Preparation and Pervaporation Performance of MoS2 Nanocomposite Hollow Fiber Membrane
-
摘要: 二维纳米材料复合膜是目前膜分离领域的研究热点。通过在具有不规则大孔结构的陶瓷中空纤维基膜上引入TiO2过渡层，有效地降低了基膜的孔径和粗糙度。在复合膜外表面构筑MoS2/PVA（聚乙烯醇）分离层，用于异丙醇脱水，通过原子力显微镜（AFM）、扫描电子显微镜（SEM）、X射线光电子能谱仪（XPS）等表征了复合膜的微观形貌，考察了分离层厚度、操作温度及料液浓度对复合膜分离性能的影响。在50 ℃下分离质量分数为90%的异丙醇水溶液时，MoS2/PVA-30复合膜表现出了较优的分离性能，其渗透通量为486 g/(m2·h)，分离系数为445。Abstract: Pervaporation (PV) process is a membrane-based separation technology that provides low-cost, environmentally friendly, and efficient characteristics in the separation of azeotropic mixtures. In this work, we provided a preparation method of a composite membrane based on molybdenum disulfide (MoS2) two-dimensional material used to dehydrate isopropanol aqueous solution. A ceramic hollow fiber (CHF) membrane was used as a substrate to prepare the MoS2 composite membrane. In order to reduce the macropores on the surface of the CHF membrane, a TiO2 intermediate layer was introduced on the outer surface of the CHF substrate. Polyvinyl alcohol (PVA) was used as a binder in the preparation of the MoS2/PVA separation layer. A MoS2/PVA separation layer was constructed on the surface of the TiO2-CHF membrane by vacuum filtration, and then crosslinked with glutaraldehyde solution to reduce the swelling degree of the MoS2/PVA separation layer in aqueous solution. The morphology and physico-chemical properties of the obtained membranes were studied by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and water contact angle (WCA) measurements. The MoS2/PVA composite membrane showed 486 g/(m2·h) of permeation flux and 445 of separation factor in a 90% IPA aqueous solution at 50 ℃.
-
Key words:
- MoS2 /
- isopropanol /
- ceramic hollow fiber /
- composite membrane /
- pervaporation
-
图 1 CHF膜（a）和TiO2-CHF膜（b）的孔径分布图
Figure 1. Pore size distribution diagram of CHF membrane (a) and TiO2-CHF membrane (b)
图 2 CHF膜（a1，a2）和TiO2-CHF膜（b1，b2）表面（上）和断面（下）的SEM图
Figure 2. SEM images of the surface (up) and cross-section (down) of CHF membrane (a1, a2) and TiO2-CHF membrane (b1, b2)
图 3 PVA膜（a1，a2），MoS2膜（b1，b2），MoS2/PVA-30复合膜（c1，c2）和MoS2/PVA-60复合膜（d1，d2）的外表面（上）和横截面（下）的SEM图像
Figure 3. SEM images of outer surface (up) and cross-section (down) of PVA membrane (a1, a2), MoS2 membrane (b1, b2), MoS2/PVA-30 composite membrane (c1, c2) and MoS2/PVA-60 composite membrane (d1, d2)
图 4 TiO2-CHF (a)、MoS2/PVA-30(b)和MoS2/PVA-60(c)复合膜的AFM拓扑结构图和表面粗糙度
Figure 4. AFM topological structure diagram and surface roughness of TiO2-CHF (a), MoS2/PVA-30 (b) and MoS2/PVA-60 (c) composite membrane
图 5 MoS2/PVA-30复合膜表面的EDS元素分布图像 （a）；PVA膜和MoS2/PVA-30复合膜表面的XPS谱图 （b）
Figure 5. EDS element distribution image of MoS2/PVA-30 composite membrane surface (a); XPS spectra of PVA membrane and MoS2/PVA-30 composite membrane surface (b)
图 6 PVA膜（a）和 MoS2/PVA-30复合膜 （b） C 1s光谱的XPS谱图
Figure 6. XPS image of C 1s spectra for PVA membrane (a) and MoS2/PVA-30 composite membrane (b)
图 7 MoS2体相材料粉末 （a）、MoS2/PVA-30复合膜 和TiO2-CHF膜（b）的XRD图谱
Figure 7. XRD patterns of bulk MoS2 (a), MoS2/PVA-30 composite membrane and TiO2-CHF membrane (b)
图 8 TiO2-CHF膜 （a）、PVA膜 （b）、MoS2膜 （c） 和MoS2/PVA-30复合膜 （d） 的水滴和WCA的图像
Figure 8. Image of water droplet and WCA degree of TiO2-CHF membrane (a), PVA membrane (b), MoS2 membrane (c) and MoS2/PVA-30 composite membrane (d)
图 9 PVA膜和MoS2/PVA-30复合膜在50 ℃ 和70 ℃下的渗透汽化性能
Figure 9. Pervaporation performance of PVA membrane and MoS2/PVA-30 composite membrane at 50 ℃ and 70 ℃
图 10 在不同抽滤时间下制备的MoS2/PVA复合膜的渗透汽化性能
