50 mL TCH solution (35–280 mg/L), then was shaken at 250 rpm. At certain intervals, the concentration of TCH was determined by UV–visible spectrophotometer at 355 nm. | 321.5 mg/g at 30°C, and high adsorption capacity in the pH range of 2–11). | [10] |
| Bi2WO6/NH2-MIL-88B(Fe) heterostructure | Tetracycline (TC) | Absorption and degradation in aqueous media | Degradation efficiency was 89.4% in 1.5 h with solar illumination. The pseudo-second-order model filled well with the data obtained, and the isotherm followed the Freundlich model (R2 = 0.99803). Also showed a longer lifetime (140.72 ns) compared to MOF (132.05 ns) and Bi2WO6 (136.39 ns). The photodegradation was carried over simulated hospital wastewater, and 60.5% TC was obtained under solar light in 6.5 h | [11] |
| MIL-125(Ti) MIL-53(Fe)/Carbon nanotube (CNT)@Alg composite microbeads. | Tetracycline (TC) | Absorption of tetracycline in aqueous media | Adsorption of TC augmented when concentration of CNT up to 15 wt%. The material showed a maximum adsorption capacity of 294.12 mg/g at 25°C and pH 6. | [12] |
| AgI/D-MIL-53(Fe) | Tetracycline (TC) | Absorption and degradation of tetracycline | Compared to the degradation efficiency of TC, the MIL-53(Fe) showed a 50.8%, compared with AgI/MIL-53(Fe) increased to 85.1% and which further increased to 96.2% by AgI/D-MIL-53(Fe) | [13] |
| MIL-101(Cr). | Sulfadiazine, Sulfamethazine, Sulfachloropyridazine, and Sulfamethoxazole. | Absorption of drugs from bottled water, tap water, river water, and wastewater. | Using 40 mg of MOF, the results showed were:
| [14] |
| MIL-53 | Trimethoprim (TMP) Sulfamethoxazole (SMX). | Absorption of sulfonamides in aqueous media | From a solution of 100 mg/L of sulfonamides, the absorption capacity was >87%. | [15, 16] |
| NH2-MIL-68@COF | Sulfadimethoxine (SDM) Sulfamethoxazole (STZ) Sulfamonomethoxine (SMX) Sulfamethazine (SMZ) Sulfamerazine (SMR) Sulfadiazine (SDZ) | Absorption of drugs from water, milk, and meat | Recovery of compounds was in a range from 68.9 to 103.8% in samples of 1 mg/mL | [17] |
| MIL-101(Cr) | Sulfadimethoxine (SDM), Sulfamonomethoxin (SMM) Sulfachloropyridazine (SCP). | Absorption of SDM, SMM, and SCP in aqueous media | Adsorption capacities >48.46 mg/g, for all compounds. | [18] |
| MIL-101(Fe) | Sulfadiazine (SDZ), Sulfapyridine (SPD), Sulfameter (SME), Sulfamethoxazole (SMX), Sulfisoxazole (SIX), Sulfabenzamide (SB) Sulfadimethoxine (SDM) | Absorption of SDZ, SPD, SME, SMX, SIX, SB, SDM in aqueous media | Absorption capacity >75.4% for all compounds. | [19] |
| MIL-101(Cr) Modified with Urea. | Dimetridazole (DMZ) metronidazole (MNZ) | The solutions were prepared from a stock solution of 20 mg/L water/methanol (90/10 v/v). The pH of each solution was 6.30; the mixture was shaken using an incubator shaker at a constant speed (250 rpm) 25 C, and the concentration was determined using UV-spectrometry, as mg/g MOF | Qo = 185 mg/g MOF Qo = 188 mg/g MOF Reused four times. | [20] |
| Fe3O4@SiO2-MIL-53 | Amoxicillin (AMX) | They performed sonophotodegradation of AMX including pH, sonophotocatalyst mass, radiation, and AMX levels as parameters. | The 5 pH was chosen because of a high efficiency of 94% of degradation with an AMX quantity of 50 mg/L. Increasing the addition of sonophotocatalyst amount enhanced the removal efficiency from 71–100%. The UV power of 36 W was the best condition to increase the degradation up to 100% in 25 min. The constant rate was 0.204 min−1. The main oxidant agents were OH. and H+ | [21] |
| Mil-125 (Ti)/PANAM G1.0 | Cefixime | They performed purification of water with cefixime antibiotic (100 ppm). | The performance was 80.04%, and the principal interactions were amine and hydroxyl groups in the Mil-Den structure. | [22] |
