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Frontiers of Environmental Science & Engineering

Front. Environ. Sci. Eng.    2018, Vol. 12 Issue (5) : 12
Static and dynamic characteristics of SO2-O2 aqueous solution in the microstructure of porous carbon materials
Shi Yin1(), Yan-Qiu Chen2, Yue-Li Li3, Wang-Lai Cen2(), Hua-Qiang Yin1
1. College of Architecture and Environment and National Engineering Research Center for Flue Gas Desulfurization, Sichuan University, Chengdu 610065, China
2. Institute of New Energy and Low Carbon Technology, Sichuan University, Chengdu 610207, China
3. Chengdu ZXTY Environmental Technologies Co. Ltd., Chengdu 610094, China
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To derive liquid fuel from waste engine oil and plastics thorough pyrolysis process.

To make equal blend of waste engine oil and plastics with diesel fuel.

To find the suitability of fuel from waste in diesel engine through performance, emission and combustion characteristics.

Porous carbon material facilitates the reaction SO2 + O2 + H2O → H2SO4 in coal-burned flue gas for sulfur resources recovery at mild conditions. It draws a long-term mystery on its heterogeneous catalysis due to the complicated synergic effect between its microstructure and chemical components. To decouple the effects of geometric structure from chemical components, classical molecular dynamics method was used to investigate the static and dynamic characteristics of the reactants (H2O, SO2 and O2) in the confined space truncated by double-layer graphene (DLG). Strong adsorption of SO2 and O2 by the DLG was observed, which results in the filling of the solute molecules into the interior of the DLG and the depletion of H2O. This effect mainly results from the different affinity of the DLG to the species and can be tuned by the separation of the two graphene layers. Such dimension dependence of the static and dynamic properties like distribution profile, molecular cluster, hydrogen bond and diffusion coefficient were also studied. The conclusions drawn in this work could be helpful to the further understanding of the underlying reaction mechanism of desulfurization process in porous carbon materials and other applications of carbon-based catalysts.

