Surfaces and Interfaces 26 (2021) 101309

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Surfaces and Interfaces

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Ice segregation induced self-assembly of graphene oxide into

graphene-based aerogel for enhanced adsorption of heavy metal ions and
phenolic compounds in aqueous media
Le Minh Huong b, Doan Ba Thinh b, Tran Hoang Tu a, c, Nguyen Minh Dat a, b, c, Tran Thi Hong b,
Phan Thi Ngoc Cam b, Dinh Ngoc Trinh a, b, c, Hoang Minh Nam b, c, Mai Thanh Phong b, c,
Nguyen Huu Hieu a, b, c, *
a
VNU-HCM Key Laboratory of Chemical Engineering and Petroleum Processing (Key CEPP Lab), Vietnam
b
Faculty of Chemical Engineering, Ho Chi Minh City University of Technology, 268 Ly Thuong Kiet Street, District 10, Ho Chi Minh City, Vietnam
c
Vietnam National University Ho Chi Minh City, Linh Trung Ward, Thu Duc District, Ho Chi Minh City, Vietnam

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, we reported the synthesis of graphene oxide aerogel (GOA) through ice segregation induced self-
Graphene oxide assembly of GO sheets. The formation mechanism of GOA was studied via Fourier transform infrared spectros­
Aerogel copy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Raman spectroscopy,
Ice segregation
Energy-dispersive X-ray spectroscopy, and Brunauer–Emmett–Teller surface area. The GOA with GO concen­
Self-assembly
Adsorption
tration of 10 mg/mL was applied as an adsorbent to remove heavy metal ions (Cd2+, Ni2+). The adsorption
Heavy metal ions processes of GOA for Cd2+, Ni2+ fitted well with pseudo-second-order kinetics and Langmuir isotherm models. The
Phenolic compounds maximum adsorption capacities for Cd2+ and Ni2+ were determined to be 108.70 and 91.74 mg/g, respectively.
Moreover, the electrostatic attraction was found to be the main interaction between GOA and Cd2+, Ni2+. The
adsorption of phenolic compounds (phenol and bisphenol A) was studied to expand the adsorption applications
of GOA. In addition, The maximum adsorption capacities for phenol and bisphenol A were determined to be
129.37 and 64.76 mg/g, respectively. Therefore, GOA has the potential to be used as a highly efficient adsorbent
for the treatment of heavy metal ions and phenolic compounds from water.

1. Introduction convulsions, and even coma meanwhile, BPA can cause various car­
diovascular diseases [7]. Adsorption is one of the most common methods
Industrial activities such as printing, electrolysis, painting, ceramic for the removal of pollutants because of its simple operation and
production, and mining have been increasing the amount of heavy metal comparably low cost of application. However, several common adsor­
ions in water sources. Cadmium (Cd2+) and nickel (Ni2+) are two of the bents such as activated carbon, zeolite, biomass, metal oxides, etc.
most common heavy metal ions found in water sources. The accumu­ possess drawbacks such as separation difficulties and low adsorption
lation of these ions in living bodies can cause a variety of health prob­ capacity [8].
lems [1–3]. A high level of Ni2+ in the human body is associated with Since 2004, graphene (Gr) has gained attention from researchers due
insomnia, renal disturbances, dermatitis, hepatitis, and allergic sensiti­ to its many potential applications such as water treatment, energy
zation [4]; while Cd2+ can cause diseases such as renal degradation, conversion, storage, sensors, etc. [9–13]. Gr is an advanced
erythrocyte destruction, chronic pulmonary problems, nausea, muscular two-dimensional (2D) one-atom-thick material, with sp2-hybridized
cramps, and skeletal deformities [5]. Aside from heavy metal ions, carbon atoms packed in a hexagon lattice structure. Graphene oxide
organic compounds have various impacts on humans as well. Amongst (GO) has negative oxygen-containing groups on the hexagon lattice
them, phenolic compounds are considered one of the most toxic organic structure, with carboxylic acid groups at the edges, and hydroxyl and
pollutants. Two common phenolic compounds are phenol and bisphenol epoxide groups at the basal plane [14]. These groups can interact with
A (BPA) [6]. Long-term exposure to phenol causes muscle weakness, pollutants via hydrogen bonding, Van Der Waals interaction, π-π