| MIL-53(Al) | Amoxicillin (AMX) | They determined adsorption in standard solutions (0.5–30 mg/L) obtained from diluting the stock solution at pH 7.5. The ionic strength effect was studied separately by adding 1 mL of 0.01 mol L− 1g/l NaCl, 1 mL of 0.1 mol L−1 NaCl, 1 mL of 1 mol L−1 NaCl, and 1 mL of deionized water. The pH effect was achieved by adding 2 mg of MIL-53(Al) into flasks containing 20 mL of 50 mg/L AMX solution within a pH range of 3.5–11.5. | The adsorption kinetic was a pseudo-second-order model. Adsorption capacity in a solution of 300 mg was 283.9 ± 1.4 mg/g Hydrogen bonding and π–π interaction/stacking were the main interactions. There no influence in adsorption by ionic strength. | [23] |
| Fe3O4@SiO2@MIL-53-NH2 (Al) nanocomposite (FeSi@MN NC) | Ampicillin (AMP) | Photocatalyst for photodegradation of AMP solution with 100 mg/L, absorbance was at 320 nm, and they used a mixture of 0.1–0.8 g/L | Fe3O4@SiO2@MIL-53-NH2 degradation efficiency was about 70% after 120 min. | [24] |
| MIL-101 (Cr) | Ciprofloxacin(CIP) | The effects of the amount of adsorbent, initial CIP concentration, temperature, and pH of antibiotic solutions were determined; the amount of adsorbent was 1–15 mg. The time interval is 1–120 min. The pH range was 1–12. CIP of 5–40 mg/L Concentration. The adsorption experiments were carried out in batches. The shaking speed is constant, 120 rpm. After the adsorption, the CIP solutions were analyzed with UV–Vis. | The maximum CIP adsorption capacity at 298 K was 63.28 mg/g. The increasing temperature caused a decrease | [25] |
| Metal organic framework sorbents (MIL-100(Fe), MOF-235(Fe)), Fe3O4 nanoparticles, and metal organic framework loaded on iron oxide nanoparticles (Fe3O4@MIL-100(Fe) and Fe3O4@MOF-235(Fe)) | Ciprofloxacin (CIP) | The sorption equilibrium studies were conducted with 50 mL of a CIP solution (250 mg/L) and 0.5 g/L of the sorbent at 298 K. The sorbent and sorbate were mixed on a shaking bath at 250 rpm until equilibrium was attained in 5 h. After, the mixture was centrifuged at 3000 rpm for 3 min, and the amount of CIP Remaining was measured at absorbance at 275 nm. | The removal of CIP was 278.39 mg/L | [26] |
| MIL-101(Cr)–SO3H | Norfloxacin (NFX) Ofloxacin (OFX) Enoxacin (ENX) | 0.010 g of adsorbent was added into 100 mL aqueous solution of adsorbate. The initial pH values of the NFX, OFX, and ENX solutions were adjusted using HCl or NaOH. The suspension was filtered after being shaken at 30°C for a specific time, and the concentration of adsorbate in the supernatant was measured using a UV–Vis spectrophotometer | The adsorption efficiency of the absorbent was studied using adsorption kinetic tests in a time range of 0–1440 min. The final removal efficiency can reach more than 99%. | [27] |
| Biochar functionalized MIL–53(Fe) MIL–BDPR | Ofloxacin (OFX) Ciprofloxacin (CPX) | Adsorption process was performed through batch adsorption experiments with an adsorbent dose of 50 mg with 100 mL of single antibiotic solutions with different concentration 50–150 mg/L, contact time 0–120 min, pH 3–9, and temperature 25–45°C. Samples were analyzed using a UV–vis spectrometer. | The adsorption process is pH, initial antibiotic concentration, and temperature dependent. Regeneration efficiency can still reach up to 92.74 and 93.64% for OFX and CPX. | [28] |
| NH2-MIL-125@TpPa-SO3H. TpPa-SO3H, NH2-MIL-125, and NH2-MIL-125@TpPa-SO3H | Enoxacin, Norfloxacin Ciprofloxacin Sparfloxacin. | Different concentrations (20–200 mg/L) were dissolved in ultrapure water containing 10% methanol. Then, HCl and NaOH were used to adjust the pH of the solution. In the experiments, 5 mg of NH2-MIL-125@TpPa-SO3H was added to 40 mL. The mixtures were shaken at 150 rpm at temperatures (30, 40, and 50°C) for 7 h. HPLC filtered and analyzed the supernatant. | Enoxacin 444.7 mg/g Norfloxacin 455.7 mg/g Ciprofloxacin 457.5 mg/g Sparfloxacin 429.1 mg/g. Reused eight cycles. | [29] |
Table 1.