Figure 10. Pervaporation performance of MoS2/PVA composite membrane prepared under different suction time
图 11 MoS2/PVA-30复合膜在不同质量分数的IPA溶液下的渗透汽化性能
Figure 11. Pervaporation performance of MoS2/PVA-30 composite membrane at different mass fractions of IPA solution
图 12 MoS2/PVA-30复合膜在不同操作温度下的渗透汽化性能
Figure 12. Pervaporation performance of MoS2/PVA-30 composite membrane at differernt operating temperatures
-
[1] LIN S H, WANG C S. Recovery of isopropyl alcohol from waste solvent of a semiconductor plant[J]. Journal of Hazardous Materials, 2004, 106(2): 161-168. [2] HU A D, KANG ONG Y, WANG P, et al. Thin-film composite tri-bore hollow fiber (TFC TbHF) membranes for isopropanol dehydration by pervaporation[J]. Journal of Membrane Science, 2014, 471: 155-167. doi: 10.1016/j.memsci.2014.07.059 [3] ZUO J, HUA D, MARICAR V, et al. Dehydration of industrial isopropanol (IPA) waste by pervaporation and vapor permeation membranes[J]. Journal of Applied Polymer Science, 2018, 135(24): 45086. doi: 10.1002/app.45086 [4] VALE A. Isopropanol[J]. Medicine, 2016, 44(3): 179. doi: 10.1016/j.mpmed.2015.12.015 [5] MEYERS C, KASS R, GOLDENBERG D, et al. Ethanol and isopropanol inactivation of human coronavirus on hard surfaces[J]. Journal of Hospital Infection, 2021, 107: 45-49. doi: 10.1016/j.jhin.2020.09.026 [6] SMITHA B, SUHANYA D, SRIDHAR S, et al. Separation of organic-organic mixtures by pervaporation: A review[J]. Journal of Membrane Science, 2004, 241(1): 1-21. doi: 10.1016/j.memsci.2004.03.042 [7] CHAUDHARI S, KWON Y, MOON M, et al. Melamine-modified silicotungstic acid incorporated into the polyvinyl alcohol/polyvinyl amine blend membrane for pervaporation dehydration of water/isopropanol mixtures[J]. Vacuum, 2018, 147: 115-125. doi: 10.1016/j.vacuum.2017.10.024 [8] CHAPMAN P, OLIVEIRA T, LIVINGSTON A, et al. Membranes for the dehydration of solvents by pervaporation[J]. Journal of Membrane Science, 2008, 318: 5-37. doi: 10.1016/j.memsci.2008.02.061 [9] BAKER R W. Membrane Separation Systems: Recent Developments and Future Directions [M]. [S.l.]: William Andrew, 1991. [10] 谢博远, 马晓华, 许振良. MOFs与碳纳米管双重改性渗透汽化复合膜及其性能研究[J]. 华东理工大学学报(自然科学版), 2020, 46(5): 608-612. [11] KIM J H, JEONG J H, KIM N, et al. Mechanical properties of two-dimensional materials and their applications[J]. Journal of Physics D: Applied Physics, 2018, 52(8): 083001. [12] LI J, MEDHEKAR N V, SHENOY V B. Bonding charge density and ultimate strength of monolayer transition metal dichalcogenides[J]. The Journal of Physical Chemistry C, 2013, 117(30): 15842-15848. doi: 10.1021/jp403986v [13] NOVOSELOV K S, GEIM A K, MOROZOV S V, et al. Electric field effect in atomically thin carbon films[J]. Science, 2004, 306(5696): 666-669. [14] CASILLAS G, SANTIAGO U, BARRON H, et al. Elasticity of MoS2 sheets by mechanical deformation observed by in situ electron microscopy[J]. The Journal of Physical Chemistry: C. Nanomaterials and Interfaces, 2015, 119: 710-715. doi: 10.1021/jp5093459 [15] LEE G H, YU Y J, CUI X, et al. Flexible and transparent MoS2 field-effect transistors on hexagonal boron nitride-graphene heterostructures[J]. ACS Nano, 2013, 7(9): 7931-7936. doi: 10.1021/nn402954e [16] WEI N, PENG X, XU Z. Understanding water permeation in graphene oxide membranes[J]. ACS Applied Materials & Interfaces, 2014, 6(8): 5877-5883. [17] TOH R J, SOFER Z, LUXA J, et al. 3R phase of MoS2 and WS2 outperforms the corresponding 2H phase for hydrogen evolution[J]. Chemical Communications, 2017, 53(21): 