Adsorption Performance of g-C3N4/graphene, and MIL-101(Fe)/graphene for the Removal of Pharmaceutical Contaminants: A Molecular Dynamics Simulation Study

Adsorption Performance of g-C3N4/graphene, and MIL-101(Fe)/graphene for the Removal of Pharmaceutical Contaminants: A Molecular Dynamics Simulation Study | Research Square window.SnipcartSettings = { analytics: { enabled: false } }; (function() { var accessVector = localStorage.getItem('access_vector') || ''; window.dataLayer = window.dataLayer || []; if (accessVector) { window.dataLayer.push({ user: { profile: { profileInfo: { snid: accessVector } } } }); } })(); (function(w,d,s,l,i){w[l]=w[l]||[];w[l].push({'gtm.start':new Date().getTime(),event:'gtm.js'});var f=d.getElementsByTagName(s)[0],j=d.createElement(s),dl=l!='dataLayer'?'&l='+l:'';j.async=true;j.src='https://www.googletagmanager.com/gtm.js?id='+i+dl;f.parentNode.insertBefore(j,f);})(window,document,'script','dataLayer','GTM-K279D39R'); Browse Preprints In Review Journals COVID-19 Preprints AJE Video Bytes Research Tools Research Promotion AJE Professional Editing AJE Rubriq About Preprint Platform In Review Editorial Policies Our Team Advisory Board Help Center Sign In Submit a Preprint Cite Share Download PDF Research Article Adsorption Performance of g-C3N4/graphene, and MIL-101(Fe)/graphene for the Removal of Pharmaceutical Contaminants: A Molecular Dynamics Simulation Study Qusai Ibrahim, Salem Gharbia This is a preprint; it has not been peer reviewed by a journal. https://doi.org/ 10.21203/rs.3.rs-4081656/v1 This work is licensed under a CC BY 4.0 License Status: Published Journal Publication published 06 Nov, 2024 Read the published version in Scientific Reports → Version 1 posted You are reading this latest preprint version Abstract The rising presence of drug-related contaminants in water sources is a major environmental and public health concern. Several studies have addressed the hazardous influence of these pollutants on the lives of over 400 million people worldwide. In this study, we used molecular dynamics simulations to evaluate the efficacy of two promising composite materials for the removal of pharmaceutical contaminants by using the adsorption technique. Graphitic carbon nitride/graphene (g-C 3 N 4 /graphene) and metal-organic framework (MIL-101(Fe))/graphene have been simulated for the first time for the removal of three of the most common pollutants (acetaminophen, caffeine, and sulfamethoxazole). The nanocomposite structure has been created and optimized using the geometry optimization task in the DFTB Modules in the Amsterdam Modeling Suite. Our results reveal the remarkable ability of the g-C 3 N 4 /graphene and MIL-101(Fe)/graphene composites to adsorb acetaminophen, caffeine, and sulfamethoxazole. Using the Reactive Forcefield (ReaxFF) software, we reveal the mechanisms of the adsorption process, calculating van der Waals interactions, and the adsorption capacity. We found that the combination of MIL-101(Fe)/graphene had a higher adsorption capacity for the removal of pharmaceutical contaminants than g-C 3 N 4 /graphene. At 40 Ps (Picosecond), 80 molecules of each pharmaceutical contaminants (Acetaminophen, Caffeine and Sulfamethoxazole) have been adsorbed by MIL-101(Fe)/graphene with higher exothermic energy equated to (-1174, -1630, and − 2347) MJ/mol respectively. While for g-C 3 N 4 /graphene at 40 Ps, 70 molecules of each pharmaceutical contaminants have been adsorbed with exothermic energy equated to (-924, -966, and − 1268) MJ/mol respectively. Finally, we summarized the condition of the essential parameters (Temperature, pressure, and density) of the simulation box during the MD-simulation, and the adsorption kinetics using Pseudo-First Order (PFO) in order to ensure the accuracy of our MD-simulation results. Graphene. G-C3N4. MIL-101(Fe). Pharmaceutical Contaminants. Simulation. Adsorption Figures Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 1. Introduction The issue of pharmaceutical contaminants in water resources has emerged as a significant and pressing environmental concern in recent years (Yadav et al., 2021 ). This phenomenon raises critical questions about the sources, fate, and impact of these contaminants, urging a comprehensive understanding of the issue to develop effective strategies for water quality management and environmental sustainability (Pal et al., 2010 ). Traditional water treatment methods may not be effective in removing these contaminants in terms of cost, and efficiency, making the development of advanced materials crucial (Amin et al., 2014 ). The cost of traditional water treatment methods can vary depending on the infrastructure required, the energy consumption, and may require extensive facilities and maintenance (Al-Karaghouli & Kazmerski, 2013 ; Ghaffour et al., 2013 ). In comparison with the adsorption technique, despite their high initial cost, adsorption techniques may offer cost savings in the long run due to their effectiveness and the potential for regeneration of the adsorbent material (de Andrade et al., 2018 ; Gupta et al., 2009 ). G-C 3 N 4 /graphene and MIL-101(Fe) demonstrates remarkable adsorption capacity and selectivity for a wide range of pharmaceutical contaminants (Kamandi et al., 2021 ; Zhang et al., 2021 ). This high adsorption performance can be attributed to the unique structural and chemical properties of these materials, such as the large surface area, abundant active sites, and strong interaction between the contaminants and the adsorbents (Wang et al., 2023 ; Giannakoudakis et al., 2022 ). These materials offer a sustainable and effective solution to mitigate the adverse impacts of pharmaceutical contamination, contributing to cleaner and safer water resources (Giannakoudakis et al., 2022 ). However, further research is necessary to optimize and scale up the use of these materials in real-world applications, ensuring their widespread adoption and positive impact on global water quality (Mauter et al., 2018 ). G-C 3 N 4 /graphene is a composite compound created by mixing graphene with g-C 3 N 4 (Zhang et al., 2017 ). The two-dimensional semiconductor material g-C 3 N 4 (graphitic carbon nitride) has interesting features for a variety of uses including photocatalytic applications, hydrogen production, and adsorption (Pourmadadi et al., 2022 ; Ismael, 2020 ; Prasad et al., 2020 ). On the other hand, graphene is a sheet of carbon atoms that is only one atom thick and is recognized for its exceptional strength and conductivity (Fuhrer et al., 2010 ). The combination of graphene and g-C 3 N 4 have improved the adsorption capacity as indicated in previous studies (Zhang et al., 2017 ; Feng et al., 2022 ). For instance, Hernández-Uresti and his colleagues synthesized polymeric g-C 3 N 4 for the degradation of different pharmaceutical compounds including tetracycline, ciprofloxacin, salicylic acid, and ibuprofen in aqueous solution under UV–vis irradiation (Hernández-Uresti et al., 2016 ). The results showed a high capacity to degrade these pollutants in the sequence: tetracycline > ciprofloxacin > salicylic acid > ibuprofen (Hernández-Uresti et al., 2016 ). Along the same line, Smýkalová and her colleagues prepared g-C 3 N 4 by thermal synthesis, and titanium dioxide P25 and CG300 for the degradation of paracetamol (PAR), ibuprofen (IBU), and diclofenac (DIC) (Smýkalová et al., 2019 ). The results showed that under VIS irradiation, g-C 3 N 4 was the most active one for the removal of pharmaceuticals contaminants after 12 h of irradiation (Smýkalová et al., 2019 ). Moreover, Wang and his colleagues developed a novel hydrogel system composed of g-C 3 N 4 and graphene for the removal of chromium (VI) from water (Wang et al., 2017 ). This system is designed to synergistically combine adsorption and photo-catalysis under visible light (Wang et al., 2017 ). The study concludes that the g-C 3 N 4 /graphene hydrogel system shows promise as an effective and sustainable solution for removing chromium (VI) from water (Wang et al., 2017 ). On the other hand, MIL-101(Fe)/graphene is an additional kind of composite material composed of graphene and MIL-101(Fe), a metal-organic framework (MOF) made of iron (Fe) clusters (Wu et al., 2021 ; Liu et al., 2021 ). MOFs have excellent potential for adsorption processes due to their highly porous nature (Wang et al., 2020 ). Several studies have investigated the potential advancements of the combination of MIL-101(Fe)/graphene in the removal of pharmaceutical contaminants (Chen et al., 2023 ; Rasheed et al., 2020 ). For instance, Sarker and his colleagues synthesized a highly porous metal-organic framework (MOF) composites combining MIL-101(Cr) with graphene oxide (GnO) (Sarker et al., 2018 ). The results showed that GnO/MIL-101 composites displayed highly improved adsorption of anti-inflammatory drugs (AIDs) such as naproxen (NAP) and ketoprofen (KTP) from water (Sarker et al., 2018 ). Table 1 shows several studies indicated the ability of the combination of MIL-101(Fe)/graphene, and other nanocomposite materials for the removal of pharmaceutical contaminants. Table 1 Literature review of the previous studies indicated the combination of MIL-101(Fe)/graphene, and other nanocomposite materials for the removal of pharmaceutical contaminants. Nanocomposite materials Pharmaceutical contaminants Results References Magnetic rod-like hydroxyapatite and MIL-101(Fe) Tetracycline, ciprofloxacin drugs. The article reports that the magnetic HAP/MIL-101(Fe)/Fe 3 O 4 ternary nanocomposite showed high adsorption efficiency for tetracycline and ciprofloxacin drugs from aqueous solutions. The adsorption rate and capacity of the nanocomposite were found to be higher than those of HAP, MIL-101(Fe), and HAP/MIL-101(Fe) samples. The optimum conditions for achieving 95% and 93% removal efficiencies of TC and CIP. (Beiranvand et al., 2022 ) CoFe 2 O 4 /MIL-101(Fe)/GO Triclosan (TCS). The research demonstrates the high performance of the combination of CoFe 2 O 4 /MIL-101(Fe)/GO in the treatment of TCS in water, indicating its potential as an effective and environmentally compatible process for micropollutant degradation in water treatment. (Moazeni et al., 2022 ) GO/MIL-101(Fe) Methyl Orange. The results show that GO/MIL-101(Fe) exhibited higher adsorption capacity for Methyl Orange compared to MIL-101(Fe). The Langmuir adsorption isotherm equation was found to describe the adsorption behaviour well. The study concludes that GO/MIL-101(Fe) has good regeneration ability and can be reused multiple times. (Liu et al., 2021 ) In this study, by using molecular dynamic simulation, and with the reference to the good adhesion of graphene to g-C 3 N 4 , and MIL-101(Fe) in terms of their chemical compatibility (Chen et al., 2021 ), a layer of graphene has been added to g-C 3 N 4 , and MIL-101(Fe) to create a bilayer nanocomposite material to increase the adsorption ability and performance in the elimination of pharmaceutical contaminants including acetaminophen, caffeine and sulfamethoxazole. The adsorption process, including van der Waals interactions, adsorption capacity, and structural alterations of the composite materials has been investigated by using the Reactive Forcefield (ReaxFF) software. The adsorption kinetics were evaluated based on the simulation results. The study aims to create a comprehensive simulation test for the elimination of these contaminants to be used for the future experimental studies in the laboratories. 2. Material and methods 2.1. Molecular Structure The molecular structure for each nanocomposite was simulated based on the crystallographic lattice parameters, as indicated in Table 2 . For g-C 3 N 4 , a hexagonal crystal system with a space group: P̅6m2, with the volume of the cell (87.3 Å 3 ) (Jain et al., 2013 ; Petousis et al., 2017 ). While for graphene, a space group of P6 3 /mmc, with cell volume: 1130.6 Å 3 (SCM, 2020). For MIL-101(Fe), the molecular structure has been generated from the Chemical Book (CHEMSOON, 2024) and optimized by using the geometry optimization task in the DFTB Modules in the Amsterdam Modeling Suite (Section 2.3.) (Debefve & Pollock, 2021 ). Table 2 shows the lattice constants for g-C 3 N 4 , graphene, and MIL-101(Fe). However, for the pharmaceutical contaminants, the molecular structure has been created by using the Amsterdam Modeling Suite software library (SCM, 2020). For acetaminophen (C 8 H 9 NO 2 ), a monoclinic form with a space group of P2 1 /a, with density of 1,293 g/cm 3 . While for caffeine, an orthorhombic form with a space group of P2.2.2., with density of 1,23 g/cm 3 . Finally, for sulfamethoxazole, a monoclinic form with a space group of P2 1 /c, with a density of 1.3915 g/cm 3 . Using the Builder task, the molecules have been generated in the simulation box within 2 cycles, distance: 2.5 Å, with a 50-maximum number of optimization loops. Figure 1 shows Molecular structure of contaminants of emerging concern (CECs). Table 2. Lattice constants for g-C 3 N 4 , graphene, and MIL-101(Fe) 2.2. Molecular dynamics simulation using the ReaxFF software. A simulation box consisting of g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene nanocomposites bilayer membranes was designed with 2205, and 3577 fixed number of atoms respectively. In this study, the membrane surface area was designed with a dimension of 66.3×66.3 Å 2 , and with the simulation box size of 66.5×66.5×70 Å 3 . For g-C 3 N 4 /graphene and MIL-101(Fe)/graphene, the concentration of g-C 3 N 4 was 40% from the whole system, while MIL-101(Fe) was 22%. However, the distance between g-C 3 N 4 , MIL-101(Fe) and graphene layer is equal to 3.316 Å. The NHC thermostat simulation method with MTK barostat (Yong & Zhang, 2013 ) was applied with a density of 0.255 Kg/L. A force field containing all elements available in the precursor (C/H/O/N) for g-C 3 N 4 /graphene, and (C/H/Cl/Fe/O) for MIL-101(Fe)/graphene nanocomposite membrane were selected from the software library (SCM, 2020). The simulation box’s specific temperature was chosen as 273.15 K with a damping constant equal to 500 fs. An external temperature of 500 K was applied on all the nanocomposite materials in the simulation box during the process. Figure 2 shows the simulation box consisting of 60 acetaminophen molecules on MIL-101(Fe)/graphene, and g-C 3 N 4 /graphene nanocomposite materials. 