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吴厚晓1 陈永伟1 梁俊杰1 石仁凤1 夏启斌1 李忠1

(1.华南理工大学化学与化工学院, 广东广州 510640)

【摘要】应用溶剂热法合成了不同氧化石墨烯(GO)负载量的MOF-505@GO复合材料,分别采用全自动表面积吸附仪、P-XRD、SEM和Raman对材料进行了性能表征,测定了CH4、C2H6和C3H8在MOF-505@GO上的吸附等温线,并进行Langmuir-Freundlich方程拟合,依据IAST理论模型计算了C2H6/CH4和C3H8/CH4二元混合气在MOF-505@5GO上的吸附选择性。研究结果表明,随着GO负载量增大,MOF-505@GO复合材料的孔容及BET比表面积先增大后减小,当GO负载量为5%(质量)时,复合材料MOF-505@5GO的孔容及BET比表面积达到最大,当GO负载量进一步增大至8%(质量)和10%(质量)时,复合材料的孔容及BET比表面积逐渐降低。在0.1 MPa和298 K条件下,MOF-505@5GO对CH4、C2H6和C3H8的吸附容量分别为0.88、4.81和5.17 mmol·g-1,相比MOF-505分别提高了14.9%、30.7%和13.1%。MOF-505@5GO对C2H6/CH4和C3H8/CH4的吸附选择性分别为40.1和3056.1,其对C2H6/CH4和C3H8/CH4具有极高的吸附选择性。

【关键词】 MOF-505@GO;甲烷;乙烷;丙烷;吸附(作用);二元混合物;


【基金资助】 国家自然科学基金项目(21576092,21276092,21436005);

Adsorption isotherms and selectivity of CH4/C2H6/C3H8 on MOF-505@5GO

WU Houxiao1 CHEN Yongwei1 LIANG Junjie1 SHI Renfeng1 XIA Qibin1 LI Zhong1

(1.School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, Guangdong, China 510640)

【Abstract】MOF-505@GO composites with different ratios of MOF-505 to graphite oxide were synthesized by solvothermal method. They were characterized by powder X-ray diffractions (PXRD), scanning electron microscopy (SEM), Raman and porosity measurement through nitrogen adsorption. The isotherms of CH4, C2H6 and C3H8 on the MOF-505@GO and MOF-505 were measured separately. The results show that MOF-505@5 GO has the largest pore volumes and BET surface area. The pore volumes and BET surface areas of MOF-505@GO increase as the GO content increases; when the GO content increases to 8% (mass) and 10% (mass), the opposite trend is observed in which the pore volumes and BET surface areas decrease. Accordingly, MOF-505@5 GO exhibits the highest CH4, C2H6 and C3H8 uptake of 0.88 mmol·g−1, 4.81 mmol·g−1 and 5.17 mmol·g−1 at 298 K and 0.1 MPa, having increases of 14.9%, 30.7% and 13.1%, respectively. Moreover, the IAST-predicted C2H6/CH4 selectivity of MOF-505@5 GO is about 40.1 and the C3H8/CH4 selectivity is about 3 056.1. It suggests that MOF-505@5 GO is a promising candidate for separation of C2H6/CH4 and C3H8/CH4.

【Keywords】 MOF-505@GO; methane; ethane; propane; adsorption; binary mixture;


【Funds】 National Natural Science Foundation of China (21576092, 21276092, 21436005);

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    [1] DUAN X, HE Y B, CUI Y J, et al. Highly selective separation of small hydrocarbons and carbon dioxide in a metal-organic framework with open copper (Ⅱ) coordination sites [J]. RSC Advances, 2014, 4 (44): 23058–23063.

    [2] HE Y B, KRISHNA B, CHEN B L. Metal–organic frameworks with potential for energy-efficient adsorptive separation of light hydrocarbons [J]. Energy & Environmental Science, 2012, 5 (10): 9107–9120.

    [3] DUAN X, ZHANG Q, CAI J F, et al. A new metal–organic framework with potential for adsorptive separation of methane from carbon dioxide, acetylene, ethylene, and ethane established by simulated breakthrough experiments [J]. Journal of Materials Chemistry A, 2014, 2 (8): 2628–2633.

