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Separation of Cyanide from an Aqueous Solution Using Armchair Silicon Carbide Nanotubes: Insights Cite This: RSC Adv.,2017,7,7502 from Molecular Dynamics Simulations

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Separation of Cyanide from an Aqueous Solution Using Armchair Silicon Carbide Nanotubes: Insights Cite This: RSC Adv.,2017,7,7502 from Molecular Dynamics Simulations RSC Advances View Article Online PAPER View Journal | View Issue Separation of cyanide from an aqueous solution using armchair silicon carbide nanotubes: insights Cite this: RSC Adv.,2017,7,7502 from molecular dynamics simulations Alireza Khataee,* Golchehreh Bayat and Jafar Azamat Separation of cyanide, as a model contaminant, from aqueous solution was investigated using molecular dynamics simulations. In this research, cyanide separation was investigated using armchair silicon carbide (SiC) nanotubes of four different diameters at different applied pressures. The systems included (5,5), (6,6), (7,7) and (8,8) SiC nanotubes placed between two graphene sheets, and an external pressure was applied to the system. The ion permeability, the radial distribution function of nanotube–water and ion– Received 28th October 2016 water, the retention time of the cyanide ions, the density of water and water flux and the hydrogen Accepted 3rd January 2017 bonding between inner water molecules were investigated. The results showed that all four studied DOI: 10.1039/c6ra25991j nanotubes accepted water molecules into their interiors, and the (5,5) SiC nanotube could provide high Creative Commons Attribution 3.0 Unported Licence. www.rsc.org/advances rejection (100%) of cyanide ions. 1. Introduction and in both cases, Cu2+ accelerated the oxidation process, acting as a catalyst.12 In a similar study, the oxidation process of Cyanide is a damaging and poisonous pollutant, which free cyanide with H2O2 catalyzed by activated alumina was threatens the environment and human health. Cyanide is studied by Chergui et al. They claimed that their proposed widely used in diverse industries including electroplating, method had advantages over the method based on copper 13 mining, photoprocessing, fertilizer production, gas production, catalyst. 1 This article is licensed under a pharmaceuticals and plating. The existence of cyanides in Akcil et al. investigated the biological degradation of cyanide wastewater poses a high risk and hence, it should be removed by specic bacteria. These bacteria could efficiently degrade from wastewaters before release.2 Cyanides cause extensive sh cyanide into less toxic compounds, namely ammonia and 14 death and affect the microscopic and invertebrate organisms in carbonate. In addition, various biodegradation methods for Open Access Article. Published on 23 January 2017. Downloaded 10/1/2021 3:49:26 AM. 15 water. It is also toxic and damaging for human health, causes cyanide removal were introduced in a review by Ibrahim et al. neurological effects (quick breathing, tremors), weight loss, Some of these methods are not economical or environmen- nerve injury and disease. Skin contact with cyanides may tally friendly because of the application of dangerous chemical produce irritation and sores.3–5 reagents. Moreover, they produce poisonous residues and 1,16 There are different ways of treating cyanide-containing cannot completely reduce all cyanide complexes. wastewaters, including chemical oxidation, physical methods In this regard, for water purication and to meet qualication and biological processes.6–10 For example, Simsek et al. con- requirements, nanotechnology has emerged as a novel and 17,18 ducted column and batch studies with a Purolite resin in order powerful tool. Nanotubes are an excellent and appropriate 19–21 to remove cyanide ions from aqueous solutions.1 Moreover, choice as ion selective materials. Although carbon nanotubes 22,23 Hijosa-Valsero et al. tested plasma discharge technology for have received more attention, other materials, such as boron 24–26 27 cyanide removal from water with an initial concentration of 1 nitride (BN) and silicon carbide (SiC), can also be used to À mg L 1.11 They proposed a coaxial DBD plasma reactor only for fabricate nanotubes. SiC nanotubes were rst synthesized in 28 the treatment of dilute solutions such as drinking water. In 2001. They exhibit better reactivity than carbon nanotubes due 29 another study, Sarla and coworkers studied the oxidation to their polar nature. For example, theoretical studies have process of cyanide in aqueous solutions with H2O2 as the shown that SiC nanotubes are an excellent material for hydrogen 2+ 30 oxidant and Cu as the catalyst. They found that chemical storage. According to these studies, SiC nanotubes exhibit a H2 oxidation by H2O2 is slow, whereas by UV/H2O2 it is much faster, binding energy that is 20% greater than that of carbon nano- tubes. In another study, the capability of SiC nanotubes as a sensor for formaldehyde detection was demonstrated. CH2O Research Laboratory of Advanced Water and Wastewater Treatment Processes, molecules were chemisorbed to SiC nanotubes