2.3. Geometry optimization using DFTB. Geometry optimization is a computational technique used in the field of molecular modeling and quantum chemistry to find the most stable and energetically favourable three-dimensional arrangement of atoms within a molecule or a material (Kanatani, 2005 ). The process involves adjusting the atomic positions iteratively until a configuration is reached where the forces acting on each atom are minimized, indicating a potential energy minimum (Kanatani, 2005 ). After constructing a crystallographic structure for the nanocomposite materials based on their fundamental lattice characteristics, the geometry optimization task is the first step in the simulation process. With a high number of iterations totalling 2143 for MIL-101(Fe), and 500 for g-C 3 N 4 , DFTB simulation code was used to complete the process. A Quasi-Newton method has been used with a medium quality of the process within the energy range of 2.0e-5 eV/atom, with a maximum displacement of 0.05 Å. The method used to minimize energy by arranging atoms in a certain structure with the lowest possible energy. 2.4. Condition of the essential parameters (Temperature, pressure, and density) during the MD-simulation. In molecular dynamics (MD) simulations, the temperature, pressure, and density of the simulation box are essential parameters that characterize the thermodynamic behaviour of the simulated system (Binder et al., 2004 ). These parameters are typically controlled through thermostats and barostats, allowing researchers to replicate specific experimental conditions and observe the dynamic behaviour of molecules over time (Binder et al., 2004 ). In our study, temperature of the simulation box was controlled to be around 500 K as shown in Fig. 3 . While the pressure was exceptionally increasing to 88 MPa at the first 20 Ps, then it decreased rapidly to 17 MPa at 40 Ps. The significant rise in pressure in the initial half of the MD simulation was related to the high interaction between the molecules (pharmaceutical contaminants) and the adsorbent surface. However, the density of the simulation box remains around 0.255 Kg/L during the MD simulation. Figure 3 shows the temperature, pressure, and density of the simulation box during the MD simulation of 60 acetaminophen on g-C 3 N 4 /graphene nanocomposite layer. However, for the other two pharmaceutical contaminants (Caffeine, and sulfamethoxazole), the condition of the essential parameters had almost the same behaviour during the MD simulation on both g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene nanocomposite. 3. Results and discussion 3.1. adsorption capacity ( qe ) Adsorption capacity refers to the maximum amount of substance that an adsorbent material can hold or capture from a surrounding medium through the process of adsorption (De Gisi et al., 2016 ). As illustrated in Fig. 4 , the results indicated that there is a difference in the number of adsorbed molecules toward the three pharmaceutical contaminants tested. For both g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene, sulfamethoxazole was the highest adsorbed molecule after 60 Ps, which is similar to results reported by previous study (Huang et al., 2018 ). In the first 10 Ps, 30 molecules of acetaminophen, 25 of caffeine, and 30 of sulfamethoxazole were adsorbed on the g-C 3 N 4 /graphene bilayer, while for MIL-101(Fe)/graphene, 35 molecules of acetaminophen, 29 of caffeine, and 35 of sulfamethoxazole were adsorbed at 10 Ps. While in the middle of the simulation at t = 40 Ps, 70 molecules of each (acetaminophen, caffeine, and sulfamethoxazole) were adsorbed on the g-C 3 N 4 /graphene bilayer. Meanwhile, for MIL-101(Fe)/graphene a higher number of molecules has been adsorbed at 40 Ps (80, 79, and 82) respectively. Finally, at t = 60 Ps, the adsorption rate was stable on g-C 3 N 4 /graphene bilayer as the number of adsorbed molecules remains constant till the end of simulation time (85, 92, and 94) respectively. While for MIL-101(Fe)/graphene, the number of adsorbed molecules was (101, 100, and 101) respectively at t = 60 Ps and remains constant till the end of simulation time, which is similar to results reported by previous study (Quintero-Álvarez et al., 2022 ; Xiong et al., 2021 ). Figure 4 shows the number of adsorbed contaminants of emerging concern on g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene. The adsorption capacity ( qe ) has been calculated for the three pharmaceutical pollutants by using the following Equation (Perera et al., 2012 ). $$qe=\frac{\left(Co-Ce\right)V}{m}$$ 1 … Where qe is the Adsorption capacity, Co is the initial concentration in (ppm), Ce is the concentration at equilibrium, V is the volume of solution, and M is the mass of the adsorbent. As shown in Fig. 5 , MIL-101(Fe)/graphene had a higher adsorption capacity on the pharmaceutical contaminants after 80 Ps of contact time. For MIL-101(Fe)/graphene at t = 20 Ps, the adsorption capacity was equal to (3.3, 3.06, and 3.4) mg/g respectively. While for g-C 3 N 4 /graphene, the adsorption capacity was equal to (2.72, 1.7, and 2.92) mg/g respectively. However, at t = 30 Ps, there was a significant increase in the adsorption capacity by approximately two-fold for both MIL-101(Fe)/graphene, and g-C 3 N 4 /graphene. Finally, at t = 60 Ps, we have reached the highest rate of adsorption for both nanocomposite materials and the relationship remain constant till the end of the simulation time with a maximum capacity of (10, 9.99, and 10.05) for MIL-101(Fe)/graphene, while for g-C 3 N 4 /graphene was equal to (8.25, 9.16, and 9.182) respectively. The adsorption kinetics data were adapted to Pseudo-First Order (PFO) (Ezzati, 2020 ), the Equation of Pseudo-First Order are shown below: $$qt=qe (1-{e}^{-k1t})$$ 2 … To characterize the adsorption kinetic behaviours, the pseudo-first order was chosen. The PFO fit the simulation data with a high R 2 value (0.973, 0.985, and 0.935) for acetaminophen, caffeine, and sulfamethoxazole on g-C 3 N 4 /graphene respectively, and (0.983, 0.979, and 0.973) for acetaminophen, caffeine, and sulfamethoxazole on MIL-101(Fe)/graphene nanocomposite respectively. Additionally, the calculated qe values from the PFO model were closer to the simulation qe values for both g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene (Table 3 , 4 ). Table 3 Kinetic data fitting parameters of the acetaminophen, caffeine, and sulfamethoxazole on g-C 3 N 4 /graphene Adsorbent Pseudo First Order q e (mg/g) (Sim) q e (mg/g) (cal) k 1 Ps − 1 R 2 Acetaminophen 8.25 11.98199 ± 2.26065 0.018 0.973 Caffeine 9.16 15.85552 ± 3.37207 0.013 0.985 Sulfamethoxazole 9.182 17.68059 ± 7.17248 0.012 0.935 Table 4 Kinetic data fitting parameters of the acetaminophen, caffeine, and sulfamethoxazole on MIL-101(Fe)/graphene Adsorbent Pseudo First Order q e (mg/g) (Sim) q e (mg/g) (cal) k 1 Ps − 1 R 2 Acetaminophen 10.05 16.07485 ± 3.04119 0.015 0.983 Caffeine 9.99 15.77317 ± 3.14511 0.016 0.979 Sulfamethoxazole 10.05 18.68059 ± 6.17248 0.012 0.973 Figure 5 shows the adsorption capacity of contaminants of emerging concern on g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene. 3.2. Potential Energy Surface (PES) The potential energy surface (PES) during the adsorption process refers to the energy landscape that describes the interaction between adsorbate molecules (the species being adsorbed) and a substrate or adsorbent surface (Collinge et al., 2020 ). During adsorption, molecules in the gas or liquid phase are attracted to the surface of a solid or liquid material (Marquardt et al., 2010 ). This surface is a representation of the potential energy of the system as a function of the coordinates that describe the positions and orientations of the adsorbate molecules on the surface (Marquardt et al., 2010 ). Mathematically, the potential energy of a system (U) can be expressed as (Lisoń et al., 2019 ): $$U=T+V$$ 3 … Where T is the kinetic energy and V is the potential energy. In this paper, we calculated the MD-potential energy surface for both g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene. Due to the attraction between the pharmaceutical contaminants and the surface of the nanocomposite materials, the results showed a negative potential energy for the molecules as it equalled to (-924, -966, and − 1268) MJ/mol for (acetaminophen, caffeine, and sulfamethoxazole) respectively on g-C 3 N 4 /graphene at t = 40 Ps. The reason of the negative potential energy can be expressed according to Coulomb's Law (Guo et al., 2013 ): $$F=-\frac{k.q1.q2}{{r}^{2}}$$ 4 … Where k is a constant, q1 and q2 are the quantities of each charge, and the scalar r is the distance between the charges. The \(-\frac{k.q1.q2}{{r}^{2}}\) term in Coulomb's Law contributes a negative value when q 1 and q 2 have opposite signs, indicating an attractive electrostatic force (Al Rabeh, 2021 ). However, for MIL-101(Fe)/graphene, the potential energy of the molecules was equal to (-1174.7, -1630.1, and − 2347.2) respectively. As the adsorption capacity was higher on MIL-101(Fe)/graphene as we indicated in section 3.1., the breaking of the molecules bonds forming a new bonds and electrons was higher on MIL-101(Fe)/graphene resulting in a lower potential energy and more heat released (exothermic reaction). Finally, we noticed that the MD-potential energy of both acetaminophen and caffeine was slightly decreasing during the MD-simulation time for both nanocomposite materials, while for sulfamethoxazole it was decreasing for g-C 3 N 4 /graphene and increasing for MIL-101(Fe)/graphene. The decreasing in the potential energy for acetaminophen and caffeine is due to the significant contribution of electrostatic energy (Nejad et al., 2017 ). When the atoms charge is moving close to the nanocomposite surface, the potential energy decrease (Khoshkava & Kamal, 2013 ). While for sulfamethoxazole on MIL-101(Fe)/graphene nanocomposite, the increase in the potential energy is due to the hydrogen-bonding sites that formed between sulfamethoxazole and the adsorbent surface (Huang et al., 2021 ). Figure 6 shows potential energy surface during the adsorption process of the contaminants of emerging concern (CECs) on g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene. 3.3. Van der Waals interactions Van der Waals interactions are weak attractive forces that arise between molecules or atoms as a result of temporary fluctuations in electron distribution (Kawai et al., 2016 ). It plays a crucial role in determining the physical and chemical properties of substances, influencing phenomena such as solubility, boiling points, and the behaviour of gases (Dudek et al., 2020 ). Despite their relatively weak nature, these interactions are fundamental to the stability and structure of a wide range of molecular systems, contributing significantly to the cohesive forces that bind molecules together in various states of matter (Dudek et al., 2020 ). The van der Waals interactions are often represented by the following Equations (Hermann et al., 2017 ): $$\left(P+\frac{an2}{V2}\right)\left(V-nb\right)=nRT$$ 5 … Where P is the pressure, R is the universal gas constant, T is the absolute temperature, V is the molar volume, and (a, b) are gas constant. The Lennard-Jones potential is often used to describe the van der Waals interaction between neutral atoms or molecules. The Equation (Hermann et al., 2017 ) is given by: $${E}_{\text{L}\text{J}}\left(r\right)=4\in [{\left(\frac{\sigma }{r}\right)}^{12}-{\left(\frac{\sigma }{r}\right)}^{6}]$$ 6 … Where r is the distance between the particles, ∈ is the depth of the potential well (related to the strength of the interaction), and σ is the finite distance at which the inter-particle potential is zero. In our study, we calculated the interaction energy of the pharmaceutical contaminants on g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene. The investigation focused on examining the change in interaction energy concerning the distance between the pharmaceutical contaminant atoms and the nanocomposite layers. Our results showed that the optimal distance between the pharmaceutical contaminants and the nanocomposite layers is ranging between 2.5 to 3 Å with an interaction energy ranging between − 250 to -360 eV for g-C 3 N 4 /graphene, and − 390 to -450 for MIL-101(Fe)/graphene. However, at R = 4 Å, the interaction energy continued to decrease, and it reached to a value ranging between − 370 to -420 eV for g-C 3 N 4 /graphene, and − 500 to -600 eV for MIL-101(Fe)/graphene. Finally, at R = 6 Å, the interaction energy began toward equilibrium for g-C 3 N 4 /graphene, while for MIL-101(Fe)/graphene, the interaction energy began toward equilibrium for acetaminophen and caffeine, while for sulfamethoxazole the interaction energy continues to decrease, and it reached around − 685 eV at R = 8 Å. The reason for this is due to the hydrogen-bonding sites that formed between sulfamethoxazole and the adsorbent surface as we indicated in the previous section 3.2. Figure 7 shows the interaction energy as a function of separation distance on g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene. 4. Conclusions A g-C 3 N 4 /graphene, and MIL-101(Fe)/graphene nanocomposite materials have been simulated to verify the adsorption capacity for the removal of pharmaceutical contaminants. The high adsorption efficiency of g-C 3 N 4 /graphene and MIL-101(Fe) for the removal of acetaminophen (paracetamol), caffeine and sulfamethoxazole have been tested for the first time by using the ReaxFF software and the DFTB Modules. In this study, we found that MIL-101(Fe)/graphene nanocomposite had a higher adsorption capacity for the removal of pharmaceutical contaminants than g-C 3 N 4 /graphene during 100 Ps simulation time. Our investigations for the elimination of acetaminophen, caffeine, and sulfamethoxazole have leaded to three important results. The first one is that sulfamethoxazole was the highest adsorbed pharmaceutical contaminant with a value equal to 9.182 mg/g on g-C 3 N 4 /graphene, and 10.05 mg/g on MIL-101(Fe)/graphene. The second one is that during the adsorption process, the MD-potential energy of both acetaminophen and caffeine was slightly decreasing due to the contribution of electrostatic energy. While for sulfamethoxazole on MIL-101(Fe)/graphene nanocomposite, the potential energy was slightly increasing due to the hydrogen-bonding sites that formed between sulfamethoxazole and the adsorbent surface. For the last one, our results showed that the optimum distance between the pharmaceutical contaminants and the nanocomposite layers is ranging between 2.5 to 3 Å based on the interaction energies that ranged between − 250 to -360 eV for g-C 3 N 4 /graphene, and − 390 to -450 for MIL-101(Fe)/graphene. Declarations -Ethical Approval: The Atlantic Technological University approved this research project as part of the Ph. D under the title “Water treatment by Adsorption Process for The Removal of Pharmaticulas Contaminants Using MIL-101(Fe)/graphene, LDH/g-C 3 N 4 , and LDH/graphene Nanocomposite Materials: A Molecular Dynamic Simulation Study”. -Consent to Participate: Not applicable. -Consent to Publish: Not applicable. -Authors Contributions: Qusai Ibrahim : Writing, Methodology, Simulation; Salem Gharbia : Supervision, Reviewing, Editing, and Validation. -Funding: This research was funded by the IT Sligo President’s bursary. -Competing Interests: The authors declare no conflict of interest. References Al-Karaghouli, A., & Kazmerski, L. L. (2013). Energy consumption and water production cost of conventional and renewable-energy-powered desalination processes. Renewable and Sustainable Energy Reviews , 24 , 343-356. Al Rabeh, R. (2021). A Single Complex Potential for Gravity and Electromagnetism. Advanced Studies in Theoretical Physics, 15(7), 299-312. Amin, M. T., Alazba, A. A., & Manzoor, U. 