Carbon 183 (2021) 958e969

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Research Article

Crumpled graphene balls adsorb micropollutants from water

selectively and rapidly
Han Fu a, Jiaxing Huang b, Kimberly Gray a, *
a
Department of Civil and Environmental Engineering, Northwestern University, Evanston, IL, 60208, USA
b
Department of Materials Science and Engineering, Northwestern University, Evanston, IL, 60208, USA

a r t i c l e i n f o a b s t r a c t

Article history: Thousands of anthropogenic materials (e.g., micropollutants, MPs) are discharged to surface and
Received 20 March 2021 groundwaters daily and their wide distribution potentially threatens ecological and human health.
Received in revised form Granular activated carbon (GAC) is a widely used adsorbent to remove MPs, but with several deficiencies
25 June 2021
such as slow adsorption kinetics and hindered performance by natural organic macromolecules (NOM).
Accepted 28 July 2021
Available online 30 July 2021
Here, we detail the synthesis of a novel adsorbent, three-dimensional (3D), stacking-resistant, crumpled
graphene oxide balls (CGBs) and their adsorbent properties by using eight persistent MPs under relevant
environmental conditions. CGBs displayed 4e8 times greater adsorption capacity than GAC for seven of
Keywords:
Micropollutant removal
the eight MPs on a surface area equivalent basis. Kinetic experiments show that seven of eight MPs in a
PPCP removal mixture reach >90 % removal efficiency after 15 min contact time (compared to 5e10 % removal of GAC).
Adsorption CGB adsorption performance was also tested as a function of varying NOM concentration, with other
Graphene oxide realistic environmental conditions of pH, ionic strength, water hardness, and alkalinity, to demonstrate
Graphene that CGB adsorption of MPs is not adversely affected by NOM even at high concentrations and is stable
3D graphene material over a range of field conditions. These findings demonstrate that CGBs are potentially a powerful
adsorbent for micropollutant removal in complex aqueous environments.
© 2021 Elsevier Ltd. All rights reserved.

1. Introduction concentrations orders of magnitude greater than the MPs.

Every day, thousands of anthropogenic materials are manufac-
tured, utilized, and discharged from industrial, commercial, and
residential areas [1e3]. These chemicals, such as pesticides, her-
bicides, industrial additives, pharmaceuticals, and personal care
products, are detected at trace levels (nanogram to microgram per
liter) in municipal wastewater treatment effluents, as well as in
surface waters and groundwaters [4,5]. Collectively these chemicals
are referred to as micropollutants (MPs) and create complex mix-
tures. Unfortunately, traditional water treatment technologies may
reduce but do not remove these materials completely [6e8]. Con-
ventional wastewater treatment is based on biological processes.
Yet, the concentrations of MPs are too low to support metabolic
processes and thus, their degradability is highly variable. In addi-
tion, MPs are typically present as trace components in an organic
matrix containing natural organic macromolecules (NOM) at
* Corresponding author. Department of Civil and Environmental Engineering,
Northwestern University, 2145 Sheridan Road, Evanston, IL, 60208, USA.
E-mail address: k-gray@northwestern.edu (K. Gray).
Although MPs persist at very low levels, several studies have
demonstrated that long-term exposure to MP mixtures may cause
endocrine-disrupting effects to fish and other aquatic organisms
[9], as well as to humans [10,11]. Furthermore, some MPs may
bioaccumulate and thus, may transfer at elevated concentrations to
higher trophic level organisms and ultimately, to humans [12]. Yet,
no government regulations have been promulgated to restrict the
discharge of most MPs in wastewater effluents. Some of the
reluctance to control MP discharge may be related to a dearth of
effective and cost-efficient treatment options. This condition, then,
drives the search for alternative treatment options either at the
point of release or point of use.
Among all the promising technologies [13e17], adsorption is an
efficient, convenient, and widely available method to remove
organic contaminants and does not produce toxic byproducts.
Among many traditional and novel adsorbents [18e21], granular
activated carbon (GAC) is the most widely used adsorbent in water
treatment to remove MPs at a variety of scales [22]. However, there
are a number of limitations to GAC performance: i.) NOM can
interfere and/or inhibit MP adsorption [23]; ii.) The adsorption