Keywords Molecular dynamics      Flue gas desulfurization      Graphene      Sulfur dioxide      Heterogeneous catalysis     
Corresponding Authors: Shi Yin,Wang-Lai Cen   
Issue Date: 20 September 2018
 Cite this article:   
Shi Yin,Yan-Qiu Chen,Yue-Li Li, et al. Static and dynamic characteristics of SO2-O2 aqueous solution in the microstructure of porous carbon materials[J]. Front. Environ. Sci. Eng., 2018, 12(5): 12.
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Shi Yin
Yan-Qiu Chen
Yue-Li Li
Wang-Lai Cen
Hua-Qiang Yin
Fig.1  The atomistic model of System A viewed from x axis. The axes are shown at the lower left corner. The blue rectangle outlines the periodic boundary. The left and right images present the system before and after randomly packing of H2O/SO2/O2 molecules in the simulation box.
Molecule Element symbol Charge (e) Parameters for LJ potential Molecular topography
ε (kcal/mol) s (Å)
DLG C 0.0000 0.070 3.550 C-C bond: 1.432 Å
H2O Ow - 0.8476 0.155 3.166 O-H bond: 1.000Å
H-O-H angle: 109.47°
Hw + 0.4238 0.000 0.000
SO2 Ss + 0.4680 0.290 3.615 S-O bond: 1.432 Å
O-S-O angle: 119.504°
Os - 0.2340 0.114 3.005
O2 O - 0.1120 0.108 3.050 O-O bond: 1.21 Å
X at the center of O-O bond
X + 0.2240 0.000 0.000
Tab.1  All the parameters used for LJ and Coulomb potential and the molecular topography in this work (Ewald, 1921; Sokolic et al., 1985; Berendsen et al., 1987; Alexiadis and Kassinos, 2008c)
Fig.2  Molar density of (a) SO2, (b) O2 and (c) H2O in System A and (d) H2O in System B along z axis. Only the molecules with xy projection on the DLG are considered. The z coordinate of DLG center is aligned to zero.
Fig.3  The snapshots of (a) System A07 and (b) System A15 viewed from z axis. For better visualization only the molecules with z coordinate between those of two graphene layers are shown. The black hexagonal grid indicates the DLG. The blue rectangle outlines the periodic boundary. The representation of H2O, SO2 and O2 molecules is exhibited on the left inset.
Fig.4  Radial distribution functions for (a) H2O-H2O in System A and C, (b) H2O-H2O in System B, (c) H2O-SO2 and (d) H2O-O2 in System A and C.
Fig.5  The coordination number between the species in System A as the function of DGP. The values in System C are marked beside the curve as a reference.
Fig.6  The lifetime of the coordinated molecular pairs between the species in System A. The values in System C are also marked beside the curve as a reference.
Fig.7  The average numbers of different hydrogen bonds in System A and System C.
Fig.8  The probability of hydrogen bonds distributed in O-M distance and H-O-M angle for (a) Ow-Hw...Ow, (b) Ow-Hw...Os and (c) Ow-Hw...O in System C.
Fig.9  The diffusion coefficients of the solution molecules: (a) the total diffusion coefficients and their components along (b) x, (c) y and (d) z axis for all the systems.
1 Alexiadis A, Kassinos S (2008a). Molecular simulation of water in carbon nanotubes. Chemical Reviews, 108(12): 5014–5034 pmid: 18980342
2 Alexiadis A, Kassinos S (2008b). Influence of water model and nanotube rigidity on the density of water in carbon nanotubes. Chemical Engineering Science, 63(10): 2793–2797
3 Alexiadis A, Kassinos S (2008c). Self-diffusivity, hydrogen bonding and density of different water models in carbon nanotubes. Molecular Simulation, 34(7): 671–678
4 Allen M P, Tildesley D J (1987). Computer Simulation of Liquids. Oxford: Clarendon Press
5 Berendsen H J C, Grigera J R, Straatsma T P (1987). The missing term in effective pair potentials. Journal of Physical Chemistry, 91(24): 6269–6271
6 Bhatnagar A, Hogland W, Marques M, Sillanpää M (2013). An overview of the modification methods of activated carbon for its water treatment applications. Chemical Engineering Journal, 219: 499–511
7 Bryk T, Haymet A D J (2004). The ice/water interface: Density–temperature phase diagram for the SPC/E model of liquid water. Molecular Simulation, 30(2-3): 131–135
8 Bukowski R, Szalewicz K, Groenenboom G C, van der Avoird A (2007). Predictions of the properties of water from first principles. Science, 315(5816): 1249–1252 pmid: 17332406
9 Chen Y, Yin S, Li Y, Cen W, Li J, Yin H (2017). Curvature dependence of single-walled carbon nanotubes for SO2 adsorption and oxidation. Applied Surface Science, 404: 364–369
10 Dreyer D R, Park S, Bielawski C W, Ruoff R S (2010). The chemistry of graphene oxide. Chemical Society Reviews, 39(1): 228–240 pmid: 20023850
11 English C A, Venables J A (1974). The structure of the diatomic molecular solids. Proceedings of the Royal Society of London. Series A, Mathematical and Physical Sciences, 340(1620): 57–80
12 Ewald P P (1921). Die Berechnung optischer und Elektrostatischer gitterpotentiale. Ann. Phys., 369(3): 253–287