* Corresponding author.
E-mail address: [email protected] (N.H. Hieu).

https://doi.org/10.1016/j.surfin.2021.101309
Received 10 April 2021; Received in revised form 27 May 2021; Accepted 26 June 2021
Available online 6 July 2021
2468-0230/© 2021 Elsevier B.V. All rights reserved.
L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

interaction, etc., making GO a potential adsorbent [2]. Furthermore, GO by the ISISA process, as shown in Fig. 1 [19]. In details, GO suspension
is considered a fundamental unit in the preparation of three-dimensional (10 mg/mL) was frozen at -60 ◦ C for 12 h to create graphene oxide
(3D) materials [15]. Constructing 3D structures such as aerogels, hydrogel (GOH). The liquid phase in the hydrogel was replaced with air
hydrogels, and foams from 2D GO have been investigated intensively. using freeze-drying techniques (FDU-2100, Eyela, Japan) for 30 h at 0.8
Aerogel, a porous material, derived generally from molecular precursors mbar to obtain GOA. The GOA samples synthesized with GO concen­
by utilizing sol-gel process, in which the liquid component for the gel has trations of 6, 8, 10, 12, 14, and 16 mg/mL were marked as GOA1, GOA2,
been replaced with a gas. With its unique structure and properties, the GOA3, GOA4, GOA5, and GOA6, respectively.
3D graphene-based aerogels with microscale structure, low density,
good mechanical strength, thermal, and electrical conductivity have 2.3. Characterization
attracted studies in recent years [15,16]. Graphene oxide aerogel (GOA)
has oxygen-containing functional groups on the surface, which can act The bulk densities (mg/cm3) of GOA samples were calculated based
as active sites to interact with positively charged species like metal ions, on the ratios between mass and total volume of sample using an
organic dyes, etc. [15]. GOA is used for applications including catalysis, analytical digital balance (Sartorius CPA225D, Germany) and digital
sensors, drug delivery, and adsorbents. The ordered structure has shown caliper (VOREL-15240-150 mm, Germany). X-ray diffraction (Bruker D8
that they are interconnected with the 2D GO sheets by depositing gra­ Advance, Germany) was used to study the structure of GO and GOA. The
phene on templates (chemical vapor deposition), cross-linking with functional groups of GO and GOA were determined using Fourier
polymer, and 3D-printing. One of the promising approaches is transform infrared spectroscopy (Bruker Tensor 27, Germany). Raman
freeze-casting or ice segregation-induced self-assembly (ISISA), as this spectroscopy (LABRAM 300 MicroRaman, Horiba JOBIN YVON, Japan)
method is convenient, cost-effective, environmentally friendly, and was utilized to characterize the properties and disorders in the structures
simple. The technique is based on the formation of ice crystals as a of GO and GOA. Scanning electron microscopy (SEM S4800, Hitachi,
catalyst and reactor to promote the phase separation; then the rejection Japan) and transmission electron microscopy (TEM JEOL-JEM 1010
of GO sheets is accumulated between the growing ice crystals. The microscope, Japan) were applied to investigate the structural changes of
entrapped GO sheets have partial overlapping and edge-to-edge as­ materials. Energy-dispersive X-ray spectroscopy (EDS) (Jeol-JMS 6490,
sembly to create the 3D–structure [17,18]. Japan) was also used to investigate the composition of elements C and O.
Herein, GOA was synthesized by the ISISA method. The effect of GO Brunauer–Emmett–Teller (BET) method (Quantachrome, NOVA 2200e,
dose on the formation of GOA was investigated. A suitable sample was USA) was used to investigate the specific surface areas of materials.
characterized and used for the adsorption of Cd2+ and Ni2+ in water
media. The adsorption kinetic studies as well as the factors that affected 2.4. Adsorption experiments
the adsorption such as contact time, pH, and GOA initial concentration
were also conducted. The adsorption of phenol and BPA onto GOA was Batch experiments were performed to study the effects of factors
also surveyed to broaden the adsorption applications of GOA. including time, pH, and initial concentration on the removal perfor­
mance of GOA. The adsorption capacity (qe, mg/g) of material was
2. Materials and methods measured using the following Eq. (1) [20].

