Elsevier

Chemical Engineering Journal

Volume 373, 1 October 2019, Pages 1190-1202
Chemical Engineering Journal

Water vapor transport properties of interfacially polymerized thin film nanocomposite membranes modified with graphene oxide and GO-TiO2 nanofillers

https://doi.org/10.1016/j.cej.2019.05.122Get rights and content

Highlights

  • GO and GO-TiO2 nanofillers were incorporated in polyamide nanocomposite membrane.

  • Improved water vapor permeance was obtained from GO and GO-TiO2 nanofillers incorporated TFN membranes.

  • Highly hydrophilic TFN membranes were obtained for water vapor separation.

  • GO-TiO2 shows superior water vapor permeance than GO.

  • Functionalized GO could improve water vapor permeation even further.

Abstract

Graphene oxide (GO) and its composite with TiO2 (GT) were utilized as nano-filler materials to prepare highly permeable and water vapor selective nanocomposite membranes. The nano-fillers were characterized using different analytical tools to determine their physicochemical properties. Nanocomposite membranes were prepared by dispersing the nano-fillers in aqueous phase monomer solution for interfacial polymerization reaction on the inner surface of Polysulfone hollow fiber membrane. Surface morphology and bonding chemistry of the nanocomposite membrane was analyzed using various analytical tools. The two types of nano-fillers were compared for their compatibility with the polyamide matrix, and consequently, the water vapor separation performance of the resulting membrane. Results revealed that both the nano-fillers are firmly attached to the polyamide layer via hydrogen and covalent bonds. GT based membranes have higher surface roughness and better hydrophilicity as compared to GO. In addition, GT membranes have more carboxyl groups and lesser degree of cross-linking due to the interference with interfacial polymerization reaction. This leads to a higher permeance (2820 GPU) and a water vapor/nitrogen selectivity when compared to other TFN membranes reported in literature. The nano-fillers act as active sites for preferential transport of water vapor molecules through the membrane thereby, significantly improving water vapor permeance.

Graphical abstract

GO and GO-TiO2 incorporation in TFN membrane by interfacial polymerization for excellent water vapor separation performance.

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Introduction

Water vapor is a dominant greenhouse gas. In clear skies, the contribution of water vapor to the greenhouse effect is approximately 60%, followed by carbon dioxide (∼25%), ozone (∼8%) and other trace gases [1]. With the amount of carbon dioxide that exists in the earth’s atmosphere, increasing water vapor content (relative humidity) amplifies the heat trapping effect of CO2, thus resulting in a potent impact on global warming. An enormous amount of water vapor is released into the atmosphere by a number of industries including power plants and chemical factories. This gradual moistening of the earth’s troposphere has increased the global warming effect of CO2 by two folds [2]. With the increased use of greener technologies to curb CO2 emissions, there is also a greater need to address the water vapor emissions from man-made sources. In addition to large industrial units such as cooling towers, removal of water vapor is also crucial in applications such as dehumidification and air conditioning of buildings [3].

Currently, water vapor is removed from industrial cooling towers and air dehumidification units by a number of techniques such as desiccant drying [4], gas condensation [5], and membrane technology [6]. Among these, the polymeric membrane technology has been commercially implemented since the 1970′s due to its smaller footprint and relatively simple operation [6]. Separation is achieved using membranes that have a dense top layer and a porous support. Thin film composite (TFC) and nanocomposite (TFN) membranes meet these requirements. These composite membranes are mostly prepared through an interfacial polymerization (IP) reaction of two or more monomers on the surface of a porous polymeric support. Research on TFC membranes for gas separation surged after Cadotte et al. [7] proposed interfacial polymerization (IP) as a feasible method to prepare a selective polyamide layer [7]. The polyamide layer possesses desirable characteristics such as mechanical strength, chemical resistance, and thermal stability coupled with high selectivity which is essential in gas separation [8]. The major aim in gas separation membranes is to overcome the upper limit of permeance-selectivity trade-off curve, commonly known as the ‘Robeson Plot’. With the optimum reaction conditions already known for TFC membranes, [9], [10], [11] it is becoming increasingly difficult to overcome this upper bound.

A new path towards developing the next generation of composite membranes was introduced when Jeong et al. successfully demonstrated that adding Zeolite A nanoparticles in the polyamide matrix during the IP reaction can give highly permselective thin film nanocomposite membranes for reverse osmosis application [12]. Nanoparticles inclusion in the polyamide layer makes it much easier to control its properties because of the high surface area and surface energy of nanoparticles [13]. Highly permeable and selective gas separation membranes can be produced by simply tuning the type of nanoparticles, their size, and surface chemical properties.