13 Gaur V, Asthana R, Verma N (2006). Removal of SO2 by activated carbon fibers in the presence of O2 and H2O. Carbon, 44(1): 46–60
14 Holt J K, Park H G, Wang Y, Stadermann M, Artyukhin A B, Grigoropoulos C P, Noy A, Bakajin O (2006). Fast mass transport through sub-2-nanometer carbon nanotubes. Science, 312(5776): 1034–1037 pmid: 16709781
15 Huang C, Li C, Shi G (2013). Graphene based catalysts. Energy & Environmental Science, 5(10): 8848–8868
16 Hummer G, Rasaiah J C, Noworyta J P (2001). Water conduction through the hydrophobic channel of a carbon nanotube. Nature, 414(6860): 188–190 pmid: 11700553
17 Kalra A, Garde S, Hummer G (2003). Osmotic water transport through carbon nanotube membranes. Proceedings of the National Academy of Sciences of the United States of America, 100(18): 10175–10180 pmid: 12878724
18 Koga K, Gao G T, Tanaka H, Zeng X C (2001). Formation of ordered ice nanotubes inside carbon nanotubes. Nature, 412(6849): 802–805 pmid: 11518961
19 Kuharski R A, Rossky P J (1985). A quantum mechanical study of structure in liquid H2O and D2O. Journal of Chemical Physics, 82(11): 5164–5177
20 Liu X, Sun F, Qu Z, Gao J, Wu S (2016). The effect of functional groups on the SO2 adsorption on carbon surface I: A new insight into noncovalent interaction between SO2 molecule and acidic oxygen-containing groups. Applied Surface Science, 369: 552–557
21 Lizzio A A, DeBar J A (1997). Mechanism of SO2 removal by carbon. Energy & Fuels, 11(2): 284–291
22 Lum K, Chandler D, Weeks J D (1999). Hydrophobicity at small and large length scales. Journal of Physical Chemistry B, 103(22): 4570–4577
23 Mark P, Nilsson L (2001). Structure and dynamics of the TIP3P, SPC, and SPC/E water models at 298 K. Journal of Physical Chemistry A, 105(43): 9954–9960
24 Martins Costa M T C (2005). QM/MM simulations of polyols in aqueous solution. Journal of Molecular Structure THEOCHEM, 729(1-2): 47–52
25 Miners S A, Rance G A, Khlobystov A N (2016). Chemical reactions confined within carbon nanotubes. Chemical Society Reviews, 45(17): 4727–4746 pmid: 27301444
26 Moin S T, Lim L H V, Hofer T S, Randolf B R, Rode B M (2011). Sulfur dioxide in water: structure and dynamics studied by an ab initio quantum mechanical charge field molecular dynamics simulation. Inorganic Chemistry, 50(8): 3379–3386 pmid: 21417290
27 Plimpton S (1995). Fast parallel algorithms for short-range molecular dynamics. Journal of Computational Physics, 117(1): 1–19
28 Raymundo-Pinero E, Cazorla-Amoros D, Salinas-Martinez de Lecea C, Linares-Solano A (2000). Factors controlling the SO2 removal by porous carbons: Relevance of the SO2 oxidation step. Carbon, 38(3): 335–344
29 Ren X, Chen C, Nagatsu M, Wang X (2011). Carbon nanotubes as adsorbents in environmental pollution management: A review. Chemical Engineering Journal, 2–3(170): 395–410
30 Ryckaert J P, Ciccotti G, Berendsen H J (1977). Numerical integration of the cartesian equations of motion of a system with constraints: Molecular dynamics of n-alkanes. Journal of Computational Physics, 23(3): 327–341
31 Shi J (2013). On the synergetic catalytic effect in heterogeneous nanocomposite catalysts. Chemical Reviews, 113(3): 2139–2181 pmid: 23190123
32 Sokolic F, Guissani Y, Guillot B (1985). Molecular dynamics simulations of thermodynamic and structural properties of liquid SO2. Molecular Physics, 56(2): 239–253
33 Striolo A (2006). The mechanism of water diffusion in narrow carbon nanotubes. Nano Letters, 6(4): 633–639 pmid: 16608257
34 Striolo A (2007). Water self-diffusion through narrow oxygenated carbon nanotubes. Nanotechnology, 18(47): 475704
35 Tomsic A, Gebhardt C R (2005). A comparative study of cluster-surface collisions: Molecular-dynamics simulations of (H2O)1000 and (SO2)1000. Journal of Chemical Physics, 123(6): 64704 pmid: 16122332
36 Wu K, Zhou B, Xiu P, Qi W, Wan R, Fang H (2010). Kinetics of water filling the hydrophobic channels of narrow carbon nanotubes studied by molecular dynamics simulations. Journal of Chemical Physics, 133(20): 204702 pmid: 21133447
37 Zawadzki J (1987). Infrared studies of SO2 on carbons–II. The SO2 species adsorbed on carbon films. Carbon, 25(4): 495–502
38 Zhang H, Cen W, Liu J, Guo J, Yin H, Ning P (2014). Adsorption and oxidation of SO2 by graphene oxides: A van der Waals density functional theory study. Applied Surface Science, 324: 61–67
39 Zhang H, Pan X, Han X, Liu X, Wang X, Shen W, Bao X (2013). Enhancing chemical reactions in a confined hydrophobic environment: An NMR study of benzene hydroxylation in carbon nanotubes. Chemical Science (Cambridge), 4(3): 1075
40 Zhu C, Dong S (2013). Recent progress in graphene-based nanomaterials as advanced electrocatalysts towards oxygen reduction reaction. Nanoscale, 5(5): 1753–1767 pmid: 23364753
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