2.2 Different variants of metal organic framework (MOFs)
Many other MOFs have been prepared and synthetized for several applications. However, MOFs based on ligands with catalytic structures like porphyrins, oxometalates, quantum dots, and imidazolates cannot only remove antibiotics from water but also degrade the drug and eliminate it more easily. Many materials based on composites with catalytic entities have been used for bioremediation of pollution in water. The next examples are MOFs based on other ligands beyond carboxylates that had allowed the removal of antibiotics and degraded them with good results (Table 2).
| MOF | Antibiotic | Experiment | Results | Ref |
|---|---|---|---|---|
| ZIF-8 | Oxitetracycline (OTC) Tetracycline (TC) Chlortetracycline (CTC) | Detection in water and milk by a chromatographic method using ZIF-8 as solid phase. Using a flow rate of 0.3 mL min−1 for 3 minutes and a mobile phase of 10% MeOH-20% ACN-70% 0.02 mol L−1 oxalic acid solution | Recovery from 50 μgL−1 OTC: 80–90% TC: 80–90% CTC: 90–100% | [5] |
| UiO-66/ZIF-8/PDA@CA | Tetracycline (TC) | Solutions of TC at a pH from 3 to 12, stirred for 60 min at 150 rpm, with 0.01 o 0.08 mg of UiO-66/ZIF-8/PDA@CA was added to TC solution at range from 50 to 300 mg/L. Temperature range from 25 to 55°C, and the unabsorbed TC concentration was evaluated using spectrophotometry at 354 nm. | 58.54 mg/g 119.03 mg/g 212.5 mg/g 286.57 mg/g Reusable eight times | [30] |
| CUST-563 Co@C-600 | Oxytetracycline (OTC) | In a 25 mL flask, MOF was added by stirring 20 mg/L of OTC in MeOH for 20 min under dark conditions, and the sample was taken every minute. | The degradation rate of OTC 89%. This system could be reused 10 times, and the activity was above of 80%. | [31] |
| 2-(4-carboxyphenyl)-1H-benzo[d]imidazole-5-carboxylic acid Zn-(CBC)- | Oxytetracycline (OTC) | Zn-CBC MACPs were added to the 10 mL water with OTC (0, 0.6, 1.2, 2.4, 3, 5, 10 mg/L) and stirred at 1000 rpm at 25°C. The concentration of OTC was determined on UV–vis. | 5.8 mg/g at pH = 8.0 | [32] |
| NiFe-MOF@AHC (NiFeopAHC) | Tetracycline (TC) | Absorption of Tetracycline in aqueous media | The maximum adsorption removal (Qmax) of NiFeopAHC for TC (568.1 mg/g) was 2.7 times higher than that of AHC. | [15] |
| MgFe2O4@UiO-66(Zr) (MFeO@UiO) | Tetracycline (TC) | Absorption of tetracycline in aqueous media | The composite material had a removal efficiency of ca. ∼94% for TC within 45-min and 120-min under visible light irradiation, which is higher compared with pristine ferrite and UiO-66(Zr). | [33] |
| 3NiO/g-C3N4 | Tetracycline (TC) | Photodegradation under visible light | 100% of TC can be degraded in 60 min by 3NiO/g-C3N4 activating Peroxyd MonoSulfate (PMS) activation under visible light, being 6.64-time that of single g-C3N4 | [34] |
| ZnS@In2S3 rhombic dodecahedron (ZnS@In2S3 RD 4) | Tetracycline (TC) | Photodegradation of Tetracycline | 100 mL, 20 mg/L TC-HCl solution can be completely degraded within 20 min, and the apparent reaction rate constant reaches 0.284 min, which far exceeds the majority of the previously reported sulfide photocatalyst | [35] |
| Eu/Zr- MOF | Tetracycline (TC) | Absorption of tetracycline in aqueous media | Eu/Zr-MOF exhibits high stability and excellent TC adsorption capacity as high as 289 mg g−1 in aqueous solution. | [36] |
| Fein/C-700 | Chlortetracycline (CTC) | Absorption of chlortetracycline in aqueous media | Adsorption capacities in a mixed antibiotic system 255.1, 143.3, and 169.6 mg/g for CTC, ciprofloxacin, and sulfamethoxazole, in water 372.9, 383.3, 390.6, and 366.7 mg/g in a different kind of water, and 366.7, 354.2, 360.4, 314.6, and 301.0 mg/g in five runs. | [37] |