Wide variety of nanomaterials have been used as nano-fillers for gas separation membranes. A filler material shall ideally have a small size (<100 nm) because most polyamide layers are of hundred nanometers thick. Furthermore, it should also be compatible with the polyamide matrix by forming covalent bonds. Recently, Gao et al. synthesized polyethyleneimine grafted ZIF-8 particles for CO2 separation [14]. The modified porous ZIF-8 particles were found to have better compatibility with the polymer matrix while maintaining high permselectivity. Shamsabadi et al. proposed TiO2 nanoparticles as nano-fillers for CO2/N2 separation membranes [15]. Similarly, other nanomaterials such as carbon nanofibers and nanotubes [16], [17], silica [18], and metal organic frameworks [19], [20] have been used as filler materials for gas separation membranes because of their tunable properties and pore structures. Recently, researchers have shown that incorporating graphene oxide in the polyamide layer for CO2 separation results in an acceptable permeance and selectivity trade-off [21], [22]. Apart from above mentioned applications, membranes are widely used in solar cells and batteries [23], [24]. Applying phase inversion method Li et al. prepared porous membranes using polyetherimide with tunable morphology and for lithium-ion batteries (LIBs) [25]. Recently researchers have also developed different eggshell membranes for lithium-ion battery along with membranes for vanadium redox flow battery applications [26], [27].

However, the use of nanoparticles in TFN membranes is mainly limited to conventional gas separation applications such as CO2/N2, CO2/CH4 etc. In our previous work, we have demonstrated that functionalized silicon nanoparticles (15–20 nm) are resistant to agglomeration at low concentrations and exhibit high water vapor permeance and selectivity [28]. Similarly, in previous research, used TiO2 nanoparticles and acid activated bentonite clay to fabricate highly hydrophilic nanocomposite membranes for improved water vapor permeance [29], [30]. Use of new nanomaterials for gas separation applications is essential in order to overcome the trade-off between permeance and selectivity.

In this work, we have improved the water vapor permeance and selectivity of TFN membranes by utilizing two types of nano-fillers. We have incorporated graphene oxide (GO) and Graphene oxide-TiO2 (GT) as a filler material in the polyamide selective layer. GO has gained wide spread attention because of its abundant hydroxyl and carboxyl groups that form hydrogen networks with water molecules [31]. Furthermore, graphene oxide has a better dispersion in water and polar solvents which makes it easier to be used in IP reaction [32]. GO based TFN membranes have already been shown to increase the water permeability for nanofiltration applications [33], [34], [35]. In addition, when coupled with TiO2 nanoparticles, GO-TiO2 composites have further increased the membrane separation performance [36]. The synergistic effects of using two nanomaterials at once can lead to an improved water vapor separation. Herein, we examine how GO and GO-TiO2 affects the polyamide layer and its bonding chemistry. The aim is to increase the water vapor permeance and selectivity while adding only minimum amount of nano-fillers. It is hoped that the findings of this research will contribute to a deeper understanding of the nanomaterials and their interaction with water vapor.

Section snippets

Materials

Polysulfone ultrafiltration hollow fiber membranes, having an outer diameter of 1400 µm and inner diameter of 1000 µm, were obtained from Guiyang Shidai Huitong Film Technology Co. Ltd. China. The molecular weight cut-off of the purchased membranes was 8000 Da. Graphene oxide dispersion solution in H2O (2 mg/ml, GO), TiO2 nanoparticles (average particle size ∼ 70 nm), m-Phenylenediamine (99%, MPD) and 1,3,5-Benzenetricarbonyl trichloride (98%, TMC) were purchased from Sigma-Aldrich. n-Hexane

ATR-FTIR

FTIR spectra of the pristine Polysulfone ultrafiltration membrane and the thin film nanocomposite membranes are presented in Fig. 1. Typical infrared spectra showing the characteristic peaks of Polysulfone (PSf) were obtained in accordance with the reported literature [41]. The peaks at 1580 cm−1 and 1486 cm−1 are assigned to the aromatic Csingle bondC stretching of the sulfone group, 1323 cm−1 and 1293 cm−1 are characteristic peaks of asymmetric SO2 stretching vibration, the peak at 1250 cm−1 can be

Conclusions

Thin film nanocomposite membranes were prepared using graphene oxide (GO) and graphene oxide-TiO2 (GT) composites as filler materials for the polyamide layer. The nano-fillers were added to the aqueous phase monomer in different concentrations. The interfacial polymerization reaction with the organic phase monomer resulted in a dense polyamide nanocomposite membrane on a porous PSf hollow fiber support. It was found that GO and GT are bonded to the polyamide layer via hydrogen bonds. This

Declaration of Competing Interest

There is no conflict of interest to declare.