2.1. Materials qe =
(Co − Ce )V
(1)
m
Graphite (CAS 7782-42-5), phenol (99 wt.%), and BPA (99% wt.%)
where Co and Ce are the initial and equilibrium concentration of Cd2+,
were purchased from Sigma-Aldrich (Germany). H2SO4 (98 wt.%),
Ni2+ ions, phenol, BPA (mg/L), respectively, V is the volume of solution
H3PO4 (98 wt.%), HCl (36 wt.%), NaOH (99 wt.%), H2O2 (30 wt.%), Ni
(L), and m is the mass of adsorbent (g).
(NO3)2 (98 wt.%), and CdCl2 (98 wt.%) were purchased from Xilong
For Cd2+ and Ni2+ adsorption experiments. Adsorbent (20 mg) was
Scientific (China). KMnO4 (99 wt.%) and C2H5OH (95 wt.%) were
added in 20 mL of solution with a concentration of 200 mg/L at 30 ◦ C
supplied from Duc Giang Detergent Chemical JSC (Vietnam).
under stirring rate of 50 rpm. The pH value of the solution was adjusted
in the range of 3-8 using 0.01 M NaOH and 0.01 M HCl. After the
2.2. Synthesis of GOA adsorption process, the residual concentrations of Cd2+, Ni2+ ions in the
solution were determined with inductively coupled plasma mass spec­
GO was synthesized by the improved Hummers’ method with trometry (ICP-MS) (Agilent ICP-MS 7700x, USA).
oxidation reagents H2SO4, H3PO4, and KMnO4 [2]. GOA was synthesized For phenol and BPA, adsorbent (20 mg) was added in 20 mL of

Fig. 1. Schematic illustration for the synthesis of GOA.

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

solution with a concentration of 100 mg/L at 30 ◦ C under stirring rate of

− 2γ Cos (θ)
50 rpm. The residual concentrations of phenol and BPA ions in the so­ p= (2)
r
lution were determined with high-performance liquid chromatography
(HPLC) (Agilent 1200 series, USA). where p is the capillary pressure, θ is the contact angle, γ is the surface
The point zero charges (pHpzc)of the materials were determined by tension, and r is the pore size [22]. The GO concentration increased the
the drift method. Briefly, the pH of 0.1 M NaCl solution was investigated pressure inside the network, leading to structural breakdown as shown
between 2 and 11 using 0.01 M NaOH and 0.01 M HCl. The GOA (20 mg) in the case of GOA5 and GOA6. As the block structures of GOA3 and
was added to 15 ml of sodium chloride solution. The former was then GOA4 samples were maintained, therefore, these samples were selected
shaken for 24 min at room temperature. The final pH was observed when to characterize. As shown in Table 1, the shrinkage ratios and densities
the pH value stabilized. The pHpzc value could be obtained by plotting of GOA have increased.
the difference between the final and initial pH (pHf – pHi) versus the The porous networks of GOA samples were investigated by SEM and
initial pH of NaCl solution. TEM images. As shown in Figs. 3–5, the 3D-interconnected structure was
The kinetic and isotherm models were used to examine the adsorp­ constructed from the self-assembly GO sheets. The pore size of the
tion process. Additionally, the adsorption experiment for binary heavy synthesized GOA samples decreased with the content of GO as it could
metal mixtures was carried out to study the adsorption mechanism and be observed that the pore diameter of GOA4 (50 µm) was smaller than
adsorption performance of the materials. that of GOA3 (100 µm). It has been reported that the 3D interconnected
structure of GO sheets could enhance the specific surface area, subse­
3. Results and discussion quently, increasing the active sites for the adsorption of heavy metal ions
and promoting the diffusion of these ions into the pores [25].
3.1. Effect of GO concentration on the synthesis of GOA

GOA samples synthesized from various GO concentrations as shown Table 1

in Fig. 2. Porosities and densities of GOA and Gr-based aerogels.
For GOA1 and GOA2, the interactions between GO sheets are weak, Materials Densities (mg/ cm3) References
not strong enough to maintain the porous network, thus the structures
GOA3 14.63 In this study
were collapsed. As the GO concentration increased, the cross-link of GO GOA4 24.3 In this study
sheets was enhanced, improving the structural integrity of GOA [21]. PVA/GOA 26.3 [23]
However, when the concentration of GO exceeded 10 mg/mL, the GO foam 20.0 [24]
overlapping of GO sheets prevents the growth of ice crystals, enhancing GO/chitosan aerogel 21-35 [24]
GO/xanthan gum aerogel 16-19 [24]
the pressure applying on the pore walls according to the Laplace Eq. (2).

