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Graphene-based membranes for CO2 separation
Accepted Manuscript Graphene-based membranes for CO2 separation Akbar Ali, Ramyakrishna Pothu, Sajid Hussain siyal, Shahnawaz Phulpoto, Muhammad Sajjad, Khalid Hussain Thebo PII: DOI: Reference:
S2589-2991(18)30121-6 https://doi.org/10.1016/j.mset.2018.11.002 MSET 39
To appear in:
Materials Science for Energy Technologies
Received Date: Revised Date: Accepted Date:
30 September 2018 7 November 2018 8 November 2018
Please cite this article as: A. Ali, R. Pothu, S. Hussain siyal, S. Phulpoto, M. Sajjad, K. Hussain Thebo, Graphenebased membranes for CO2 separation, Materials Science for Energy Technologies (2018), doi: https://doi.org/ 10.1016/j.mset.2018.11.002
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Graphene-based membranes for CO2 separation Akbar Ali, a,b Ramyakrishna Pothu,c Sajid Hussain siyal,d Shahnawaz Phulpoto,e Muhammad Sajjad,f Khalid Hussain Thebo,a,g* a
University of CAS, Beijing 100049, People’s Republic of China CAS State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China c College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, PR China d Department of Metallurgy and Material Engineering, Dawood University of Engineering and Technology, Karachi Pakistan e Department of Physics and Electronics, Shah Abdul Latif University Khairpur Mir’s, Sindh Pakistan f Department of Physics, Kohat University of Science and Technology, Kohat 26000, b
Khyber Pakhtunkhwa, Pakistan g
Dr. M. A. Kazi Institute of Chemistry, University of Sindh, Jamshoro, Sindh Pakistan *Corresponding author: [email protected]
Abstract Increasing concentration of carbon dioxide (CO2) in the atmosphere is responsible for global warming in the world. Up to date, many technologies have been investigated to reduce the concentration of CO2 in the environment but no technology has got significant successes yet. Recently graphene based membrane has attracted significant attention for their potential applications in gas separation. In this review, we focus on separation of CO2 from gas mixtures through graphene-based membranes. More specifically, the separation of gas mixtures such as CO2/H2, CO2/CH4, CO2/N2 and CO2/O2 which have similar compositions in flue gas treatment, hydrogen purification and natural gas purification will be discussed. The advantages and disadvantages of these membranes will also be part of discussion and finally, the review ends with several recommendations and suggestions on the future prospect for CO2 separation. Key words: Carbon dioxide, global warming, graphene, membrane, separation, purification.
Energy and environment are serious issues faced by both devloping and developed nation in the globe [1-6]. The conusmption of energy by industrial separation processes are increased day by day in the world; due to rapid progress in industrialization and growth in population [4, 7]. In this regard significant efforts have been carried out to reduced their energy and operational cost [7-10]. The separation of gases have important role in various academia, industrial and medical applications [11-13]. The development of more efficient gas separation process is always remain area of interest for both industrial and academic research. Membrane–based technology has got significant attention for their vital applications in gas separation processes including requirement of pure gas supplies, hydrogen production from syngas, natural gas separation (CH4/CO2), CO2 capture (H2/CO2 and CO2/N2 sepration), separation of isotopes for nuclear uses and for reduction of greenhouse gases owing to its several advantanges such as reliability, environmental friendliness, easy operation, low cost and low energy consumption [14]. It is great challenge to fabircate more energy efficient membrane with high separation performance. Up to date, several materials such as polymers, ionic liquids, zeolites, silica and metal-organic framework (MOFs) have been exploited for the CO2 separation both on a laboratory and large-scale applications [7, 15-17] but seem to be failed due to significant energy cost and several environmental problems. Recently, graphene and derivatives considered as perfect materials for membrane technology and have been widely explored in gas separation, water filtration, desalination and organic separation [18-26] due to its mono-atomic thickness, 2D structure, high aspect ratio (>1000), good mechanical strength, chemical inertness and thermally stability [27-31]. Graphene is used in form of nanoporous graphene, graphene laminate and graphene-based composites for separation of single gas component and gas mixtures [27]. Theoretically, studies revealed that graphene and derivatives is an ideal materials for CO2 gas separation, but experimentally seldom reports have been published yet (Figs 1b) [3238]. Lee and coworkers [35] reported that nanoporous graphene (NPG) membrane can separate CO2 from CO2/N2, CO2/CH4, CO2/H2 and CO2/O2. Due to its mono-atomic thickness which provides a good selectivity and high permeability for gas molecules as compared to other carbon material such as carbon nanotube (Fig. 1c). Koenig et al.[36] used graphene nanosheets with controlled nanopore for permeation of CO2 gas along with
other gas molecules (Fig. b,c). Authors have used photolithography and mechanical exfoliation methods for fabrication of membrane over a micrometer-sized holes silicon wafer. Several defects were introduced onto graphene sheets using ultraviolet-induced oxidative etching technique. The defective graphene was used to measure the transport behavior of various gases such as Ar, H2, CO2, N2, CH4 and SF6 by using pressurized blister test and mechanical resonances tests. However, these membranes were limited only for separation of single gas components. Further studies are required of gas mixture in the future.