| Fe3O(BDC)3 (Fe-MOF) | Sulfadiazine (SDZ) and sulfamethazine (SMZ) | Absorption of sulfadiazine and sulfamethazine in aqueous media | The adsorption of SDZ and SMZ sulfonamides on material nanocomposite was a thermodynamically spontaneous process. With high maximum adsorption capacities (223.0 mg/g for SDZ and 135.1 mg/g for SMZ), | [38] |
| Cu-based MOFs derivative (CuxO@C composite) | Sulfamerazina (SMR) | Absorption of sulfamerazine in aqueous media | The absorption efficiency of SMR was 100% in the CuxO@C/air system at pH of 4.0, air flow rate of 100 mL·min −1 in CuxO@C dosage of 1 g ·L−1 in a time of 30 min. | [39] |
| Magnetic Ti3+-TiO2/Ar-Fe2O3 type II heterojunction | Norfloxacin (NOR) | Degradation under visible light | Ti3+-TiO2/Ar-Fe2O3 degrades 97.80% of NOR in 5 min in a solution of 30 mg/L | [40] |
| p-Ag3PO4/n-ZnO/C heterojunction with IRMOF-3 | Norfloxacin (NOR) | Photodegradation of norfloxacin | The degradation reached 89.48% under the conditions tested, which is three times faster than pure Ag3PO4, and also the material has better catalytic capacity than Ag3PO4. | [41] |
| α-Fe2O3/ZIF-67 | Ciprofloxacin (CIP) | Degradation of ciprofloxacin | The CIP was completely degraded in 30 min when placing 1 mg of catalyst in a CIP dissolution of 10 mg/L | [42] |
| Chitosan coated Fe3O4@Cd-MOF microspheres (Fe3O4@Cd-MOF@CS) | Amoxicillin (AMX) | Absorption of amoxicillin in aqueous media | Under the best conditions, 75% of AMX was removed from a dissolution of AMX with a concentration of 50 ppm using only 50 mg of material. The maximum adsorption capacity was ∼103.09 mg/g. | [43] |
| Zirconium−porphyrin-based metal–organic framework (MOF), PCN-224 | Sulfamerazine (SMR) | Absorption of sulfamerazine in aqueous media | Considering the maximum concentrations of antibiotics in water, PCN-224 exhibited the highest adsorption capacity (Q0) for NDX and OFL compared to other adsorbents and MOFs, 671 mg/g for NDX (50 ppm) and1030 mg/g for OFL (125 ppm) | [44] |
| Fe3O4@SiO2 | Sulfadiazine (SDZ) Sulfamerazine (SMR) Sulfadimidine (SDD) Sulfisoxazole (SIZ) Sulfathiazole (STZ). | Absorption of drugs in tap water, river water, and rainwater | Absorption capacity >83.4% in samples of 5 mL of tap water, river water, and rainwater | [45] |
| HKUST-1 | Sulfachloropyridazine (SCP) | Absorption of drug in aqueous media | Adsorption capacity of 384 mg/g at 298 K in A solution of sulfachloropyridazine with a concentration of 500 ppm, adding 100 mg of MOF. | [46] |
| Mn(cam)(bpy). | Sulfamethazine (SDD), Sulfamerazine (SMR) Sulfanitran (SN) Sulfadiazine (SDZ), Sulfadimethoxine (SDM), Sulfamonomethoxine (SMT), Sulfachloropyridazine (SCD), Sulfamethoxazole (SMZ), Sulfamethizole (SMI) Phthalylsulfathiazole (PST). | Absorption of sulfonamides from tap water samples | Absorption capacity >71.53% in a solution of a mixture of sulfonamides with a concentration of 20 mg/L | [47] |
| PCN-224 | Sulfadiazine (SD) Sulfathiazole (ST) Sulfapyridine (SP) Sulfamerazine (SM 1) Sulfamethazine (SM 2) Sulfamethoxazole (SMX). | Absorption of sulfonamides from tap and drinking water. | Absorption capacity >87.3% was obtained in a solution of sulfonamides in samples de tap and drinking water | [48] |
| Fe3O4 @COFs | Sulfadiazine (SDZ) Sulfamerazine (SMR), Sulfamethazine (SMZ), Sulfamonomethoxine (SMX) Sulfamethoxazole (STZ) Sulfadimethoxine (SDM). | Absorption of drugs from Jingsi Lake at the campus of Wuhan Institute of Technology | Absorption capacity in a range from 63.5 to 107.3% | [49] |