https://doi.org/10.1016/j.carbon.2021.07.081
0008-6223/© 2021 Elsevier Ltd. All rights reserved.
H. Fu, J. Huang and K. Gray
process is slow [24,25]; iii.) The regeneration of activated carbon is
energy intensive requiring high temperature and pressure and
hence, costly [22]. Despite its widespread use, given these limita-
tions, there is need to develop a robust adsorbent better tailored to
the challenging conditions of micropollutant control in water
treatment.
Graphene-based nanomaterials are potential adsorbents based
on their highly reactive surface properties and strong sorption af-
finity for organic chemicals [26e31]. Owing to strong van der Waals
interaction between their two-dimensional sheet structures, gra-
phene and graphene oxide tend to stack and aggregate in water,
reducing the exposed surface area and limiting their efficacy as a
practical adsorbent for water contaminants [32e34]. A promising
approach to rectify this problem is to assemble three-dimensional
(3D) structures from the graphene/graphene oxide nanosheets.
For example, 3D graphene sponges and beads have been synthe-
sized via hydrothermal and chemical methods [35e37]. These
materials have low density but high surface area and porosity and
their performance to remove dyes, oil, hydrocarbons, and heavy
metal ions from water has been reported [35e39]. Spray drying is
also an efficient method to generate micro-/nano-size 3D graphene
materials; graphene oxide sheets dispersed in aerosol droplets
generated via a spray head can undergo evaporation to form
crumpled paper ball-like structures [40e45]. There are several
studies reporting the advanced properties and application of
crumpled graphene balls (CGBs) and related structures as electro-
chemical capacitors [40], lubricant additives [41], solar absorbers
[42], coating thickeners [43], solid-phase extraction adsorbent [45],
but only a limited number reports CGB efficacy for organic
contaminant adsorption in the water treatment [44,45].
In the present study, we explored the application of CGB as
robust adsorbent well suited to micropollutant removal in complex
aqueous environments. We first modified the CGB synthesis
method and characterized the resulting structure. In addition, we
detail the adsorptive behavior of CGB with eight model micro-
pollutants, individually and in a mixture, comparing its perfor-
mance to that of GAC. We also studied the adsorption kinetics of the
MP mixture and CGB thermodynamic behavior using two repre-
sentative MPs. Finally, we investigate how MP adsorption by CGBs
is influenced by important environmental parameters such as the
presence of NOM, calcium ions (water hardness), and carbonate/
bicarbonate ions (alkalinity), ionic strength, and pH.
2. Methods and materials
2.1. Materials and reagents
Eight micropollutants were selected in this study based on their
chemical properties (both hydrophilic and hydrophobic com-
pounds), different sectors of use (personal care products, plasti-
cizers, pharmaceuticals, pesticides and etc.), and their persistence
and distribution in nature waters [7,8]. The model MPs are caffeine,
sucralose, sulfamethoxazole, bisphenol S, carbamazepine, valsar-
tan, metolachlor and oxybenzone. Detailed information on the
supplier, uses, chemical structures and physicochemical properties
is listed in Table S1. Formic acid (EMD™ 98 %) and ammonia hy-
droxide (Honeywell 5.0 M solution) were used to adjust pH. Sodium
nitrate (Sigma-aldrich, >¼ 99 %) was used to study the effect of
ionic strength. Calcium nitrate (Alfa Aesar, 99 %) was used to test
the effect of water hardness. Sodium bicarbonate (Sigma-aldrich,
99.7e100.3 %) was used to study the effect of alkalinity. Suwannee
River fulvic acid (code 2S101F), used to model the effect of natural
organic matter, was acquired from the International Humic Sub-
stance Society (Denver, CO, USA). A commercial Granular Activated
Carbon (NORIT(R) GAC 1240, 12e40 mesh, ACROS Organics™) was
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Carbon 183 (2021) 958e969
employed for comparing adsorption capability. Its physical prop-
erties including surface area and pore size distribution were veri-
fied (Fig. 1d and e). NORIT(R) GAC 1240 is a bituminous coal-based
carbon, and it is activated via steam (96 % particles with the size
between 0.42 and 1.68 mm). It is widely used in both industrial
water treatment and laboratory research [46e48].
2.2. Synthesis and characterization
Graphene oxide nanosheets were synthesized by a modified
Hummer's method as previously reported [49,50]. Briefly, graphite
was first pretreated with K2S2O8, P2O5 and H2SO4 by stirring at
80  C, diluting with water and then filtering with filtration paper
(Whatman Grade 3). The pre-treated graphite was dispersed in
H2SO4 and KMnO4, kept at 35 ± 5  C for 2 h and then slowly diluted
with purified water and then add of 30 mL of 30% H2O2 solution.
The mixture was again filtered via Millipore polytetrafluoro-
ethylene (PTFE) membrane and rinsed with diluted HCl (3.4%).
After drying at room temperature via vacuum overnight, the GO
powder was re-dispersed and washed in acetone, filtered via PTFE
membrane again and eventually dispersed in water for future use.
Crumpled graphene oxide balls were made from the GO suspension
by droplet generation method using a spray dryer (Buchi Nano-
spray Dryer B-90). A 100 mL 0.5 mg/mL GO aqueous suspension
was prepared and sprayed at 95  C while continuously stirring the
suspension. The CGBs were collected in the particle collection
chamber at the exit of the instrument and annealed at 150  C for
30 min to remove surface impurities and moisture. All the chem-
icals were purchased from Sigma-Aldrich, or Fisher Chemical.
The synthesized CGBs were characterized with a variety of
techniques. AFM images of synthesized GO nanosheets were taken
via Bruker Dimension Fast Scan Atomic force microscopy at a scan
rate of 2 Hz in the air-tapping mode. SEM images were acquired
with a Hitachi SU8030 and TEM images with the JEOL JEM-2100F
Field Emission Electron Microscope. Surface area and pore size
analyses were conducted by Micromeritics 3Flex Surface Area
Analyzer and its related software MicroActive™. X-ray Photoelec-
tron Spectroscopy (XPS) was performed on the Thermo Scientific
ESCALAB 250Xi. FTIR spectroscopy measurements were made with
a Bruker Tensor 27 FTIR spectrometer (Absorbance mode, 4 cm1
resolution, 4000-400 cm1 wavelength range, 16 scans). RAMAN
spectra results were obtained with a Horiba LabRam Confocal
Raman Microscope with laser wavelength 532 nm.
2.3. Adsorption isotherm experiments
Adsorption isotherms were performed through batch adsorp-
tion experiments in Milli-Q water (Milli-Q RG QPAK 1 column,
water resistivity 18.2 MU-cm at 25  C). For single-component
adsorption isotherms, the initial concentrations varied from 1 to
50 mg/L except with sucralose (its initial concentrations varied
from 500 mg/L to 2 mg/L due to its low adsorption capacity). For
multiple-component adsorption tests, the initial concentrations
varied from 1 to 5 mg/L for each component. For both single-
component and multiple-component adsorption isotherms, the
pH of the prepared solutions was adjusted to 7.5 ± 0.1 with formic
acid or ammonia hydroxide. The prepared solutions were
dispensed into 20 mL Teflon-lined screw-top glass vials and the
adsorbent (dosage 0.1 mg/mL) was then added. All sample vials
were mixed on a VWR incubator orbital shaker (200 rpm, 25  C) for
24 h to reach equilibrium. After 24 h of shaking, the vials were
sampled via a syringe (BD 1 mL TB Syringe) and 0.2 mm PTFE syringe
filter (Whatman™).
We also investigated the effects of various environmental con-
ditions (NOM, pH, ionic strength, water hardness and alkalinity)
H. Fu, J. Huang and K. Gray Carbon 183 (2021) 958e969