Figs 1. Separation of CO2 though NPG membrane; (a,b) theoretically nanopore: separation of CO2 from O2 and configuration of CO2 in the graphene pore (a), the membrane is separating CO2 from N2 (b), A CO2 molecule is passing through the pore while N2 molecules are too large to pass through. (c) Experimentally visualization of UV etching on suspended graphene, AFM analysis of prepared membranes, etched for a longer time to visualize the pore growth. The red area show the pits which is created by UV etching and (d) Compilation of measured leak rates [35, 36].
As compared to NPG, graphene oxide (GO) functional derivatives of graphene and its composites are excellent material for the CO2 separation (Table 1). GO can be easily synthesized at large scale and can be fabricated into laminates. The nanochannels between GO layers can act as molecular sieve by blocking all species. Initial work by Geim et al. [39] suggest that GO membranes (GOMs) are impermeable to liquids and gases but only allowed water vapors. After that, GOMs have been widely explored in wastewater treatment and desalination applications. Later, studies suggest that GOMs can also show a good properties for gas separation, if their microstructural properties can carefully controlled [25]. GO exhibits a series of exciting properties as compared to pristine graphene due to presence several functional groups such as hydroxyl, epoxy and carboxyl groups on its basal plane and edges. Several studies suggest that the selectivity of CO2 gas can be increased by introducing more amino and oxygen functional groups within GO layers. This increasing selectivity is due to reversible reactions between CO2 and amino/oxygen groups [40]. Kim et al. [41] have measured the gas permeation behavior of selective gas (i.e. CO2 and H2) through GO laminates. In order to fabricate high quality membranes, authors have used spin coating method to obtain uniform thin GOMs. Authors have measured permeation of several gas molecules and observed gas permeation trend which varies in the following order CO2>H2> He>CH4>O2>N2 at room temperature. Selective gas diffusion can be achieved by controlling the gas flow channel and pores visa different stacking processes. They observed that heating as well as pressure are also important parameter for better selectivity of system. During the permeability / flux process, gas molecule interact with both pores and interlayers. Thus, the functional groups at the edges of pore and between layers can also increase the selectivity of system. This study on CO2 gas separation is certainly one of pioneer step in the field of GOMs technology. Recently, GO-composites membranes have been widely investigated for better selectivity and permeability for the CO2 as compared to pristine GO laminates. Due to presence of strong conjugated π system within these membranes, offers a better selectivity for CO2 [42]. Shen and coworkers [43] developed GO-composite membranes (thickness 6-15 nm) on polyvinylidene fluoride (PVDF) substrates. Membranes were fabricated by dispersing GO powder in ethanol / water (70:30) solvent with sonication
and followed by addition of poly (ether block amide) (PEBA) with continuous stirring. PEBA is a family of copolymers, having –N-H-, H-N=O, and O-C=O functional groups. It was found that the PEBA exhibits good permselectivity for polar and nonpolar gas pairs such as CO2/N2, and CO2/H2. Due to presence of these different functional, high selectivity of CO2 were observed. Such functional groups provide several active sites for hydrogen bonding between functional groups of GO and PEBA chain (Fig. 2a). Here, hydrogen atoms act as proton due to the strong electrostatic attraction of nitrogen atoms, and several positive centers were produced in PEBA. While many negative centers are produced there due to O atoms of GO, resulting hydrogen bonding formed between hydrogen atoms of PEBA and the oxygen atoms of GO. Authors have studied selective gas-transport channels of GOMs by measuring the gas permeation properties. CO2 molecules showed much higher transportation than other gas molecules such as H2, CH4, N2. The gas permeability of these gases are as CO2>H2>CH2>N2 (Fig. 2b,c). The permeability and selectivity of CO2 are also significantly increased as the number of GO nanosheets increased. The permeability of CO2 reaches at 100 barrer and selectivity of CO2/N2 achieved 91 (Fig. 2b,c). Further, authors measured continuous permeation of CO2 and N2 up to 6000 min and membranes are very stable for practical application.