3054-3057. doi: 10.1039/C6CC09952A [18] SIM D M, HAN H J, YIM S, et al. Long-term stable 2H-MoS2 dispersion: Critical role of solvent for simultaneous phase restoration and surface functionalization of liquid-exfoliated MoS2[J]. ACS Omega, 2017, 2(8): 4678-4687. doi: 10.1021/acsomega.7b00841 [19] ZHANG H, TAYMAZOV D, LI M P, et al. Construction of MoS2 composite membranes on ceramic hollow fibers for efficient water desalination[J]. Journal of Membrane Science, 2019, 592: 117369. doi: 10.1016/j.memsci.2019.117369 [20] GOVIND R A, SRESHT V, PÁDUA A A H, et al. Dominance of dispersion interactions and entropy over electrostatics in determining the wettability and friction of two-dimensional MoS2 surfaces[J]. ACS Nano, 2016, 10(10): 9145-9155. doi: 10.1021/acsnano.6b04276 [21] WANG Z, MI B. Environmental applications of 2D molybdenum disulfide (MoS2) nanosheets[J]. Environmental Science & Technology, 2017, 51(15): 8229-8244. [22] CASTELLANOS-GOMEZ A, POOT M, STEELE G A, et al. Mechanical properties of freely suspended semiconducting graphene-like layers based on MoS2[J]. Nanoscale Research Letters, 2012, 7(1): 233. doi: 10.1186/1556-276X-7-233 [23] PENG Q, DE S. Outstanding mechanical properties of monolayer MoS2 and its application in elastic energy storage[J]. Physical Chemistry Chemical Physics, 2013, 15(44): 19427-19437. doi: 10.1039/c3cp52879k [24] DENG M, KWAC K, LI M, et al. Stability, molecular sieving, and ion diffusion selectivity of a lamellar membrane from two-dimensional molybdenum disulfide[J]. Nano Letters, 2017, 17(4): 2342-2348. doi: 10.1021/acs.nanolett.6b05238 [25] HIRUNPINYOPAS W, PRESTAT E, WORRALL S D, et al. Desalination and nanofiltration through functionalized laminar MoS2 membranes[J]. ACS Nano, 2017, 11(11): 11082-11090. doi: 10.1021/acsnano.7b05124 [26] LI Y, YANG S, ZHANG K, et al. Thin film nanocomposite reverse osmosis membrane modified by two dimensional laminar MoS2 with improved desalination performance and fouling-resistant characteristics[J]. Desalination, 2019, 454: 48-58. doi: 10.1016/j.desal.2018.12.016 [27] LI M N, SUN X F, WANG L, et al. Forward osmosis membranes modified with laminar MoS2 nanosheet to improve desalination performance and antifouling properties[J]. Desalination, 2018, 436: 107-113. doi: 10.1016/j.desal.2018.02.008 [28] SONG Y, JIANG Z, GAO B, et al. Embedding hydrophobic MoS2 nanosheets within hydrophilic sodium alginate membrane for enhanced ethanol dehydration[J]. Chemical Engineering Science, 2018, 185: 231-242. doi: 10.1016/j.ces.2018.03.057 [29] BEREAN K J, OU J Z, DAENEKE T, et al. 2D MoS2 PDMS nanocomposites for NO2 separation[J]. Small, 2015, 11(38): 5035-5040. doi: 10.1002/smll.201501129 [30] PAN F, DING H, LI W, et al. Constructing facilitated transport pathway in hybrid membranes by incorporating MoS2 nanosheets[J]. Journal of Membrane Science, 2018, 545: 29-37. doi: 10.1016/j.memsci.2017.09.054 [31] ABA N F D, CHONG J Y, WANG B, et al. Graphene oxide membranes on ceramic hollow fibers: Microstructural stability and nanofiltration performance[J]. Journal of Membrane Science, 2015, 484: 87-94. doi: 10.1016/j.memsci.2015.03.001 [32] TAO K, KONG C, CHEN L. High performance ZIF-8 molecular sieve membrane on hollow ceramic fiber via crystallizing-rubbing seed deposition[J]. Chemical Engineering Journal, 2013, 220: 1-5. doi: 10.1016/j.cej.2013.01.051 [33] PAN X L, STROH N, BRUNNER H, et al. Deposition of sol-gel derived membranes on α-Al2O3 hollow fibers by a vacuum-assisted