Fig. 2. Effect of GO concentration on the formation of GOA.

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

Fig. 3. SEM images of GOA3 (a, b) surface and (c, d) structure.

Fig. 4. TEM images of GOA3 surface.

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

Fig. 5. SEM images of (a, b) GOA4.

GOA3, owing to its large pore size, would promote the diffusion of Certainly, many oxygen-containing groups in the GO layers promote
pollutants, increase the contact surface between the pollutants and hydrogen bonding among others. Hence, the growth of ice crystals in the
active sites, subsequently, increasing the removal efficiency. From the freezing process is to fix that matrix and then via the freeze-drying
above results, the suitable GO concentration for GOA synthesis was process, the water molecule was sublimated, the formation of pores
determined to be 10 mg/mL. was taken place in the aerogel without affecting the structure of the 3D
The self-assembly via the growth of the ice crystals of GO to form sample. Normally, GO with 2D structure could create the stable colloid
GOA was shown in Fig. 6. The synthesis of GOA consisted of two stages, in a water solvent, however, in the formation of GOA, the GO layers
including (1) freezing and (2) sublimation drying. Typically, it was randomly interact with each other by hydrogen bonding, π-π interaction
claimed that there was an interaction including hydrogen bond of or Van der Waals intermolecular force, the size of 3D GOA is much
oxygen-containing functional group, π-π interaction, or Van der Waals higher, which lead to the stability structure in water solvent although its
intermolecular force among the GO layers. When GO concentration precursor (GO) is hydrophilic.
exceeded a critical concentration (10 mg/L), the GO density in the so­ GO at a certain concentration would promote the layer interact with
lution increases rapidly, which enhances the probability of their inter­ each other by the Van der Waals intermolecular force or the hydrogen
action as well as their bonding strength to entrap the GO layers together. bonding generated by the oxygen-containing group on the edge or the
The 2D structure of GO with the functional groups on edge that are backbone of each sheet. Besides, no further treatment (for example sol-
acting as bridges could randomly cross-link with adjacent GO sheets via gel, chemical reduction, cross-linking with polymer, or hydrothermal
hydrogen bondings. During freezing, the water molecules transformed reaction) was applied in the synthesis of GOA, making the procedure
into ice crystals which replaced part of the material from its volume took simple and environmentally friendly. This synthesis route neither pro­
the role of porogens, and fit the matrix structure. During the drying duced by-products or required any further purification. Therefore, it
process, the water molecule in the form of solid ice crystal would sub­ could be claimed as the simplest pathway to produce 3D porous
limate under the gradual pressure drop, the pore structure was main­ materials.
tained, resulting in the formation of the aerogel.

Fig. 6. Schematic illustration for the synthesis mechanism of GOA3.