Figs 2. (a) Schematic representation of chemical linkage between different functional groups on GO and the PEBA chain, (b) Permeabilities of different gases i.e. CO2, H2, N2, CH4 and (c) CO2/N2 separation through GO-composite membranes. [25] To improve this work, Wu et al. [40], fabricated GO based mixed matrix membrane (MMMs). The GO was functionalized with polyethylene glycol and polyethyleneimine (GO-PEG-PEI) and incorporated into a commercial PEBAX (Fig. 3a). This cross-linking plays multiple roles in separation efficiency of the membrane with good chemical stability. PEG and PEI provide excellent affinity for CO2 molecule due to presence of EO and amine functional groups respectively which react reversibly with CO2 to increase its selectivity. By adopting this strategy, authors have measured the excellent permeability of CO2 (~1330 barrier) with a good selectivity of 45 and 120 for CO2/CH4 and CO2/N2 respectively (Fig. 3b,c). From these studies, it is cleared that the separation performances of CO2 can be increased by developing or introducing suitable
cross-linkage of functional groups within GO layers and no doubt the choice of the substrate should be on priority.
Figs 3. (a) Schematic representation of fabrication of PEG-PEI-GO membranes; (b) Effect of PEG-PEI-GO contents on separation performances of gas; (c) The permeability of pure gas and selectivity of the humidified membranes [40].
Conclusions and future prospective: Separation of CO2 seems to be one of the serious issue in the world. There is an urgent need to reduce or capture CO2 from environment, to prevent global warming and climate change [8]. Although sufficient efforts have been carried out on the potential benefits of graphene-based membranes for CO2 separation, but still need to addressed several key issues to achieve state of the art membrane based on graphene with excellent CO2 permeability (flux) and selectivity under practical operation conditions, with good lifetime of at least one year, chemical resistance against impurities such as SO2, NOx and trace metals, grain boundary, defects, pressure, temperature etc. However, the current fabrication methods, materials, and equipment are expensive and time-consuming,
making them unsuitable for industrial production. The manufacturing cost of graphene with additional price for pre-treatment of graphene prior to its application might impose a significant cost to the overall separation process, which will remain economically unfavorable. Moreover, the incorporating of functional materials within large area membranes and measurement of transport properties are main hurdles. There are several other issues arise during scale up of the technology from laboratory scale to large scale level. Therefore, the platform for experimentally verifying these predictions is in urgent need. However, it is strongly believed that these issues will be definitely resolved with passage of time, if the performances enhancement proves practically achievable [27]. Besides these issues, much effort should also be taken to precisely control the pore size and interlayer spacing, especially to realize sub-nanometer channels within membranes. Efforts should also be taken for designing and fabricating self-standing graphene-based membranes or to find out some suitable substrate which provide better separation. The humidity is also one of the factors which affect the selectivity in CO2 separation because of sorption and plasticization [12, 44, 45]. However, the microstructural properties of membranes intensely affected due to absorption of water molecules. This behavior is typically related to sorption between CO2 and water molecule, resulting cluster is formed which hinder the transportation of CO2 gas. The GO is a hydrophilic molecule in nature due to the presence of different oxygen containing functional groups, so it can easily adsorb water molecules and show similar behavior. These adsorbed water molecules between GO can hinder the diffusion of CO2 gas through the GOMs [12]. Therefore, the effect of humidity can be further investigated to understand the permeation behavior of GOMs. This is very important to improve the current design of CO2 separation membrane in order to scale up the process and used for commercial applications [45]. The current techniques such as vacuum filtration used for fabrication of membranes is easily hydrated by water molecules [12]. So there is a serious need to fabricate these membranes under an inert atmosphere and find out some suitable alternative for fabrication method. Chemical and mechanical stability of these membranes should also be investigated at different operational conditions because GOMs contain much oxygen-containing groups which are susceptible to any harsh condition such as high temperature [46]. The future work with this system will be directed at clarifying more exact transport and separation mechanism.