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Zhang, X., Li, C., Chen, T., Tan, Y., Liu, X., Yuan, F., ... & Sun, Z. (2021). Enhanced visible-light-assisted peroxymonosulfate activation over MnFe2O4 modified g-C3N4/diatomite composite for bisphenol A degradation. International Journal of Mining Science and Technology, 31(6), 1169-1179. Cite Share Download PDF Status: Published Journal Publication published 06 Nov, 2024 Read the published version in Scientific Reports → Version 1 posted You are reading this latest preprint version Research Square lets you share your work early, gain feedback from the community, and start making changes to your manuscript prior to peer review in a journal. As a division of Research Square Company, we’re committed to making research communication faster, fairer, and more useful. We do this by developing innovative software and high quality services for the global research community. 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Also discoverable on Platform About Our Team In Review Editorial Policies Advisory Board Help Center Resources Author Services Accessibility API Access RSS feed Manage Cookie Preferences © Research Square 2026 | ISSN 2693-5015 (online) Privacy Policy Terms of Service Do Not Sell My Personal Information {"props":{"pageProps":{"initialData":{"identity":"rs-4081656","acceptedTermsAndConditions":true,"allowDirectSubmit":true,"archivedVersions":[],"articleType":"Research Article","associatedPublications":[],"authors":[{"id":289758906,"identity":"469c5998-f240-4136-ae50-11ac5ffb6abc","order_by":0,"name":"Qusai Ibrahim","email":"data:image/png;base64,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","orcid":"https://orcid.org/0000-0002-2252-5153","institution":"Atlantic Technological University - Sligo","correspondingAuthor":true,"prefix":"","firstName":"Qusai","middleName":"","lastName":"Ibrahim","suffix":""},{"id":289758907,"identity":"850fbad7-411b-47f8-91cd-53cd8d502a80","order_by":1,"name":"Salem Gharbia","email":"","orcid":"https://orcid.org/0000-0003-2130-1841","institution":"Atlantic Technological University - Sligo","correspondingAuthor":false,"prefix":"","firstName":"Salem","middleName":"","lastName":"Gharbia","suffix":""}],"badges":[],"createdAt":"2024-03-12 08:21:26","currentVersionCode":1,"declarations":"","doi":"10.21203/rs.3.rs-4081656/v1","doiUrl":"https://doi.org/10.21203/rs.3.rs-4081656/v1","draftVersion":[],"editorialEvents":[{"content":"https://doi.org/10.1038/s41598-024-75443-9","type":"published","date":"2024-11-07T00:00:00+00:00"}],"editorialNote":"","failedWorkflow":false,"files":[{"id":54670377,"identity":"7b83289a-e34e-4f70-b6fe-04a3b3ed4ce9","added_by":"auto","created_at":"2024-04-15 04:50:48","extension":"png","order_by":1,"title":"Figure 1","display":"","copyAsset":false,"role":"figure","size":85034,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003e\u003cstrong\u003eMolecular structure of contaminants of emerging concern (CECs). 1. Acetaminophen (paracetamol), 2. Caffeine and 3. Sulfamethoxazole.\u003c/strong\u003e\u003c/em\u003e\u003c/p\u003e","description":"","filename":"1.png","url":"https://assets-eu.researchsquare.com/files/rs-4081656/v1/823e00343fb7de5bc17944a4.png"},{"id":54670985,"identity":"96dba8b2-b586-420b-a338-51785ef75045","added_by":"auto","created_at":"2024-04-15 04:58:48","extension":"png","order_by":2,"title":"Figure 2","display":"","copyAsset":false,"role":"figure","size":293924,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003e\u003cstrong\u003eSimulation box consisting of 60 acetaminophens on a) G-C\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003eN\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003e/graphene and b) MIL-101(Fe)/graphene.\u003c/strong\u003e\u003c/em\u003e\u003c/p\u003e","description":"","filename":"2.png","url":"https://assets-eu.researchsquare.com/files/rs-4081656/v1/e5e039141a59131d77cd0b3d.png"},{"id":54670378,"identity":"121805dd-2bac-4e51-83cb-6bc580a346aa","added_by":"auto","created_at":"2024-04-15 04:50:48","extension":"png","order_by":3,"title":"Figure 3","display":"","copyAsset":false,"role":"figure","size":191193,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003e\u003cstrong\u003eTemperature, pressure, and density of the simulation box during the MD simulation (60 Acetaminophen on g-C\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003eN\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003e/graphene nanocomposite layer).\u003c/strong\u003e\u003c/em\u003e\u003c/p\u003e","description":"","filename":"3.png","url":"https://assets-eu.researchsquare.com/files/rs-4081656/v1/793ebeb75b2623b3f45c908f.png"},{"id":54670383,"identity":"6ede0c09-4345-4235-8c33-dcdb91750d21","added_by":"auto","created_at":"2024-04-15 04:50:49","extension":"png","order_by":4,"title":"Figure 4","display":"","copyAsset":false,"role":"figure","size":159381,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003e\u003cstrong\u003eNumber of adsorbed contaminants of emerging concern (CECs) on a) G-C\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003eN\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003e/graphene, and b) MIL-101(Fe)/graphene.\u003c/strong\u003e\u003c/em\u003e\u003c/p\u003e","description":"","filename":"4.png","url":"https://assets-eu.researchsquare.com/files/rs-4081656/v1/2829d1986a67901de783b9f1.png"},{"id":54670381,"identity":"9a86fec4-2a2e-4d40-a187-42b0274d3ce7","added_by":"auto","created_at":"2024-04-15 04:50:48","extension":"png","order_by":5,"title":"Figure 5","display":"","copyAsset":false,"role":"figure","size":156857,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003e\u003cstrong\u003eAdsorption capacity of contaminants of emerging concern (CECs) on a) G-C\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003eN\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003e/graphene, and b) MIL-101(Fe)/graphene.\u003c/strong\u003e\u003c/em\u003e\u003c/p\u003e","description":"","filename":"5.png","url":"https://assets-eu.researchsquare.com/files/rs-4081656/v1/e35cce01aac2a216ef003a1d.png"},{"id":54670382,"identity":"bf2689a3-0b48-420a-9ba9-d0934afaa36e","added_by":"auto","created_at":"2024-04-15 04:50:48","extension":"png","order_by":6,"title":"Figure 6","display":"","copyAsset":false,"role":"figure","size":119817,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003e\u003cstrong\u003ePotential energy surface during the adsorption process of the contaminants of emerging concern (CECs) on a) G-C\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003eN\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003e/graphene, and b) MIL-101(Fe)/graphene.\u003c/strong\u003e\u003c/em\u003e\u003c/p\u003e","description":"","filename":"6.png","url":"https://assets-eu.researchsquare.com/files/rs-4081656/v1/694af6e1eba212f53e07e92a.png"},{"id":54670379,"identity":"0946f811-0d38-480c-93a7-fc3af0d0ce37","added_by":"auto","created_at":"2024-04-15 04:50:48","extension":"png","order_by":7,"title":"Figure 7","display":"","copyAsset":false,"role":"figure","size":143402,"visible":true,"origin":"","legend":"\u003cp\u003e\u003cem\u003e\u003cstrong\u003eThe interaction energy as a function of separation distance on a) G-C\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e3\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003eN\u003c/strong\u003e\u003c/em\u003e\u003csub\u003e\u003cem\u003e\u003cstrong\u003e4\u003c/strong\u003e\u003c/em\u003e\u003c/sub\u003e\u003cem\u003e\u003cstrong\u003e/graphene, and b) MIL-101(Fe)/graphene.\u003c/strong\u003e\u003c/em\u003e\u003c/p\u003e","description":"","filename":"7.png","url":"https://assets-eu.researchsquare.com/files/rs-4081656/v1/c4bda094d36fdceb092b66d6.png"},{"id":68578811,"identity":"a9e603eb-35f1-4ade-bc2f-355020c228b8","added_by":"auto","created_at":"2024-11-08 17:48:54","extension":"pdf","order_by":0,"title":"","display":"","copyAsset":false,"role":"manuscript-pdf","size":2007554,"visible":true,"origin":"","legend":"","description":"","filename":"manuscript.pdf","url":"https://assets-eu.researchsquare.com/files/rs-4081656/v1/f1ec69a1-6d22-40ae-95cf-1a01c657c2ca.pdf"}],"financialInterests":"","formattedTitle":"Adsorption Performance of g-C3N4/graphene, and MIL-101(Fe)/graphene for the Removal of Pharmaceutical Contaminants: A Molecular Dynamics Simulation Study","fulltext":[{"header":"1. Introduction","content":"\u003cp\u003eThe issue of pharmaceutical contaminants in water resources has emerged as a significant and pressing environmental concern in recent years (Yadav et al., \u003cspan citationid=\"CR52\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). This phenomenon raises critical questions about the sources, fate, and impact of these contaminants, urging a comprehensive understanding of the issue to develop effective strategies for water quality management and environmental sustainability (Pal et al., \u003cspan citationid=\"CR37\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). Traditional water treatment methods may not be effective in removing these contaminants in terms of cost, and efficiency, making the development of advanced materials crucial (Amin et al., \u003cspan citationid=\"CR3\" class=\"CitationRef\"\u003e2014\u003c/span\u003e). The cost of traditional water treatment methods can vary depending on the infrastructure required, the energy consumption, and may require extensive facilities and maintenance (Al-Karaghouli \u0026amp; Kazmerski, \u003cspan citationid=\"CR1\" class=\"CitationRef\"\u003e2013\u003c/span\u003e; Ghaffour et al., \u003cspan citationid=\"CR17\" class=\"CitationRef\"\u003e2013\u003c/span\u003e). In comparison with the adsorption technique, despite their high initial cost, adsorption techniques may offer cost savings in the long run due to their effectiveness and the potential for regeneration of the adsorbent material (de Andrade et al., \u003cspan citationid=\"CR10\" class=\"CitationRef\"\u003e2018\u003c/span\u003e; Gupta et al., \u003cspan citationid=\"CR20\" class=\"CitationRef\"\u003e2009\u003c/span\u003e). G-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene and MIL-101(Fe) demonstrates remarkable adsorption capacity and selectivity for a wide range of pharmaceutical contaminants (Kamandi et al., \u003cspan citationid=\"CR27\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Zhang et al., \u003cspan citationid=\"CR55\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). This high adsorption performance can be attributed to the unique structural and chemical properties of these materials, such as the large surface area, abundant active sites, and strong interaction between the contaminants and the adsorbents (Wang et al., \u003cspan citationid=\"CR48\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Giannakoudakis et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). These materials offer a sustainable and effective solution to mitigate the adverse impacts of pharmaceutical contamination, contributing to cleaner and safer water resources (Giannakoudakis et al., \u003cspan citationid=\"CR18\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). However, further research is necessary to optimize and scale up the use of these materials in real-world applications, ensuring their widespread adoption and positive impact on global water quality (Mauter et al., \u003cspan citationid=\"CR34\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). G-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene is a composite compound created by mixing graphene with g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e (Zhang et al., \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The two-dimensional semiconductor material g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e (graphitic carbon nitride) has interesting features for a variety of uses including photocatalytic applications, hydrogen production, and adsorption (Pourmadadi et al., \u003cspan citationid=\"CR40\" class=\"CitationRef\"\u003e2022\u003c/span\u003e; Ismael, \u003cspan citationid=\"CR25\" class=\"CitationRef\"\u003e2020\u003c/span\u003e; Prasad et al., \u003cspan citationid=\"CR41\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). On the other hand, graphene is a sheet of carbon atoms that is only one atom thick and is recognized for its exceptional strength and conductivity (Fuhrer et al., \u003cspan citationid=\"CR16\" class=\"CitationRef\"\u003e2010\u003c/span\u003e). The combination of graphene and