Fig. 1. (a)-(b) SEM images of CGBs, (c) TEM images of CGBs, (d) nitrogen adsorption/desorption isotherms and Specific Surface Area (SSA) of CGBs and GAC; (e) Pore size distribution
of CGBs and GAC; (f) C1s XPS spectra of CGBs. (A colour version of this figure can be viewed online.)

and all the experiments were performed in duplicate. The influence
of NOM on adsorption was investigated at four SRFA concentrations
(5 mg/L, 10 mg/L, 20 mg/L and 50 mg/L as the total concentration).
The pH of the MP mixtures was adjusted to 6, 7.5 or 9 (which
represents the common pH range of surface water, groundwater
and tap water) via formic acid or ammonia hydroxide before adding
the adsorbent to determine its effect on adsorption. The effect of
ionic strength was evaluated at 1 mM, 5 mM or 10 mM, a typical
range in freshwaters, via the addition of sodium nitrate. The in-
fluence of water hardness was assessed at 100 mg/L as CaCO3
(moderately hard water) and 150 mg/L as CaCO3 (hard water) via
the addition of calcium nitrate. For the alkalinity studies, bicar-
bonate concentrations were adjusted at 100 mg/L and 150 mg/L via
addition of sodium bicarbonate. For both the water hardness and
the alkalinity experiments, the ionic strength was adjusted to 5 mM
960
and pH was adjusted to 7.5 ± 0.1. The water matrix at different SRFA
concentrations, ionic strength, water hardness and alkalinity were
prepared beforehand, stored in the 4  C refrigerator, and stirred at
200 rpm, in room temperature 30 min before usage.
2.4. Adsorption kinetics experiments
Adsorption kinetic studies were performed through batch
adsorption experiments within an initial concentration 1 mg/L per
each MP. The kinetic studies were conducted in a 100 mL beaker
stirring at 400 rpm and the temperature was controlled at 25  C via
a temperature-controlled magnetic agitator. After the adsorbent
was added, the solution was sampled via a 1 mL syringe and 0.2 mm
PTFE syringe filter at periodic intervals over 24 h (1, 2, 3, 6, 9,15, 30,
45, 60 min, 6 h, and 24 h).
H. Fu, J. Huang and K. Gray
2.5. Adsorption thermodynamics
The effect of temperature (25, 35 and 45  C) on the adsorption
properties of CGBs was studied by setting the adsorbent dosage at
0.1 mg/mL and the initial MP concentration at 50 mg/L and main-
taining the set temperature in the orbital shaker for 24 h. After the
24-h equilibrium time, the residual solution concentration was
sampled via a 1 mL syringe and PTFE syringe filter. Two MPs were
selected (one hydrophilic compound caffeine and one hydrophobic
compound valsartan) and studied individually.
2.6. Micropollutant analytical methods
The quantification of analytes in the adsorption isotherm and
kinetics experiments was performed by HPLC-MS/MS (QExactive,
Thermo-Fisher Scientific) using a C18 column (Thermo-scientific
BDS Hypersil C18) using the following protocol: 10 mL of sample
was injected by pumping at a speed 0.4 mL/min the mobile phase of
deionized water and acetonitrile (both mobile phases contain 0.1 %
Formic acid). The MS was operated with electrospray ionization in
positive and negative polarity modes. The quantification of analytes
was determined from calibration standards based on linear
regression calculation. The detailed ionization mode, retention
time and the exact mass of the adduct are listed in the SI (Table S2).
3. Results and discussion
3.1. Characterization of CGBs
As the SEM images show in Fig. 1a, GO nanosheets (AFM image
in Figure S4) are arranged in a crumpled paper ball-shaped struc-
ture after aerosol generation and evaporation in the nano-sprayer.
The particle size of the CGBs is approximately 1e5 mm (Fig. 1b). TEM
images illustrate that the folds and wrinkles on CGBs are created via
the bridging of several GO nanosheets (Fig. 1c). The nitrogen
adsorption-desorption isotherm of CGBs exhibited an IUPAC Type
IV isotherm curve (Fig. 1d) that is consistent with a micro/meso-
porous material. The specific surface area of CGBs is 177 m2/g,
which is 6 times less than the commercial GAC (1069 m2/g) used for
comparison. Hysteresis is also observed, implying the presence of
mesopores and micropores. The pore size distribution (Fig. 1e) in-
dicates the existence of both micropores (<2 nm) and mesopores
(2e100 nm). Compared to CGBs, GAC has micropores as the
dominant pore size. More detailed properties of two adsorbents are
summarized in Table S7.
XPS, FTIR and RAMAN spectra were employed to investigate the
