Research article Special Issues

Theoretical study of the effect of halogen substitution in molecular porous materials for CO2 and C2H2 sorption

  • Received: 10 January 2018 Accepted: 07 March 2018 Published: 20 March 2018
  • Grand canonical Monte Carlo (GCMC) simulations of carbondioxide (CO$_2$) and acetylene (C$_2$H$_2$) sorption were performed in MPM-1-Cl and MPM-1-Br, two robust molecular porous materials (MPMs) that were synthesized by the addition of adenine to CuX$_2$ (X = Cl or Br) by solvent diffusion. Previous experimental studies revealed that both MPMs are selective for C$_2$H$_2$ over CO$_2$ [Xie DY, et al. (2017) ${CIESC J}$ 68: 154--162]. Simulations in MPM-1-Cl and MPM-1-Br were carried out using polarizable and nonpolarizable potentials of the respective sorbates; this was done to investigate the role of explicit induction on the gas sorption mechanism in these materials. The calculated sorption isotherms and isosteric heat of adsorption ($Q_{st}$) valuesfor both sorbates are in reasonable agreement with the corresponding experimental measurements, with simulations using the polarizable models producing the closest overall agreement. The modeled CO$_2$ binding sitein both MPMs was discovered as sorption between the halide ions of two adjacent [Cu$_2$(adenine)$_4$X$_2$]$^{2+}$ (X = Cl, Br) units.In the case of C$_2$H$_2$, it was found that the sorbate molecule prefers to align along the X--Cu--Cu--X axis of the copper paddlewheels suchthat each H atom of the C$_2$H$_2$ molecule can interact favorably with the coordinated X$^-$ ions. The simulations revealed that both MPMs exhibit stronger interactions with C$_2$H$_2$ than CO$_2$, which is consistent with experimental findings. The effect of halogen substitution toward CO$_2$ and C$_2$H$_2$ sorption in two isostructural MPMs was also elucidated in our theoretical studies.

    Citation: Douglas M. Franz, Mak Djulbegovic, Tony Pham, Brian Space. Theoretical study of the effect of halogen substitution in molecular porous materials for CO2 and C2H2 sorption[J]. AIMS Materials Science, 2018, 5(2): 226-245. doi: 10.3934/matersci.2018.2.226

    Related Papers:

  • Grand canonical Monte Carlo (GCMC) simulations of carbondioxide (CO$_2$) and acetylene (C$_2$H$_2$) sorption were performed in MPM-1-Cl and MPM-1-Br, two robust molecular porous materials (MPMs) that were synthesized by the addition of adenine to CuX$_2$ (X = Cl or Br) by solvent diffusion. Previous experimental studies revealed that both MPMs are selective for C$_2$H$_2$ over CO$_2$ [Xie DY, et al. (2017) ${CIESC J}$ 68: 154--162]. Simulations in MPM-1-Cl and MPM-1-Br were carried out using polarizable and nonpolarizable potentials of the respective sorbates; this was done to investigate the role of explicit induction on the gas sorption mechanism in these materials. The calculated sorption isotherms and isosteric heat of adsorption ($Q_{st}$) valuesfor both sorbates are in reasonable agreement with the corresponding experimental measurements, with simulations using the polarizable models producing the closest overall agreement. The modeled CO$_2$ binding sitein both MPMs was discovered as sorption between the halide ions of two adjacent [Cu$_2$(adenine)$_4$X$_2$]$^{2+}$ (X = Cl, Br) units.In the case of C$_2$H$_2$, it was found that the sorbate molecule prefers to align along the X--Cu--Cu--X axis of the copper paddlewheels suchthat each H atom of the C$_2$H$_2$ molecule can interact favorably with the coordinated X$^-$ ions. The simulations revealed that both MPMs exhibit stronger interactions with C$_2$H$_2$ than CO$_2$, which is consistent with experimental findings. The effect of halogen substitution toward CO$_2$ and C$_2$H$_2$ sorption in two isostructural MPMs was also elucidated in our theoretical studies.
    加载中
    [1] Zhou H, Long J, Yaghi O (2012) Introduction to Metal–Organic Frameworks. Chem Rev 112: 673–674. doi: 10.1021/cr300014x
    [2] Long J, Yaghi O (2009) The pervasive chemistry of metal–organic frameworks. Chem Soc Rev 38: 1213–1214. doi: 10.1039/b903811f
    [3] Pham T, Forrest K, Franz D, et al. (2017) Experimental and theoretical investigations of the gas adsorption sites in rht-metal–organic frameworks. CrystEngComm 19: 4646–4665. doi: 10.1039/C7CE01032J
    [4] Nugent P, Belmabkhout Y, Burd S, et al. (2013) Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 495: 80–84. doi: 10.1038/nature11893
    [5] Mason J, Sumida K, Herm Z, et al. (2011) Evaluating metal–organic frameworks for postcombustion carbon dioxide capture via temperature swing adsorption. Energ Environ Sci 4: 3030–3040. doi: 10.1039/c1ee01720a
    [6] Caskey S, Wong-Foy A, Matzger A (2008) Dramatic Tuning of Carbon Dioxide Uptake via Metal Substitution in a Coordination Polymer with Cylindrical Pores. J Am Chem Soc 130: 10870–10871. doi: 10.1021/ja8036096
    [7] Yang D, Cho H, Kim J, et al. (2012) CO2 capture and conversion using Mg-MOF-74 prepared by a sonochemical method. Energ Environ Sci 5: 6465–6473. doi: 10.1039/C1EE02234B
    [8] Collins D, Zhou H (2007) Hydrogen storage in metal-organic frameworks. J Mater Chem 17: 3154–3160. doi: 10.1039/b702858j
    [9] Collins D, Ma S, Zhou H (2010) Hydrogen and Methane Storage in Metal–Organic Frameworks, Metal-Organic Frameworks: Design and Application, John Wiley & Sons Inc., 249–266.
    [10] Suh M, Park H, Prasad T, et al. (2012) Hydrogen Storage in Metal–Organic Frameworks. Chem Rev 112: 782–835. doi: 10.1021/cr200274s
    [11] Lin X, Telepeni I, Blake A, et al. (2009) High Capacity Hydrogen Adsorption in Cu(II) Tetracarboxylate Framework Materials: The Role of Pore Size, Ligand Functionalization, and Exposed Metal Sites. J Am Chem Soc 131: 2159–2171. doi: 10.1021/ja806624j
    [12] Yan Y, Lin X, Yang S, et al. (2009) Exceptionally high H2 storage by a metal–organic polyhedral framework. Chem Commun 1025–1027.
    [13] Mohammed M, Elsaidi S, Wojtas L, et al. (2012) Highly Selective CO2 Uptake in Uninodal 6-Connected "mmo" Nets Based upon MO42- (M = Cr, Mo) Pillars. J Am Chem Soc 134: 19556–19559. doi: 10.1021/ja309452y
    [14] Wu H, Yao K, Zhu Y, et al. (2012) Cu-TDPAT, an rht-Type Dual-Functional Metal–Organic Framework Offering Significant Potential for Use in H2 and Natural Gas Purification Processes Operating at High Pressures. J Phys Chem C 116: 16609–16618. doi: 10.1021/jp3046356
    [15] Franz D, Forrest K, Pham T, et al. (2016) Accurate H2 Sorption Modeling in the rht-MOF NOTT-112 Using Explicit Polarization. Cryst Growth Des 16: 6024–6032. doi: 10.1021/acs.cgd.6b01058
    [16] Pham T, Forrest K, Franz D, et al. (2017) Predictive models of gas sorption in a metal–organic framework with open-metal sites and small pore sizes. Phys Chem Chem Phys 19: 18587–18602. doi: 10.1039/C7CP02767B