dip-coating process[J]. Journal of Membrane Science, 2003, 226(1/2): 111-118. [34] ZHU L, CHEN M, DONG Y, et al. A low-cost mullite-titania composite ceramic hollow fiber microfiltration membrane for highly efficient separation of oil-in-water emulsion[J]. Water Research, 2016, 90: 277-285. doi: 10.1016/j.watres.2015.12.035 [35] CAO Y, WANG M, XU Z L, et al. A novel seeding method of interfacial polymerization-assisted dip coating for the preparation of zeolite NaA membranes on ceramic hollow fiber supports[J]. ACS Applied Materials & Interfaces, 2016, 8(38): 25386-25395. [36] LI L, CHEN M, DONG Y, et al. A low-cost alumina-mullite composite hollow fiber ceramic membrane fabricated via phase-inversion and sintering method[J]. Journal of the European Ceramic Society, 2016, 36(8): 2057-2066. doi: 10.1016/j.jeurceramsoc.2016.02.020 [37] LIU Y, WANG X, YANG F, et al. Excellent antimicrobial properties of mesoporous anatase TiO2 and Ag/TiO2 composite films[J]. Microporous and Mesoporous Materials, 2008, 114(1): 431-439. [38] WANG J, LI H, LI H, et al. Mesoporous TiO2 thin films exhibiting enhanced thermal stability and controllable pore size: Preparation and photocatalyzed destruction of cationic dyes[J]. ACS Applied Materials & Interfaces, 2014, 6(3): 1623-1631. [39] WANG M, CAO Y, XU Z L, et al. Facile fabrication and application of superhydrophilic stainless steel hollow fiber microfiltration membranes[J]. ACS Sustainable Chemistry & Engineering, 2017, 5(11): 10283-10289. [40] SUN L, HUANG H, PENG X. Laminar MoS2 membranes for molecule separation[J]. Chemical Communications, 2013, 49(91): 10718-10720. doi: 10.1039/c3cc46136j [41] RAN J, ZHANG P, CHU C, et al. Ultrathin lamellar MoS2 membranes for organic solvent nanofiltration[J]. Journal of Membrane Science, 2020, 602: 117963. doi: 10.1016/j.memsci.2020.117963 [42] ZHANG Z, LIU Y, LIN S, et al. Preparation and properties of glutaraldehyde crosslinked poly(vinyl alcohol) membrane with gradient structure[J]. Journal of Polymer Research, 2020, 27(8): 228. doi: 10.1007/s10965-020-02223-0 [43] MA X H, ZHANG H X, GU S W, et al. Process optimization and modeling of membrane reactor using self-sufficient catalysis and separation of difunctional ceramic composite membrane to produce methyl laurate[J]. Separation and Purification Technology, 2014, 132: 370-377. doi: 10.1016/j.seppur.2014.04.038 [44] SREEDHAR B, CHATTOPADHYAY D K, KARUNAKAR M S H, et al. Thermal and surface characterization of plasticized starch polyvinyl alcohol blends crosslinked with epichlorohydrin[J]. Journal of Applied Polymer Science, 2006, 101(1): 25-34. doi: 10.1002/app.23145 [45] KURU C, CHOI C, KARGAR A, et al. MoS2 nanosheet-Pd nanoparticle composite for highly sensitive room temperature detection of hydrogen[J]. Advanced Science, 2015, 2(4): 1500004. doi: 10.1002/advs.201500004 [46] LIU X W, CAO Y, LI Y X, et al. High-performance polyamide/ceramichollow fiber TFC membranes with TiO2 interlayer for pervaporation dehydration of isopropanol solution[J]. Journal of Membrane Science, 2019, 576: 26-35. doi: 10.1016/j.memsci.2019.01.023 [47] TELI S B, GOKAVI G S, SAIRAM M, et al. Highly water selective silicotungstic acid (H4SiW12O40) incorporated novel sodium alginate hybrid composite membranes for pervaporation dehydration of acetic acid[J]. Separation and Purification Technology, 2007, 54(2): 178-186. doi: 10.1016/j.seppur.2006.09.002 -
下载:
点击查看大图
计量
- 文章访问数: 488
- HTML全文浏览量: 184
- PDF下载量: 46
- 被引次数: 0