g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e have improved the adsorption capacity as indicated in previous studies (Zhang et al., \u003cspan citationid=\"CR54\" class=\"CitationRef\"\u003e2017\u003c/span\u003e; Feng et al., \u003cspan citationid=\"CR15\" class=\"CitationRef\"\u003e2022\u003c/span\u003e). For instance, Hern\u0026aacute;ndez-Uresti and his colleagues synthesized polymeric g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e for the degradation of different pharmaceutical compounds including tetracycline, ciprofloxacin, salicylic acid, and ibuprofen in aqueous solution under UV\u0026ndash;vis irradiation (Hern\u0026aacute;ndez-Uresti et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). The results showed a high capacity to degrade these pollutants in the sequence: tetracycline\u0026thinsp;\u0026gt;\u0026thinsp;ciprofloxacin\u0026thinsp;\u0026gt;\u0026thinsp;salicylic acid\u0026thinsp;\u0026gt;\u0026thinsp;ibuprofen (Hern\u0026aacute;ndez-Uresti et al., \u003cspan citationid=\"CR22\" class=\"CitationRef\"\u003e2016\u003c/span\u003e). Along the same line, Sm\u0026yacute;kalov\u0026aacute; and her colleagues prepared g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e by thermal synthesis, and titanium dioxide P25 and CG300 for the degradation of paracetamol (PAR), ibuprofen (IBU), and diclofenac (DIC) (Sm\u0026yacute;kalov\u0026aacute; et al., \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). The results showed that under VIS irradiation, g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e was the most active one for the removal of pharmaceuticals contaminants after 12 h of irradiation (Sm\u0026yacute;kalov\u0026aacute; et al., \u003cspan citationid=\"CR46\" class=\"CitationRef\"\u003e2019\u003c/span\u003e). Moreover, Wang and his colleagues developed a novel hydrogel system composed of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e and graphene for the removal of chromium (VI) from water (Wang et al., \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). This system is designed to synergistically combine adsorption and photo-catalysis under visible light (Wang et al., \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2017\u003c/span\u003e). The study concludes that the g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene hydrogel system shows promise as an effective and sustainable solution for removing chromium (VI) from water (Wang et al., \u003cspan citationid=\"CR49\" class=\"CitationRef\"\u003e2017\u003c/span\u003e).\u003c/p\u003e \u003cp\u003eOn the other hand, MIL-101(Fe)/graphene is an additional kind of composite material composed of graphene and MIL-101(Fe), a metal-organic framework (MOF) made of iron (Fe) clusters (Wu et al., \u003cspan citationid=\"CR50\" class=\"CitationRef\"\u003e2021\u003c/span\u003e; Liu et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2021\u003c/span\u003e). MOFs have excellent potential for adsorption processes due to their highly porous nature (Wang et al., \u003cspan citationid=\"CR47\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). Several studies have investigated the potential advancements of the combination of MIL-101(Fe)/graphene in the removal of pharmaceutical contaminants (Chen et al., \u003cspan citationid=\"CR8\" class=\"CitationRef\"\u003e2023\u003c/span\u003e; Rasheed et al., \u003cspan citationid=\"CR43\" class=\"CitationRef\"\u003e2020\u003c/span\u003e). For instance, Sarker and his colleagues synthesized a highly porous metal-organic framework (MOF) composites combining MIL-101(Cr) with graphene oxide (GnO) (Sarker et al., \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). The results showed that GnO/MIL-101 composites displayed highly improved adsorption of anti-inflammatory drugs (AIDs) such as naproxen (NAP) and ketoprofen (KTP) from water (Sarker et al., \u003cspan citationid=\"CR44\" class=\"CitationRef\"\u003e2018\u003c/span\u003e). Table\u0026nbsp;\u003cspan refid=\"Tab1\" class=\"InternalRef\"\u003e1\u003c/span\u003e shows several studies indicated the ability of the combination of MIL-101(Fe)/graphene, and other nanocomposite materials for the removal of pharmaceutical contaminants.\u003c/p\u003e \u003cp\u003e \u003cdiv class=\"gridtable\"\u003e\u003ctable float=\"Yes\" id=\"Tab1\" border=\"1\"\u003e \u003ccaption language=\"En\"\u003e \u003cdiv class=\"CaptionNumber\"\u003eTable 1\u003c/div\u003e \u003cdiv class=\"CaptionContent\"\u003e \u003cp\u003eLiterature review of the previous studies indicated the combination of MIL-101(Fe)/graphene, and other nanocomposite materials for the removal of pharmaceutical contaminants.\u003c/p\u003e \u003c/div\u003e \u003c/caption\u003e \u003ccolgroup cols=\"4\"\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c1\" colnum=\"1\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c2\" colnum=\"2\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c3\" colnum=\"3\"\u003e\u003c/div\u003e \u003cdiv align=\"left\" class=\"colspec\" colname=\"c4\" colnum=\"4\"\u003e\u003c/div\u003e \u003cthead\u003e \u003ctr\u003e \u003cth align=\"left\" colname=\"c1\"\u003e \u003cp\u003eNanocomposite materials\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c2\"\u003e \u003cp\u003ePharmaceutical contaminants\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c3\"\u003e \u003cp\u003eResults\u003c/p\u003e \u003c/th\u003e \u003cth align=\"left\" colname=\"c4\"\u003e \u003cp\u003eReferences\u003c/p\u003e \u003c/th\u003e \u003c/tr\u003e \u003c/thead\u003e \u003ctbody\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eMagnetic rod-like hydroxyapatite and MIL-101(Fe)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTetracycline, ciprofloxacin drugs.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eThe article reports that the magnetic HAP/MIL-101(Fe)/Fe\u003csub\u003e3\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e ternary nanocomposite showed high adsorption efficiency for tetracycline and ciprofloxacin drugs from aqueous solutions. The adsorption rate and capacity of the nanocomposite were found to be higher than those of HAP, MIL-101(Fe), and HAP/MIL-101(Fe) samples. The optimum conditions for achieving 95% and 93% removal efficiencies of TC and CIP.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e(Beiranvand et al., \u003cspan citationid=\"CR4\" class=\"CitationRef\"\u003e2022\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eCoFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/MIL-101(Fe)/GO\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eTriclosan (TCS).\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eThe research demonstrates the high performance of the combination of CoFe\u003csub\u003e2\u003c/sub\u003eO\u003csub\u003e4\u003c/sub\u003e/MIL-101(Fe)/GO in the treatment of TCS in water, indicating its potential as an effective and environmentally compatible process for micropollutant degradation in water treatment.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e(Moazeni et al., \u003cspan citationid=\"CR35\" class=\"CitationRef\"\u003e2022\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003ctr\u003e \u003ctd align=\"left\" colname=\"c1\"\u003e \u003cp\u003eGO/MIL-101(Fe)\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c2\"\u003e \u003cp\u003eMethyl Orange.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c3\"\u003e \u003cp\u003eThe results show that GO/MIL-101(Fe) exhibited higher adsorption capacity for Methyl Orange compared to MIL-101(Fe). The Langmuir adsorption isotherm equation was found to describe the adsorption behaviour well. The study concludes that GO/MIL-101(Fe) has good regeneration ability and can be reused multiple times.\u003c/p\u003e \u003c/td\u003e \u003ctd align=\"left\" colname=\"c4\"\u003e \u003cp\u003e(Liu et al., \u003cspan citationid=\"CR32\" class=\"CitationRef\"\u003e2021\u003c/span\u003e)\u003c/p\u003e \u003c/td\u003e \u003c/tr\u003e \u003c/tbody\u003e \u003c/colgroup\u003e \u003c/table\u003e\u003c/div\u003e \u003c/p\u003e \u003cp\u003eIn this study, by using molecular dynamic simulation, and with the reference to the good adhesion of graphene to g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, and MIL-101(Fe) in terms of their chemical compatibility (Chen et al., \u003cspan citationid=\"CR7\" class=\"CitationRef\"\u003e2021\u003c/span\u003e), a layer of graphene has been added to g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, and MIL-101(Fe) to create a bilayer nanocomposite material to increase the adsorption ability and performance in the elimination of pharmaceutical contaminants including acetaminophen, caffeine and sulfamethoxazole. The adsorption process, including van der Waals interactions, adsorption capacity, and structural alterations of the composite materials has been investigated by using the Reactive Forcefield (ReaxFF) software. The adsorption kinetics were evaluated based on the simulation results. The study aims to create a comprehensive simulation test for the elimination of these contaminants to be used for the future experimental studies in the laboratories.\u003c/p\u003e"},{"header":"2. Material and methods","content":"\u003cdiv id=\"Sec3\" class=\"Section2\"\u003e\n \u003ch2\u003e2.1. Molecular Structure\u003c/h2\u003e\n \u003cp\u003eThe molecular structure for each nanocomposite was simulated based on the crystallographic lattice parameters, as indicated in Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e. For g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, a hexagonal crystal system with a space group: P̅6m2, with the volume of the cell (87.3 Å\u003csup\u003e3\u003c/sup\u003e) (Jain et al., \u003cspan class=\"CitationRef\"\u003e2013\u003c/span\u003e; Petousis et al., \u003cspan class=\"CitationRef\"\u003e2017\u003c/span\u003e). While for graphene, a space group of P6\u003csub\u003e3\u003c/sub\u003e/mmc, with cell volume: 1130.6 Å\u003csup\u003e3\u003c/sup\u003e (SCM, 2020). For MIL-101(Fe), the molecular structure has been generated from the Chemical Book (CHEMSOON, 2024) and optimized by using the geometry optimization task in the DFTB Modules in the Amsterdam Modeling Suite (Section 2.3.) (Debefve \u0026amp; Pollock, \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e). Table \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e shows the lattice constants for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, graphene, and MIL-101(Fe).\u003c/p\u003e\n \u003cp\u003eHowever, for the pharmaceutical contaminants, the molecular structure has been created by using the Amsterdam Modeling Suite software library (SCM, 2020). For acetaminophen (C\u003csub\u003e8\u003c/sub\u003eH\u003csub\u003e9\u003c/sub\u003eNO\u003csub\u003e2\u003c/sub\u003e), a monoclinic form with a space group of P2\u003csub\u003e1\u003c/sub\u003e/a, with density of 1,293 g/cm\u003csup\u003e3\u003c/sup\u003e. While for caffeine, an orthorhombic form with a space group of P2.2.2., with density of 1,23 g/cm\u003csup\u003e3\u003c/sup\u003e. Finally, for sulfamethoxazole, a monoclinic form with a space group of P2\u003csub\u003e1\u003c/sub\u003e/c, with a density of 1.3915 g/cm\u003csup\u003e3\u003c/sup\u003e. Using the Builder task, the molecules have been generated in the simulation box within 2 cycles, distance: 2.5 Å, with a 50-maximum number of optimization loops. Figure \u003cspan class=\"InternalRef\"\u003e1\u003c/span\u003e shows Molecular structure of contaminants of emerging concern (CECs).\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003eTable 2. Lattice constants for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, graphene, and MIL-101(Fe)\u003c/strong\u003e\u003c/p\u003e\n \u003cp\u003e\u003cstrong\u003e\u003cimg 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znMIfAYB+SprxV6JOaX5wVXrEPqZB7TJmrTUpjYdzVvqaa3QnJ3ZyzrGvPSkNdDXFO5nG6fXzf1jBFgfYa01eU1b3Sv85Y3q4jsaS8aWNVa+TH7dF32fwydpA59SPjp49oQOtdHZe739pXVffux21j67Ldy7LfJZ5oHvV277u9zDBh7wqX6isWVcPGlt0diOxt7HCDmNv/TQbl1T8EFPPCuu2Lr3o191aZ+2av9oizx8TX2QXeRxP0rYor5zHa2n7ssjPVVHZ26jZ4sfa/w6ukf9VB59XEs3iY6wK5ORa0BVhwlbnQFHkTPhzIBiYJUHNDnXqD1vW/fIeUInunEMZNA5WzyQxeElix3VZnR3dcomv1YHUtko3/siOa7Yr0mCrdiMTaOEXvGc9Yd24A4n9CPni8eabUwktYGuagv2agJgr8Z6ZG/yQuCzCOC7Ps/8Hv9emmdLNjMfmE/o19qiecZcGG1wVR/yyNZNnHz0LiXmnifNVe+f9Ltc7vcnMFpLNQ74Buu6/GE01sjWwAX/ku9yrXtmXc8liy7s8T3P21fvXV62jq7IeVpb95dYVP2ul/4yFzSXlvZ0r3fl+5GvwFdJga3vzZWxPzOWI50uQ3nXN7yexxayb3Zd01/rMXcUG9HmLNZY8706x7Rmeuy4xsf5Vzt53uLH4lftGuldykPPWrpJdITXlKX8eQTkFFwfdYznWRnNIXBeAv7G1eeb37PJPDtpI9Q81+ajYHHP9rU5vqJfe9p9Vl0E7O5Po3sCkGcm+RdtrwUuz7QjukPgLAQ4DDBfmDuvTjrQcdh5NNGHtXST6AivKUv58wgwPvooWHhea9EcAu9JwN8yab759RWbgjYBtfvMIDGHgtf7eefw+Uyrcih4Jt3ovioBXpywJvu3Bc/uK98m8I0Y34b5tzz3tov9a+km0RFeU5by5xFQgMA1h4LncY7m9yWgRX/0Rl5vePd4W/O+hNNzHfhGP6HA79j8CQKemXIoeCbd6L4yAf3U7hUHA/Yc1oO9DgSMSyfOz6HgBB7MCdEPBaMN5QTdiIkhcGgC+t0ob3L9rQzBGnkEa/q99qE7EuMOS0AHT65++MTfCDTwsWev7wQZ2k+wIykEQqBPgJeyr/jGmLm598/7cijoj/OhJbWA+/UVTnloKDEuBHYmQJDGmyAPmphzPNcgbuemo+5NCBD8c8D0t/X4GAdSvoV69rfAtV3tKW+CP90MgbcmwHxfSzcJLQ65/vvb/bAIi/hAfCA+EB+ID8QH4gPxgSv4wKZDwZpwykMgBI5DgAUqKQRCIARCIARCIATWCHRihltU0RFeazDlIRACryOQOfs61mkpBEIgBEIgBM5MoBMz5FBw5hGO7W9NoDPB3xpQOh8CIRACIRACIfCVQCdmyKEgznJpAvo3wfmLfFf7l2M6E/zSg5vOhUAIhEAIhEAItAh0YoYcClooI3RGAvxrMvxrG/yLH7o/Yz9mNncm+Kxu8kMgBEIgBEIgBN6HQCdmuNyhgH/WjX/r2f8N6PcZ8vfqqf4JyVmvdRDgUMC3BEv/jCvfKDz7nwOc2XlvfmeC36s79UIgBEIgBEIgBK5DoBMz3H0o4D9VoIHR5zMR5lDwmfRf1zZBPv+m/Fra8vMh/tOgjs61Nl9V3pngr7Llqu1woOQlw5b/RAb50bpIHmU1oVv/cRoyrGFX+6lb7XOe9yGgfXiLNvc3/JE1Dz9fS3oJo//HY8ucWNOd8s8nwEsxjS3rEP83S8cv3HL3rbW1zGW3+KG3l/ttBBiTtXST6AhXZTiM/jMUNrVnvGmdLTy09Yz2ah+v+Dxj+oy+PmOcCJhYvDoLFu3j290+E5B1ZZ/Ba4vOe+bsFv2R/fgaoG/xH/5XWuRZF+uHja/+D7IEZORrLcOnkSEv33bGA5cIsA7ia1vWAXxL/ukB4Np6ygsTfJIPL1pyaF0amfOVMb74BWNLYu3BJxjvzj5LnS1r2b1+eD6yx7K4s1Y8dCiguwRQNFQ3uz1Q4Iw45Six4WojHZUnb0xgiem4xmO5e48T9nMAZRHrJC0+1Okk8TmDb3UmeKfPkRkTIMBX4NQ9KOJvs4CJtQydSmy8jOHIl8k/07dW6lOuryPA2qpvmDqt6mWKHzZZ5/BL/E0BYdWlb1vXDg61Xp7PQUB7Xl1vtD7hZ2tJsp217F4/XLMh5esEOjHDboeC7qa5bvb/JHBUbci1jgK9MwRu1fbPfF5i+gy7njFO+NnsoFj7wEKFrDbO0YJV6/CM3d1DxKj+q/I6E/xVtlytHc0VvfnvrG/UmfkYeqrfsn4xhqM6+B9+mBQCIwL4I8E6AVt3HUAeH60J/0PHKPhTWQ4Eldp1nnXoG8VT8i8/SI56vmUtu8cPR20mbzuBzlrxKYcCFiZ91YSRbJY8a8HCARXIUa4PjicnVR5XbdjUk94RLhY4HTRok01XbUqeZ/IpRzfyo8ki+XpFlp+gyL7Z74M5LVe52g62MIFgQRl11H/yePZE/1WO/ehXYLHEFB20