| SCAU-1 y SNW-1 | Sulfadiazine (SDZ) Sulfadimidine (SMZ) Sulfamethoxydiazine (SME) Sulfadoxine (SDO) Sulfachloropyridazine (SCP). | Absorption of SDZ, SMZ, SME, SDO, and SCP in aqueous media (drinking water, river water, lake water, and wastewater). | Absorption capacity >5.8 μg/mL. | [50] |
| [H]@ UiO-66-Br | Sulfadiazine (SD) Sulfamerazine (SM) Sulfamethazine (SMT) Sulfamethoxypyridazine (SMPD) Sulfamethoxazole (SMX), Sulfamonomethoxine (SMM) Sulfamethoxypyrazine (SMPZ). | Absorption of SD, Sm, SMT, and SMPD in aqueous media. | Absorption capacity >94%. | [51] |
| ZnO-Co3O4 | Sulfadiazine | Absorption of sulfadiazine. | Absorption capacity >96%. | [52] |
| Fe-MOF | Sulfadiazine (SDZ) Sulfamethazine (SMZ). | Absorption of SDZ and SMZ. | Absorption capacity >135.1 mg/g. | [38] |
| UiO-66 UiO-66-BC | Sulfamethoxazole (SMX). | Absorption of SMX in aqueous media. | Absorption capacity >106.93 mg/g at 298 K. | [53] |
| CoZn-ZIF CoZn-ZIF-melamine | Sulfamethoxazole (SMX). | Absorption of SMX in aqueous media. | Degradation capacity >97.09%. | [54] |
| VNU-1 | Sulfamethoxazole | Absorption of sulfamethoxazole in aqueous media. | Adsorption of 74.8% sulfamethoxazole after stirring for 1 h. | [55] |
| HP-NU-902-X | Sulfadiazine (SDZ) Sulfapyridine (SPY) Sulfamethoxydiazine (SMD) Sulfachloropyridazine (SCP) Sulfabenzamide (SBZ) Sulfamethazine (SMT). | Absorption of SDZ, SPY, SMD, SCP, SBZ, and SMT in aqueous media. | Absorption capacity >70.34%. | [56] |
| AlFum Bio-MOF. | Sulfadiazine. | Absorption of sulfadiazine in aqueous media in an ultrasonic bath. | Average recoveries >84%. | [57] |
| BUT-12 BUT-13 | Nitrofurazone (NZF) Nitrofurantoin (NFT) | The adsorption isotherms were obtained by mixing 15 mg MOFs with 50 mL NZF or NFT solution of different concentrations (100 to 1600 mg/L) at 298 K with stirring for 4 h. | NZF and NFT were removed in 70–75%, respectively, and this system is reused. | [58] |
| Al-TCPP | Ornidazole (ONZ) Metronidazole (MNZ) | 5 mg Al-TCPP was added to 10 ml solution containing ONZ or MNZ. The adsorption experiments were carried out at 30 C at 150 rpm on an orbital shaker, and then the adsorbed mixture was filtered using a 0.22 mm membrane. The concentration was determined at 320 nm and 317 nm by UV–Vis spectroscopy | Qo = 320.5 mg/g MOF Qo = 609.8 mg/g MOF | [59] |
| AgN/MOF-5 (1:3) | Metronidazole (MNZ) | Solution 100 mL of MNZ at different concentrations (10, 30, 50, 80, and 100 mg/L) and 50 mg of AgN/MOF-5 were shaken at 250 rpm for 1 h, at pH of 6.60 tight with HCl 0.1 M. Then, the solution was filtered. Concentration of MNZ was determined at pH different (4, 5, and 6) and temperatures of 298, 308, and 318 K. | 298 K Q0 = 101.9 mg/g 308 K Q0 = 154.5 mg/g 318 K Q0 = 191.1 mg/g The system was reusable three times. | [60] |
| MOF-1 | Beta-lactam | An aggregate called amoxicillin@MOF1 was obtained after immersing crystals in saturated Dimethylformamide (DMF) solutions of amoxicillin for 72 h. With interactions of amoxicillin, except nitrogen and oxygen. Purification by selective degradation of four-member ring. The uptake efficiency of MOF 1 for amoxicillin, ceftriaxone and clindamycin was evaluated by HPLC-UV analyses in water, with a great selectivity between other ligands. | They showed the appearance of 1 new peak increased as the relative area to amoxicillin original peak after 4 hours. Ceftriaxone also shows a degradation product by the hydrolysis at the sulfur atom of the carbamimidothioate group after 12 h. The conversion was more than 80% after 24 h. | [61] |