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

3.2. Characterizations of GOA3 Table 2

BET surface areas and pore volumes of GOA3 and other materials.
The FTIR spectra of GO and GOA3 are shown in Fig. 7a. Several Materials BET surface areas (m2/g) Pore volume (cm3/g) References
absorption bands of GO at 1045, 1619, 1723, and 3190 cm− 1 are
GO 84.67 - This study
assigned to the stretching vibrations of –C–O, –C=C, –C=O, and –O–H, GOA3 510.59 2.08 – 2.16 This study
respectively [26]. The presence of absorption peaks of oxygenated GOA 42. 0 4.37 [32]
functional groups suggested the successful functionalization of GOA 42.1 0.3 [26]
oxygenated functional groups on graphite layers. For GOA, the down­ Fe3O4/GO 119.50 - [33]
CoFe2O4/Gr 126.36 - [33]
shifted–C–O, –C=O, and –O–H bands showed that GO sheets assembled
via intermolecular hydrogen bonds [27]. This result is in good agree­
ment with the formation mechanism of GOA [28]. The intra-particle diffusion model was applied to examine the
XRD patterns of GO and GOA3 are shown in Fig. 7b. GO had a diffusion process of Cd2+, Ni2+ adsorption, which is presented in Eq. (3):
diffraction peak at 2θ = 10.25o, which was the characteristic peak for
the (002) reflection. The interplanar spacing between GO sheets was qe = ki t0.5 + Ci (3)
determined to be 0.85 nm, which was higher than that of graphite (0.34
where ki is the adsorption rate constant and Ci is the diffusion constant.
nm), confirmed the successful functionalization of oxygenated func­
Fig. 9 presents the plots consisting of two curves that show stages of
tional groups onto graphite layers. For GOA3, it could be observed that
the adsorption process, including surface and porous diffusion. The GOA
the crystal lattice (002) diffraction peak at 2θ = 9.83◦ corresponded to
with a large surface area and pore volume increased the diffusion rate
the distance spacing of 0.90 nm. The similar in interlayer spacing be­
and exposure of metal ions to adsorption sites on the GOA structure. The
tween GO and GOA3 could be related to the sublimation of intercalated
diffusion process of metal ions occurred from the bulk solution to the
ice crystals between GO sheets [29].
surface of GOA through the fluid boundary surrounding the adsorption
The surface area and the porous volume of GOA3 were 510.59 m2/g
sites. Then, the metal ions were gradually transported into porous
and 0.124 cm3/g, respectively. Moreover, the surface area of GOA3 was
structure due to the concentration gradient between surfaces and
higher compared to other materials from previous studies as shown in
interacted with adsorption sites on the porous structure as shown in the
Table 2. According to other studies, GOA was mainly synthesized by the
second curve. The number of free adsorption sites in GOA remains un­
freeze-casting method, but the overlapping of the GO sheets during self-
changed, after a certain time, these sites were filled with a metal cation,
assembly occurred, reducing the specific surface area of materials. In
which leads to the saturation of binding site in GOA, hence the
this study, the GO sol was converted into gel by increasing the con­
adsorption process reached an equilibrium. Table 3 shows the parame­
centration, enhancing the number of active sites on the basal planes of
ters of the intra-particle diffusion model of GOA for Cd2+, Ni2+.
GO, which interacted with the GO sheets via bridges on the edges [30].
Furthermore, none of these lines passed through the origin, indicated
The 3D-structure of GOA contributed to the enhancement of the surface
that the intraparticle diffusion was not the only rate-determining step
area of material [31].
[34].
The pseudo-first order and pseudo-second order rate laws in the
3.3. Adsorption performance of GOA for Cd2+, Ni2+ modeling of adsorption kinetics are described as Eqs. (4) and (5):
ln(qe − qt ) = lnqe − k1 t (4)
The adsorption kinetics of GOA for Cd2+, Ni2+ ions were studied by
changing contact time intervals from 30 to 480 min, as shown in Fig. 8. t 1 1
= + t (5)
Upon the introduction of GOA into the solution, the adsorption capac­ qt k2 q2e qe
ities of Cd2+, Ni2+ by GOA3 increased rapidly after 90 min, and equi­
librium was achieved after 120 min. After the equilibrium, the where qt and qe are the adsorption capacities at time t and at equilibrium
adsorption sites on the GOA surface were filled up by Cd2+, Ni2+ ions, (mg/g), respectively; and k1 and k2 are the rate constants, respectively
thus the adsorption process reaches saturation. The most suitable time [35]. The adsorption of Cd2+, Ni2+ for GOA was well-fitted with pseu­
for Cd2+, Ni2+ adsorption of GOA3 was 120 min. do-second-order kinetics with high correlation coefficients (R2Cd = 0.9823

Fig. 7. (a) FTIR spectra and (b) XRD patterns of GO and GOA3.

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

Fig. 8. Effect of contact time on the adsorption capacity of GOA3 for (a) Cd2+ and (b) Ni2+.

Fig. 9. The plots of intra-particle diffusion for (a) Cd2+ and (b) Ni2+ adsorption of GOA3.

