Single layer Graphene Oxide functionalized with

Ionic Liquid for Selective Removal of Inorganic Salts

Ioannis Zuburtikudis
Chemical Engineering
Department
Abu Dhabi University
Abu Dhabi, United Arab
Emirates
ioannis.zuburtikudis@adu.ac.ae
Hadil Abu Khalifeh
Chemical Engineering
Department
Abu Dhabi University
Abu Dhabi, United Arab
Emirates
hadil.abukhalifeh@adu.ac.ae
Inas M. Alnashef Botagoz Zhuman
Chemical Engineering Chemical Engineering
Department Department
Khalifa University of Science and Abu Dhabi University
Technology Abu Dhabi, United Arab
Abu Dhabi, UAE Emirates
enas.nashef@ku.ac.ae botagoz.zhuman@adu.ac.ae

Abstract— The drive for minimizing the environmental
impact, while making the whole process more efficient, generated
the idea of investigating the use of some well-known green solvents,
the Ionic Liquids (ILs), and their ability to extract salts from
seawater as a step in the entire desalination process. However,
most of ILs, which exhibit high solubility towards some of the salts
known to cause inorganic fouling problems to the membranes used
in relevant water desalination technology, are hydrophilic and
thus, they cannot be used directly for extraction. Studies in the
literature have shown that this type of ILs will not be dissolved in
water, if they are properly attached on suitable carriers. Carbon
nanostructures with their unique properties have already been
used as carriers for a wide variety of chemical species. In this
work, we present our results for loading a selected IL
(Propylammonium Nitrate) on single layer Graphene Oxide (GO)
and the extraction capability of this composite material towards
CaCl2, MgCl2 and NaCl salts.
Keywords—ionic liquids, graphene oxide, functionalization,
adsorbent, inorganic salts, sea water pretreatment, desalination
I. INTRODUCTION
Graphene is considered a promising new adsorbent material
and its use as a highly efficient adsorbent material in analytical
extraction has been shown in several studies [1, 2]. However,
the layers of graphene sheets tend to aggregate due to π-π
stacking, which can decrease significantly their surface area.
Therefore, it is necessary to modify or insert a spacer material
between the graphene sheets to mitigate its aggregation and
increase the specific surface area. These factors are highly
important in order to enhance the adsorption properties [3].
Ionic liquids (ILs) comprise an organic cation and an organic
or inorganic anion, exhibit superior characteristics such as high
chemical and thermal stability, non-flammability, very low
vapor pressure, and high ionic conductivity [4, 5]. They are
capable of multiple types of interaction; π–π, n–π, and hydrogen
bonding [6]. Due to positively or negatively charged groups, an
IL can be used to modify graphene in order to enhance its
adsorption capacity. Moreover, ILs with electron-rich aromatic
π-systems improves the extraction efficiencies [7]. Therefore,
surface functionalization of Graphene with ionic liquids is
gaining popularity, because of their properties, their
environmental benign characteristics and their ability to
dissolve well a wide range of compounds. It is worth
mentioning that the covalent attachment of ionic materials to
graphene surfaces has first been done in 2009 [8]. The covalent
functionalization of graphene is mostly performed by acylation,
esterification, isocyanate formation, nucleophilic ring opening,
amide formation, and diazotization and cycloaddition reactions.
Whereas, non-covalent functionalization mostly involves
electrostatic forces, hydrogen bonding, π–π interactions, van
der Waals interaction and donor–acceptor interactions. [9].
The widespread use of membrane-assisted sea-water
desalination technologies has resulted in an increase of interest
in the quest for developing new functional materials for salt
extraction. ILs are already used in separation and extraction
processes of several heavy metals in sea water and waste water
[10]. However, ILs which have good solubility towards
inorganic salts present in sea water, specifically MgCl2 and
CaCl2, are hydrophilic[11]. Therefore, there can be cross
contamination of the water during the extraction process [12,
13]. However, if ILs are supported on a proper structure such
as that of graphene, graphene oxide (GO) or other types of
Carbon Nanostructures (CNS), this problem can be avoided.
The main idea of the research presented here is to utilize GO
functionalized with a proper IL for extracting sea salts as a
pretreatment step for the Reverse Osmosis (RO) desalination
process. The idea behind is to reduce the concentration of these
inorganic salts, namely CaCl2, MgCl2 and NaCl2, causing the
inorganic fouling (scaling) in membranes [14]. By addressing
the problem of fouling in the membranes, the overall load on
desalination plants can be decreased and RO membrane
performance and lifetime can be increased.
II. EXPERIMENTAL
A. Chemicals and materials
Graphene oxide with the following specifications: flake size
of 0.5-2.0μm, thickness 0.6-1.2nm, single-layer ratio: >80%,
diameter 1~5 μm, purity ~99%, bulk density 0.26g/cm3 and
surface area of 600 m2/g was purchased from ACS Materials.
Ionic Liquid, namely Propylammonium Nitrate (PAN) with