    [17] Franz D, Dyott Z, Forrest K, et al. (2018) Simulations of hydrogen, carbon dioxide, and small hydrocarbon sorption in a nitrogen-rich rht-metal–organic framework. Phys Chem Chem Phys 20: 1761–1777. doi: 10.1039/C7CP06885A
    [18] Li J, Kuppler R, Zhou H (2009) Selective gas adsorption and separation in metal–organic frameworks. Chem Soc Rev 38: 1477–1504. doi: 10.1039/b802426j
    [19] Wang H, Yao K, Zhang Z, et al. (2014) The first example of commensurate adsorption of atomic gas in a MOF and effective separation of xenon from other noble gases. Chem Sci 5: 620–624. doi: 10.1039/C3SC52348A
    [20] Lee J, Farha O, Roberts J, et al. (2009) Metal–organic framework materials as catalysts. Chem Soc Rev 5: 1450–1459.
    [21] Maeda C, Miyazaki Y, Ema T (2014) Recent progress in catalytic conversions of carbon dioxide. Catal Sci Technol 4: 1482–1497. doi: 10.1039/c3cy00993a
    [22] Cho S, Ma B, Nguyen S, et al. (2006) A metal–organic framework material that functions as an enantioselective catalyst for olefin epoxidation. Chem Commun 2563–2565.
    [23] Song J, Zhang Z, Hu S, et al. (2009) MOF-5/n-Bu4NBr: an efficient catalyst system for the synthesis of cyclic carbonates from epoxides and CO2 under mild conditions. Green Chem 11: 1031–1036. doi: 10.1039/b902550b
    [24] Ma D, Li B, Zhou X, et al. (2013) A dual functional MOF as a luminescent sensor for quantitatively detecting the concentration of nitrobenzene and temperature. Chem Commun 8964–8966.
    [25] Wang J, Li M, Li D (2013) A dynamic, luminescent and entangled MOF as a qualitative sensor for volatile organic solvents and a quantitative monitor for acetonitrile vapour. Chem Sci 4: 1793–1801. doi: 10.1039/c3sc00016h
    [26] Larsen R, Wojtas L (2013) Photoinduced inter-cavity electron transfer between Ru(II)tris(2,2'- bipyridne) and Co(II)tris(2,2'-bipyridine) Co-encapsulated within a Zn(II)-trimesic acid metal organic framework. J Mater Chem A 1: 14133-14139. doi: 10.1039/c3ta13422a
    [27] Larsen R, Wojtas L (2012) Photophysical Studies of Ru(II)tris(2,2'-bipyridine) Confined within a Zn(II)–Trimesic Acid Polyhedral Metal–Organic Framework. J Phys Chem A 116: 7830–7835. doi: 10.1021/jp302979a
    [28] Whittington C, Wojtas L, Gao W, et al. (2015) A new photoactive Ru(II)tris(2,2'-bipyridine) templated Zn(II) benzene-1,4-dicarboxylate metal organic framework: structure and photophysical properties. Dalton T 44: 5331–5337. doi: 10.1039/C4DT02594F
    [29] Larsen R, Wojtas L (2015) Fixed distance photoinduced electron transfer between Fe and Zn porphyrins encapsulated within the Zn HKUST-1 metal organic framework. Dalton T 44: 2959– 2963. doi: 10.1039/C4DT02685C
    [30] McKinlay A, Morris R, Horcajada P, et al. (2010) BioMOFs: metal–organic frameworks for biological and medical applications. Angew Chem Int Edit 49: 6260–6266. doi: 10.1002/anie.201000048
    [31] Hinks N, McKinlay A, Xiao B, et al. (2010) Metal organic frameworks as NO delivery materials for biological applications. Micropor Mesopor Mat 129: 330–334. doi: 10.1016/j.micromeso.2009.04.031
    [32] Eddaoudi M, Moler D, Li H, et al. (2001) Modular Chemistry: Secondary Building Units as a Basis for the Design of Highly Porous and Robust Metal–Organic Carboxylate Frameworks. Accounts Chem Res 34: 319–330. doi: 10.1021/ar000034b
    [33] Nouar F, Eubank J, Bousquet T, et al. (2008) Supermolecular Building Blocks (SBBs) for the Design and Synthesis of Highly Porous Metal–Organic Frameworks. J Am Chem Soc 130: 1833–1835. doi: 10.1021/ja710123s
    [34] Figueroa J, Fout T, Plasynski S, et al. (2008) Advances in CO2 capture technology-The U.S. Department of Energy's Carbon Sequestration Program. Int J Greenh Gas Con 2: 9–20.
    [35] Chen K, Scott H, Madden D, et al. (2016) Benchmark C2H2/CO2 and CO2/C2H2 Separation by Two Closely Related Hybrid Ultramicroporous Materials. Chem 1: 753–765. doi: 10.1016/j.chempr.2016.10.009
    [36] Scott H, Shivanna M, Bajpai A, et al. (2017) Highly Selective Separation of C2H2 from CO2 by a New Dichromate-Based Hybrid Ultramicroporous Material. ACS Appl Mater Inter 9: 33395–33400. doi: 10.1021/acsami.6b15250
    [37] Xie DY, Xing HB, Zhang ZG, et al. (2017) Porous hydrogen-bonded organometallic frameworks for adsorption separation of acetylene and carbon dioxide. CIESC J 68: 154–162.
    [38] Thomas-Gipson J, Beobide G, Castillo O, et al. (2011) Porous supramolecular compound based on paddle-wheel shaped copper (II)–adenine dinuclear entities. CrystEngComm 13: 3301–3305. doi: 10.1039/c1ce05195d