The effect of pH on the adsorption capacities of Cd2+, Ni2+ are shown

Table 3
in Fig. 12a and b. As pH was raised from 3 to 6, the adsorption capacities
The parameters of intra-particle diffusion model for Cd2+ and Ni2+.
of GOA3 also increased. When pH is low, the competitive interaction
Adsorbates Film diffusion Porous diffusion between Cd2+, Ni2+, and H+ ions with GOA3 occurred. Furthermore, the
kfd R2fd kpd R2pd repulsive interaction between these ions and the surface charge of the
Cd2+ 8.121 0.9937 0.315 0.8824 adsorbent inhibited the adsorption process on GOA3 surface [37].
Ni2+ 8.213 0.9865 0.440 0.9378 Additionally, the adsorption capacities of GOA3 slightly decreased when
pH is controlled to 8. This can be explained that when pH was higher, the
concentration of H+ was lower, leading to a decrease in competitive
and R2Ni = 0.9935) as shown in Fig. 10c and d. This result indicated that adsorption between H+ and Cd2+, Ni2+. Furthermore, the GOA surface
the adsorption process of GOA3 for Cd2+, Ni2+ was chemisorption, was negatively charged at all investigated pH levels, which further
which could be related to the complexation between Cd2+, Ni2+ and increased the attractive forces between the adsorbent and the metal
active sites of GOA. ions. Thus, the suitable pH for Cd2+, Ni2+ adsorption process was 6 [38].
The pHpzc plays a vital role in the study of adsorption study of gra­ The effect of initial concentrations on the adsorption capacities of
phene and its derivatives. The pHpzc value of GOA was found to be 2.52 GOA3 for Cd2+, Ni2+ is shown in Fig. 13c and d. The increase in con­
as shown in Fig. 11, suggesting that the surface of GOA was positively centration enhanced the adsorption capacity. When Co was low, the
and negatively charged at pH below and above pHpzc, respectively as Cd2+, Ni2+ ions diffused and interacted with adsorption sites. When the
demonstrated in Eqs. (6)–(9) [36]. Co was higher than 150 mg/L, qe increased slowly, indicating that the
GOA3–OH + H+ → GOA3–OH+ (6) equilibrium was achieved. When the initial concentration was high, the
adsorption sites of GOA3 were filled by Cd2+, Ni2+ ions, leading to slight
2

GOA3–COOH + H+ → GOA3–COOH+
2 (7) increases in adsorption capacities of GOA3 for Cd2+, Ni2+. The collision
between metal ions inhibited the movement and adsorption of these
GOA3–OH → GOA3–O + H – +
(8)
ions, which reduced the adsorption efficiency of GOA3 [39].
GOA3–COOH → GOA3–COO + H – +
(9) The Langmuir and Freundlich isotherm models are described as

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

Fig. 10. Pseudo-first-order kinetic model of GOA3 for (a) Cd2+ and (b) Ni2+; Pseudo-second-order kinetic model of GOA3 for (c) Cd2+ and (d) Ni2+.

1
logqe = logkf + logCe (11)
n

where qmax is the maximum adsorption capacity (mg/g); qe is the

adsorption capacity at equilibrium (mg/g); Ce is the concentration of the
metal at equilibrium (mg/L); kL and kF are the Langmuir and Freundlich
constants, and n is the heterogeneous factor [35]. The linear plots of
Langmuir and Freundlich isotherm models of Cd2+, Ni2+ are presented
in Fig. 13a and b, respectively. The parameters of these models of Cd2+,
Ni2+ are presented in Table 4. These results indicated that the adsorption
of GOA3 for Cd2+, Ni2+ by GOA3 fitted well with the Langmuir isotherm
model (R2Cd = 0.9952 and R2Ni = 0.9929). The maximum adsorption
capacities of GOA3 for Cd2+, Ni2+ were determined to be 108.70 and
91.74 mg/g from the Langmuir model. The obtained results further
confirmed the adsorption of Cd2+ and Ni2+ onto GOA3 was mainly
chemisorption.
The adsorption properties of GOA3 are compared with other mate­
rials from other studies, which are presented in Table 5.
As shown in Table 5, GOA3 exhibited a higher adsorption capacity
compared to other materials from previous studies. The improved ability
could be attributed to the oxygen-containing groups at GO, which means
Fig. 11. Point of zero charge of GOA3.
more adsorption sites are exposed to accommodate the metal ions. The
types of interaction in the adsorption process included (1) electrostatic
shown in Eqs. (10) and (11): attractions and (2) complex surface interactions between metal ions and
Ce Ce 1 oxygen-containing groups on GOA, as shown in Eqs. (12)–(17). More­
= + (10) over, the cation – π interaction between the hexagon lattice of Gr sheets
qe qmax qmax kL
with metal ions was formed to enhance the removal performance of GOA

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

Fig. 12. Effect of pH on the adsorption capacity of GOA3 for (a) Cd2+ and (b) Ni2+; Effect of initial concentrations on the adsorption capacities of GOA3 for (c) Cd2+
and (d) Ni2+.