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purity>97% was purchased from IoLiTec-Ionic Liquids
Technologies (Germany). NaOH solution was prepared from
NaOH purchased from Sigma Aldrich with Deionized (DI)
Water. MgCl2, CaCl2 and NaCl were purchased from Acros
Chemicals and solutions were prepared by proper dilution with
DI water.
B. Modification of Graphene Oxide (GO) by Ionic Liquid (IL)
Solution of 200 mg of GO was sonicated in 40 ml of DI
water (5mg per 1 ml) for 1 hour in water bath. 0.5 M of NaOH
solution was added dropwise till pH reached 11. The mixture
was sonicated in water bath for 3 hours. Afterwards 2 ml of the
IL, Propylammonium Nitrate (PAN), was added to the solution
(2 ml of IL per 40 ml of DI/GO) and was sonicated at 50 ℃ for
6 hours. Then, the solution was filtered. The paper-filter
collected material was put in pre-freeze at -80℃ overnight in
the freezer and, subsequently, was dried in the Freeze Drier
(FD) under low pressure and low temperature for 24 hours. The
functionalization process reaction mechanism is depicted in
Fig.1
Figure 1. Proposed reaction mechanism for IL (PAN) modified GO
E. Experimental procedure for quantification of IL leaching
15 mg of adsorbent were placed in 30 ml of DI water in 50
ml flask. Using mechanical shaker, the solution would be
shaken for 7 hours at 300 rpm at room temperature. The residue
solution was analyzed for its TOC. Leaching of the IL was
calculated using (1).
∆𝑇𝑂𝐶∗𝑉𝑠
  𝐿𝑒𝑎𝑐ℎ𝑖𝑛𝑔 (%) = ∗ 100 ∗ 𝐶𝐼𝐿  
𝑚𝐼𝐿
where ∆𝑇𝑂𝐶 (𝑚𝑔 𝐿−1 ) is the measured concertation of TOC in
the sample after the leaching minus measured TOC which is
already present in the solution. 𝑉𝑠 (𝐿) is the volume of the feed
solution and 𝑚𝐼𝐿 (𝑚𝑔) is the mass of IL used. 𝐶𝐼𝐿 is the carbon
content of the IL. Calculated value represents the percentage of
IL leached from the GO matrix [15].
III. RESULTS AND DISCUSSION
A. Surface Morphology
Surface morphology of Graphene Oxide before and after
functionalization with IL (PAN) was studied using SEM (SEM
Nano Nova). From Fig. 2 (a) it can be noticed that GO is mostly
single layer graphene, which is also specified in the Material
Specifications of the manufacturer (more than 80 % single layer
Graphene Oxide with the flake size: 0.5-2.0 μm and
thickness: 0.6-1.2 nm). After the modification of GO with IL,
it is observed (Fig. 2 (b)) that graphene layers are less
agglomerated and more free space is created between the layers.
(a) (b)

C. Characterization
The surface morphology of the modified GO was
investigated using High Resolution Scanning Electron
Microscopy (HRSEM) (Nova NanoSEM, FEI, The
Netherlands). Raman Spectroscopy analysis was performed
using Raman-AFM combination Alpha300 RA (WITec,
Germany) at 532 nm laser wavelength. Thermogravimetry
Figure 2. Scanning Electron Microscopy images of a) GO before
Analysis (TGA) of the materials was done using Netzsch STA modification with IL; b) GO after modification with IL, Scale = 10 μm
449 F3 Jupiter TGA, Germany with a heating rate of 10 ℃/min
and under inert (N2) atmosphere. Leaching has been tested B. Thermal Gravimetric Analysis
using Total Carbon Content (TOC) analyzer TOC-LCSH/CSN
(Shimadzu, Japan). All the adsorption studies involved the use
100
of Inductively Coupled Plasma - Optical Emission GO
GO-IL
Spectrometry (ICP-OES Model 5100 SVDV, Agilent, USA) 80 IL-PAN
after calibration with the proper standards.
D. Experimental procedure for MgCl2, CaCl2 and NaCl 60
Weight %

adsorption
40
25 mg of adsorbent was placed in 50 ml of
MgCl2/CaCl2/NaCl solution with different concentrations (200 20

ppm and 1000 ppm) in a 50 ml flask. Using a mechanical

shaker, the solution would be shaken for 24 hours at 300 rpm at 0

20°C. Afterwards, the solution was filtered using a filter syringe 0 200 400 600 800 1000 1200
and was analyzed for the concentration of salt using ICP-OES. Temperature, ° C

Figure 3. TGA of GO with and w/o IL funtionalization (in N2 atmosphere)