surface chemical characteristics of CGBs (Fig. 1f, S1, S2 and S3). The
XPS spectra reveal oxygen (34.78 atomic %) and carbon (65.22
atomic %) are major components of CGBs (Fig S1). The C 1s XPS
spectra (Fig. 1f) further demonstrate the presence of the oxygen-
containing functional groups such as CeOeC, C]O and COO. The
FTIR results (Fig S2) confirm this observation. The eOH and C]O
peaks became weaker in the CGBs and the C]C peak was enhanced
compared to GO. These results indicate that during CGB synthesis, a
certain number of oxygen-functional groups remain at the CGB
surface. In the RAMAN spectra (Fig S3), the D peak (near 1350 cm1)
represents the defect lattice structure of the graphene; the G peak
(near 1620 cm1) indicates the vibration of C]C sp2 bonding. The
ID/IG ratio is utilized to evaluate the degree of graphitization of the
material. The ID/IG of CGBs (0.98) is similar to GO (0.97), but much
greater than graphite (0.21). The difference suggests that CGBs have
many defects attributable to the residual GO functional groups.
Overall, CGBs retain oxygen-containing functional groups after
synthesis, and their surface chemical characteristics are more
similar to GO than to graphite.
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Carbon 183 (2021) 958e969
3.2. Single-component adsorption isotherms
The adsorption isotherms of the eight MPs and the two adsor-
bents, CGBs and GAC, are presented in Figure S5. Two isotherm
models (Langmuir and Freundlich) were fit to the experimental
data and the model parameters are listed in Table S3. The Langmuir
model fits the results well (with relatively high R2 values) and
better than the Freundlich model. In Fig. 2, we utilized the octanol-
water distribution coefficient (log Kow) as an index of MP hydro-
phobicity (a hydrophobic compound has a higher log Kow value).
Fig. 2a compares the Langmuir maximum adsorption capacity, qm,
between CGBs and GAC on a mass equivalent basis and illustrates
that CGBs have a greater adsorption capacity for four of eight MPs:
sulfamethoxazole (log Kow 0.79), metolachlor (log Kow 3.56), oxy-
benzone (log Kow 3.83) and valsartan (logKow 3.85). In a surface area
equivalent comparison (Fig. 2b), seven of the eight MPs (with the
exception of sucralose) showed 4 to 8 times greater adsorption
capacity on CGBs than GAC, which suggests that the CGB surface
has a greater affinity for MPs than GAC.
Fig. 2c shows the linear relationship between the qm of each MP
on CGBs and their log Kow, illustrating that in general, the degree of
hydrophobicity has a positive impact on the adsorption maximum
capacity. There are two outliers, however, to this trend: sulfa-
methoxazole, which displays the highest qm of the 8 MPs at a
relatively low Kow, and sucralose, which shows poor adsorption on
CGBs. Hydrophobic attraction is an important adsorption mecha-
nism for graphene-based adsorbents [28,29] and our observations
are consistent with the findings for many other graphene-based
materials that hydrophobic MPs are better adsorbed by CGBs
than hydrophilic MPs [28e30]. Pi-pi (p - p) interactions, or more
specifically, aromaticearomatic interactions, describe the attractive
force between the C]C sp2 -hybrid orbitals in the aromatic rings of
the MPs and the CGBs and are another important adsorption
mechanism to consider. Usually, more aromatic rings in the struc-
ture promote more p - p interactions; six of the eight selected MPs
have one or two aromatic rings and as illustrated in Fig. 2c, have a
higher adsorption capacity than those MPs with no aromatic ring
structure (caffeine and sucralose).
Other critical mechanisms also affect CGB adsorption processes.
We propose that the oxygen-containing functional groups on CGBs
contribute to MP adsorption via three mechanisms: (i) improving
CGB dispersion in water; (ii) promoting hydrogen bonding between
the CGBs and MPs; (iii) enhancing electron donor acceptor (EDA)
interactions.
First, CGBs retain many oxygen-functional groups as evidenced
by the XPS, FTIR, and Raman spectra (Fig. 1, S2 and S3) and hence,
are amphiphilic with a hydrophobic graphene platform and hy-
drophilic surface groups. We have modified the CGB synthesis
temperature to 150  C, which is much lower than the previously
reported studies >400  C [40e45,51] and as a result, our CGBs have
a smaller water contact angle and are more hydrophilic (Figure S6c)
than CGBs synthesized at high temperature (400  C). The hydro-
philic CGB surface resists aggregation, disperses better in water