More, theoretically and experimentally work is required to achieve completely understand the role and mechanism of GOMs. Research works are in progress to remove these engineering hurdles to achieve a considerable separation using graphene-based membrane for practical applications. Table 1. Benchmarking of graphene-based membranes for CO2 gas separation Types of Membranes
Fabrication Method
Types of feed
Permeability
Selectivity
Ref.
GO/PEBA composite
Film casting
CO2
100 barrer
-
[25]
CO2/N2 CO2
650 GPU
91 -
[9]
CO2/CH4
-
75
CO2
1330 Barrer
-
CO2/CH4
-
45
CO2/N2 CO2
143 Barrer
120 -
[47]
CO2/N2 CO2
10-10 mol m-2 s-1 Pa-1 100 GPU
73 -
[37]
102 -
[41]
20 -
[48]
GO/Borate membranes
MP-MMM
PEO– PBT/GO membranes Porous graphene bilayer Few-layered GO/PES ZIF-8/GO composite
Vacuum filtration
Solutioncasting method
Solvent evaporation Focused ion beam (FIB). Spinning coating Layer-bylayer
H2/CO2 CO2 CO2/N2 CO2
10 mol m-2 s-1 Pa-1 7
H2/CO2 HPEI-GO/ PVAm-Cs/PS membranes
Casting solution method
[40]
15
CO2
36 GPU
-
CO2/N2
-
107
[49]
Abbreviation: AAO: anodic aluminum oxide; PES: polyether sulfone; PEBA: Polyether block amide; MP-MMM; Multi-permselective mixed matrix membrane; PU, polyurethane; HPEI, hyperbranched polyethylenimine. (1 GPU = 10-6 cm3; and 1 Barrer = 10-10 cm3 & 10-12 mol m-2 s-1 Pa-1)
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Conflict of Interest The authors declare that there is no conflict of interest.
Highlights This review focus on recent advances and challenging issues for graphene based membranes. The applications and separation efficiency of membranes for CO2 gas have been discussed and compared. Future direction to improve CO2 gas separation performances of graphene based membrane are discussed.
S2589-2991(18)30121-6 https://doi.org/10.1016/j.mset.2018.11.002 MSET 39
To appear in:
Materials Science for Energy Technologies
Received Date: Revised Date: Accepted Date:
30 September 2018 7 November 2018 8 November 2018
Please cite this article as: A. Ali, R. Pothu, S. Hussain siyal, S. Phulpoto, M. Sajjad, K. Hussain Thebo, Graphenebased membranes for CO2 separation, Materials Science for Energy Technologies (2018), doi: https://doi.org/ 10.1016/j.mset.2018.11.002
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Graphene-based membranes for CO2 separation Akbar Ali, a,b Ramyakrishna Pothu,c Sajid Hussain siyal,d Shahnawaz Phulpoto,e Muhammad Sajjad,f Khalid Hussain Thebo,a,g* a
University of CAS, Beijing 100049, People’s Republic of China CAS State Key Laboratory of Multi-phase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China c College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, PR China d Department of Metallurgy and Material Engineering, Dawood University of Engineering and Technology, Karachi Pakistan e Department of Physics and Electronics, Shah Abdul Latif University Khairpur Mir’s, Sindh Pakistan f Department of Physics, Kohat University of Science and Technology, Kohat 26000, b
Khyber Pakhtunkhwa, Pakistan g
Dr. M. A. Kazi Institute of Chemistry, University of Sindh, Jamshoro, Sindh Pakistan *Corresponding author: [email protected]
Abstract Increasing concentration of carbon dioxide (CO2) in the atmosphere is responsible for global warming in the world. Up to date, many technologies have been investigated to reduce the concentration of CO2 in the environment but no technology has got significant successes yet. Recently graphene based membrane has attracted significant attention for their potential applications in gas separation. In this review, we focus on separation of CO2 from gas mixtures through graphene-based membranes. More specifically, the separation of gas mixtures such as CO2/H2, CO2/CH4, CO2/N2 and CO2/O2 which have similar compositions in flue gas treatment, hydrogen purification and natural gas purification will be discussed. The advantages and disadvantages of these membranes will also be part of discussion and finally, the review ends with several recommendations and suggestions on the future prospect for CO2 separation. Key words: Carbon dioxide, global warming, graphene, membrane, separation, purification.