with a more Department of Applied Chemistry, Faculty of Chemistry, University of Tabriz, 51666-16471 Tabriz, Iran. E-mail: [email protected]; ar_khataee@yahoo. noticeable adsorption energy, relative to that of carbon nano- com; Fax: +98 4133340191; Tel: +98 4133393165 tubes. Zhao et al. studied the catalytic behavior of SiC 7502 | RSC Adv.,2017,7,7502–7508 This journal is © The Royal Society of Chemistry 2017 View Article Online Paper RSC Advances nanotubes. Their theoretical calculations showed that SiC model42 was used to exactly reproduce the entropic and nanotubes can efficiently break the N–H bond of ammonia and hydrogen bonding behavior of water. – – ¼ 31 the O HbondofHOX (X H, CH3, and C2H5). Moreover, NAMD 2.10 (ref. 43) was used for performing MD simula- some researchers have shown the ion selectivity of SiC nano- tions, similar to previous study,44–47 and visualized via 21,32 48 tubes. In our previous study, separation of nitrate ions was VMD1.9.2. The van der Waals interaction energies (ELJ) are studied using armchair SiC nanotubes. We found that (8,8) SiC dened by eqn (1) as follows:49 nanotubes can remove nitrate ions from aqueous solutions.32 In " # pffiffiffiffiffiffiffiffi ðs þ s Þ 12 ðs þ s Þ 6 q q a similar study, Hilder and coworkers demonstrated the ion- E ¼ 4 3 3 a b À 2 a b þ a b LJ a b 2r 2r 4p3 r (1) selectivity of (6,6) and (7,7) SiC nanotubes. They found that no ab ab 0 ab sodium ions were able to pass through the nanotubes, whereas where 3a and sa are the Lennard-Jones parameters for atom a, chloride ions were able to pass.21 rab is the distance between two atoms, and qa and qb are the Fluid-particle dynamics simulations consist of computa- partial charges associated to atoms. The armchair SiC nano- tional methods for macroscale (smoothed particle hydrody- 33 tubes were placed between two graphene sheets that were xed namics (SPH)), mesoscale (dissipative particle dynamics 34 32 during the simulation. As indicated by Bucior et al. the exi- (DPD)), and microscale (molecular dynamics (MD)) systems. bility of the nanotubes is important when the diameter of the In the eld of computational chemistry, MD simulation is an nanotube and the size of the molecules are about the same.50 invaluable method for studying the atom ow through nano- 35,36 However, in this study, the molecule size was smaller than the pores. The atom resolution can be simulated accurately via pore size. Thus, xing the nanotube did not affect the MD, and therefore it is possible to investigate the transport results.51 characteristics because of the tunable long timescale of MD, The simulation box was exposed to zero-temperature energy which allows researchers to collect adequate statistics. More- minimization for 40 ps, then equilibrated at 298 K for 10 ps and over, numerous permeation events for single ions and water 37 nally, MD simulation was performed for 5 ns. The temperature Creative Commons Attribution 3.0 Unported Licence. molecules through nanopores can be studied via MD. Thus, in was xed at 298 K using the Langevin dynamics method. this study, the passage of cyanide ions through SiC nanotubes External constant forces perpendicular to the cross-section of under pressure was studied via MD simulations. the nanotube were applied to the water molecules in a selected area of the system (within a distance of 9 A˚ to the le or right boundary of the system). 2. Simulation details The applied forces generate a pressure difference through the Four types of armchair SiC nanotubes, including (5,5), (6,6), SiC nanotubes that forces the uid to ow, which is known as 52,53 ¼ (7,7) and (8,8) nanotubes with a length of 20 A˚ were selected. pressure-driven ow. The applied force was de ned as F DPA/n,whereF is the force exerted to the chosen section of the This article is licensed under a The system domain contained an armchair SiC nanotube D ff placed between two graphene sheets, potassium and cyanide box (in pN), P is the pressure di erence (in Pa), A is the cross 2 ions, and water molecules. The concentration of dissolved sectional area of the system (in m ), and n is the number of water potassium and cyanide ions was 0.3 M. The dimensions of the molecules in the selected region (see Fig. 1). Pressure ranged from Open Access Article. Published on 23 January 2017. Downloaded 10/1/2021 3:49:26 AM. simulation box were (x  y  z)30 30  80 A˚3. The periodic 10 to 200 MPa and was applied to nearly 542 water molecules. boundary conditions were used in all three directions. The – short-range Lennard Jones interaction parameters are 3. Results and discussion summarized in Table 1. Long-range electrostatic interactions 38 were calculated using the PME (Particle Mesh Ewald) method In this study, single-walled (5,5), (6,6), (7,7) and (8,8) SiC ˚ ff with a 12 A cut-o for van der Waals interactions. The optimized nanotubes with a length of 20 A,˚ xed between two graphene geometries of these nanotubes were obtained at the B3LYP level of theory with the 6-31G** basis set using the GAMESS program.39 The value of 1.8 A˚ was obtained for the optimized Si– C bond length.
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