| 3 MOF Zn II based with (Zn6(IDC)4(OH)2(Hprz)2)n (imidazole-4,5-dicarboxylate) | Amoxicillin (AMX) | They measured the adsorption capacity of three antibiotics, amoxicillin, ampicillin, and cloxacillin, dissolved in desionized water, 100 mL of the solution with a concentration of 60 ppm in a reactor. | MOF-VII exhibits a removal of 92% of AMX within 240 min, 89% CLX and 88% AMP. This great adsorption capability is attributed to the smaller size of MOF-VII particles and morphology obtained by this method of synthesis (Sonochemical). Also surface area increased the adsorption capability between MOF-I and MOF-VII, which exhibit a great absorption and more surface area. A comparison between crystals obtained by solvothermal synthesis of MOF showed a decrease in concentration of just 38.5%, which was inefficient for purification. | [62] |
| Zn-MOF (Zinc nitrate and 1,4 -benzendicarboxylic acid) (MC-0.3) | Ceftazidime | Adsorption experiment in a 150 mL solution of ceftazidime in Erlenmeyer, they compared the effect of pH, temperature, and amount of adsorbent on the adsorption process. | The adsorption has pseudo-first-order and a capacity of 371.18 mg/g. At pH 4 the capacity increases up to 404.28 mg/g due to the presence of carboxyl groups and better adsorption. NaCl increases the adsorption. | [63] |
| Silver organic framework loaded with sulfanilamide to remove AMX (Ag-MOF-NH2) | Amoxicillin (AMX) | They adsorbed AMX by Ag-MOF-NH2 in the prepared analytical water. They also applied the MOF in real wastewater samples collected from Industrial Wastewater Treatment Plant in Port Said, Egypt and spiked with 1 mg/L of a solution standard of AMX. | The adsorption capacity was 2.4 mmol/g. The interactions were π–π stacking or aromatic-aromatic interconnections among the benzene rings of AMX and Ag-MOF-NH2, with a pH of 7.5, which was the best. Ethanol was the best option to restore the adsorbent by elimination of the adsorbate. In real wastewater they achieved a removal rate of 85.4–98.19%. | [64] |
| β-lactamase@ZIF-8 | Amoxicillin (AMX) | They studied the catalytic activity of β-lactamase@ZIF-8 against AMP in different concentrations 4, 20, 40, 100 μL of 25 μg/mL. | At 10 min AMP was degraded by about 45% and reached 94% in 60 min. In contrast, only β-lactamase AMP was degraded 30% in 10 min. | [65] |
| Fe3O4@Cd-MOF Fe3O4@Cd a MOF@chitosan (CS) prepared via coating of Fe3O4@Cd-MOF with CS biopolymer in the microsphere shape. | Amoxicillin (AMX) | They studied the adsorption of AMX for an aqueous solution. 50 mg of microsphere Fe3O4@Cd-MOF@CS. The microspheres were immersed in 100 mL of AMX 50 ppm solution. | The adsorption of AMX was increased after 50 min, reaching 75.40 mg/g, and the equilibrium of adsorption was reached after 240 min. The percentage of the AMX removal increased from 22.07% for pH 3 to 73.92% for pH 8. Main interactions were hydroxyl, amine and aromatic rings, which can interact with π-π stacking. | [43] |
| ZnMOF@MGO Zn metal organic framework doped magnetic graphene oxide composite | Cefixime | They determined the extraction of cefixime with ZnMOF@MGO. 15 mg of ZnMOF@MGO. | The absorption of cefixime was up to 95.1%. The best results were in phosphate buffer (15 mM and pH 6), 15 mg of ZnMOF@MGO. | [66] |
| Zirconium−porphyrin-based metal–organic framework (MOF), PCN-224 | Nalidixic acid (NDX) Ofloxacin | NDX with concentrations of 20, 25, 30, 40, and 50 pp. was dissolved in 1 L of water. Then, the pH was adjusted to 7. 25 mg PCN-224 was put into each solution. The samples were stirred at different times (0, 10, 20, 30, 60, 120, 240, 360, 540, and 720 min) at 450 rpm at 25°C. After each adsorption time, it was extracted and filtered. The concentration of antibiotic was analyzed in 200–500 nm. | NDX = 671 mg/g OFL = 1030 mg/g | [43] |