Energy and environment are serious issues faced by both devloping and developed nation in the globe [1-6]. The conusmption of energy by industrial separation processes are increased day by day in the world; due to rapid progress in industrialization and growth in population [4, 7]. In this regard significant efforts have been carried out to reduced their energy and operational cost [7-10]. The separation of gases have important role in various academia, industrial and medical applications [11-13]. The development of more efficient gas separation process is always remain area of interest for both industrial and academic research. Membrane–based technology has got significant attention for their vital applications in gas separation processes including requirement of pure gas supplies, hydrogen production from syngas, natural gas separation (CH4/CO2), CO2 capture (H2/CO2 and CO2/N2 sepration), separation of isotopes for nuclear uses and for reduction of greenhouse gases owing to its several advantanges such as reliability, environmental friendliness, easy operation, low cost and low energy consumption [14]. It is great challenge to fabircate more energy efficient membrane with high separation performance. Up to date, several materials such as polymers, ionic liquids, zeolites, silica and metal-organic framework (MOFs) have been exploited for the CO2 separation both on a laboratory and large-scale applications [7, 15-17] but seem to be failed due to significant energy cost and several environmental problems. Recently, graphene and derivatives considered as perfect materials for membrane technology and have been widely explored in gas separation, water filtration, desalination and organic separation [18-26] due to its mono-atomic thickness, 2D structure, high aspect ratio (>1000), good mechanical strength, chemical inertness and thermally stability [27-31]. Graphene is used in form of nanoporous graphene, graphene laminate and graphene-based composites for separation of single gas component and gas mixtures [27]. Theoretically, studies revealed that graphene and derivatives is an ideal materials for CO2 gas separation, but experimentally seldom reports have been published yet (Figs 1b) [3238]. Lee and coworkers [35] reported that nanoporous graphene (NPG) membrane can separate CO2 from CO2/N2, CO2/CH4, CO2/H2 and CO2/O2. Due to its mono-atomic thickness which provides a good selectivity and high permeability for gas molecules as compared to other carbon material such as carbon nanotube (Fig. 1c). Koenig et al.[36] used graphene nanosheets with controlled nanopore for permeation of CO2 gas along with
other gas molecules (Fig. b,c). Authors have used photolithography and mechanical exfoliation methods for fabrication of membrane over a micrometer-sized holes silicon wafer. Several defects were introduced onto graphene sheets using ultraviolet-induced oxidative etching technique. The defective graphene was used to measure the transport behavior of various gases such as Ar, H2, CO2, N2, CH4 and SF6 by using pressurized blister test and mechanical resonances tests. However, these membranes were limited only for separation of single gas components. Further studies are required of gas mixture in the future.
Figs 1. Separation of CO2 though NPG membrane; (a,b) theoretically nanopore: separation of CO2 from O2 and configuration of CO2 in the graphene pore (a), the membrane is separating CO2 from N2 (b), A CO2 molecule is passing through the pore while N2 molecules are too large to pass through. (c) Experimentally visualization of UV etching on suspended graphene, AFM analysis of prepared membranes, etched for a longer time to visualize the pore growth. The red area show the pits which is created by UV etching and (d) Compilation of measured leak rates [35, 36].