[47,48]. ion (d10) is octahedral with a hydrated radius of 0.426 nm, which
resulted in a higher hydration free energy for Ni2+. The higher
GOA3–O− + M2+ → (GOA3–O)M+ (12) hydration-free energy-restricted the removal of water molecules in their
2GOA3–O + M − 2+
→ (GOA3–O)2M (13) hydration form, preventing the interactions between Ni2+ and GOA
[50].
GOA3–COO + M − 2+
→ (GOA3–COO)M +
(14)
3.5. Adsorption of phenolic compounds
2GOA3–COO− + M2+ → (GOA3–COO)2M (15)

GOA3–COO− + M2+ + H2O → GOA3–COOMOH + H+ (16) As shown in Fig. 15, the adsorption of phenol onto GOA3 was fast
and easy for the first 60 min of adsorption. The adsorption speed for
GOA3–O− + M2+ + H2O → GOA3–OMOH + H+ (17) phenol slowed down after 60 min as the vacant sites on the surface
2+
* M : Cd , Ni 2+ 2+ GOA3 were occupied. The equilibrium for the adsorption of phenol
could be observed at 240 min as the adsorption capacity of GOA toward
phenol increases sluggishly after this certain point. Meanwhile, the
3.4. Competitive adsorption of Cd2+ and Ni2+ adsorption of BPA onto GOA3 was much lower than that of phenol.
Furthermore, the adsorption capacities of BPA increased rapidly for the
In binary metal-ion systems, there might be three possible types of first 240 min of adsorption. After this point, the adsorption speed of BPA
effects including (1) synergism, (2) antagonism, and (3) non-interaction. slowed down due to the diffusion of BPA from larger pore into smaller
The competitive adsorption capacities of GOA for Cd2+ and Ni2+ are pore. No significant changes in the adsorption capacities of BPA
demonstrated in Fig. 14. occurred after 480 min, suggesting that the equilibrium was achieved
The Cd2+, Ni2+ ions were competitively adsorbed on the GOA sur­ after 480 min of adsorption. The difference in the adsorption capacities
face, leading to decreases of 30.37 and 53.61 % compared to that of and adsorption equilibria of phenol and BPA could be related to the
individual adsorption. The adsorption of metal ions was suppressed by difference in their molecular structure [51]. The maximum adsorption
the competitiveness of other metals on the adsorption sites of GOA [49]. capacities for phenol and BPA were determined to be 129.37 and 64.76
This phenomenon was confirmed by the antagonism effect. Besides, the mg/g, respectively. The obtained result confirmed the utilization of GOA
removal ability of Cd2+ was higher than that of Ni2+, which could be as an efficient adsorbent toward pollutants.
attributed to the higher hydration free energies of Ni2+ (-2106 kJ/mol)
in comparison with Cd2+ (-1979 kJ/mol). The hydrated Ni2+ ion (d8) is
octahedral with a hydrated radius of 0.404 nm, and the hydrated Cd2+

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

Fig. 13. Linear plots of Langmuir isotherm model of GOA3 for the adsorption of (a) Cd2+ and (b) Ni2+; Linear plots of Freundlich isotherm model of GOA3 for the
adsorption of (c) Cd2+ and (d) Ni2+.

Table 4
The parameters of adsorption isotherm models for Cd2+ and Ni2+.
Adsorbates Langmuir model Freundlich model

kL (l/ qm (mg/ R2 n kf (mg/g) (L/ R2

mg) g) mg)1/n

Cd2+ 0.47 108.70 0.9952 2.67 19.85 0.9313

Ni2+ 0.4 91.74 0.9929 2.61 15.02 0.8874

Table 5
The maximum adsorption capacities of GOA3 and other materials.
Adsorbates Materials qmax (mg/g) References