(Figure S 6a-b) and hence, provides more interactions with MPs.
Second, CGB oxygen-containing functional groups provide
hydrogen bonding between the eCOOH, eOH, CeOeC and eNH2
groups on the MPs, which is an often invoked adsorption mecha-
nism for organic pollutants removal by graphene-based materials
[52e54].
Third, we propose that electron donor-acceptor (EDA) in-
teractions may also enhance MP adsorption [55e57]. Unlike the
evenly distributed electron density provided by the fused benzene
rings of pure graphene, the oxygen-containing functional groups on
CGB promote both pi-electron-depleted or rich regions, which is
attractive to pi-electron-donating (-NH2 or eOH substituted) MPs
H. Fu, J. Huang and K. Gray
Fig. 2. Comparison of the Langmuir maximum adsorption capacity qm of eight micropollutants with CGBs and GAC as calculated from single-component adsorption isotherm
experiments based on (a) an equivalent mass bass (0.1 mg/mL) and (b) an equivalent surface area (SA) basis (normalized by the surface areas of two adsorbents) (c) The relationship
between the qm and log Kow of eight micropollutants (dotted line is the linear fit). (A colour version of this figure can be viewed online.)
(such as bisphenol S or carbamazepine) or pi-electron-
withdrawing MPs (such as the sulfonamide structured MP,
sulfamethoxazole).
As noted above, sulfamethoxazole (well adsorbed) and sucralose
(poorly adsorbed) do not follow the trend of the other 6 MPs in
Fig. 2c. Although sulfamethoxazole has a lower log Kow and single
aromatic ring, plentiful nitrogen-containing and the sulfonamide
functional groups in its structure likely contribute to its strong
adsorption on oxygen-containing CGBs due to EDA interactions,
and possibly hydrogen bonding. In contrast, the poor adsorption of
sucralose is only partly explained by its relative hydrophilicity,
which is similar to caffeine, a compound that follows the log Kow
trend. As illustrated in Table S1, the disaccharide structure of
sucralose bears fully saturated carbons and thus, its adsorption
lacks hydrophobic or p-p interactions. Only hydrogen bonding,
then, accounts for its sorption on CGBs suggesting that H-bonding
may be a minor interaction at the CGB surface relative to the other
mechanisms.
Electrostatic attraction is also reported as the one possible
mechanism for MP adsorption [56]. However, in the Milli-Q water
environment (pH ¼ 6), six of eight studied MPs are neutral and the
remaining two MPs are negatively charged (Table S1) which would
create electrostatically unfavorable interactions at the negatively
charged CGB surface. In this study, however, we did not observe
obvious inhibition of adsorption with negative charged MPs;
therefore, electrostatic repulsion is likely not a dominant adsorp-
tion mechanism.
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Carbon 183 (2021) 958e969
3.3. Multiple-component competitive adsorption isotherms
Since micropollutants form complex mixtures in the environ-
ment, we investigated how individual MP adsorption is influenced
by a mixture. We then applied various adsorption models to
describe the adsorptive trends of the MP mixture. Among the
models tested, the Langmuir Single-component Isotherm (LSI)
model fit the data best (detailed explanation in table S4). Fig. 3
presents the adsorption isotherms for mixture of the 8 MPs and
compares adsorption on CGBs to GAC and GO.
As shown in Fig. 3a, when present in a mixture, those MPs,
which exhibited higher adsorption capacities to CGBs in the single-
component system (valsartan, oxybenzone and sulfamethoxazole)
also showed high adsorption capacities in the mixture. In the
mixture, however, the maximum Langmuir adsorption capacities,
qm, are reduced approximately 5 to 15-fold, which indicates that
there are a limited number of MP adsorption sites on the CGB
surface.
We considered the Langmuir adsorption constant, KL, to probe
the affinity between the MP and CGB surface (the larger the KL value,
the stronger the affinity is). In the single component system
(Table S3), the top four MPs with the largest KL values (surculose is
exclude due to its poor adsorption) are valsartan > bisphenol
S > caffeine > oxybenzone. In the multiple component system
(Table S4), the identical four MPs also showed the largest KL values,
albeit the order slightly changed: oxybenzone > caffeine > bisphenol
S > valsartan. This observation suggests that the affinity between
H. Fu, J. Huang and K. Gray Carbon 183 (2021) 958e969