Funding agency: Abu Dhabi Department of Education and Knowledge (ADEK) – Research Grant AARE 2018-019

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 Thermal Gravimetric Analysis was done for GO, IL(PAN)
and modified GO with IL. The TGA analysis results identified
that 10 wt. % of IL has been loaded on the GO. In case of GO
modified with IL, the onset decomposition temperature has
been decreased from 195℃ to 168 ℃ and the weight loss was
increased to 20 wt. %, as it can be seen in Table I. The
decomposition temperature for IL-PAN was measured and is
240℃, which is in good agreement with the literature [16].
Table I summarizes these results.
TABLE I. TGA ANALYSIS: ONSET TEMPERATURE, MASS LOSS %
Name Onset Temperature, °𝑪
GO 195,1
GO-IL 167,6
IL-PAN 240,0
C. Raman Spectroscopy Analysis
Raman Spectroscopy Analysis results can be observed in
Fig. 4. Generally, the G band is related to sp2-bonded carbon
atoms in the hexagonal lattice of the graphene structure.
However, the D band reflects the presence of defects or
disorders caused by sp3 hybridized carbon in the lattice, while
G′ is caused by second-order, zone boundary phonons that are
related to the assembly of the multilayers [17]. The intensity
ratio of ID/IG provides an indication of degree of oxidation
and/or functionalization [18]. Results of ID/IG ratio can be seen
in Table II. This ratio increases for GO modified with IL from
1.01 to 1.06. This indicates an increase in the functional groups
for the modified GO. Functionalization can add different
functional groups on graphene oxide sheets, which results in
increase of ID/IG value.
D Band G Band
4500
4000
3500
Intensity
D. Leaching of IL from GO matrix analysis
Leaching percentage has been identified following the
methodology and procedure of Pirkwieser et al [15]. The TOC
analysis has identified that the filtered solution of IL-modified
GO (IL-GO) has almost 65 mg/L of TOC and 39 % of leaching
after 7 hours of continious shaking. The results can be seen in
Table III. The cross contamination of the feed water is
undesirable and less degrees of leaching are expected after
adding another washing step with DI water in the methodology
of preperation of the GO-IL adsorbent.
Mass Loss, % TABLE III. LEACHING AND TOC ANALYSIS DATA
10,87 TOC results
20,77 TOC of IL-GO leaching after 7 hours of
90,01 64.97 mg/L
stirring, ppm
Leaching degree
Leaching degree of IL-GO after 7 hours of
39 %
stirring, ppm
E. Adsorption of MgCl2 and CaCl2 and NaCl salts
Adsorption capacities of the materials, GO before and after
modification with IL(PAN), are shown in Fig. 5 and Table IV
for different initial concentrations of CaCl2, MgCl2 and NaCl
salts. The adsorption capacity is described as qe – adsorption
coefficient and represents the mass of adsorbed salt (in mg) per
mass of the adsorbent (in grams). 200 ppm and 1000 ppm of
salt concentrations have been used to study the effect of
concentration on the adsorption coefficient qe (mg-salt/g-
adsorbent).
The adsorption capacity increased for almost all the salts
and for both concentrations, as it can be seen in Table IV. For
lower concentration of CaCl2, the adsorption capacity increased
over three times from 32 mg/g to 98 mg/g. Likewise, for lower
GO
concentration of MgCl2, IL-GO gave 30 % higher adsorption
GO-IL coefficient. However, for lower concentration of NaCl, the
adsorption capacity did not increase. On the contrary, for higher
concentration of NaCl, the adsorption capability of IL-GO
increased from 27 mg/g to 178 mg/g, which is around 7 times
higher than the adsorption capacity of GO alone. Similarly, the

3000 adsorption coefficient for CaCl2 and MgCl2 at higher

concentrations was higher for GO functionalized with IL
2500 compared to GO.
IL functionalized GO has an enhanced adsorption capacity
2000 due to less agglomerated structure created by the
functionalization. Moreover, the positively and negatively
1500 charged groups of IL have the ability to attract CaCl2, MgCl2
0 500 1000 1500 2000 2500 3000 3500 4000
and NaCl salt ions (electrostatic attractions). Additionally, high
Raman Shift (cm-1)
solubility of the specific IL (PAN) towards these inorganic salts
Figure 4. Raman Spectroscopy of GO and IL-modified GO
increases the affinity of such ions to be attracted to the surface
of GO, where it can be further adsorbed. This resulted in greater
TABLE II. RAMAN SPECTROSCOPY ANALYSIS DATA, ID/IG VALUES FOR adsorption capabilities of GO functionalized with IL-PAN
BOTH GO AND IL-MODIFIED GO compared to GO without the functionalization.
Material 𝑰𝑫
𝑰𝑮
Origin GO 1.01
GO functionalized with PAN 1.06

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(ADEK Award for Research Excellence (AARE-2018) –
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