ReaxFF molecular dynamics of graphene oxide/NaCl aqueous solution interfaces.

In this work, the interaction of NaCl aqueous solution with graphene (G), graphene oxide (GO), and graphite oxide (GTO) is studied using the ReaxFF module of Amsterdam Modeling Suite (AMS) software. We consider four models using the NaCl aqueous solution, containing a graphene sheet (G), a single sheet of GO with epoxide and hydroxyl groups on its surface, 4 layers of GO to model GTO, and a bulk NaCl solution as a reference. The structural and dynamical properties of G, GO, and GTO were quantified by analyzing the functional groups, radial distribution functions, density profiles and diffusivities of water and ions. Due to the reactive force field, the systems underwent spontaneous modification of surface functional groups during the first 750 ps after which the structure stabilizes (the energy stabilizes in less than 400 ps). Pristine graphene in contact with the NaCl solution formed hydroxyl groups on the edges, i.e., converted to partially reduced graphene oxide. The epoxy groups (Oe) on the initial GO were rather unstable, leading to a reduction of their number, however, there was an increase in the number of hydroxyl groups (Oh), mainly at the edges. The interactions of NaCl with the carbon-based sheets are rather weak, including GO and GTO which are decorated with numerous functional groups. Diffusion coefficients of water agree with the available data, but discrepancies in Na+ and Cl- diffusivity compared to other references underscore the need for further development in the dynamic parameters of the reactive force field used. In essence, our research provides specific data previously unreported, laying a foundation for advancing water desalination system design. The study's novelty lies in its realistic approach to graphene/graphene oxide modification, comprehensive characterization, and the application of the reactive force field to explore the graphene oxide-NaCl aqueous interface, contributing to the development of a practical membrane system for water desalination.

Design of Multi-Layer Graphene Membrane with Descending Pore Size for 100% Water Desalination by Simulation Using ReaxFF.

The performance of a desalination membrane depends on a specific pore size suitable for both water permeability and salt rejection. To increase membrane permeability, the applied pressure should be increased, which creates the need to improve membrane stability. In this research article, a molecular dynamics (MD) simulation was performed using ReaxFF module from Amsterdam Modeling suite (AMS) software to simulate water desalination efficiency using a single and multi-layer graphene membrane. The graphene membrane with different pore sizes and a multi-layer graphene membrane with descending pore size in each layer were designed and studied under different pressures. The stability of the membrane was checked using Material Studio 2019 by studying the dynamics summary. The single-layer graphene membrane was evaluated under pressures ranging from 100 to 500 MPa, with the salt rejection ranging from 95% to 82% with a water permeability of 0.347 × 10-9 to 2.94 × 10-9 (mm.g.cm-2s-1.bar-1), respectively. Almost 100% salt rejection was achieved for the multi-layer graphene membrane. This study successfully demonstrated the design and optimization of graphene membrane performance without functionalization.

A Novel BiOCl Based Nanocomposite Membrane for Water Desalination.

In this study, BiOCl based nanocomposites were used as photocatalytic membranes for a simulated study on water desalination in reverse osmosis membrane systems. Through molecular dynamic simulation, the molecular structure of BiOCl, BiOCl/Ag2S and BiOCl/Bi2O3 heterojunctions were designed and their electronic properties, mechanical properties, and membrane performance for water desalination were evaluated for the first time. The molecular structure was created, and a geometry optimization task was used to optimize it. Material Studio 2019 CASTEP was used for simulation of the electronic and mechanical properties and water desalination was performed by ReaxFF software under pressures between 0 and 250 MPa. The novel BiOCl based nanocomposites showed improved electronic and mechanical properties and, most importantly, improvements in salt rejection and water permeability as compared to well-known materials such as graphene and MoS2. BiOCl and BiOCl/Ag2S had a bandgap around two, which is the ideal bandgap for semiconductor photocatalysts. A salt rejection of 98% was achieved under an applied pressure of 10 MPa. Salt rejection was higher for BiOCl/Bi2O3, while water permeability was higher for BiOCl/Ag2S. The monolayer BiOCl was unstable under pressures higher than 50 MPa, but the mechanical stability of BiOCl/Ag2S increased twofold and increased fourfold for BiOCl/Bi2O3, which is even higher than MoS2. However, between the three nanocomposites, BiOCl/Ag2S was found to be the most ideal photocatalytic nanocomposite membrane.

Prediction of electronic properties of novel ZnS-ZnO-recycled expanded polystyrene nanocomposites by DFT.

DFT calculations using Material Studio (2019) were used to ascertain the changes in electronic properties of recycled expanded polystyrene (rEPS) after modification with nanoparticles of ZnS and ZnO. The nanocomposites were obtained using rEPS and suitable metal salt precursors via a solvothermal method. The XRD analysis was conducted to obtain the crystallography data of the new rEPS-based nanocomposites. Using Material Studio simulation software, the potential photocatalytic properties of the new prepared material was predicted and information on the electronic band structure was extracted. The calculated band gap values for rEPS and ZnS-ZnO-rEPS nanocomposite were 4.217 eV and 2.698 eV, respectively. Furthermore, our results showed that the nanocomposite is a p-type semiconductor. From the electronic structure and the band gap narrowing, these nanocomposites obtained from a waste material may have some potential in photocatalytic applications.