    [4] PLONKA A M, CHEN X Y, WANG H, et al. Light hydrocarbon adsorption mechanisms in two calcium–based microporous metal organic frameworks [J]. Chemistry of Materials, 2016, 28 (6): 1636–1646.

    [5] HUANG L, CAO D P. Selective adsorption of olefin–paraffin on diamond-like frameworks: diamondyne and PAF–302 [J]. Journal of Materials Chemistry A, 2013, 1 (33): 9433–9439.

    [6] GEIER S J, MASON J A, BLOCH E D, et al. Selective adsorption of ethylene over ethane and propylene over propane in the metal–organic frameworks M2 (dobdc) (M = Mg, Mn, Fe, Co, Ni, Zn)[J]. Chemical Science, 2013, 4 (5): 2054–2061.

    [7] JIANG J W, SANDLER S I. Monte Carlo simulation for the adsorption and separation of linear and branched alkanes in IRMOF-1 [J]. Langmuir, 2006, 22 (13): 5702–5707.

    [8] SHEN W L, LI J X, YANG Y, et al. Binary adsorption equilibrium of CH4, N2 and CO2 on zeolite ZSM-5 [J]. CIESC Journal, 2014, 65 (9): 3490–3498 (in Chinese).

    [9] LI M, TU S, ZHAO X, et al. Adsorption equilibrium prediction for CH4-C2H6 on activated carbon by real adsorption solution theory [J]. CIESC Journal, 2013, 64 (11): 4082–4089 (in Chinese).

    [10] HOWARTH A J, PETERS A W, VERMEULEN N A, et al. Best practices for the synthesis, activation, and characterization of metalorganic frameworks [J]. Chemistry of Materials, 2017, 29 (1): 26–39.

    [11] HARTMANN M, BOHME U, HOVESTADT M, et al. Adsorptive separation of olefin/paraffin mixtures with ZIF-4 [J]. Langmuir, 2015, 31 (45): 12382–12389.

    [12] CAI J F, WANG H Z, WANG H L, et al. An amino-decorated NbO-type metal–organic framework for high C2H2 storage and selective CO2 capture [J]. RSC Advances, 2015, 5: 77417–77422.

    [13] ZOU R Y, REN X L, HUANG F, et al. A luminescent Zr-based metalorganic framework for sensing/capture of nitrobenzene and highpressure separation of CH4/C2H6 [J]. Journal of Materials Chemistry A, 2015, 3: 23493–23500.

    [14] XIA T F, CAI J F, WANG H Z, et al. Microporous metal–organic frameworks with suitable pore spaces for acetylene storage and purification [J]. Microporous and Mesoporous Materials, 2015, 215: 109–115.

    [15] LIU K, MA D X, LI B Y, et al. High storage capacity and separation selectivity for C2 hydrocarbons over methane in the metal–organic framework Cu-TDPAT [J]. Journal of Materials Chemistry A, 2014, 2 (38): 15823–15828.

    [16] HE Y B, XIANG S C, ZHANG Z J, et al. A microporous lanthanidetricarboxylate framework with the potential for purification of natural gas [J]. Chemical Communications, 2012, 48 (88): 10856–10858.

    [17] HE Y B, ZHANG Z J, XIANG S C, et al. A microporous metal–organic framework for highly selective separation of acetylene, ethylene, and ethane from methane at room temperature [J]. Chemistry—A European Journal, 2012, 18 (2): 613–619.

    [18] HE Y B, ZHANG Z J, XIANG S C, et al. High separation capacity and selectivity of C2 hydrocarbons over methane within a microporous metal–organic framework at room temperature [J]. Chemistry—A European Journal, 2012, 18 (7): 1901–1904.

    [19] CHEN Y W, QIAO Z E, LV D F, et al. Selective adsorption of light alkanes on a highly robust indium based metal–organic framework [J]. Industrial&Engineering Chemistry Research, 2017, 56 (15): 4488–4495.

    [20] PRASANTH K P, RALLAPALLI P, RAJ M C, et al. Enhanced hydrogen sorption in single walled carbon nanotube incorporated MIL-101 composite metal–organic framework [J]. International Journal of Hydrogen Energy, 2011, 36 (13): 7594–7601.