JXbYXsdEMl17ZIc4cNU4qS2VIctnLVFP/VqTpZz+aPOkrU4b1NNG6G91O+29WoY+3ZM0huKPn+AfSf8SgAnjz7yDk3z3X4ltd8xDzUXVxJ/RzVzmXomxIL+uByrP9b0J6E0rFLTOPkJEPo7Pe8IPtQ9mfXAy17pnbZutNypjz1hKe6xlMz9cajdl2wgwzmvpJtERHimT02zZNFl8WGwU1LJZ0n7VMVvw1KZvmjgl+VrEqq20QYCvxQ0np03ylNDBs+zAPh1OZKtkR1eCSdqXXdShDfLULvX09lETjTLaRRYdSpQrn3v6gG7ZXoNctx2dlFeZGdPOmGy1ZzRO9I1gnfbgzYdn+r6WFKxrfJbk0SvuuqeNzjhqcapB3FJ7n1HWYVbtku/Iz8S0+kmt907PzE8FSPKFjs8tMcIXR4dM+b4O+fgq81jjs6QzZe9JAP/QOjZbz7eQkY9Xn5NvHn0d3NLXyH5PQPs0e0NNKuusf/KXe9eymR9Wm/J8P4FOzHCLxDrCI1O2OI3q05YHIWyENQ/Z2YKnNnGimkZ15Gwur0ARB1ZCr9tFvgJ4BQmSrVfpq5MHfQQEWsQlVxdagngYIIuMkvrKhPNU+6kDiNflvvan1pPOyp+6NQ/Zrj0u69zJHwVIbHRrSYvOKLiqdVngnDH39Mfzah1/1lh43tHusXFrGo0/7O/RtbXtM8jj96wJmkdaO+q83tIX5iY+P0vyTcaA8dFaMZNP/vsSwA/dF0fzeSsdDgN130EHefgk7eGjeo6PbiV8bPmlF0OMvXyg04tH1rKZH3bajUyPQGefv0UVHeFRs1udBh1sujXIpX0WG0+zBU9t1mCTuqM6BPQe/Hsbfs+iV0/LCrbX+OgNrH8j4Lp1rwk4Cmw1odyGWV/VTzHQoQIdnlwX+arnMtx3x6RrDzpnsrRFIKrAC9lqZ7WPZ9muPo9klEcbHlyJD+Po7Uq+XpFbG/Na59XP99iHf9QDmLi+2v4jtsda4XNzj0MBa12dl7Xv+Kt8bk221s3zexBgPXvG3MX33Oeh6fse67j2Ne1z7JXKew/61+6lXgyx9rA/8lGQzrrU2Z9F6N61bOSH0pnrPgQ6McOnHAq8ezieHJLgxNMsWJkFm9Qd1QFE1e3tcO9Bozbnel1aBEft1jZ4JuhA7yiw1YLrts76qvZcDxMa3UwuuI6S6o3KlLc0JlvsmcmiHzvZWJDpBOnYJtu9z7LZr+h3hioTe9pcSxr7tbbW9DyzHBsfSfRNTB7V9YgdR6lLYAQPTzCCTcdnvJ7fL212+D7rHz5LW3obm4OBE8w9BPATf9FBntbEewmx54x8TX5PmzVpnxnVq7J5PgcB1iGNK+sd6yDrIfd8qt+NevXIWjbzw1E7ybufAGO5lm4SHeGRMgV+WzdNnIANEEfUW4kayM0WPLXJwlXTqA59q7prPS2C9Y1JlZs9j9odyUpuZLtscFtnfZ3pEVf6vHUTUd2lMdliz0wWLvRVbxTwgw73WZ8rZ8nBYPShvbWkeqNxWqv7qnJsvCeJPZzgLl736LpKHTY0/JGrJ81JfPmexNq25G+w9+AKeeYtY3tvm/fYmTrHJoAvjPzhkbmLr1G/+jwk5PeU16T9mvmSdF0CennXHed717IlP7wu3c/pWSdmuEUVHeFRN1iotm5gbIJslDiDEjrqAsTzyC61OQrYRnXQMdKjtrlqoas/a3KZpXu1O7LJ60mOALwmLcQeJMz6Kj2j9ljkVQ/O/g2H6tW2u2MivbVd6fX8may3zcKDjYzP2sFg1Ibr4p72Z4sYXNQW7S6ljs8s1X9F2ZpPj2zQQu/9F9eR/LvkyVc17rMrclvS0k+HtOb4nEE38xU/nfnxlvYjew0CM3+s+d3eshay5o8OBOiQb7I2jBLt4qNJ1ySAX7D+MM5r+zIE5C9b17I1P7wm3c/rFeO5lm4SHeGRMm2ma5ulgmAFJXqWTtqvC9AsWFGb1QHRNaqjPA+E1C46cGiSNuLRQjmqKx1cZZMH9CpHn+rTb/paf6aALJOPMsm63tpX9anmq02uasvHRvVcjvZotzMm6mdtV3o9fybrbXOvBQUdS4kAq/Kp8vD3/tZy2TT6Wtxlaefomx42bkn6iVz1PY3dFl1Xk8Vv8Y36wZ/gDCPK3L87DNhYfT57HfniSKd83eVz/74Eql/qWYGbnjuEuoGYdI90MifqOjKSS945CWjdG8Uzox7ds5Z1/XDUXvLuI9CJGW5RRUd4ZIacgessEfTpDbzkPQDFObTxuo4arOiNt3RoM1U+dWsd8hT0EuTpAEA+9x4caiKQ5zqRW1sAFXDRDw8C6Jvr4xk7kPM2sIf2WYg91b6qTP0UA67OVHK042OjeirHBrXh9WdjIlm1Kz3S6/lVVv0dsaQ+n6WkQ5P3x+XRD1tsnyX1Cy5uq8sz3pSP7HS5z77Hxi2J/o76hX9u1bWl3TPLitnI5/C3mQ/RZ/nRzB9VPtLNWrA2H87MNbbvQ0Dr7kgbvqk1V+X4InVqPuX4o+8BWr89Dzmtw0u+r/ZyPR8BvZDAT0ZrF3mMvZdtXcu2+OH5CB7X4s4+f4sqOsK1qxpY6npwLTnKCZA9GMeZkCePxYVygi/PI5+kIJ3FCTkF21yRpx6y2lRpT283JCtbtHhSj3vsdbuQo74CpCU56axXLaLURY/arLbIfmS0OLPwYk9daMVGhyrZqX5qwRZXnukHCXvQqTbIGzFV3c6YdO2hLfWzjhN8sEN2qX2N+1fjJ39gI/pqQhc84SK9VYZnymifD7IsZjVhB+Ude2rdVz5j45aEX8CPevgJ/YOlfInxkj9t0XtlWfmm1hjvq3PzfN0zZ0e+qnKumo/izhhxzziNfNPr5j4EtMdUElp78VEl7W/kUc8/2ve0d6gOMvgi84DElWf8Nuk6BBh39gP5k8cbtZdas6oPKH9tLbvHD6sNeb6PQCdmuEUVHWE3wwNg6i59fGFCh06iLC7abLX4yKGQI4CjrsvJBjkvjoiTafN2O6SbOsjQLrqQof5o00VOzo0cm/pITnbUK/ZjM3W5zgJL8rUQz9ohv35G/aQv5CsoVp1RH2dMO2MivX6d2SMudZzIh4v3fYmT9OjKmDKGNblN3PvYS3Zk60iW8cemoyds35oIFjQHNHdghS58AP9P+peAfGbkT/CD5Wx9wIfgvZbQjSxjwGfrmrOmP+XXJaD1tfYQn8Q38VElX3Pla34dHWDrvomf+h4t3bmel4DWOMYWf+F5KenAOVrbOmvZPX64ZE/K+gSY72vpJtERXlOW8hB4NgE2qW6wdY8t6GczXVsY79G9d53M2b2JRl8IhEAIhEAIXJNAJ2bIoeCaY3/pXvEWjLcNz3irzZuO0VvhIwLtTPAj2h2bQiAEQiAEQiAEXkugEzPkUPDaMUlrOxHgYMBX53seDPg6lJ/QnCV1JvhZ+hI7QyAEQiAEQiAEnkegEzPkUPA8/tH8ZAL8/Yi93urzdzxmf//jyd24W31nguVOt/wAACAASURBVN+tPBVDIARCIARCIAQuQ6ATM+RQcJnhTkfejUBngr8bk/Q3BEIgBEIgBELgewKdmCGHgu+5JScETkGgM8FP0ZEYGQIhEAIhEAIh8FQCnZghh4KnDkGUh8DzCHQm+PNaj+YQCIEQCIEQCIGzEOjEDDkUnGU0Y2cIFAKdCV6q5DEEQiAEQiAEQuANCXRihhwK3tAx0uVrEOhM8Gv0NL0IgRAIgRAIgRB4hEAnZsih4BHCqRsCn0igM8E/0bw0HQIhEAIhEAIhcBACnZghh4KDDFbMCIGtBDoT3HXyfzrwfzHwP0Lv9U+5uv7ch0AIhEAIhEAIHJNAJ2bIoeCYYxerQmCVQGeCu5IvX758/Z+gqZdDgZNZv+c/yuPTTT///PMHnGcf/vM9T/wfGfwv3ZLn/mz/b4b3J/fPI4DvuH/hK3/++edDDbIe4HtriRcLrCPMBeS3zIk13Sn/fAL83z/uW4xvXavWrNyyllVZ2saGpOcQ6Mzx2yrQEX6OmdEaAiFwD4F75qw2/xwK+sQJgrYEQAROyBOssan6h29p+HhiY0SedpTUZg4GIpIrBAjQfvjhh68+hF9xj+/w4VvAexI6pWOpPnL4LrL8z++PHkSW2krZ6wnIt3755ZcP1jA+3DPe3bHespbhr+jWOikfxKexJWl/AjBeSzeJjvCaspSHQAi8jsA9czaHgm3jw1srgi9Yc+0kAvpZgMabMAIqTwRabL410R4bZlIIiAD+44dHD9wIpu5J+JmC/Vl9gkL0J2CbETp//my9wTcYd3xtLW1Zy5D1wwZrLesday1+nrQ/gU7MkEPB/tyjMQReQqAzwashORRUIsvPbJR6k8p9J3nQ5vJsqoxZfQtG3uhQQB4bZ1IIiMDsGz78BD/yIEt1lq7ow1/x7dl6ojfIORAskTx3mda4kX9pz5i96PCed9cy/HTkqxwM0DHzRW8r99sJdLjmULCda2qEwCEIdCZ4NVQLPFcWZb2Z4TpapGv9d3omWNJbfVh3DwUzRmyqoyBfY1APC8iONumZ/uS/LwEF9dWHloggi++RVH8kL//sBIWj+sk7PgHWfta40Xqjss7be/lK9cMtaxl2cABN2p9AJ2bIoWB/7tEYAi8h0Jng1RAdCggCWMB5VkCAvrqY1/rv8qyvsvWVOWzg9Ega/XQIffodLhuhAi++JRh9e/BI+6l7XQL45ujAudRj5r/mu9aAKi/f3Kq76snzsQksBf4q66x/8pdH1jLW2qx9z/GXTsyQQ8Fz2EdrCDydQGeCVyN0KKhvfXgjvkfgW9s76zMbIJuh0h5sln5+wWGANvgQgLG5JoVAl8CWN7HoZB3gozQ7FLBO4JMEaawRtBMfFbXrXPWzHdYovQhR77YcCqjzyFomO3ztlR25Pk6AubuWbhId4TVlKQ+BEHgdgXvmrA4FHhDIYjYEdNZNQeXvcvWfDanPcOm8KZN8vRLkr71tJfCiHT68xX33cagM8zwmQBCGv3ST/2xIdWaHAq0JHA70rQIBm/JzeBXB81/1YghfIjgnMb48sybVF0lLPb53LdPhc0l3yu4nwDiupZtER3hNWcpDIAReR+CeObt0KFBg8M5vaerPhjSasH7kULC22VHOR+3TXg4Gop/rjAAHR/xEAftMzvNH8pr7Lsc9fsinHlD1NnjtoFv15fnYBNgfdODDT3TgxAdm/4BC7dG9a5kOq9XXqv4830+AcVxLN4mO8JqylIdACLyOwD1zNoeC5fEhOBodimD9yKGAjXYWuDEmHlyxKepnG4+0udzTlF6BAAEYgVs34Wt8alo7FFR5nhU86q3ySCZ55ybA2LL28emM871rGWsePjhbI89N8TjWd2KGHAqOM16xJAQ2EehM8KqQRZt6S4FBZ/Gveq/wzGEANmufrYH62k+HCK5G48GbOmx51/G4gk89sw8cBrYcCLBlzbdVLrsV+OvZrzpIJJBzKte618sJ/Stsa727dy1Df/xoje7j5czvtXST6AivKUt5CITA6wjcM2eXDgUEof7G+nU9OUZLBN/wGX1gDRvKtgZi+jp91EsdRNBbE4cJ2h19c1Fl8/xeBO45EEBo5Nvk4dv4mspFE9+d+SCHAoLApGsSwMcYe/aFzk967l3LciB4nf8wnmvpJtERXlOW8hAIgdcRuGfOsulTj6snLej5i4NO5d97mI2+IWCzhN3SpkngtMSV8pFuNmXKlnT/a2Hu3oUAfjF7c0sQ74m3r503sHrr73W517pQ/5IpPjlaR2r9PJ+TgF5IcFic+Q++Ub/F3LqW4a+jtRH/mvn4OYkew+pOzJBDwTHGKlaEwGYCnQlelfKXxajngSqLO881oKh13/kZZqPAXW9SZ+zY8GC7lPRGDh06AKgeZUkhIALyFXyxfvAzD6QI2PBbPjV4kz5dZ4cCyvUiQX/RFF28Pe6+QVYbuR6fAHuB1jR8QutRtVx+WL9ZVn5nLUMGn61+LF8cHRaqHXneRoC1YC3dJDrCa8pSHgIh8DoC985ZFn79VhQdbO5ZgJfHDU5sVjVpE+Q6Smx8fNYS/BkH2smYrNF6z3J8RP4xu/pbXQK6bvCuQGxGlgOBfmKkw8csYJzpSP6xCeBTjC17w2w9Uw/wM2RHa1tnLePwOvNh2aG2ct2PAGzX0k2iI7ymLOUhEAKvI5A5+zrWaSkEQiAEQiAEzkygEzPkUHDmEY7tb02gM8HfGlA6HwIhEAIhEAIh8JVAJ2bIoSDOEgInJdCZ4CftWswOgRAIgRAIgRDYkUAnZsihYEfgURUCryTQmeCvtCdthUAIhEAIhEAIHJNAJ2bIoeCYYxerQmCVQGeCryqJQAiEQAiEQAiEwOUJdGKGHAou7wbp4FUJdCb4VfuefoVACIRACIRACPQJdGKGHAr6PCMZAoci0JnghzI4xoRACIRACIRACHwKgU7MkEPBpwxNGg2Bxwl0JvjjrURDCIRACIRACITA2Ql0YoYcCs4+yrH/bQl0JvjbwknHQyAEQiAEQiAEbgQ6MUMOBTdcuQmBcxHoTPBz9SjWhkAIhEAIhEAIPINAJ2bIoeAZ5KMzBF5AoDPBX2DGpZr4+eefP+A6+/z111+t/v75558fP/3001c9P/7448cff/wxrffbb799IKM2saHbzlRpCt6KgPvQDz/88PHrr79+/PPPP1MGv//++83f5Hf4a9J7E8Bn8CV8aCmxPml9Q/aXX35Z9LeZrvjhjMxz8pnra+km0RFeU5byEAiB1xHInN2XNRsiTNns/vvf/37zIWjn00na6L58+fJVnAMCesmvieCNTRUZEjawwZL3999/V/E8h8B3BPAX/AufVaAmP54dDEY+vnRw/a7RZFyOAOOPD+E7fGaJAwFrIWsXH73QoO7WFD/cSuwx+aVxlebbyHeEVSnXEAiBzyeQObvvGBDEjwJ3WuHtPRvgWiII05szlx0F+gT9jOGoTfI77XkbuX8/Anpj6wdIDpj4ID6kg6mTwd94G5wUAiMCCvJHZeSxFvphU2se/uZ+OKuv/PihSLzuyhitpZtER3hNWcpDIAReRyBzdl/WowCKFtj0YN35SQ/BFrL1rau+LfBAX3mjQwEbMweJpBBYIoDPeoAmWXwKPxy9vcW3tgRv0pnrexDQtwWz3o78jXWtu0ZKb/xQJF53ZYzW0k2iI7ymLOUhEAKvI3DvnGVR998gszjnzeF83AiwYNRJ+vnG6ADBeLkeHTbI841W3yDoJ0WddiMTAk5AB07e6nrSYQGf49AZH3M6uYfA2qFgRAk/87VtJON58UOn8br7TsyQQ8HrxiMthcCuBDoTvDZI8EngSkCgQJQFHV3+FrvWe+dn+HTZwHE2LioTd5jqDRsbKgcJjQ+bZlII3EtAh4LqR8x7fE2+yNXXgnvbS73rENh6KGDdwo9GL0JmVOKHMzLPzWec1tJNoiO8pizlIRACryNwz5zlGwF+b+yBqQIIFuqk7wnAq7PhieNsXMjnU9/Owl1lbMidtr63Mjkh8C8BDgN1nv9b+r+fxGktwPfwu6QQgED3UMAeIj+7d+9AR/zwdX7HXF9LN4mO8JqylIdACLyOwD1zlkDh3gX8dT07Tkv83YDu1+L3Hgrorb+9zfgcZ/zPagn+VP9ey6gv/FRNP3mr3yqM5JN3fQLdQwH7j3+o5y+btpCKH26hdb9sJ2bIoeB+vqkZAp9KoDPB3UAFrfn7A05l+Z4AvfvTIfGdjYs2UP+mgE2UoIyAjHwObcjlYLA8LimdE+AvH2/xH/38o/79g3kLKbkyge6hAAYE8/6m/5G9JX74fK+a7U3ecg4FTiP3IXAiAp0J7t1R0PrIwu363uG++9MhsVDgr2e/jsrYgD2AY2PUm9uMk9PLfYcA/nPPG1vq8EkKAfzg3r2l+63qjHL8cEZmn/zOuOZQsA/raAmBlxPoTHA3SoeCbP5OZX6/5adD0qKfAdWv0fUvCvmmqTdj/s0BepDlMOKy0p9rCMwI4HMcMKvvzeQ9nwNo1gUn8r739xwKoMXLDNatR1L88BF663U7MUMOBescIxEChyTQmeDVcOrwIfCsafbv9Fe5d3kmwPK3+J1+618Tqr/n5hnu/lMkNkDy6qGAdqSn02ZkQuCRAwH0+OlQ/k5B/AgC9x4KqPfoT9Dih8/1QfabtXST6AivKUt5CITA6wjcM2cJcqnHWx1/o0hAsDUAfl1PP6cl3nrV4N4t4WBVA3q95a8seUafH8b0TcHoZ0LI582t0879jADzGF9x35IsPrZ22EeG9SApBCBwz6EAH+Sbzboeoo+8kW9W2vHDSmT/507MkEPB/tyjMQReQqAzwashLN4Ep9TlygbAYl4PCbXeuz1zGIDPUoIbHOsbVp49n6DMn10nwT9lCtwYH+5pm00yKQSWCOAvzF18kbnsH/LxLWRI8kPexipIw8+pI5mltlJ2fQL4hfaHUYDPmoRP4TMqpw6+pjXMKWktxD+V4oci8forY7eWbhId4TVlKQ+BEHgdgXvnLIs4gQH1+RCYJij4dtxgwmcpUT4L3gm2dGhgw9QGOtLHNwWSZTwYmxwIRqSSVwko8Ndcrld8SYk5TjAnmVkgJ/lc34uA+4Z8hDxP1YdY//Cx2frGOoaMr6VVR/zQCT/3nnFdSzeJjvCaspSHQAi8jkDm7OtYp6UQCIEQCIEQODOBTsyQQ8GZRzi2vzWBzgR/a0DpfAiEQAiEQAiEwFcCnZghh4I4SwiclEBngp+0azE7BEIgBEIgBEJgRwKdmCGHgh2BR1UIvJJAZ4K/0p60FQIhEAIhEAIhcEwCnZghh4Jjjl2sCoFVAp0JvqokAiEQAiEQAiEQApcn0IkZcii4vBukg1cl0JngV+17+hUCIRACIRACIdAn0IkZcijo84xkCByKQGeCH8rgGBMCIRACIRACIfApBDoxQw4FnzI0aTQEHifQmeCPtxINIRACIRACIRACZyfQiRlyKDj7KMf+tyXQmeBvCycdD4EQCIEQCIEQuBHoxAw5FNxw5SYEzkWgM8HP1aNYGwIhEAIhEAIh8AwCnZghh4JnkI/OEHgBgc4Ef4EZaSIEQiAEQiAEQuDgBDoxQw4FBx/EmBcCMwKdCT6rm/wQCIEQCIEQCIH3IdCJGXIoeB9/SE8vRqAzwS/W5XQnBEIgBEIgBELgDgKdmCGHgjvApkoIHIFAZ4Ifwc7YEAIhEAIhEAIh8LkEOjFDDgWfO0ZpPQTuJtCZ4HcrT8UQCIEQCIEQCIHLEOjEDDkUXGa405F3I9CZ4O/GJP0NgRAIgRAIgRD4nkAnZsih4HtuyQmBUxDoTPBTdCRGhkAIhEAIhEAIPJVAJ2bIoeCpQxDlIfA8Ap0J/rzWozkEQiAEQiAEQuAsBDoxQw4FZxnN2BkChUBngpcqeQyBEAiBEAiBEHhDAp2YIYeCN3SMdPkaBDoT/Bo9TS9CIARCIARCIAQeIdCJGXIoeIRw6obAJxLoTPBPNC9Nh0AIhEAIhEAIHIRAJ2bIoeAggxUzQmArgc4E36oz8iEQAiEQAiEQAtcj0IkZcii43rinR29CoDPB3wRFuhkCIRACIRACIbBAoBMz5FCwADBFIXBkAp0JfmT7Y1sIhEAIhEAIhMBrCHRihhwKXjMWaSUEdifQmeC7NxqFIRACIRACIRACpyPQiRlyKDjdsMbgEPgfgc4ED6sQCIEQCIEQCIEQ6MQMORTET0LgpAQ6E/ykXYvZIRACIRACIRACOxLoxAw5FOwIPKpC4JUEOhP8lfakrRAIgRAIgRAIgWMS6MQMORQcc+xiVQisEuhM8FUlEQiBEAiBEAiBELg8gU7MkEPB5d0gHbwqgc4Ev2rf068QCIEQCIEQCIE+gU7MkENBn2ckQ+BQBDoT/FAGx5gQCIEQCIEQCIFPIdCJGXIo+JShSaMh8DiBzgR/vJVoCIEQCIEQCIEQODuBTsyQQ8HZRzn2vy2BzgR/WzjpeAiEQAiEQAiEwI1AJ2bIoeCGKzchcC4CnQl+rh7F2hAIgRAIgRAIgWcQ6MQMORQ8g3x0hsALCHQm+AvMSBMhEAIhEAIhEAIHJ9CJGXIoOPggxrwQmBHoTPBZ3eSHQAiEQAiEQAi8D4FOzJBDwQX84Z9//vn48uXLx48//vjx22+/fdMj8nGEP/7445v8d3v4/fffP/773/9+x+fMHDoT/Mz9i+0hEAIhEAIhEAL7EOjEDLsdCghMCUh/+umnr0EojROk/vLLLx9///3316D1zz//3Kdn0fINAbgT8MI8h4Jv0Hx94ED0888/D/l8L32enM4EP09vjmUp69mvv/768cMPP3z1G9aypYM1a5x8jDp1HnZ6x/qo9fOZ7XFARr/W6KV+deyOzOcQOLqPbvHnStDnHnvbX3/9VUXyfAeBrT7zyBjKPL2wZL1ZG8tH2ovPiPj82okZdjkUsMmwEbLRcI/jkdgo2Ry1sTLgSc8hoG8E7glGnmPRsbTie0yIK/HpTPBjjcI5rGH9IjjnwxpGWppfBCyscbwAoS51WAt57ibWTcaTdkjyV/JreqQ96UUHtuogo37WtvJ8TAJH99Et/lwJs0Yzf3wu8Zz0GIGtPvPIGMpS1kDWRsV+igdHh7xH2ovPiPjytRMzPHwo0ECygeJ0o6RN7EoB2aifn5mnzT6Mx6NwRT6dCT6mkdwlAswh2Nb1jA2OfG1w0sHbrxq0aF3svIWnHR0qpJOrNtQasD/SHjqpr0Tb9Cnrhoic43pkH93qz5U4c8n9kTk0mne1Xp6XCWzxmUfHEEu057IWemJ8iRc9PdpefMZpzu+ZR2vpJtERrsrYrPQtQN24qiyO4RO9luf5MQKagGE85nhFPvfM2TGd5DoB1jQPnFUmHyKwVlIeX13XxPjUza/K8KzNuh4gRrpHedLZaU/fDKgOV+pl3XAix78/so9u8ecR6do3+TzXpPsJVK7SJL6+rj06huhmDWVtIeD3NNI9yqOObButr66z9k314jNO6X9r/bc53z89dChgoBh0NppO0lfjLoszcMpDj0571Yk4UOBgyPKtA3I4AfccRvRbMvTKJndw9PFMHdpho67Ogh45MXL0yXXUdrBF+pCrNmPLqN16akYGLvQJm+iT7CCP51Gq3NRv8pWqbuXXvhCM0BZsaHvUF2yDGzKjj3TPrrX+aAyQgSU2kJwx/RulqrfapjrIUeZ8VAZjBUvIcA+joydsvSe5rzPuCkZhj86Zz93T1hnrwEA+WO2njHmvpHk3Wts0j9d8SfNqxJ32GCOlR9vTW1etbcwL+rNmo9rP9RgEjuyjW/x5RFM+rr2SNRudSY8R2OIzj44hMURdK2W99mKtQeQ/2l58RnSXr4zJWrpJdISrMgXFo0Cryo6ecQQ+2pDYWLGDPAWmbGIK2Bh4Nlpttv/3f//3TeCIHTgadmnjRg/6ZCMbrwJg34RdRkGTAgOcWE6HfdzTDjrFQLLqJzooQw4b+HBPfa5K9Jm2yeeeMtoTi6qXesigGzmSZNGhfipfuiWLHW63vsGhXPa5DvRQ5rp5Vr+1cH81ZPIHnL3fPFOfD/aQyBNj+sw9ummr9kHNbLGrykoH7XpgrKCJPNkm2aNdYbo10Se4w5R7/JR7Xe/RudWGo8vDAEajRJkzwld5xr9qUpkOXbVcz1Wn8rmqTL4onY+0x7zSGsjYMweSzkUAvziqj8pnR0RVJn8eyZDH+k//kGf/X5Of6Un+vwS2+IzG6d/a/96pbGlMtN+yXtWkMtYeJenUs19VttQe8vEZpza+h+Vaukl0hF0ZQYQGa7RBuezonsCT+ujxNApM5UQsEnIMb1MbpYJZdEovedUxFfix2JDYFLFFusnjvtbTRuqBMO1o8ao2IV+TdLisWODUntQvz6NtbPX6lI+4kS/dVV66a8CC7tpvJm/dgKSXdteSZN0G+jrqB3m0pfFDN/XIR4+nLXbNdNDXqle2cdg6coLJ1qSx8HHHp5Rfx36r/ivIj+ao+gVz565n923Jao5V/1I5V/ml6/Tyqr8+u2ynPZfP/XkJHNVHt/rzeUfgfJZ3fWaPMVzaT6r++lzJLq15VTbPywRm+4zXukUVHWGv6APJ/daEg/pJUfUJBrHFg1C1NdtctRlKh1/RU4M7HQLUZ7VZA9xab9aOgkgF9dKnZ7dHQb0OJJRpAlWOas/zYQa7mqS3MlrTXfXARFxUxjO2eNKY1HyX0T221UB/ZteWtrbIyl7nIz+ob0r1zUunb+rjZ1zrOHVs0MbgB2DqKX/ksx29V5LRSwN8VnMPH9E3lr42MQZ8JOccNH/d57yce/nlbCyr/vrs+jrtuXzuz0vgqD661Z/POwLns7zrM3uMofb30R5a9dfnSnZpzauyeV4mMNtnvNanHAoUjI0cBuPYdDEeZyHJaWabqzZD7xj3Cs7lVKMrMiS9aSc4IogdpVk7sk/9UVA5sld998HRBFJ/1bbaU776o3Ykx1U21DbXdLsO7sXI88mrBxG154cbrzO7pw+wrmMsedqq/VNbNX+LXdLhfHSQUp/rtfZZNh7lir1bk/pY6+lgO/P9Kn/1ZzZQHZS44jdaI9znxRP/qknz132uysgvZ2NZ9ddn19dpz+Vzf24CR/TRrf587hE4n/Udn9ljDBV31D0bYlV/fa5Ul9a8KpvnZQKzfcZr3aKKjrBX5F6DtTWQkBOMHAa92tyQI0l+trlK/quw/aF6TIROIphXsMob+foGea0d9UcTYmavuMkmyau/yld7yld/1I7kuKqstrmm23VwX20jT29IdYAiD6bIdseeuthNgEUdBaHqm+xAZ+2f+lbzt9glHc5HbOpbc9ly9CustqbR+KJDAW/1+a36ryyvQ4L7PD4J0+rHcFgqc06zMUGmli3pXCrz9nJ/XQJH8NHqs057qczlcv86AiOfWRqnpTJZrf2WNammUdmSzqWyqjvPywRguZZuEh3hqkxBGQHFliSn8K/hvb42NwWhkveAbiTvedzrrfyWn0QQICpYxD7ZgD7ZVduRfeKg+v5G0evAmomoJHn0eFJ7ylc7SxOtMlrT7e1xP5qAcIQF7cKHD4em0c+/qj6eVV98yJvZRfu1f7N+S2/HLulwPvpGp3toHPXtM/PumbOj8aUPjOVsPn5mH4/Stnyl+rwOUyMf0mbra8ioP5Krh1PqMV6+VuzR3siG5J2fwFF8dIs/n5/6uXsw85lHx1BrV10vocVLFdY1jwcebe/co/A66zsxw0OHAgVaNLS28dFtD8gIQKhHYFcTjuQbodrx+l6HoHDWWdpBV91wqe9v/Fwf95os3uasnfrWnD5hzyjIwg7KfELQBnn005PaU77qIlv7M2O0ptvb4x7dfGqChw6B9Av7qw21jp7hX1nM7KJt+u1Jfav5yHTtkg4fT43T7PC25B9u32fdj8ZpzRYtvi6nBXzE1+Xe9V6HT3y4rlea+/XFg+bqaFOsHPWtWT1YjHSP8tC3pb3afp7PT+BIPrrFn89P/rw9WPKZPcaQtY89qsYJI92jPMjO1rvzUv9cyzsxwy366wiPuqM3VzhAHXyXZ9D94KCg0INj5BWgeECmgA4do6TgedS+2+ftMyEUDKKf4LImmHgQOWuHNggYvH3Jej/QzzN63RaxwA5P0uH5yqvcNHncXnSt6fb2uMe26gvYXNur9Zae0VcPBVoEvG9qnz56QgYdNX+LXdJR+ShIpn8+fuiusm7TEe7rOHVsop/Uw1+U5CM6PMOhBr+SfbcrHHSoxSdGqb7EQAbZypl85n31efKYH3WO8Uy+rxXo2NLeyN7kXYvA3j6Kvjr/t/joFtlrjcR5erPmM1vHcOQziknqusl6yhrmaWt7Xjf3fQKdmOHhQwHmKNBgsHEABlgJxyCYq4sMgQeOgZEKyKlHnoJ16fCgxXVTzjPtomcUxHk7yGALbbDZyiYFjNihwBBddUOmLjqwT3ZQhzwPsrAL3dTnoyCAK8/qr/qHPnT4oQc71C+Xl17ZgU6Yyzb65vLS7QGH63a70Y1ePmKDjdiB3TDRhzZpWxzUl9FVtmEDdbhq7Omzxk3t05brFWPs0PhstUs6aNd1OE/axVbaqXKjfn12HuO0NcGVfqp/6j/9ZkzxFz4+/lvbuII8/dcagD8s8RBDzTHNcz07D3QxbrD2xLPny1+rHHW2tOdt5P5aBJ7ho6wP+CEfX4Mht8VHt8hea1SO3ZstPtMdwyWfYQ1kv6Fd9l1/rqS67dV6ee4TYF6vpZtER3hJmYI9bXroI/BgY/UgzHW4kyBPXQWIklNASbk+tEXiqjxdka9J7UimBj3owVa3HT04sifZQiCLo6OPeh5Yuzz1FZTPZGWTX9f6hV7Zgh0