As compared to NPG, graphene oxide (GO) functional derivatives of graphene and its composites are excellent material for the CO2 separation (Table 1). GO can be easily synthesized at large scale and can be fabricated into laminates. The nanochannels between GO layers can act as molecular sieve by blocking all species. Initial work by Geim et al. [39] suggest that GO membranes (GOMs) are impermeable to liquids and gases but only allowed water vapors. After that, GOMs have been widely explored in wastewater treatment and desalination applications. Later, studies suggest that GOMs can also show a good properties for gas separation, if their microstructural properties can carefully controlled [25]. GO exhibits a series of exciting properties as compared to pristine graphene due to presence several functional groups such as hydroxyl, epoxy and carboxyl groups on its basal plane and edges. Several studies suggest that the selectivity of CO2 gas can be increased by introducing more amino and oxygen functional groups within GO layers. This increasing selectivity is due to reversible reactions between CO2 and amino/oxygen groups [40]. Kim et al. [41] have measured the gas permeation behavior of selective gas (i.e. CO2 and H2) through GO laminates. In order to fabricate high quality membranes, authors have used spin coating method to obtain uniform thin GOMs. Authors have measured permeation of several gas molecules and observed gas permeation trend which varies in the following order CO2>H2> He>CH4>O2>N2 at room temperature. Selective gas diffusion can be achieved by controlling the gas flow channel and pores visa different stacking processes. They observed that heating as well as pressure are also important parameter for better selectivity of system. During the permeability / flux process, gas molecule interact with both pores and interlayers. Thus, the functional groups at the edges of pore and between layers can also increase the selectivity of system. This study on CO2 gas separation is certainly one of pioneer step in the field of GOMs technology. Recently, GO-composites membranes have been widely investigated for better selectivity and permeability for the CO2 as compared to pristine GO laminates. Due to presence of strong conjugated π system within these membranes, offers a better selectivity for CO2 [42]. Shen and coworkers [43] developed GO-composite membranes (thickness 6-15 nm) on polyvinylidene fluoride (PVDF) substrates. Membranes were fabricated by dispersing GO powder in ethanol / water (70:30) solvent with sonication
and followed by addition of poly (ether block amide) (PEBA) with continuous stirring. PEBA is a family of copolymers, having –N-H-, H-N=O, and O-C=O functional groups. It was found that the PEBA exhibits good permselectivity for polar and nonpolar gas pairs such as CO2/N2, and CO2/H2. Due to presence of these different functional, high selectivity of CO2 were observed. Such functional groups provide several active sites for hydrogen bonding between functional groups of GO and PEBA chain (Fig. 2a). Here, hydrogen atoms act as proton due to the strong electrostatic attraction of nitrogen atoms, and several positive centers were produced in PEBA. While many negative centers are produced there due to O atoms of GO, resulting hydrogen bonding formed between hydrogen atoms of PEBA and the oxygen atoms of GO. Authors have studied selective gas-transport channels of GOMs by measuring the gas permeation properties. CO2 molecules showed much higher transportation than other gas molecules such as H2, CH4, N2. The gas permeability of these gases are as CO2>H2>CH2>N2 (Fig. 2b,c). The permeability and selectivity of CO2 are also significantly increased as the number of GO nanosheets increased. The permeability of CO2 reaches at 100 barrer and selectivity of CO2/N2 achieved 91 (Fig. 2b,c). Further, authors measured continuous permeation of CO2 and N2 up to 6000 min and membranes are very stable for practical application.
Figs 2. (a) Schematic representation of chemical linkage between different functional groups on GO and the PEBA chain, (b) Permeabilities of different gases i.e. CO2, H2, N2, CH4 and (c) CO2/N2 separation through GO-composite membranes. [25] To improve this work, Wu et al. [40], fabricated GO based mixed matrix membrane (MMMs). The GO was functionalized with polyethylene glycol and polyethyleneimine (GO-PEG-PEI) and incorporated into a commercial PEBAX (Fig. 3a). This cross-linking plays multiple roles in separation efficiency of the membrane with good chemical stability. PEG and PEI provide excellent affinity for CO2 molecule due to presence of EO and amine functional groups respectively which react reversibly with CO2 to increase its selectivity. By adopting this strategy, authors have measured the excellent permeability of CO2 (~1330 barrier) with a good selectivity of 45 and 120 for CO2/CH4 and CO2/N2 respectively (Fig. 3b,c). From these studies, it is cleared that the separation performances of CO2 can be increased by developing or introducing suitable
cross-linkage of functional groups within GO layers and no doubt the choice of the substrate should be on priority.
Figs 3. (a) Schematic representation of fabrication of PEG-PEI-GO membranes; (b) Effect of PEG-PEI-GO contents on separation performances of gas; (c) The permeability of pure gas and selectivity of the humidified membranes [40].