    [21] ZHAO Y X, SEREDYCH M, ZHONG Q, et al. Aminated graphite oxides and their composites with copper-based metal–organic framework: in search for efficient media for CO2 sequestration [J]. RSCAdvances, 2013, 3 (25): 9932–9941.

    [22] KAYE S S, DAILLY A, YAGHI O M, et al. Impact of preparation and handling on the hydrogen storage properties of Zn4O (1, 4-benzenedicarboxylate)3 (MOF–5) [J]. Journal of the American Chemical Society, 2007, 129 (46): 14176–14177.

    [23] SUN X J, XIA Q B, ZHAO Z X, et al. Synthesis and adsorption performance of MIL-101 (Cr)/graphite oxide composites with high capacities of n-hexane [J]. Chemical Engineering Journal, 2014, 239: 226–232.

    [24] PETIT C, BURRESS J, BANDOSZ T J. The synthesis and characterization of copper-based metal–organic framework/graphite oxide composites [J]. Carbon, 2011, 49 (2): 563–572.

    [25] AMELOOT R, LIEKENS A, ALAERTS L, et al. Silica–MOF composites as a stationary phase in liquid chromatography [J]. European Journal of Inorganic Chemistry, 2010, 24: 3735–3738.

    [26] SOMAYAJULU R P B, RAJ M C, PATIL D V, et al. Activated carbon @ MIL-101 (Cr): a potential metal–organic framework compositematerial for hydrogen storage [J]. International Journal of Energy Research, 2013, 37 (3): 746–753.

    [27] LI Y J, MIAO J P, SUN X J, et al. Mechanochemical synthesis of CuBTC@GO with enhanced water stability and toluene adsorption capacity [J]. Chemical Engineering Journal, 2016, 298: 191–197.

    [28] CHEN B L, OCKWIG N W, MILLWARD A R, et al. High H2adsorption in a microporous metal–organic framework with open metal sites [J]. Angewandte Chemie International Edition, 2005, 44 (30): 4745–4749.

    [29] CHEN Y W, LV D F, WU J L, et al. A new MOF-505@GO composite with high selectivity for CO2/CH4 and CO2/N2 separation [J]. Chemical Engineering Journal, 2017, 308: 1065–1072.

    [30] KOVTYUKHOVA N I, OLLIVIER P J, MARTIN B R, et al. Layer-by-layer assembly of ultrathin composite films from micron-sized graphite oxide sheets and polycations [J]. Chemistry of Materials, 1999, 11 (3): 771–778.

    [31] HSIAO M C, LIAO S H, YEN M Y, et al. Preparation of covalently functionalized graphene using residual oxygen-containing functional groups [J]. ACS Applied Materials and Interfaces, 2010, 2 (11): 3092–2099.

    [32] MYERS A L, PRAUSNITZ J M. Thermodynamics of mixed-gas adsorption [J]. AIChE J., 1965, 11 (1): 121–127.

    [33] WALTON K S, SHOLL D S. Predicting multicomponent adsorption: 50 years of the ideal adsorbed solution theory [J]. AICh E J., 2015, 61 (9): 2757–2762.

    [34] BLOCH E D, QUEEN W L, KRISHNA R, et al. Hydrocarbon separations in a metal-organic framework with open iron (Ⅱ) coordination sites [J]. Science, 2012, 335: 1606.

    [35] PIERS J, PINTO M L, SAINI V K. Ethane selective IRMOF-8 and its significance in ethane–ethylene separation by adsorption [J]. ACS Appl. Mater. Interfaces, 2014, 6: 12093–12099.

    [36] BANERJEE D, WANG H, PLONKA A M, et al. Direct structural identification of gas induced gate-opening coupled with commensurate adsorption in a microporous metal–organic framework [J]. Chem. Eur. J., 2016, 22: 1–11.

    [37] HE Y B, ZHANG Z J, XIANG S C, et al. A robust doubly interpenetrated metal–organic framework constructed from a novel aromatic tricarboxylate for highly selective separation of small hydrocarbons [J]. Chem. Commun., 2012, 48: 6493–6495.

This Article


CN: 11-1946/TQ

Vol 69, No. 04, Pages 1500-1507

April 2018


Article Outline


  • Introduction
  • 1 Experimental section
  • 2 Results and discussion
  • 3 Conclusion
  • References