The electronic properties and water desalination performance of a photocatalytic TiO2/MoS2 nanocomposites bilayer membrane: a molecular dynamic simulation.

Due to the rapid depletion of water resources, more interest is paid for the efficient desalination process in recent years. MoS2 membrane aroused attention due to its high mechanical stability and electronic properties, which can sustain extra-large strains. In this study, the electronic properties and water desalination performance of TiO2/MoS2-hexagonal, and TiO2/MoS2-rhombohedral nanocomposites bilayer membranes were studied and simulated for the first time. The effect of TiO2 in the performance of MoS2 was observed in water desalination under the defined applied pressure ranging from 50 to 250 MPa with a 6.4 Å pore diameter. The membrane structure is created and optimized. The energy minimized for TiO2 from - 19,596.4282 kcal/mol for the initial structure to - 19,605.1611 kcal/mol for the final structure. For TiO2/MoS2-hexagonal, the energy minimized from - 4955.54271 eV) to - 4955.62091 eV and TiO2/MoS2-rhombohedral from - 6042.26925 eV to - 6046.91835 eV. A molecular dynamic (MD) simulation was performed using Material Studio 2019 to study the electronic properties under 0-1 eV electric field using the CASTEP code. The results showed a better photocatalytic performance under the external electric field. The effect of external electric field significantly intensifies absorption in the visible range and achieved a high photocatalytic activity on TiO2/MoS2. TiO2, TiO2/MoS2-hexagonal and TiO2/MoS2-rhombohedral nanocomposites bilayer membranes are simulated and evaluated for the water desalination using ReaxFF software. Both MoS2 phases with TiO2 have achieved a high salt rejection up to 97% (P-value = 0.0036, R2 = 0.958), while TiO2/MoS2-rhombohedral achieved the highest permeability (6.0*10-8 mm g cm-2 s-1 bar-1) (P-value = 0.000296, R2 = 0.972) under 250 MPa applied pressure.

Highly efficient visible-driven reduction of Cr(VI) by a novel black TiO2 photocatalyst.

Finding a facile and practical method to produce black TiO2 remains a challenge. Bismuth-vanadium co-doped black TiO2 (BVBT) was synthesized as a visible light driven photocatalyst by a simple one-pot hydrothermal method. The synthesized BVBT was characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRD), UV-vis diffuse reflectance spectroscopy (UV-Vis DRS). The light absorption of the synthesized Bi-V co-coped black TiO2 nanoparticles was significantly improved in the visible and infrared regions. The XRD patterns indicated that the black TiO2 contained mixed phases of brookite, anatase, and rutile of TiO2. This was further confirmed by Raman spectroscopy. The photocatalytic activity of the sample was evaluated by reduction of hexavalent chromium (Cr(VI)) under visible light irradiation. Among investigated hole (h+) scavengers, ethylenediaminetetraacetic acid (EDTA) led to the highest reduction of Cr(VI) with a molar ratio of 1:5 (EDTA:Cr(VI)). The results indicated that the Bi-V co-coped black TiO2 nanocomposite can reduce 94% of 1 mg/L of Cr(VI) within 20 min irradiation time (pH 3 and catalyst dose of 1 g/L). Introducing a simple method to synthesize black TiO2 which has absorption in the visible and infrared region can open up new applications.

A photocatalytic TiO2/graphene bilayer membrane design for water desalination: a molecular dynamic simulation.

The research about finding the effective membrane material is in progress; however, there are pros and cons for each material. Graphene membrane is a single layer of atoms in a two-dimensional hexagonal lattice which achieved high performance in water purification field. Addition of TiO2 to the graphene membrane has been studied for the membrane modifications due to its high stability and photocatalytic performance. In this study, graphene/TiO2 bilayer nanocomposite membrane has been simulated to enhance the mechanical and electronic properties of graphene membrane. Anatase TiO2 (A-TiO2), rutile TiO2 (R-TiO2), and their composite with graphene (G) have been simulated to evaluate the stability of the nanocomposite bilayers in water desalination for higher salt rejection percentage and water permeation. The membrane structure has been created and optimized using the geometry optimization task. The simulation of electronic and mechanical properties has been done by using Material Studio 2019. TiO2 consisting rutile and anatase phases showed a band gap of 2.248 eV, which was reduced to 1.175 eV in combination with graphene. The bilayer composite of TiO2 and graphene achieved higher membrane stability, and the salt rejection was 98% under applied pressure of 100 MPa. The graphene/TiO2 bilayer nanocomposite membranes have been evaluated by simulation for water desalination process using molecular dynamics by ReaxFF software. In comparison with a graphene membrane, the results showed an increment in salt rejection and water permeability under different applied pressure.

Fabrication of novel 2D Ag-TiO2/γ-Al2O3/Chitosan nano-composite photocatalyst toward enhanced photocatalytic reduction of nitrate.