wow72M7HE23VyT52ZbnRUeY2F3urXcj3T5lLCXrEVV9nBM4vKrH31U21xpS6pa9eSDvRUnixcYrjUr88ug8U9if7it9THf+BIf/nwjM++c5K/cCU47/iC+xC+cnx+XwAAFlNJREFUTr1RWtoUWUc0Txgf+flIT7e9Ud3knZ/As3wUX8f3+Iz8fouPbpE9/4gcvwf3+ExnDNd8hr1d8RJ7Sz1sOrlOey6f+20EOjHDLaroCG9r/nrSmlTX69lyjwhOmNhcOQBwrw+TnAn/Gemodr2KRebsq0innRAIgRAIgRA4N4FOzJBDwYYxfsdDgd5ILmGCy6vTUe16JYfOBH+lPWkrBEIgBEIgBELgmAQ6MUMOBRvGTj+52FDl9KJ8E0C/Z4ngnG8NXp2OatcrOXQm+CvtSVshEAIhEAIhEALHJNCJGXIoaI4dwS9A+XD/Lkm/2+e3zgT//OZPPyPi99F8PiMd1a5XsuhM8Ffak7ZCIARCIARCIASOSaATM+RQcMyxi1UhsEqgM8FXlUQgBEIgBEIgBELg8gQ6MUMOBZd3g3TwqgQ6E/yqfU+/QiAEQiAEQiAE+gQ6MUMOBX2ekQyBQxHoTPBDGRxjQiAEQiAEQiAEPoVAJ2bIoeBThiaNhsDjBDoT/PFWoiEEQiAEQiAEQuDsBDoxQw4FZx/l2P+2BDoT/G3hpOMhEAIhEAIhEAI3Ap2YIYeCG67chMC5CHQm+KxH/EtS+t9z+c/nzvK/OM/6k/wQCIEQCIEQCIE5gU7MkEPBnF9KQuDQBDoTfNQBDgAcBPinZUlceV76/yhGeq6c9/fff3/wf2HAmA//Qd/SP0UMQ/0/Jhy2+Kd7t6YvX77cDmpr7W2RdTv++eefb/qVw6DTOde9+xw+ujaW9/qMqOA7/FPQrBXPbC8+KuL7X+Mz+zM9k0bm7Vq6SXSE15SlPARC4HUE7pmzBLvUY3P3xDcH5P/++++e/Zb3BP/+7QlBCgEXfNhUa4IZZQRdJGS2sqwHNcYDG0YHkS2y1VYOGxx23E70JZ2LQPU55jWHUnwGf63pEZ9BFzrRz4e2FLjzvHd78dE6evs8x2f24XhmLexLa+km0RFeU5byEAiB1xG4Z87yBnsUsCqQJRh990RQQrBTE98A1KCLgEgHCJdXEEYAtZbEvh7IaK/asUW2tqsDITqU9J8A6jnX4xOQz9WDvcYX//X0iM9Ij14auD+rvWrHI+1JZ3xU5Pe5xmf24Xh2LZ2YIYeCs49y7H9bAp0JXuFoc/dNFxlt5O9+KODNPFxHHMTOg3fl1Z8LiWcNmOp48EwQR5v1jetI9xbZ2taob2qjyub5uAT4Rgp/qXMYi+UfHrwrr+Nfo14roKwHVG/PdT/SXnx0NAKP58VnHmd4BQ2dmCGHgiuMdPrwlgQ6E7yCURBYA4qlTaPquPKzgnk41aQy/fyGcgIlxmH0Mx/yedu/lAimkOPbhprUnn7es0W26tIz9tIW9qKPvnQOLqqf6+cTmM1hLFOZfsq2h8/o20X3e1FQezoo79FefFR097tqnOq6H5/Zj/EZNHVihhwKzjCSsTEEBgQ6E7xWq5sDmwRvFXm7p+Cz1nmnZwXiowBIZbBSYgxm46AyAqVZGumUrMr0hlbP3v5MVvn1qoMAtnE4yIGgEjr+s+awAn+3WGVcSXv4TNU5ak9+tEd78VEnvM+9xjA+sw/Ps2qZ7VXenxwKnEbuQ+BEBDoTvHZHmwObtzZwBYijt921/tWf9ZtmAuYazIuXgnI9z8aBfD7IzZLGQzpdrurfIut6cn8tAvoLoyOfkY9wJel5JFv9a0aJuvixdLpc1V+fXbbbntfJ/T4E4jP7cDy7ltle5f3KocBp5D4ETkSgM8Frd7RpK1DVz0j4lgB9+hlArfdOz7z1hAVv6PXbbH5CwTP5+hZhLchBlo9YjxhqPDpB2xbZUVvJuw4B+SLzlsMrH+Yuh1l8Tm+E9/CZHAqu4TfxmWuM4yO9YG1YSzeJjvCaspSHQAi8jsA9c1ZBQg1UCSoIKPgoEH5dT47XEpwUYLGZEnBpU1XAlUPB8cbtXSxivuogzzrAQVW//edZ3/ppvncOnTN2ORTMyJwrPz5zrvF6hrWdmCGHgmeQj84QeAGBzgSvZihIqIcC5Ags0JlvCyq1j68HJdjw8UOT8r6v8fFVlvKlpIPFUtCmsi2yS22m7JoEmLf4m//l9j18RmsG15pq2R7t1Tby/DwC8ZnnsT2i5rX9CJtvO1ZH+IidjE0h8K4E7pmz2sTZvGtS2Wjzr7Lv9qwDk/5CpfpPAMY48BbOk/5uggdoXq57yfEtRE3asPUXwLfIVl15vjYB/E++6P887h4+Iz+svg9RfVuBDGmP9q49UsfpXXzmOGPxKks6MUMOBa8ajbQTAjsT6Ezw2qQC/9GhQL+l96Ci1n/HZwVFBO41+J8x0085RoFUZaifJXV0b5Gt7eT5ugQUnOsA6T191GfwS9Ya9NQ00j3Ko95srlSdeX4NgfjMazgfqZVOzJBDwZFGLLaEwAYCnQle1elQMAr8edPI7+hrcFp1vNOzgnvY6Hfa3n/ejMKsBmM8j/5+Bocx6nhSG3rbqjLarIHYFlnpyfXaBBRs8zOz0dzd6jMjH1Ub7rv6VqAefLe2d+3ROWbvNJ7xmWOOz7Os6sQMORQ8i370hsCTCXQmeDVBhwICVn1bQCCht0Zs6En/+/fdxWS2cYqTvklQUM9fRGZs9FzlCPZr0iHC/zUoxmh0ENkiW9vJ8zUIMGeZq/gmvlYD89rLrs/Il6uP0h4HVD7ccyDw53vbq/Xy/DwC8ZnnsT2L5k7MkEPBWUYzdoZAIdCZ4KXK7d8tJ3BVQIEefjOvQ0Kt827P8CAgh0kN7GcsCNAIpKhLsDRiSYCPXgK0UeLARrnGw9/KVvktsrVuns9NAN/CR/A3fGnka6MednxmyUcJKmlP84ODCHmz1GlvVjf5+xKIz+zL86zamLtr6SbREV5TlvIQCIHXEbhnzrJRU68bSLyuN2kpBEIgBEIgBELgWQQ6MUMOBc+iH70h8GQCnQleTcihoBLJcwiEQAiEQAhcn0AnZsih4Pp+kB5elEBngteu51BQieQ5BEIgBEIgBK5PoBMz5FBwfT9IDy9KoDPBa9dzKKhE8hwCIRACIRAC1yfQiRlyKLi+H6SHFyXQmeC16/rLxTU/zyEQAiEQAiEQAtcl0IkZcii47vinZxcn0JngF0eQ7oVACIRACIRACDQIdGKGHAoaICMSAkck0JngR7Q7NoVACIRACIRACLyWQCdmyKHgtWOS1kJgNwKdCb5bY1EUAiEQAiEQAiFwWgKdmCGHgtMObwx/dwKdCf7ujNL/EAiBEAiBEAiBj6//R9EahxwK1gilPAQOSiCHgoMOTMwKgRAIgRAIgYMR6MQMORQcbNBiTgh0CXQmeFdX5EIgBEIgBEIgBK5LoBMz5FBw3fFPzy5OoDPBL47gad37+++/P3755ZcP/gnXpcT/+/Djjz9+/Vr2hx9++Pj1118//vnnn2EV8ilHjrFD/0x2qODj4wO7fv7551t7tD9Lj7T3119/ffz000+tdmbtJ/95BL58+fKN3y35wRafmVn8559/3vwBf//jjz9mopt8tCr5/fffb/1aa6fWzfNjBPAT1ifN+5FPud+xNrJObElb16R726MdrZP3rrVb+nUW2U7MkEPBWUYzdoZAIdCZ4KVKHhsE6kY0q0JQzxiwOWoj5Zn7GuzzTD4fNl9tWiPZWXtswBwodJhAD4ETzzU90h51aQcOJIID+kXAlvT5BBhvxodAncSV59EBdovPzHrGuDP+8gfam/nDI+1JLzo0P2gHP096LgHGGB/SvGcMaqp+x7qA/Ei21uV565r0SHvMBQ4FJPnVaJ0c2XnlPObTWrpJdITXlKU8BELgdQQyZ5/HmkAEvqNAi1bZCBXgywoFZ9RTAKUyBdYe4KgN3s51ErZwCPCkgK2+uX2kPen0dujrjIXL5f65BBTg1PHWmDHunrb4jNfTvQ6INaBSwOb+TJ1H2kOn+xhtM5dqn2RbrvsQYK2C89ILCvkdfuaJ9Yh6nbRlTXqkPa2r6FBijaWP7546DG6UOsLvDjT9D4EjEcicfe5owNeDFG+NjZSgpSYFZ15PgdVo80SOdka6XLc2ydEBgvqu+9H2FCT4poqd3ie3LfevI6CfRIxaxA/80LjFZ0b6yFMgVw8hI92jPOmtPqp8v476Rr0cCpzSvvdar5YOBLQ4W6dm/lGt3LomPdIeL2yq38jOate7PcNlLd0kOsJrylIeAiHwOgJb5yyLJUEDX/nWTZ5NAX01/3W9OV5L8NgaCCsw0lfX9Aqm6PI89VabVX0Dp3Jd9aarfgNBuTZQvbV9tD304CMKFHjGb+IbGo3Pu2qsRxaoTD/n2OIzI33kaV2QTpfDp/0Q8mh78lt9K8Fcwg/l19527h8noHnOOC4xJqBHhrGoSeudxqyW61lj21kD92gPv8Ve/BZ9tDt6oSL73uXKOK6lm0RHeE1ZykMgBF5HYOuc1cJI8OCbuRZhz3tdL47bEnxhtSVpk/QgX4E/15pUtrZhKeBDf00qU9AunY+0x2aqgBC/8P7U9vP8OgIa61GQrjL5SH12K1Umn/Eyv2cOzNYZlbF+kKRT7bsela21h5/hb+jG/0b9dL25v5+ADnFrAb3WNMawJpUxVktpy5oknY+0p4MAfsThYG19XbL9SmWzuex9zKHAaeQ+BE5EoDPBvTu+MLLxasNlI0bX6C2013+3e5iMNqYlDrBkE1KghKwCoqUgfa0dbOGzFHBJ/x7tLfUxZZ9HgAAOP9BYuyUad/nIFp9xPbpXcIaeUar667PXkW0ju10u968jwDrFmDEm+JWeGSvtDVhDOXLk17TmI5JfGv+qvz5LB9due14n9/8SYBzX0k2iI7ymLOUhEAKvI7B1zrLYKnFA0CFAG4IHspJ75+tsI1xiwmGrvg3dsiHOdGMLHwV8Llf112eXXdpwXS73xyTgP/nQ/CVP44qPKKDb4jOj3q4FYFV/fXadSz7pcrl/DQF8ROOF7+jnQ/gU+RwQlCffYgxrWvMRyS+Nf9Vfn6WDa7c9r5P7fwkwtmvpJtERXlOW8hAIgdcReGTOErjqmwMC2bWvkF/Xq+O0BN/RRjizkA11xHHLhjjTjS18ciiYEXqffAI6+RTBGz7nwZxIbPEZ1fHrWgBW9ddn1yV7CfiSPp+Axnb0sx/8ibHUWrZHkL40/lV/fXZashv7krYT6HC7ke0IbzchNUIgBJ5F4JE5y7cCLNS8DUKP3go9y9Yz6oULjDpJgdro2xZtclxrWipzWW2qS4cClS3pXCrz9nJ/LgI1kMP6LT4z6y1zYLbO1LI92pvZkfx9CSi4Hq1v+haBl0WkJdmlMrd4ad2pZUs6l8q8vdyPCczmskvnUOA0ch8CJyLQmeBL3WHR5w3j6F+EWKr3LmXwHW2atf8cBAjKRgcCZPV3NvTNjNdXMIfMUpJc/WkSdRhHbNXBbo/2lmxJ2bEIKIjzn3xg4RafmfVIvlV9Wy8TFDju1d7MjuTvS0A+M1vfWE/wJ5LGevStgtYafG0pSa6zBu7R3pIt71zWiRlyKHhnD0nfT02gM8GXOsiGwIGAty9J3xOA72zTlPTagQA5ZNA12lTJo6wGXdKvK4cB5OqmOtI9ypOebnuSz/XYBBhrjWk9WG7xmVkv8Tf8rh5GR7pHeehd8sdZu8l/PgEd+EYtMeb+skg+xlh6mvmHy3C/5AMj3aM89HTbq+3n+X8EGNe1dJPoCK8pS3kIhMDrCDw6Z1lgWXyTxgTgu3QoYKOjXG/oXQtv4vgWRkmbmcvqjRhlntDLQa1uwIyVv5mljt7A1aBtS3vedu7PQ0D+h59WH1IvtvgM/lhfEJCnv7cgnVx5M1y/mSB/S3uuL/evJ6Cf7fg6hRU63LkvKK8ePFmPRnsIdX2tQ++WNWlre6+nd84WOzFDDgXnHNtYHQJf3+A9goFNoS7yj+i7Ul1tSmx6dXOjnwRkCoA4GPiHfBZfD+olTxn36ORez85OP/uoX8lz0PAAjY3Xn13Hlva8Xu6PTwDfYd7im4z/0hze4jPow2+rPp49X3+pucpBbkt7xyd9fQtZt/AhHQCW1hQdBBlj1hd/dlLyF/zJ09Y1yfUvtedt5H6ZQA4Fy3xSGgKnJtCZ4Esd5M2NNoMluXcrg2v9cIDypMC/yunZv3pXPW1syLARw5+8mrSpzoIuNnJ0sOnWt3yuq9ue18n9sQno7S7+h/+MDqy1BwRxHZ/xIKzq4JCsQwNtL60b3fZqG3l+PQHWCPyI9aizpuB/kmWNG/lfPRh6r7auSZ32XH/ulwkwxmvpJtERXlOW8hAIgdcReHTO+hui11mdlkIgBEIgBEIgBF5NoBMz5FDw6lFJeyGwE4HOBJ81xZs+6i+98ZvVTX4IhEAIhEAIhMC5CHRihhwKzjWmsTYEbgQ6E/wmXG70M4QcCgqYPIZACIRACITABQl0YoYcCi448OnSexDoTPAZiRwKZmSSHwIhEAIhEALXI9CJGXIouN64p0dvQqAzwWco+Eus/J2CpBAIgRAIgRAIgesT6MQMORRc3w/Sw4sS6Ezwi3Y93QqBEAiBEAiBENhAoBMz5FCwAWhEQ+BIBDoT/Ej2xpYQCIEQCIEQCIHPIdCJGXIo+JyxSash8DCBzgR/uJEoCIEQCIEQCIEQOD2BTsyQQ8HphzkdeFcCnQn+rmzS7xAIgRAIgRAIgX8JdGKGHAr+5ZW7EDgVgc4EP1WHYmwIhEAIhEAIhMBTCHRihhwKnoI+SkPg+QQ6E/z5VqSFEAiBEAiBEAiBoxPoxAw5FBx9FGNfCEwIdCb4pGqyQyAEQiAEQiAE3ohAJ2bIoeCNHCJdvRaBzgS/Vo/TmxAIgRAIgRAIgXsIdGKGHAruIZs6IXAAAp0JfgAzY0IIhEAIhEAIhMAnE+jEDDkUfPIgpfkQuJdAZ4Lfqzv1QiAEQiAEQiAErkOgEzPkUHCd8U5P3oxAZ4K/GZJ0NwRCIARCIARCYECgEzPkUDAAl6wQOAOBzgQ/Qz9iYwiEQAiEQAiEwHMJdGKGHAqeOwbRHgJPI9CZ4E9rPIpDIARCIARCIAROQ6ATM+RQcJrhjKEh8C2BzgT/tkaeQiAEQiAEQiAE3pFAJ2bIoeAdPSN9vgSBzgS/REfTiRAIgRAIgRAIgYcIdGKGHAoeQpzKIfB5BDoT/POsS8shEAIhEAIhEAJHIdCJGXIoOMpoxY4Q2EigM8E3qox4CIRACIRACITABQl0YoYcCi448OnSexDoTPD3IJFehkAIhEAIhEAILBHoxAw5FCwRTFkIHJhAZ4If2PyYFgIhEAIhEAIh8CICnZghh4IXDUaaCYG9CXQm+N5tRl8IhEAIhEAIhMD5CHRihhwKzjeusTgEvhLoTPCgCoEQCIEQCIEQCIFOzJBDQfwkBE5KoDPBT9q1mB0CIRACIRACIbAjgU7MkEPBjsCjKgReSaAzwV9pT9oKgRAIgRAIgRA4JoFOzJBDwTHHLlaFwCqBzgRfVRKBEAiBEAiBEAiByxPoxAw5FFzeDdLBqxLoTPCr9j39CoEQCIEQCIEQ6BPoxAzfHAqokE8YxAfiA/GB+EB8ID4QH4gPxAeu5QNrR4jboWBNMOUhEAIhEAIhEAIhEAIhEALXJJBDwTXHNb0KgRAIgRAIgRAIgRAIgTaBHAraqCIYAiEQAiEQAiEQAiEQAtck8P9JqAvIqTW+dQAAAABJRU5ErkJggg==\"\u003e\u003c/strong\u003e\u003cbr\u003e\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec4\" class=\"Section2\"\u003e\n \u003ch2\u003e2.2. Molecular dynamics simulation using the ReaxFF software.\u003c/h2\u003e\n \u003cdiv class=\"BlockQuote\"\u003e\n \u003cp\u003eA simulation box consisting of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene nanocomposites bilayer membranes was designed with 2205, and 3577 fixed number of atoms respectively. In this study, the membrane surface area was designed with a dimension of 66.3×66.3 Å\u003csup\u003e2\u003c/sup\u003e, and with the simulation box size of 66.5×66.5×70 Å\u003csup\u003e3\u003c/sup\u003e. For g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene and MIL-101(Fe)/graphene, the concentration of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e was 40% from the whole system, while MIL-101(Fe) was 22%. However, the distance between g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, MIL-101(Fe) and graphene layer is equal to 3.316 Å. The NHC thermostat simulation method with MTK barostat (Yong \u0026amp; Zhang, \u003cspan class=\"CitationRef\"\u003e2013\u003c/span\u003e) was applied with a density of 0.255 Kg/L. A force field containing all elements available in the precursor (C/H/O/N) for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and (C/H/Cl/Fe/O) for MIL-101(Fe)/graphene nanocomposite membrane were selected from the software library (SCM, 2020). The simulation box’s specific temperature was chosen as 273.15 K with a damping constant equal to 500 fs. An external temperature of 500 K was applied on all the nanocomposite materials in the simulation box during the process. Figure \u003cspan class=\"InternalRef\"\u003e2\u003c/span\u003e shows the simulation box consisting of 60 acetaminophen molecules on MIL-101(Fe)/graphene, and g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene nanocomposite materials.\u003c/p\u003e\n \u003c/div\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec5\" class=\"Section2\"\u003e\n \u003ch2\u003e2.3. Geometry optimization using DFTB.\u003c/h2\u003e\n \u003cp\u003eGeometry optimization is a computational technique used in the field of molecular modeling and quantum chemistry to find the most stable and energetically favourable three-dimensional arrangement of atoms within a molecule or a material (Kanatani, \u003cspan class=\"CitationRef\"\u003e2005\u003c/span\u003e). The process involves adjusting the atomic positions iteratively until a configuration is reached where the forces acting on each atom are minimized, indicating a potential energy minimum (Kanatani, \u003cspan class=\"CitationRef\"\u003e2005\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eAfter constructing a crystallographic structure for the nanocomposite materials based on their fundamental lattice characteristics, the geometry optimization task is the first step in the simulation process. With a high number of iterations totalling 2143 for MIL-101(Fe), and 500 for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, DFTB simulation code was used to complete the process. A Quasi-Newton method has been used with a medium quality of the process within the energy range of 2.0e-5\u0026nbsp;eV/atom, with a maximum displacement of 0.05 Å. The method used to minimize energy by arranging atoms in a certain structure with the lowest possible energy.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec6\" class=\"Section2\"\u003e\n \u003ch2\u003e2.4. Condition of the essential parameters (Temperature, pressure, and density) during the MD-simulation.\u003c/h2\u003e\n \u003cp\u003eIn molecular dynamics (MD) simulations, the temperature, pressure, and density of the simulation box are essential parameters that characterize the thermodynamic behaviour of the simulated system (Binder et al., \u003cspan class=\"CitationRef\"\u003e2004\u003c/span\u003e). These parameters are typically controlled through thermostats and barostats, allowing researchers to replicate specific experimental conditions and observe the dynamic behaviour of molecules over time (Binder et al., \u003cspan class=\"CitationRef\"\u003e2004\u003c/span\u003e). In our study, temperature of the simulation box was controlled to be around 500 K as shown in Fig. \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e. While the pressure was exceptionally increasing to 88 MPa at the first 20 Ps, then it decreased rapidly to 17 MPa at 40 Ps. The significant rise in pressure in the initial half of the MD simulation was related to the high interaction between the molecules (pharmaceutical contaminants) and the adsorbent surface. However, the density of the simulation box remains around 0.255 Kg/L during the MD simulation. Figure \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e shows the temperature, pressure, and density of the simulation box during the MD simulation of 60 acetaminophen on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene nanocomposite layer.\u003c/p\u003e\n \u003cp\u003eHowever, for the other two pharmaceutical contaminants (Caffeine, and sulfamethoxazole), the condition of the essential parameters had almost the same behaviour during the MD simulation on both g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene nanocomposite.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"3. Results and discussion","content":"\u003cdiv id=\"Sec8\" class=\"Section2\"\u003e\n \u003ch2\u003e3.1. adsorption capacity (\u003cem\u003eqe\u003c/em\u003e)\u003c/h2\u003e\n \u003cp\u003eAdsorption capacity refers to the maximum amount of substance that an adsorbent material can hold or capture from a surrounding medium through the process of adsorption (De Gisi et al., \u003cspan class=\"CitationRef\"\u003e2016\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eAs illustrated in Fig.