    [39] Thomas-Gipson J, Beobide G, Castillo O, et al. (2014) Paddle-Wheel Shaped Copper(II)-Adenine Discrete Entities As Supramolecular Building Blocks To Afford Porous Supramolecular Metal–Organic Frameworks (SMOFs). Cryst Growth Des 14: 4019–4029. doi: 10.1021/cg500634y
    [40] Chui S, Lo S, Charmant J, et al. (1999) A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n. Science 283: 1148–1150. doi: 10.1126/science.283.5405.1148
    [41] Pham T, Forrest K, Chen K, et al. (2016) Theoretical Investigations of CO2 and H2 Sorption in Robust Molecular Porous Materials. Langmuir 32: 11492–11505. doi: 10.1021/acs.langmuir.6b03161
    [42] Nugent P, Rhodus V, Pham T, et al. (2013) A robust molecular porous material with high CO2 uptake and selectivity. J Am Chem Soc 68: 154–162.
    [43] Belof J, Stern A, Space B (2008) An Accurate and Transferable Intermolecular Diatomic Hydrogen Potential for Condensed Phase Simulation. J Chem Theory Comput 4: 1332–1337. doi: 10.1021/ct800155q
    [44] Rappé A, Casewit C, Colwell K, et al. (1992) UFF, a full periodic table force field for molecular mechanics and molecular dynamics simulations. J Am Chem Soc 114: 10024–10035. doi: 10.1021/ja00051a040
    [45] Van Duijnen P, Swart M (1998) Molecular and Atomic Polarizabilities: Thole's Model Revisited. J Phys Chem A 102: 2399–2407. doi: 10.1021/jp980221f
    [46] Forrest K, Pham T, McLaughlin K, et al. (2012) Simulation of the Mechanism of Gas Sorption in a Metal–Organic Framework with Open Metal Sites: Molecular Hydrogen in PCN-61. J Phys Chem C 116: 155 38–155549.
    [47] Breneman C, Wiberg K (1990) Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis. J Comput Chem 11: 361–373.
    [48] Valiev M, Bylaska EJ, Govind N, et al. (2010) NWChem: A comprehensive and scalable opensource solution for large scale molecular simulations. Comput Phys Commun 181: 1477–1489. doi: 10.1016/j.cpc.2010.04.018
    [49] Mullen A, Pham T, Forrest K, et al. (2013) A Polarizable and Transferable PHAST CO2 Potential for Materials Simulation. J Chem Theory Comput 9: 5421–5429. doi: 10.1021/ct400549q
    [50] Potoff J, Siepmann J (2001) Vapor–liquid equilibria of mixtures containing alkanes, carbon dioxide, and nitrogen. AIChE J 47: 16761682.
    [51] Metropolis N, Rosenbluth A, Rosenbluth M, et al. (1953) Equation of state calculations by fast computing machines. J Chem Phys 21: 1087–1092. doi: 10.1063/1.1699114
    [52] Massively Parallel Monte Carlo (MPMC), 2012. Available from: https://github.com/mpmccode/mpmc.
    [53] Monte Carlo-Molecular Dynamics (MCMD), 2017. Available from: https://github.com/khavernathy/mcmd.
    [54] Kirkpatrick S, Gelatt C, Vecchi M (1983) Optimization by Simulated Annealing. Science 220: 671–680. doi: 10.1126/science.220.4598.671
    [55] Dincă M, Dailly A, Liu Y, et al. (2006) Hydrogen Storage in a Microporous Metal–Organic Framework with Exposed Mn2+ Coordination Sites. J Am Chem Soc 128: 16876–16883. doi: 10.1021/ja0656853
    [56] Pham T, Forrest K, McLaughlin K, et al. (2013) Theoretical Investigations of CO2 and H2 Sorption in an Interpenetrated Square-Pillared Metal–Organic Material. J Phys Chem C 117: 9970–9982. doi: 10.1021/jp402764s
    [57] Nicholson D, Parsonage N (1982) Computer Simulation and the Statistical Mechanics of Adsorption, Academic Press.
    [58] Bae Y, Mulfort K, Frost H, et al. (2008) Separation of CO2 from CH2 Using Mixed-Ligand Metal–Organic Frameworks. Langmuir 24: 8592–8598. doi: 10.1021/la800555x
    [59] Goj A, Sholl D, Akten E, et al. (2002) Atomistic Simulations of CO2 and N2 Adsorption in Silica Zeolites: The Impact of Pore Size and Shape. J Phys Chem B 106: 8367–8375. doi: 10.1021/jp025895b
    [60] Akten E, Siriwardane R, Sholl D (2003) Monte Carlo Simulation of Single- and Binary-Component Adsorption of CO2, N2, and H2 in Zeolite Na-4A. Energ Fuel 17: 977–983. doi: 10.1021/ef0300038
    [61] Harris J, Yung K (1995) Carbon dioxide's liquid-vapor coexistence curve and critical properties as predicted by a simple molecular model. J Phys Chem 99: 12021–12024. doi: 10.1021/j100031a034

    © 2018 the Author(s), licensee AIMS Press. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0)
  • Reader Comments
通讯作者: 陈斌, bchen63@163.com
  • 1. 

    沈阳化工大学材料科学与工程学院 沈阳 110142

  1. 本站搜索
  2. 百度学术搜索
  3. 万方数据库搜索
  4. CNKI搜索

Metrics

Article views(1166) PDF downloads(907) Cited by(1)

Article outline

Figures and Tables

Figures(9)  /  Tables(2)

/

DownLoad:  Full-Size Img  PowerPoint
Return
Return

Catalog