Fig. 3. (a) The adsorption isotherms of a mixture of 8 micropollutants. The dash-line is the Langmuir Single-component Isotherm (LSI) fit for each MP; (b) Comparison of the
Langmuir maximum adsorption capacity, qm, in the single-component system and the multiple-component system (dash line is the linear fit, R2 ¼ 0.861); (c) Comparison of qm of
eight micropollutants in a mixture with CGBs and GAC/GO as calculated from LSI based on an equivalent mass basis; (d) Comparison of SA normalized qm of eight micropollutants in
a mixture with CGBs and GAC. (A colour version of this figure can be viewed online.)

MPs and the CGB surface does not change much when they are
present in a mixture. Yet, the small changes in the relative adsorption
affinity of the four MPs may also indicate that there are small
competitive adsorption effects on the adsorbing chemicals. Fig. 3b
shows the trend of qm between the single component and the
multiple component systems. The adsorption of two MPs, valsartan
and oxybenzone (with high log Kow values and KL values), appears
relatively less sensitive to mixture effects, while the adsorption of
three MPs, carbamazepine, metolachlor and particularly sulfameth-
oxazole, is relatively depressed in the mixture. Although more
research is needed to explore these phenomena and many factors are
at play, mixture effects may decrease as the log Kow increases.
For comparison, adsorption on GAC and graphene oxide (the
original material of CGBs), was tested with the MP mixture. Fig. 3c
compares the LSI adsorption capacity, qm, of CGBs to GAC/GO (more
details in Table S4). In the mass equivalent comparison with GAC
(Fig. 3c), CGBs show greater adsorption capacity for the two MPs
(valsartan and oxybenzone) having the highest log Kow, and similar
qm with sulfamethoxazole and caffeine, whereas greater maximum
adsorption occurs with bisphenol S, metolachlor, carbamazepine
and sucralose on GAC than CGBs. In the surface area equivalent
comparison with GAC (Fig. 3d), however, CGBs display superior
adsorption capacity for seven of the eight MPs, with sucralose being
963
the outlier, which is consistent with the observations in the single-
component system (Fig. 2b).
If we focus on the comparison of CGBs with GO (Fig. 3b), GO
shows some adsorption capacity with the more hydrophobic MPs
such as valsartan and oxybenzone, but poorer adsorption affinity
with the relatively hydrophilic MPs than CGBs. Stacking of the 2D
GO nanosheets (Fig. S7) reduces their exposed and effective
adsorptive surface area and may explain this behavior [58,59].
3.4. Adsorption kinetics
Fig. 4a shows the time-dependent adsorption curves of CGBs for
the mixture of eight MPs. The adsorption curves of GAC and GO
under the same experimental conditions are presented in Figure S8.
In Fig. 4a, the CGB adsorption process is rapid over the initial 15 min
and then reaches equilibrium thereafter. Fig. 4b summarizes the %
removal of the eight micropollutants after 15 min (solid bar) and
24 h (hollow bar) adsorption under four different scenarios: 0.6 mg/
mL CGBs (equivalent surface area to 0.1 mg/mL GAC), 0.1 mg/mL
CGBs (equivalent mass basis), 0.1 mg/mL GO and 0.1 mg/mL GAC.
Overall, CGBs show much faster adsorption kinetics compared to
GAC for all the MPs. On an equivalent mass basis, 90 % of CGB
maximum removal occurs in the first 15 min of the experiment.
H. Fu, J. Huang and K. Gray
Fig. 4. (a) The reduction of in a mixture of 8 micropollutants (initial concentration 1 mg/L per each MP) via addition of 0.1 mg/mL CGBs in a 24 h batch experiment; (b) The removal
% of a mixture of 8 micropollutants (micropollutant concentration 1 mg/L per each MPs) under 4 different adsorbent conditions. Solid bar ¼ removal % at 15 min; Hollow
bar ¼ additional removal % between 15 min and 24 h. (A colour version of this figure can be viewed online.)
More surprisingly, on an equivalent surface area basis (CGB mass
dose of 0.6 mg/mL), six of eight MPs were fully removed in the first
15 min, Metolachlor reached 90 % removal and only sucralose
reached 60 % of removal. In comparison, GAC exhibits a relatively
slow process over the initial 15 min, taking more than 24 h to reach
equilibrium. The fast adsorption process of CGBs is explained by its
uniform dispersion in water and its mesoporous structure. In
comparison, a long-time is required for MPs to diffuse into the
micropores of GAC. In Fig. 4b, GO also showed a rapid, albeit
limited, adsorption process. For all MPs, adsorption on GO at
equilibrium is less than that on CGBs, presumably due to GO
stacking and reduction of its adsorptive surface area.
3.5. Adsorption thermodynamics
The effect of temperature on CGB adsorption for two MPs,
caffeine, and valsartan, was studied at three different tempera-
tures: 25  C, 35  C and 45  C. As shown in Figure S9, the adsorption
capacities for both MPs increases with increasing temperatures,
which implies an endothermic adsorption process with valsartan
being more sensitive to temperature changes than caffeine. The
relationship between thermodynamic properties and temperature
is expressed by Gibbs free energy and Van't Hoff equations (details
in Table S5). The values of DGo ; DSo and DH o (summarized in
Table S5) are determined from the slope and the intercept by
plotting ln Ke and 1/T (Figure S9). Both MPs show negative DGo
964
Carbon 183 (2021) 958e969
indicating that the adsorption of MPs on CGBs is a spontaneous
process. The positive values of DH o confirms it is an endothermic
process and high temperatures favor greater MP removal from
water. The positive DSo may be attributed the release of surface and
solvation water molecules into solution due to interactions at the
solid/solution interface during MP adsorption [60,61].
3.6. Effect of NOM
We tested the effects of varying levels of NOM, as modelled by a
standard mixture of organic material (degraded tannins, lignins,
carbohydrates and lipids) extracted from a natural source,
Suwannee River fulvic acid (SRFA), on MP adsorption [62]. Fig. 5
summarizes the Langmuir maximum adsorption capacity, qm, of
the eight MPs at different SRFA concentrations for CGBs and GAC.
The ratios in percentage between the qm at different NOM levels
and qm.0 (with no NOM) are also displayed in Fig. 5.
For CGBs, increasing NOM concentration has a small effect on
qm. At the high concentrations (20 mg/L and 50 mg/L SRFA), NOM
showed a negligible change on adsorption of four MPs (caffeine,
bisphenol S, carbamazepine, and valsartan) and less than 20 %
reduction on the remaining four MPs (sucralose, sulfamethoxazole,
metolachlor, and oxybenzone). In contrast, the maximum MP
adsorption capacity by GAC was reduced from 35 % to 80 % with
increasing NOM concentrations. The inhibitory effect of NOM on
adsorption by activated carbon, graphene and graphene oxide has
H. Fu, J. Huang and K. Gray Carbon 183 (2021) 958e969