Acknowledgements

This work was supported by the National Research Council of Science & Technology (NST) grant by the Korea government (MSIP) (No. CRC-15-07-KIER). PGI would like to acknowledge Council of Scientific and Industrial Research (CSIR), New Delhi in-house Project No. OLP-2021.

References (65)

  • L. Ansaloni et al.

    Facilitated transport membranes containing amino-functionalized multi-walled carbon nanotubes for high-pressure CO2 separations

    J. Membr. Sci.

    (2015)
  • J. Ahn et al.

    Polysulfone/silica nanoparticle mixed-matrix membranes for gas separation

    J. Membr. Sci.

    (2008)
  • K.C. Wong et al.

    Highly permeable and selective graphene oxide-enabled thin film nanocomposite for carbon dioxide separation

    Int. J. Greenh. Gas Control.

    (2017)
  • H. Li et al.

    Porous graphene nanosheets functionalized thin film nanocomposite membrane prepared by interfacial polymerization for CO2/N2 separation

    J. Membr. Sci.

    (2017)
  • C.M. Costa et al.

    Mesoporous poly(vinylidene fluoride-co-trifluoroethylene) membranes for lithium-ion battery separators

    Electrochim. Acta

    (2019)
  • N. Sarabchi et al.

    Exergoeconomic analysis and optimization of a novel hybrid cogeneration system: high-temperature proton exchange membrane fuel cell/Kalina cycle, driven by solar energy

    Energy. Convers. Manage.

    (2019)
  • D. Li et al.

    Porous polyetherimide membranes with tunable morphology for lithium-ion battery

    J. Membr. Sci.

    (2018)
  • V.H. Nguyen et al.

    Recycling different eggshell membranes for lithium-ion battery

    Mater. Lett.

    (2018)
  • Y. Shi et al.

    Recent development of membrane for vanadium redox flow battery applications: a review

    Appl. Energy

    (2019)
  • M.I. Baig et al.

    Synthesis and characterization of thin film nanocomposite membranes incorporated with surface functionalized Silicon nanoparticles for improved water vapor permeation performance

    Chem. Eng. J.

    (2017)
  • S. Xia et al.

    Preparation of graphene oxide modified polyamide thin film composite membranes with improved hydrophilicity for natural organic matter removal

    Chem. Eng. J.

    (2015)
  • G.S. Lai et al.

    Tailor-made thin film nanocomposite membrane incorporated with graphene oxide using novel interfacial polymerization technique for enhanced water separation

    Chem. Eng. J.

    (2018)
  • J. Yin et al.

    Graphene oxide (GO) enhanced polyamide (PA) thin-film nanocomposite (TFN) membrane for water purification

    Desalination

    (2016)
  • L. Chen et al.

    Graphene oxide based membrane intercalated by nanoparticles for high performance nanofiltration application

    Chem. Eng. J.

    (2018)
  • M.I. Baig et al.

    Water vapor selective thin film nanocomposite membranes prepared by functionalized Silicon nanoparticles

    Desalination

    (2019)
  • M.I. Baig et al.

    Development of carboxylated TiO2 incorporated thin film nanocomposite hollow fiber membranes for flue gas dehydration

    J. Membr. Sci.

    (2016)
  • C.Y. Tang et al.

    Effect of membrane chemistry and coating layer on physiochemical properties of thin film composite polyamide RO and NF membranes. I. FTIR and XPS characterization of polyamide and coating layer chemistry

    Desalination

    (2009)
  • M.E.A. Ali et al.

    Thin film composite membranes embedded with graphene oxide for water desalination

    Desalination

    (2016)
  • Y. Gao et al.

    Membrane surface modification with TiO2-graphene oxide for enhanced photocatalytic performance

    J. Membr. Sci.

    (2014)
  • T.D. Nguyen-Phan et al.

    The role of graphene oxide content on the adsorption-enhanced photocatalysis of titanium dioxide/graphene oxide composites

    Chem. Eng. J.

    (2011)
  • G. Hurwitz et al.

    Probing polyamide membrane surface charge, zeta potential, wettability, and hydrophilicity with contact angle measurements

    J. Membr. Sci.

    (2010)
  • C.Y. Tang et al.

    Probing the nano- and micro-scales of reverse osmosis membranes-A comprehensive characterization of physiochemical properties of uncoated and coated membranes by XPS, TEM, ATR-FTIR, and streaming potential measurements

    J. Membr. Sci.

    (2007)
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