Cd2+ GOA3 108.7 This study

GO 83.8 [40]
S doped SiO2 30.7 [27]
Ca(II)-chitosan 50.8 [41]
Activated carbon 27.3 [42]
Ni2+ GOA3 91.74 This study
GO 62.3 [40]
Triethylenetetramine/chitosan 70.77 [43] Fig. 14. The individual and competitive adsorption capacities of Cd2+ and Ni2+
Polyacrylic acid - carbon nanotubes 3.90 [44] on GOA3.
Activated carbon 73.56 [45]
Zeolite 24.65 [46]
GOA3 structure with a porous size of 50 µm. The adsorption process of
GOA3 for Cd2+, Ni2+ suited well with pseudo-second-order kinetic and
4. Conclusions Langmuir isotherm models. The maximum adsorption capacities of
GOA3 for Cd2+, Ni2+, phenol, and BPA were measured to be 108.70,
In this study, GOA was successfully synthesized using the ISISA 91.74, 129.37, and 64.76 mg/g, respectively. In binary metal-ion-
method with an appropriate concentration of GO of 10 mg/mL (GOA3). adsorption systems, the adsorption capacities of GOA3 for Cd2+ and
SEM images showed that the GO sheets were evenly arranged in the Ni2+ were lower than that of the individual adsorption case.

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L.M. Huong et al. Surfaces and Interfaces 26 (2021) 101309

Fig. 15. Adsorption capacities of phenol and BPA onto GOA3 comparison.

Furthermore, The adsorption of phenolic compounds confirmed that applications, Phys. Status Solidi - Rapid Res. Lett. 14 (2020), https://doi.org/
10.1002/pssr.201900534.
BPA was much harder to be removed when compared to phenol. Based
[10] N. Cao, Q. Lyu, J. Li, Y. Wang, B. Yang, S. Szunerits, R. Boukherroub, Facile
on these results, GOA3 could be used as an effective adsorbent for water synthesis of fluorinated polydopamine/chitosan/reduced graphene oxide
remediation. composite aerogel for efficient oil/water separation, Chem. Eng. J. 326 (2017)
17–28.
[11] A.S. Eltaweil, G.S. Elgarhy, G.M. El-Subruiti, A.M. Omer, Carboxymethyl cellulose/
Declaration of Competing Interest carboxylated graphene oxide composite microbeads for efficient adsorption of
cationic methylene blue dye, Int. J. Biol. Macromol. 154 (2020) 307–318.
[12] S.P. Lee, G.A.M. Ali, H.H. Hegazy, H.N. Lim, K.F. Chong, Optimizing reduced
The authors declare that they have no known competing financial graphene oxide aerogel for a supercapacitor, Energy Fuels 35 (2021) 4559–4569.
interests or personal relationships that could have appeared to influence [13] J. Zhu, X. Yang, Z. Fu, C. Wang, W. Wu, L. Zhang, Facile fabrication of ultra-low
density, high-surface-area, broadband antireflective carbon aerogels as ultra-black
the work reported in this paper. materials, J. Porous Mater. 23 (2016) 1217–1225.
[14] W. Peng, H. Li, Y. Liu, S. Song, A review on heavy metal ions adsorption from water
Acknowledgment by graphene oxide and its composites, J. Mol. Liq. 230 (2017) 496–504.
[15] H. Huang, P. Chen, X. Zhang, Y. Lu, W. Zhan, Edge-to-edge assembled graphene
oxide aerogels with outstanding mechanical performance and superhigh chemical
This research is funded by Vietnam National University HoChiMinh activity, Small 9 (2013) 1397–1404.
City (VNU-HCM) under grant number C2021-20-32. We acknowledge [16] A. Ehsani, M. Esfahaniha, R. Safari, H. Parsimehr, Functionalized graphene oxide
aerogel as a high efficient material for electrochemical sensing of organic pollutant,
the support of time and facilities from Ho Chi Minh City University of Surf. Interfaces 22 (2021), 100817.
Technology (HCMUT), VNU-HCM for this study. [17] B.Y.Z. Hiew, L.Y. Lee, X.J. Lee, S. Thangalazhy-Gopakumar, S. Gan, S.S. Lim, G.-
T. Pan, T.C.-K. Yang, W.S. Chiu, P.S. Khiew, Review on synthesis of 3D graphene-
based configurations and their adsorption performance for hazardous water
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