| Cadmium-based MOFs (Fe3O4@Cd-MOF) modified with chitosan | Amoxicillin (AMX) | The adsorption was studied in a conical glass vessel. The pH of the adsorption solutions was adjusted by using NaOH or HCl solution. Fe3O4@Cd-MOF@CS 50 mg was immersed in 100 mL of AMX with 50 ppm. The vessel was sealed and shaken at 150 rpm at ambient temperature. He remained AMX in the solution, which was measured using UV–Vis spectroscopy. | The maximum adsorption capacity was found ∼103.09 mg/g. Recycling capability was five cycles. | [43] |
| Carbon nano sheets (CNS)@ZIF67 | Ciprofloxacin (CIP) | A ciprofloxacin concentration of 0.1–100 ppm at pH = 7. The composites are used here as an adsorbent (40 mg) for an aqueous solution of antibiotics at room temperature (303 K). The mixture was agitated for 5 to 120 minute at 120–130 rpm in a room temperature. The analysis of aliquot solution is done by UV–Vis spectrometer. The influence of pH on antibiotic adsorption was studied by pH values in the acidic and basic regions. | The pristine MOF and CNS do not show any impressive result. | [67] |
| UiO-66 and UiO-66-NH2 | Norfloxacin Ciprofloxacin oxytetracycline hydrochloride | The adsorption capability was tested under dark in a water bath shaker at 180 rpm under room temperature. The adsorbents were added to 20 mL of 20 ppm norfloxacin solution for 2 h. After the adsorption time was over, they were separated using centrifugation and filtration; the optical absorbance was measured by UV–vis spectrometer. | The amine-functionalized MOF shows the best adsorption capacity, 93%, followed by UiO-66 at 88%, respectively. It has been found that UiO-66-NH2 adsorbs 92% of OxyTCH and 89% of CIP. | [68] |
| Aluminum-based metal organic framework (MOF) | Tetracycline (TC) Ciprofloxacin (CIP) | Stock solutions of TC and CIP were dissolved in EtOH and ultrapure water, respectively. The batch adsorption studies were conducted by immersing an adsorbent (10 mg) in a 50 mL glass vial containing 30 mL of TC or CIP solution with an initial concentration of 10 mg/L, and the solution was shaken at a speed of 150 rpm. After adsorption, the adsorbent materials were separated by filtration. The residual concentrations of TC and CIP were measured. Using HPLC. | Hydrogel beads, Alg@MOF-rGO, showed maximum adsorption capacities of 43.76 and 40.76 mg/g for TC and CIP. The maximum adsorption capacity was at neutral pH. | [69] |
| HKUST-1-derived carbon (HDC-1100) | Ciprofloxacin (CIP) | In the batch adsorption experiments, 10 mg of HDC-1100 was added to a triangular beaker with 20 mL of a CIP solution with CIP concentrations (10–500 mg/L). The samples were shaken at 150 rpm for 48 h. The concentration of the CIP HPLC. | Within 48 h, HDC-1100 reach adsorption for 30 mg/L CIP. The maximum adsorption capacity was as high as 592 mg/g | [70] |
| P2W18O62/Fe-MIL-101/NiF2O4 | Tetracycline (TC) Ciprofloxacin (CIP) | Batch adsorption was conducted by adding 40 mg of adsorbent for each 50 mg/L and agitating vigorously. After filtration, the supernatant was assessed using UV–Vis at λ = 275–328 and 273–360 nm. | TC had an adsorption efficiency of approximately 90% within 20 min, whereas CIP had a higher adsorption efficiency of around 100% within 10 min. The structure t unaffected by the presence of solvents, drugs, or changes in pH. | [71] |
| MOF/hydrogel. Three-dimensional zeolitic imidazolate framework-8 (ZIF-8)/polysaccharide (sodium alginate-kappa-carrageenan, SC) hydrogel beads | Ciprofloxacin (CIP) | A CIP solution of 200 mg/L and 5 mg of the adsorbents into a 30 mL, and shaken at 160 rpm. | The adsorption capacity value in the one-step method was 951.61 ± 33.74 mg/g, reused four times. | [72] |