Fig. 5. Comparison of the Langmuir maximum adsorption capacity, qm, for eight micropollutants individually at different SRFA concentration. Red bars represent CGB and blue bars
represent GAC. The ratio in percentage between qm (at certain SRFA concentrations) and qm.0 (no SRFA) is also presented. The error bar represents the standard deviation of
duplicate experiments. (A colour version of this figure can be viewed online.)

965
H. Fu, J. Huang and K. Gray
been investigated previously (humic acids as the model) [30,63,64],
showing that graphene/graphene oxide are more NOM-resistant
than GAC. NOM molecules may block the micropores of GAC and
prevent the MPs diffusion to the micropores which are the domi-
nant adsorptive sites of GAC [30]. Meanwhile, the mesoporous
structure (shown in Fig. 1e) of CGBs is less affected by NOM
macromolecules.
NOM had a dramatic effect on GAC adsorption of four MPs
(sulfamethoxazole, valsartan, metolachlor, and oxybenzone) and
even at lower NOM levels, CGBs performance was approximately
2e5 times greater than GAC for these four MPs. The NOM effect had
an equalizing effect for carbamazepine and bisphenol S where the
qm for GAC and CGBs are similar. GAC still showed a superior per-
formance for the two hydrophilic compounds (caffeine and sucra-
lose) compared to CGBs.
The 10 mg/L SRFA concentration is equal to about 5 ppm as total
organic carbon (TOC) which is a moderate TOC level for surface
waters [64,65]. At this moderate TOC level, the NOM effect on CGB
adsorption is negligible but most MP adsorption on GAC is affected
significantly with an average 46 % decline (range 9e78 %). Overall,
considering the resistance of CGBs to NOM effects at moderate TOC
levels, we conclude that CGBs are a very promising adsorbent under
realistic environmental conditions.
3.7. Effect of pH
Fig. 6 summarizes the qm of a mixture of eight MPs at pH 6, 7.5
and 9, reflecting a narrow but a realistic environmental pH range.
There is a small reduction (around 10e15 %) in adsorption capacity
of six MPs at high pH ¼ 9, likely due to an increase in electrostatic
repulsion. High pH may promote deprotonation of many MPs and
make both CGBs and MPs more negatively charged (zeta potential
of CGBs at different pHs shown in Fig. S10). Overall, we still
conclude that high pH has a small negative impact on MP adsorp-
tion by CGBs, although negligible effect on caffeine or sucralose
adsorption.
3.8. Effects of ionic strength, water hardness and bicarbonate ions
To further investigate the adsorption performance of CGBs un-
der environmental conditions, we tested the effects of varying ionic
Fig. 6. Langmuir maximum adsorption capacity qm of 8 micropollutant mixture at pH 6, 7.5 and 9 (CGB dosage ¼ 0.1 mg/mL, room temperature, 24 h equilibration). The error bar
represents the standard deviation of duplicate experiments. (A colour version of this figure can be viewed online.)
966
Carbon 183 (2021) 958e969
strength and specific ionic composition on MP and CGB in-
teractions. Ionic strength can influence absorption by graphene-
based materials in three ways: (i) Ionic strength may change the
surface charge of the adsorbent at neutral pH. Cations may reduce
negatively charge-assisted hydrogen bonding (negative CAHB), but
on the other hand may also lessen electrostatic repulsion and create
more electrostatic attraction for negatively charged MPs [65]; (ii) A
high salt concentration may create a compact aggregation of ad-
sorbents; the aggregation of carbon nanotubes and graphene
nanosheets at the high salt concentrations has been reported
[30,66]; (iii) Co-existence of different ions and MPs in water may
reduce the solubility of MPs due to a “salting-out” effect and
enhance MPs’ adsorption [30,66].
Three sequential experiments were performed to probe these
phenomena (Fig. 7) where MilliQ water served as the control
experiment (pH adjusted to 7.5, negligible ionic strength). In the
first experiment, we varied the ionic strength from 1 mM to 10 mM
(using NaNO3) in a mixture of 8 MPs. No obvious adsorption
decrease was observed. The adsorption capacity of some MPs (such
as valsartan, metolachlor and oxybenzone) was enhanced slightly,
possibly caused by a “salting-out” effect.
Subsequently, the effects of calcium ions were interrogated.
Moderately hard (100 mg/L) and hard (150 mg/L) water conditions
were studied (while the ionic strength was set at 5 mM and pH at
7.5). As shown in Fig. 7b, a slight enhancement in adsorption was
observed for 3 negatively charged MPs (sulfamethoxazole, valsar-
tan and oxybenzone) and 1 neutral, but hydrophilic, MP (caffeine).
The presence of calcium ions lessens the negative charge of CGB at
neutral pH reducing unfavorable electrostatic interactions.
Finally, the effects of alkalinity, due primarily to carbonate/bi-
carbonate ions, were probed at two common concentrations
100 mg/L and 200 mg/L as CaCO3 for surface waters. The presence
of bicarbonate sharply decreased the adsorption capacity of two
MPs (sulfamethoxazole and valsartan), likely caused by bicarbonate
modification of the CGB surface. Some researchers report that bi-
carbonate can activate deoxygenation on GO, removing oxygen-
containing functional groups from GO [67]. We confirmed the
same observation by stirring only CGBs in the 200 mg/L bicarbonate
solutions for 24 h. XPS spectra showed the atomic ratio of oxygen
and the peak intensity of carbon-oxygen bonding in CGBs
decreased after 24 h contact with bicarbonate (Fig. S11). The
H. Fu, J. Huang and K. Gray Carbon 183 (2021) 958e969