\u0026nbsp;\u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e, the results indicated that there is a difference in the number of adsorbed molecules toward the three pharmaceutical contaminants tested. For both g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene, sulfamethoxazole was the highest adsorbed molecule after 60 Ps, which is similar to results reported by previous study (Huang et al., \u003cspan class=\"CitationRef\"\u003e2018\u003c/span\u003e). In the first 10 Ps, 30 molecules of acetaminophen, 25 of caffeine, and 30 of sulfamethoxazole were adsorbed on the g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene bilayer, while for MIL-101(Fe)/graphene, 35 molecules of acetaminophen, 29 of caffeine, and 35 of sulfamethoxazole were adsorbed at 10 Ps. While in the middle of the simulation at t\u0026thinsp;=\u0026thinsp;40 Ps, 70 molecules of each (acetaminophen, caffeine, and sulfamethoxazole) were adsorbed on the g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene bilayer. Meanwhile, for MIL-101(Fe)/graphene a higher number of molecules has been adsorbed at 40 Ps (80, 79, and 82) respectively. Finally, at t\u0026thinsp;=\u0026thinsp;60 Ps, the adsorption rate was stable on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene bilayer as the number of adsorbed molecules remains constant till the end of simulation time (85, 92, and 94) respectively. While for MIL-101(Fe)/graphene, the number of adsorbed molecules was (101, 100, and 101) respectively at t\u0026thinsp;=\u0026thinsp;60 Ps and remains constant till the end of simulation time, which is similar to results reported by previous study (Quintero-\u0026Aacute;lvarez et al., \u003cspan class=\"CitationRef\"\u003e2022\u003c/span\u003e; Xiong et al., \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e shows the number of adsorbed contaminants of emerging concern on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene.\u003c/p\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n \u003cp\u003eThe adsorption capacity (\u003cem\u003eqe\u003c/em\u003e) has been calculated for the three pharmaceutical pollutants by using the following Equation (Perera et al., \u003cspan class=\"CitationRef\"\u003e2012\u003c/span\u003e).\u003c/p\u003e\n \u003cdiv id=\"Equ1\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ1\" name=\"EquationSource\"\u003e$$qe=\\frac{\\left(Co-Ce\\right)V}{m}$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e1\u003c/div\u003e\n \u003c/div\u003e\u0026hellip;\u003cp\u003eWhere \u003cem\u003eqe\u003c/em\u003e is the Adsorption capacity, Co is the initial concentration in (ppm), Ce is the concentration at equilibrium, V is the volume of solution, and M is the mass of the adsorbent.\u003c/p\u003e\n \u003cp\u003eAs shown in Fig. \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e, MIL-101(Fe)/graphene had a higher adsorption capacity on the pharmaceutical contaminants after 80 Ps of contact time. For MIL-101(Fe)/graphene at t\u0026thinsp;=\u0026thinsp;20 Ps, the adsorption capacity was equal to (3.3, 3.06, and 3.4) mg/g respectively. While for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, the adsorption capacity was equal to (2.72, 1.7, and 2.92) mg/g respectively. However, at t\u0026thinsp;=\u0026thinsp;30 Ps, there was a significant increase in the adsorption capacity by approximately two-fold for both MIL-101(Fe)/graphene, and g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene. Finally, at t\u0026thinsp;=\u0026thinsp;60 Ps, we have reached the highest rate of adsorption for both nanocomposite materials and the relationship remain constant till the end of the simulation time with a maximum capacity of (10, 9.99, and 10.05) for MIL-101(Fe)/graphene, while for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene was equal to (8.25, 9.16, and 9.182) respectively.\u003c/p\u003e\n \u003cp\u003eThe adsorption kinetics data were adapted to Pseudo-First Order (PFO) (Ezzati, \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e), the Equation of Pseudo-First Order are shown below:\u003c/p\u003e\n \u003cdiv id=\"Equ2\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ2\" name=\"EquationSource\"\u003e$$qt=qe (1-{e}^{-k1t})$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e2\u003c/div\u003e\n \u003c/div\u003e\u0026hellip;\u003cp\u003eTo characterize the adsorption kinetic behaviours, the pseudo-first order was chosen. The PFO fit the simulation data with a high R\u003csup\u003e2\u003c/sup\u003e value (0.973, 0.985, and 0.935) for acetaminophen, caffeine, and sulfamethoxazole on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene respectively, and (0.983, 0.979, and 0.973) for acetaminophen, caffeine, and sulfamethoxazole on MIL-101(Fe)/graphene nanocomposite respectively. Additionally, the calculated qe values from the PFO model were closer to the simulation qe values for both g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene (Table \u003cspan class=\"InternalRef\"\u003e3\u003c/span\u003e, \u003cspan class=\"InternalRef\"\u003e4\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003e\u003c/p\u003e\u0026nbsp;\u003ctable id=\"Tab3\" border=\"1\" style=\"margin-right: calc(57%); width: 43%;\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 3\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eKinetic data fitting parameters of the acetaminophen, caffeine, and sulfamethoxazole on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" style=\"width: 21.5086%;\"\u003e\n \u003cp\u003eAdsorbent\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 19.5395%;\"\u003e\u0026nbsp;\u003c/th\u003e\n \u003cth align=\"left\" colspan=\"3\" style=\"width: 42.1085%;\"\u003e\n \u003cp\u003ePseudo First Order\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" style=\"width: 21.5086%;\"\u003e\u0026nbsp;\u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 19.5395%;\"\u003e\n \u003cp\u003eq\u003csub\u003ee\u003c/sub\u003e (mg/g) (Sim)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 23.4777%;\"\u003e\n \u003cp\u003eq\u003csub\u003ee\u003c/sub\u003e (mg/g) (cal)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 10.1484%;\"\u003e\n \u003cp\u003ek\u003csub\u003e1\u003c/sub\u003e Ps\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 8.4823%;\"\u003e\n \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" style=\"width: 21.5086%;\"\u003e\n \u003cp\u003eAcetaminophen\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 19.5395%;\"\u003e\n \u003cp\u003e8.25\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 23.4777%;\"\u003e\n \u003cp\u003e11.98199\u0026thinsp;\u0026plusmn;\u0026thinsp;2.26065\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 10.1484%;\"\u003e\n \u003cp\u003e0.018\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 8.4823%;\"\u003e\n \u003cp\u003e0.973\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" style=\"width: 21.5086%;\"\u003e\n \u003cp\u003eCaffeine\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 19.5395%;\"\u003e\n \u003cp\u003e9.16\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 23.4777%;\"\u003e\n \u003cp\u003e15.85552\u0026thinsp;\u0026plusmn;\u0026thinsp;3.37207\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 10.1484%;\"\u003e\n \u003cp\u003e0.013\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 8.4823%;\"\u003e\n \u003cp\u003e0.985\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" style=\"width: 21.5086%;\"\u003e\n \u003cp\u003eSulfamethoxazole\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 19.5395%;\"\u003e\n \u003cp\u003e9.182\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 23.4777%;\"\u003e\n \u003cp\u003e17.68059\u0026thinsp;\u0026plusmn;\u0026thinsp;7.17248\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 10.1484%;\"\u003e\n \u003cp\u003e0.012\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 8.4823%;\"\u003e\n \u003cp\u003e0.935\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003c/p\u003e\n \u003cp\u003e\u003cbr\u003e\u003c/p\u003e\n \u003cp\u003e\u003c/p\u003e\u0026nbsp;\u003ctable id=\"Tab4\" border=\"1\" style=\"margin-right: calc(64%); width: 36%;\"\u003e\n \u003ccaption language=\"En\"\u003e\n \u003cdiv class=\"CaptionNumber\"\u003eTable 4\u003c/div\u003e\n \u003cdiv class=\"CaptionContent\"\u003e\n \u003cp\u003eKinetic data fitting parameters of the acetaminophen, caffeine, and sulfamethoxazole on MIL-101(Fe)/graphene\u003c/p\u003e\n \u003c/div\u003e\n \u003c/caption\u003e\n \u003cthead\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" style=\"width: 25.1366%;\"\u003e\n \u003cp\u003eAdsorbent\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 18.3971%;\"\u003e\u0026nbsp;\u003c/th\u003e\n \u003cth align=\"left\" colspan=\"3\" style=\"width: 40.4372%;\"\u003e\n \u003cp\u003ePseudo First Order\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003cth align=\"left\" style=\"width: 25.1366%;\"\u003e\u0026nbsp;\u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 18.3971%;\"\u003e\n \u003cp\u003eq\u003csub\u003ee\u003c/sub\u003e (mg/g) (Sim)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 22.4044%;\"\u003e\n \u003cp\u003eq\u003csub\u003ee\u003c/sub\u003e (mg/g) (cal)\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 9.6539%;\"\u003e\n \u003cp\u003ek\u003csub\u003e1\u003c/sub\u003e Ps\u003csup\u003e\u0026minus;\u0026thinsp;1\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003cth align=\"left\" style=\"width: 8.1967%;\"\u003e\n \u003cp\u003eR\u003csup\u003e2\u003c/sup\u003e\u003c/p\u003e\n \u003c/th\u003e\n \u003c/tr\u003e\n \u003c/thead\u003e\n \u003ctbody\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" style=\"width: 25.1366%;\"\u003e\n \u003cp\u003eAcetaminophen\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 18.3971%;\"\u003e\n \u003cp\u003e10.05\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 22.4044%;\"\u003e\n \u003cp\u003e16.07485\u0026thinsp;\u0026plusmn;\u0026thinsp;3.04119\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 9.6539%;\"\u003e\n \u003cp\u003e0.015\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 8.1967%;\"\u003e\n \u003cp\u003e0.983\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" style=\"width: 25.1366%;\"\u003e\n \u003cp\u003eCaffeine\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 18.3971%;\"\u003e\n \u003cp\u003e9.99\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 22.4044%;\"\u003e\n \u003cp\u003e15.77317\u0026thinsp;\u0026plusmn;\u0026thinsp;3.14511\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 9.6539%;\"\u003e\n \u003cp\u003e0.016\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 8.1967%;\"\u003e\n \u003cp\u003e0.979\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003ctr\u003e\n \u003ctd align=\"left\" style=\"width: 25.1366%;\"\u003e\n \u003cp\u003eSulfamethoxazole\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 18.3971%;\"\u003e\n \u003cp\u003e10.05\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 22.4044%;\"\u003e\n \u003cp\u003e18.68059\u0026thinsp;\u0026plusmn;\u0026thinsp;6.17248\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 9.6539%;\"\u003e\n \u003cp\u003e0.012\u003c/p\u003e\n \u003c/td\u003e\n \u003ctd align=\"char\" style=\"width: 8.1967%;\"\u003e\n \u003cp\u003e0.973\u003c/p\u003e\n \u003c/td\u003e\n \u003c/tr\u003e\n \u003c/tbody\u003e\n \u003c/table\u003e\n \u003cp\u003e\u003c/p\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e5\u003c/span\u003e shows the adsorption capacity of contaminants of emerging concern on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec9\" class=\"Section2\"\u003e\n \u003ch2\u003e3.2. Potential Energy Surface (PES)\u003c/h2\u003e\n \u003cp\u003eThe potential energy surface (PES) during the adsorption process refers to the energy landscape that describes the interaction between adsorbate molecules (the species being adsorbed) and a substrate or adsorbent surface (Collinge et al., \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e). During adsorption, molecules in the gas or liquid phase are attracted to the surface of a solid or liquid material (Marquardt et al., \u003cspan class=\"CitationRef\"\u003e2010\u003c/span\u003e). This surface is a representation of the potential energy of the system as a function of the coordinates that describe the positions and orientations of the adsorbate molecules on the surface (Marquardt et al., \u003cspan class=\"CitationRef\"\u003e2010\u003c/span\u003e). Mathematically, the potential energy of a system (U) can be expressed as (Lisoń et al., \u003cspan class=\"CitationRef\"\u003e2019\u003c/span\u003e):\u003c/p\u003e\n \u003cdiv id=\"Equ3\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ3\" name=\"EquationSource\"\u003e$$U=T+V$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e3\u003c/div\u003e\n \u003c/div\u003e\u0026hellip;\u003cp\u003eWhere \u003cem\u003eT\u003c/em\u003e is the kinetic energy and \u003cem\u003eV\u003c/em\u003e is the potential energy.\u003c/p\u003e\n \u003cp\u003eIn this paper, we calculated the MD-potential energy surface for both g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene. Due to the attraction between the pharmaceutical contaminants and the surface of the nanocomposite materials, the results showed a negative potential energy for the molecules as it equalled to (-924, -966, and \u0026minus;\u0026thinsp;1268) MJ/mol for (acetaminophen, caffeine, and sulfamethoxazole) respectively on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene at t\u0026thinsp;=\u0026thinsp;40 Ps. The reason of the negative potential energy can be expressed according to Coulomb\u0026apos;s Law (Guo et al., \u003cspan class=\"CitationRef\"\u003e2013\u003c/span\u003e):\u003c/p\u003e\n \u003cdiv id=\"Equ4\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ4\" name=\"EquationSource\"\u003e$$F=-\\frac{k.q1.q2}{{r}^{2}}$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e4\u003c/div\u003e\n \u003c/div\u003e\u0026hellip;\u003cp\u003eWhere \u003cem\u003ek\u003c/em\u003e is a constant, \u003cem\u003eq1\u003c/em\u003e and \u003cem\u003eq2\u003c/em\u003e are the quantities of each charge, and the scalar \u003cem\u003er\u003c/em\u003e is the distance between the charges.