The presence of excess nitrate in groundwater limits it use as a drinking water supply and its removal is critical to balance the nitrogen cycle in aquatic systems. In this study, ultra-thin 2-dimensional Ag-TiO2/γ-Al2O3/Chitosan (Ag-TiO2/Al2O3/CS) nano-composite was synthesized for the fast reduction of nitrate under UVA irradiation from aqueous solutions. As-synthesized nano-composite was well characterized by X-ray diffraction, transmission electron microscopy, N2 adsorption-desorption isotherms, Fourier-transform infrared spectroscopy and UV-vis diffuse reflectance spectroscopy. Experimental variables including pH, nitrate concentration, photocatalyst dose and contact time were considered to demonstrate their effect on the rate of nitrate reduction. Formic acid was used as a radical scavenger at optimal concentration of 2:1 (formic acid:nitrate). The results showed that upon UVA irradiation, the synthesized nano-composite exhibited fast nitrate reduction in broad pH range (about 74% removal at pH 11 in 5 min reaction time) in diverse water chemical conditions. The Ag-doped and hybrid heterostructures can effectively utilize UV-visible-light to remove nitrate and degrade formic acid. For the 3 cycles the photocatalyst efficiency remained same and after the third cycle, its efficacy decreased gradually. This work suggests 2D Ag-TiO2/Al2O3/CS nano-composite for the fast removal of nitrate in drinking water treatment.

One-Pot Synthesized Visible Light-Driven BiOCl/AgCl/BiVO4 n-p Heterojunction for Photocatalytic Degradation of Pharmaceutical Pollutants.

A novel enhanced visible light absorption BiOCl/AgCl/BiVO4 heterojunction of photocatalysts could be obtained through a one-pot hydrothermal method used with two different pH solutions. There was a relationship between synthesis pH and the ratio of BiOCl to BiVO4 in XRD planes and their photocatalytic activity. The visible light photocatalytic performances of photocatalysts were evaluated via degradation of diclofenac (DCFF) as a pharmaceutical model pollutant. Furthermore, kinetic studies showed that DCF degradation followed pseudo-first-order kinetics. The photocatalytic degradation rates of BiOCl/AgCl/BiVO4 synthesized at pH = 1.2 and pH = 4 for DCF were 72% and 47%, respectively, showing the higher activity of the photocatalyst which was synthesized at a lower pH value. It was concluded that the excellent photocatalytic activity of BiOCl/AgCl/BiVO4 is due to the enhanced visible light absorption formation of a heterostructure, which increased the lifetime of photo-produced electron-hole pairs by creating a heterojunction. The influence of pH during synthesis on photocatalytic activity in order to create different phases was investigated. This work suggests that the BiOCl/AgCl/BiVO4 p-n heterojunction is more active when the ratio of BiOCl to BiVO4 is smaller, and this could be achieved simply by the pH adjustment. This is a promising method of modifying the photocatalyst for the purpose of pollutant degradation under visible light illumination.

New development of atomic layer deposition: processes, methods and applications.

Atomic layer deposition (ALD) is an ultra-thin film deposition technique that has found many applications owing to its distinct abilities. They include uniform deposition of conformal films with controllable thickness, even on complex three-dimensional surfaces, and can improve the efficiency of electronic devices. This technology has attracted significant interest both for fundamental understanding how the new functional materials can be synthesized by ALD and for numerous practical applications, particularly in advanced nanopatterning for microelectronics, energy storage systems, desalinations, catalysis and medical fields. This review introduces the progress made in ALD, both for computational and experimental methodologies, and provides an outlook of this emerging technology in comparison with other film deposition methods. It discusses experimental approaches and factors that affect the deposition and presents simulation methods, such as molecular dynamics and computational fluid dynamics, which help determine and predict effective ways to optimize ALD processes, hence enabling the reduction in cost, energy waste and adverse environmental impacts. Specific examples are chosen to illustrate the progress in ALD processes and applications that showed a considerable impact on other technologies.

Chitosan modified N, S-doped TiO2 and N, S-doped ZnO for visible light photocatalytic degradation of tetracycline.

N, S-doped TiO2 (NST), N, S-doped ZnO (NSZ) and their composite with chitosan (NST/CS, NSZ/CS) were synthesized by sol gel-hydrothermal method. The prepared samples were characterized using XRD, FTIR, TEM and BET techniques. These photocatalysts were used for the photocatalytic degradation of tetracycline under visible light irradiation. At screening test, NST/CS had the highest tetracycline degradation efficiency of 91% for duration of 20 min under visible light. The blending of chitosan with NST increases the rate of photocatalytic degradation of tetracycline about 2 times. A detail characterization including HRTEM, SEM, EDS and DRS were conducted for NST/CS, the most active photocatalyst in this study. Photocatalytic activity test was conducted by varying tetracycline concentration, irradiation time, catalyst's concentration and pH using response surface methodology to find out the optimum condition for photocatalytic activity. The reusability of as-synthesized NST/CS was assessed which due to its high recoverability can be applied as an effective catalyst for degradation of organic substances in water and wastewater especially for degradation of emerging pollutants such pharmaceutical pollutants. The results from this work show a promising material for local authorities and pharmaceutical facilities to use for the treatment of pharmaceutical pollutants and tetracycline removal in water resource.