Table 2.
MOFs beyond carboxylates used in antibiotic removal and degradation.
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3. Discussion
Nowadays, pollution is becoming one of the great challenges facing humanity. This deterioration of the environment comes from many human activities, one of which has begun to arouse interest is pollution produced by medicines. In recent years, efforts have begun to carry out studies that demonstrate the presence of different medications in the environment; one type of drug that is being detected is antibiotics.
This situation contributes, on the one hand, to water contamination, which generates toxicity problems for the living beings of the ecosystem that is contaminated, but it is also helping the phenomenon of resistance; for these two reasons, the investigation of possible solutions to this problem, a line of work on the subject is the use of MOFs to eliminate the presence of antibiotics in water. MOFs offer several characteristics that make them suitable for this purpose: they have a large surface area, adjustable pore sizes when prepared, the nature of secondary building units (SBUs) is very varied, in the last two decades, the work around the preparation of these reticular materials has been very active, which is reflected in the little more than 84 thousand structures registered in the Cambridge Crystallographic Data Centre.
In the period from 2013 to 2023, a large number of works have been published with the use of different MOFs to eliminate some type of antibiotic; however, the most used type of MOF is the MIL type, and the vast majority of works use a model of water prepared with an antibiotic, they have also determined the mechanism by which the antibiotic is eliminated from the water, in general, it is by adsorption based on electrostatic interactions between the MOF and the antibiotic, the efficiency achieved in these cases varies, but it ranges from 80% to the total elimination of the antibiotic in the water.
They have carried out degradation tests of the antibiotic using photochemical methods that have given good results with the total disappearance of the antibiotic.
Although there is still a lot to advance on the subject, these years have shown very interesting advances on the subject, which opens the possibility of reaching a solution to this problem.
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4. Conclusions
Metal organic frameworks have a wide variety of applications due to their features, which allow materials to be modified and synthesized for different purposes. This has been demonstrated by several reports that put MOFs as emergent materials with some great absorption capacities. Therefore, using MOFs to remove and/or degrade molecules like antibiotics might be a real solution to the problem of the presence of antibiotics in water. The research and synthesis of new MOFs for solving environmental problems have to be an investigation line that must be attendant, and also composites materials with some matrix like zeolites, silices, and polyoxometalates can be conjugated with MOFs for the obtain of materials with enhanced absorption and selectivity.
In this review, a wide variety of MOFs are reported, which were used to eliminate antibiotics from samples of solutions with the antibiotics in different concentrations and achieve the elimination of quantities greater than 80% of the test antibiotics, and reusable, a situation that opens the possibility of more studies and converts these materials into a solution to the problem of antibiotic contamination in water.
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