Conclusions and future prospective: Separation of CO2 seems to be one of the serious issue in the world. There is an urgent need to reduce or capture CO2 from environment, to prevent global warming and climate change [8]. Although sufficient efforts have been carried out on the potential benefits of graphene-based membranes for CO2 separation, but still need to addressed several key issues to achieve state of the art membrane based on graphene with excellent CO2 permeability (flux) and selectivity under practical operation conditions, with good lifetime of at least one year, chemical resistance against impurities such as SO2, NOx and trace metals, grain boundary, defects, pressure, temperature etc. However, the current fabrication methods, materials, and equipment are expensive and time-consuming,
making them unsuitable for industrial production. The manufacturing cost of graphene with additional price for pre-treatment of graphene prior to its application might impose a significant cost to the overall separation process, which will remain economically unfavorable. Moreover, the incorporating of functional materials within large area membranes and measurement of transport properties are main hurdles. There are several other issues arise during scale up of the technology from laboratory scale to large scale level. Therefore, the platform for experimentally verifying these predictions is in urgent need. However, it is strongly believed that these issues will be definitely resolved with passage of time, if the performances enhancement proves practically achievable [27]. Besides these issues, much effort should also be taken to precisely control the pore size and interlayer spacing, especially to realize sub-nanometer channels within membranes. Efforts should also be taken for designing and fabricating self-standing graphene-based membranes or to find out some suitable substrate which provide better separation. The humidity is also one of the factors which affect the selectivity in CO2 separation because of sorption and plasticization [12, 44, 45]. However, the microstructural properties of membranes intensely affected due to absorption of water molecules. This behavior is typically related to sorption between CO2 and water molecule, resulting cluster is formed which hinder the transportation of CO2 gas. The GO is a hydrophilic molecule in nature due to the presence of different oxygen containing functional groups, so it can easily adsorb water molecules and show similar behavior. These adsorbed water molecules between GO can hinder the diffusion of CO2 gas through the GOMs [12]. Therefore, the effect of humidity can be further investigated to understand the permeation behavior of GOMs. This is very important to improve the current design of CO2 separation membrane in order to scale up the process and used for commercial applications [45]. The current techniques such as vacuum filtration used for fabrication of membranes is easily hydrated by water molecules [12]. So there is a serious need to fabricate these membranes under an inert atmosphere and find out some suitable alternative for fabrication method. Chemical and mechanical stability of these membranes should also be investigated at different operational conditions because GOMs contain much oxygen-containing groups which are susceptible to any harsh condition such as high temperature [46]. The future work with this system will be directed at clarifying more exact transport and separation mechanism.
More, theoretically and experimentally work is required to achieve completely understand the role and mechanism of GOMs. Research works are in progress to remove these engineering hurdles to achieve a considerable separation using graphene-based membrane for practical applications. Table 1. Benchmarking of graphene-based membranes for CO2 gas separation Types of Membranes
Fabrication Method
Types of feed
Permeability
Selectivity
Ref.
GO/PEBA composite
Film casting
CO2
100 barrer
-
[25]
CO2/N2 CO2
650 GPU
91 -
[9]
CO2/CH4
-
75
CO2
1330 Barrer
-
CO2/CH4
-
45
CO2/N2 CO2
143 Barrer
120 -
[47]
CO2/N2 CO2
10-10 mol m-2 s-1 Pa-1 100 GPU
73 -
[37]
102 -
[41]
20 -
[48]
GO/Borate membranes
MP-MMM
PEO– PBT/GO membranes Porous graphene bilayer Few-layered GO/PES ZIF-8/GO composite
Vacuum filtration
Solutioncasting method
Solvent evaporation Focused ion beam (FIB). Spinning coating Layer-bylayer
H2/CO2 CO2 CO2/N2 CO2
10 mol m-2 s-1 Pa-1 7
H2/CO2 HPEI-GO/ PVAm-Cs/PS membranes
Casting solution method
[40]
15
CO2
36 GPU
-
CO2/N2
-
107
[49]
Abbreviation: AAO: anodic aluminum oxide; PES: polyether sulfone; PEBA: Polyether block amide; MP-MMM; Multi-permselective mixed matrix membrane; PU, polyurethane; HPEI, hyperbranched polyethylenimine. (1 GPU = 10-6 cm3; and 1 Barrer = 10-10 cm3 & 10-12 mol m-2 s-1 Pa-1)
Acknowledgements: Dr. Thebo is thankful to University of Chinese academy of Science and University of Sindh Jamshoro Pakistan. Reference: 1.
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Conflict of Interest The authors declare that there is no conflict of interest.
Highlights This review focus on recent advances and challenging issues for graphene based membranes. The applications and separation efficiency of membranes for CO2 gas have been discussed and compared. Future direction to improve CO2 gas separation performances of graphene based membrane are discussed.