Fig. 7. Langmuir maximum adsorption capacity qm of 8 micropollutants in a mixture (a) Ionic strength (NaNO3 concentration) 1 mM to 10 mM; (b) Hardness 100 mg/L and 150 mg/L
as CaCO3; (c) Bicarbonate 100 mg/L and 150 mg/L. Experimental conditions for all three studies: CGB dosage ¼ 0.1 mg/mL, room temperature, equivalent time 24 h. The error bars
represent the standard deviation of duplicate experiments. (A colour version of this figure can be viewed online.)

reduction of oxygen-containing functional groups suggests the loss
of active adsorption sites associated with hydrogen bonding and
EDA interactions. In the same experiment, we also observed the
enhanced adsorption capacity of other MPs (caffeine, bisphenol S,
carbamazepine and oxybenzone). Three of these MPs have strong
affinity (large KL values) with CGBs as shown in adsorption
isotherm experiments (Table S4). Both the enhancement or
suppression of the MPs adsorption suggests that the adsorption
process is a combination of several mechanisms: some adsorption
mechanisms are still functioning well while other mechanisms are
suppressed. Further investigation is necessary to determine the
dominant adsorption mechanism(s) as a function of chemical
structure when CGB serves as the adsorbent in the realistic water
environment.

967
H. Fu, J. Huang and K. Gray
4. Conclusions
Efficient, stable, and economical methods are needed to solve
the emerging MP issues in drinking water and wastewater treat-
ment systems. Although activated carbon is the leading adsorbent
in the water treatment industry, there are numerous limitations
associated with its use in real water matrices. The results of this
research demonstrate that an engineered 3D graphene-based ma-
terial, CGBs, may serve as a practical adsorbent to remove MPs
under a wide range of environmental conditions. The CGB synthesis
method is also simple, only requiring a portable spray device and a
150  C oven. CGB adsorption capacity performance is superior to
GAC for all selected MPs (except sucralose) on an equivalent surface
area basis and the adsorption kinetics are much faster than GAC.
More importantly, MP adsorption on CGB is not diminished in the
presence of NOM or under various environmental conditions (pH,
ionic strength, and water hardness). Bicarbonate changes the sur-
face characteristics of CGBs which leads to both enhancement and
suppression of different MPs in a mixture. Based on all these fea-
tures, CGBs are a promising alternative adsorbent for the removal of
emerging MPs. Future research will be directed to further modify
the 3D graphene structure to maximize its effective surface area per
mass.
CRediT authorship contribution statement
Han Fu: Conceptualization, Methodology, Investigation, Data
curation, Writing e original draft. Jiaxing Huang: Conceptualization,
Methodology, Validation, Writing e review & editing. Kimberly
Gray: Conceptualization, Methodology, Validation, Supervision,
Writing e review & editing.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The SEM, TEM AFM, Raman spectra and XPS were performed in
the EPIC, KECK-II, and SPID facility of Northwestern University's
NUANCE Center, which receives support from the SHyNE Resource
(NSF ECCS-2025633), the IIN, and Northwestern's MRSEC program
(NSF DMR-1720139). HPLC-MS/MS analysis was performed with
the help of Dr. Arsen Gaisin of the NU IMSERC facility, which has
received support from the Soft and Hybrid Nanotechnology
Experimental (SHyNE) Resource (NSF ECCS-2025633), and North-
western University. Nitrogen isotherms were recorded at the
Reactor Engineering and Catalyst Testing (REACT) core facility at
Northwestern University with the help of Dr. Neil M Schweitzer. We
also acknowledge Zhenyu Bo for the water contact angle mea-
surement and Haiyue Huang for graphene oxide synthesis and AFM
measurement.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2021.07.081.
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