\u003c/p\u003e\n \u003cp\u003eThe \u003cspan class=\"InlineEquation\"\u003e\u003cspan class=\"mathinline\"\u003e\\(-\\frac{k.q1.q2}{{r}^{2}}\\)\u003c/span\u003e\u003c/span\u003e term in Coulomb\u0026apos;s Law contributes a negative value when \u003cem\u003eq\u003c/em\u003e1 and \u003cem\u003eq\u003c/em\u003e2 have opposite signs, indicating an attractive electrostatic force (Al Rabeh, \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eHowever, for MIL-101(Fe)/graphene, the potential energy of the molecules was equal to (-1174.7, -1630.1, and \u0026minus;\u0026thinsp;2347.2) respectively. As the adsorption capacity was higher on MIL-101(Fe)/graphene as we indicated in section 3.1., the breaking of the molecules bonds forming a new bonds and electrons was higher on MIL-101(Fe)/graphene resulting in a lower potential energy and more heat released (exothermic reaction). Finally, we noticed that the MD-potential energy of both acetaminophen and caffeine was slightly decreasing during the MD-simulation time for both nanocomposite materials, while for sulfamethoxazole it was decreasing for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene and increasing for MIL-101(Fe)/graphene. The decreasing in the potential energy for acetaminophen and caffeine is due to the significant contribution of electrostatic energy (Nejad et al., \u003cspan class=\"CitationRef\"\u003e2017\u003c/span\u003e). When the atoms charge is moving close to the nanocomposite surface, the potential energy decrease (Khoshkava \u0026amp; Kamal, \u003cspan class=\"CitationRef\"\u003e2013\u003c/span\u003e). While for sulfamethoxazole on MIL-101(Fe)/graphene nanocomposite, the increase in the potential energy is due to the hydrogen-bonding sites that formed between sulfamethoxazole and the adsorbent surface (Huang et al., \u003cspan class=\"CitationRef\"\u003e2021\u003c/span\u003e).\u003c/p\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e6\u003c/span\u003e shows potential energy surface during the adsorption process of the contaminants of emerging concern (CECs) on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene.\u003c/p\u003e\n\u003c/div\u003e\n\u003cdiv id=\"Sec10\" class=\"Section2\"\u003e\n \u003ch2\u003e3.3. Van der Waals interactions\u003c/h2\u003e\n \u003cp\u003eVan der Waals interactions are weak attractive forces that arise between molecules or atoms as a result of temporary fluctuations in electron distribution (Kawai et al., \u003cspan class=\"CitationRef\"\u003e2016\u003c/span\u003e). It plays a crucial role in determining the physical and chemical properties of substances, influencing phenomena such as solubility, boiling points, and the behaviour of gases (Dudek et al., \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e). Despite their relatively weak nature, these interactions are fundamental to the stability and structure of a wide range of molecular systems, contributing significantly to the cohesive forces that bind molecules together in various states of matter (Dudek et al., \u003cspan class=\"CitationRef\"\u003e2020\u003c/span\u003e). The van der Waals interactions are often represented by the following Equations (Hermann et al., \u003cspan class=\"CitationRef\"\u003e2017\u003c/span\u003e):\u003c/p\u003e\n \u003cdiv id=\"Equ5\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ5\" name=\"EquationSource\"\u003e$$\\left(P+\\frac{an2}{V2}\\right)\\left(V-nb\\right)=nRT$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e5\u003c/div\u003e\n \u003c/div\u003e\u0026hellip;\u003cp\u003eWhere P is the pressure, R is the universal gas constant, T is the absolute temperature, V is the molar volume, and (a, b) are gas constant.\u003c/p\u003e\n \u003cp\u003eThe Lennard-Jones potential is often used to describe the van der Waals interaction between neutral atoms or molecules. The Equation (Hermann et al., \u003cspan class=\"CitationRef\"\u003e2017\u003c/span\u003e) is given by:\u003c/p\u003e\n \u003cdiv id=\"Equ6\" class=\"Equation\"\u003e\n \u003cdiv class=\"mathdisplay\" id=\"FileID_Equ6\" name=\"EquationSource\"\u003e$${E}_{\\text{L}\\text{J}}\\left(r\\right)=4\\in [{\\left(\\frac{\\sigma }{r}\\right)}^{12}-{\\left(\\frac{\\sigma }{r}\\right)}^{6}]$$\u003c/div\u003e\n \u003cdiv class=\"EquationNumber\"\u003e6\u003c/div\u003e\n \u003c/div\u003e\u0026hellip;\u003cp\u003eWhere r is the distance between the particles, \u0026isin; is the depth of the potential well (related to the strength of the interaction), and \u0026sigma; is the finite distance at which the inter-particle potential is zero.\u003c/p\u003e\n \u003cp\u003eIn our study, we calculated the interaction energy of the pharmaceutical contaminants on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene. The investigation focused on examining the change in interaction energy concerning the distance between the pharmaceutical contaminant atoms and the nanocomposite layers. Our results showed that the optimal distance between the pharmaceutical contaminants and the nanocomposite layers is ranging between 2.5 to 3 \u0026Aring; with an interaction energy ranging between \u0026minus;\u0026thinsp;250 to -360 eV for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and \u0026minus;\u0026thinsp;390 to -450 for MIL-101(Fe)/graphene. However, at \u003cem\u003eR\u003c/em\u003e\u0026thinsp;=\u0026thinsp;4 \u0026Aring;, the interaction energy continued to decrease, and it reached to a value ranging between \u0026minus;\u0026thinsp;370 to -420 eV for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and \u0026minus;\u0026thinsp;500 to -600 eV for MIL-101(Fe)/graphene. Finally, at \u003cem\u003eR\u003c/em\u003e\u0026thinsp;=\u0026thinsp;6 \u0026Aring;, the interaction energy began toward equilibrium for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, while for MIL-101(Fe)/graphene, the interaction energy began toward equilibrium for acetaminophen and caffeine, while for sulfamethoxazole the interaction energy continues to decrease, and it reached around \u0026minus;\u0026thinsp;685 eV at R\u0026thinsp;=\u0026thinsp;8 \u0026Aring;. The reason for this is due to the hydrogen-bonding sites that formed between sulfamethoxazole and the adsorbent surface as we indicated in the previous section 3.2.\u003c/p\u003e\n \u003cp\u003eFigure \u003cspan class=\"InternalRef\"\u003e7\u003c/span\u003e shows the interaction energy as a function of separation distance on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene.\u003c/p\u003e\n\u003c/div\u003e"},{"header":"4. Conclusions","content":"\u003cp\u003eA g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and MIL-101(Fe)/graphene nanocomposite materials have been simulated to verify the adsorption capacity for the removal of pharmaceutical contaminants. The high adsorption efficiency of g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene and MIL-101(Fe) for the removal of acetaminophen (paracetamol), caffeine and sulfamethoxazole have been tested for the first time by using the ReaxFF software and the DFTB Modules.\u003c/p\u003e \u003cp\u003eIn this study, we found that MIL-101(Fe)/graphene nanocomposite had a higher adsorption capacity for the removal of pharmaceutical contaminants than g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene during 100 Ps simulation time. Our investigations for the elimination of acetaminophen, caffeine, and sulfamethoxazole have leaded to three important results. The first one is that sulfamethoxazole was the highest adsorbed pharmaceutical contaminant with a value equal to 9.182 mg/g on g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and 10.05 mg/g on MIL-101(Fe)/graphene. The second one is that during the adsorption process, the MD-potential energy of both acetaminophen and caffeine was slightly decreasing due to the contribution of electrostatic energy. While for sulfamethoxazole on MIL-101(Fe)/graphene nanocomposite, the potential energy was slightly increasing due to the hydrogen-bonding sites that formed between sulfamethoxazole and the adsorbent surface. For the last one, our results showed that the optimum distance between the pharmaceutical contaminants and the nanocomposite layers is ranging between 2.5 to 3 \u0026Aring; based on the interaction energies that ranged between \u0026minus;\u0026thinsp;250 to -360 eV for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene, and \u0026minus;\u0026thinsp;390 to -450 for MIL-101(Fe)/graphene.\u003c/p\u003e"},{"header":"Declarations","content":"\u003cp\u003e\u003cstrong\u003e-Ethical Approval:\u0026nbsp;\u003c/strong\u003eThe Atlantic Technological University approved this research project as part of the Ph. D under the title \u0026ldquo;Water treatment by Adsorption Process for The Removal of Pharmaticulas Contaminants Using MIL-101(Fe)/graphene, LDH/g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e, and LDH/graphene Nanocomposite Materials: A Molecular Dynamic Simulation Study\u0026rdquo;.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e-Consent to Participate:\u0026nbsp;\u003c/strong\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e-Consent to Publish:\u0026nbsp;\u003c/strong\u003eNot applicable.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e-Authors Contributions:\u0026nbsp;\u003c/strong\u003e\u003cstrong\u003eQusai Ibrahim\u003c/strong\u003e: \u0026nbsp;Writing, Methodology, Simulation; \u003cstrong\u003eSalem Gharbia\u003c/strong\u003e: Supervision, Reviewing, Editing, and Validation.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e-Funding:\u0026nbsp;\u003c/strong\u003eThis research was funded by the IT Sligo President\u0026rsquo;s bursary.\u003c/p\u003e\n\u003cp\u003e\u003cstrong\u003e-Competing Interests:\u0026nbsp;\u003c/strong\u003eThe authors declare no conflict of interest.\u003c/p\u003e"},{"header":"References","content":"\u003col\u003e\n \u003cli\u003eAl-Karaghouli, A., \u0026amp; Kazmerski, L. 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International Journal of Mining Science and Technology, 31(6), 1169-1179.\u003c/li\u003e\n\u003c/ol\u003e"}],"fulltextSource":"","fullText":"","funders":[],"hasAdminPriorityOnWorkflow":false,"hasManuscriptDocX":true,"hasOptedInToPreprint":true,"hasPassedJournalQc":"","hasAnyPriority":false,"hideJournal":false,"highlight":"","institution":"","isAcceptedByJournal":true,"isAuthorSuppliedPdf":false,"isDeskRejected":"","isHiddenFromSearch":false,"isInQc":false,"isInWorkflow":false,"isPdf":false,"isPdfUpToDate":true,"isWithdrawnOrRetracted":false,"journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true},"keywords":"Graphene. G-C3N4. MIL-101(Fe). Pharmaceutical Contaminants. Simulation. Adsorption","lastPublishedDoi":"10.21203/rs.3.rs-4081656/v1","lastPublishedDoiUrl":"https://doi.org/10.21203/rs.3.rs-4081656/v1","license":{"name":"CC BY 4.0","url":"https://creativecommons.org/licenses/by/4.0/"},"manuscriptAbstract":"\u003cp\u003eThe rising presence of drug-related contaminants in water sources is a major environmental and public health concern. Several studies have addressed the hazardous influence of these pollutants on the lives of over 400\u0026nbsp;million people worldwide. In this study, we used molecular dynamics simulations to evaluate the efficacy of two promising composite materials for the removal of pharmaceutical contaminants by using the adsorption technique. Graphitic carbon nitride/graphene (g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene) and metal-organic framework (MIL-101(Fe))/graphene have been simulated for the first time for the removal of three of the most common pollutants (acetaminophen, caffeine, and sulfamethoxazole). The nanocomposite structure has been created and optimized using the geometry optimization task in the DFTB Modules in the Amsterdam Modeling Suite. Our results reveal the remarkable ability of the g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene and MIL-101(Fe)/graphene composites to adsorb acetaminophen, caffeine, and sulfamethoxazole. Using the Reactive Forcefield (ReaxFF) software, we reveal the mechanisms of the adsorption process, calculating van der Waals interactions, and the adsorption capacity. We found that the combination of MIL-101(Fe)/graphene had a higher adsorption capacity for the removal of pharmaceutical contaminants than g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene. At 40 Ps (Picosecond), 80 molecules of each pharmaceutical contaminants (Acetaminophen, Caffeine and Sulfamethoxazole) have been adsorbed by MIL-101(Fe)/graphene with higher exothermic energy equated to (-1174, -1630, and \u0026minus;\u0026thinsp;2347) MJ/mol respectively. While for g-C\u003csub\u003e3\u003c/sub\u003eN\u003csub\u003e4\u003c/sub\u003e/graphene at 40 Ps, 70 molecules of each pharmaceutical contaminants have been adsorbed with exothermic energy equated to (-924, -966, and \u0026minus;\u0026thinsp;1268) MJ/mol respectively. Finally, we summarized the condition of the essential parameters (Temperature, pressure, and density) of the simulation box during the MD-simulation, and the adsorption kinetics using Pseudo-First Order (PFO) in order to ensure the accuracy of our MD-simulation results.\u003c/p\u003e","manuscriptTitle":"Adsorption Performance of g-C3N4/graphene, and MIL-101(Fe)/graphene for the Removal of Pharmaceutical Contaminants: A Molecular Dynamics Simulation Study","msid":"","msnumber":"","nonDraftVersions":[{"code":1,"date":"2024-04-15 04:50:44","doi":"10.21203/rs.3.rs-4081656/v1","editorialEvents":[{"type":"communityComments","content":0}],"status":"published","journal":{"display":true,"email":"[email protected]","identity":"researchsquare","isNatureJournal":false,"hasQc":true,"allowDirectSubmit":true,"externalIdentity":"","sideBox":"","snPcode":"","submissionUrl":"/submission","title":"Research Square","twitterHandle":"researchsquare","acdcEnabled":true,"dfaEnabled":false,"editorialSystem":"","reportingPortfolio":"","inReviewEnabled":false,"inReviewRevisionsEnabled":true}}],"origin":"","ownerIdentity":"b7ef7ba1-31f3-48a2-bad5-93bc14c50974","owner":[],"postedDate":"April 15th, 2024","published":true,"recentEditorialEvents":[],"rejectedJournal":[],"revision":"","amendment":"","status":"published-in-journal","subjectAreas":[],"tags":[],"updatedAt":"2024-11-08T17:48:43+00:00","versionOfRecord":{"articleIdentity":"rs-4081656","link":"https://doi.org/10.1038/s41598-024-75443-9","journal":{"identity":"scientific-reports","isVorOnly":false,"title":"Scientific Reports"},"publishedOn":"2024-11-07 00:00:00","publishedOnDateReadable":"November 7th, 2024"},"versionCreatedAt":"2024-04-15 04:50:44","video":"","vorDoi":"10.1038/s41598-024-75443-9","vorDoiUrl":"https://doi.org/10.1038/s41598-024-75443-9","workflowStages":[]},"version":"v1","identity":"rs-4081656","journalConfig":"researchsquare"},"__N_SSP":true},"page":"/article/[identity]/[[...version]]","query":{"redirect":"/article/rs-4081656","identity":"rs-4081656","version":["v1"]},"buildId":"qtupq5eGEP_6zYnWcrvyt","isFallback":false,"isExperimentalCompile":false,"dynamicIds":[84888],"gssp":true,"scriptLoader":[]}