Diamond & Related Materials 109 (2020) 108002

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Diamond & Related Materials

journal homepage: www.elsevier.com/locate/diamond

Adsorption and kinetic study of Reactive Red 2 dye onto graphene oxides T
and graphene quantum dots
Miguel de la Luz-Asuncióna,b, Eduardo E. Pérez-Ramíreza,c, Ana Laura Martínez-Hernándeza,
⁎
Perla E. García-Casillasb, J. Gabriel Luna-Bárcenasc, Carlos Velasco-Santosa,
a
Tecnológico Nacional de México - Campus Querétaro, División de Estudios de Posgrado e Investigación, Av. Tecnológico s/n Esq. Gral. Mariano Escobedo, Col. Centro
Histórico, C.P. 76000 Santiago de Querétaro, México
b
Instituto de Ingeniería y Tecnología, Universidad Autónoma de Ciudad Juárez, Av. del Charro No. 610 Norte, Col. Partido Romero, C.P. 32320 Ciudad Juárez,
Chihuahua, México
c
Centro de Investigación y Estudios Avanzados del Instituto Politécnico Nacional Unidad Querétaro, Libramiento Norponiente No. 2000, Fraccionamiento Real de
Juriquilla, C.P. 76230 Santiago de Querétaro, México

A R T I C LE I N FO A B S T R A C T

Keywords: The increase of the water pollution has led to the search of new methods and materials for its remediation. In
Graphene quantum dots recent years, different carbon nanomaterials have gained importance in the removal of dyes from water. In this
Graphene oxide research was investigated the adsorption of Reactive Red 2 (RR2) dye onto different graphene oxides and gra-
Reactive red 2 phene oxide quantum dots at pH values of 2 and 5. The graphene oxide samples were obtained modifying the
Adsorption
amount of KMnO4 used and replacing the magnetic stirring by ultrasonic bath in the oxidation reaction. In order
Dimension
Elovich's equation
to know the surface and structural properties of carbon nanomaterials, these were analyzed by infrared, Raman
and energy dispersive X-ray spectroscopies, transmission electron microscopy and field emission scanning
electron microscopy, nitrogen-adsorption and through potentiometric titrations was obtained the point of zero
charge. The decrease in the amount of KMnO4 used in the Hummers´ reaction induced an increase in the oxygen
content of graphene oxide. All carbon nanomaterials presented a high affinity by the RR2 dye at pH = 2,
however graphene quantum dots showed the best performance. The removal of RR2 is dependent of the pH,
surface area, oxygenated groups and the dimensionality of the carbon nanomaterials. The experimental data are
analyzed using pseudo-first order, pseudo-second order, Elovich and intraparticle diffusion models to describe
the adsorption kinetics from RR2 in aqueous solutions. Based on the highest coefficient of determination values
and the lowest standard deviation values, the experimental kinetic data are better adjusted by the Elovich's
equation. The adsorption behavior is studied according to the RE values of the dimensionless Elovich's equation.

1. Introduction Azo dyes are an important class of dyes characterized by N]N

The increase in the use of dyes in industries such as paper, textile,
pigments, paint, plastics, among others, has positioned to the dyes as
one of the most important pollutants of water in the worldwide [1–4].
Most of these dyes are considered toxic and possess a complex and
stable aromatic structure, which makes these difficult to degrade
[2,5–7].
The presence of dyes in lakes, lagoon, rivers, and other water bodies
can cause foul odor, increase in the chemical oxidation demand [8],
decrease in the photosynthetic process of aquatic plants [1,9] and da-
mages to the aquatic organisms [10,11]. In humans, the exposure to
dyes can provoke respiratory problems, skin irritation, kidney dys-
function, mutagenicity and toxicity [7,12–16].
chromophore, which are used mainly in the textile industry due to af-
finity with cellulosic fibers for the creation of covalent bonds. However,
some groups make that these dyes have low fixation and thus produce
large quantities of colored effluents [17].
For the removal of dyes from water have been employed different
methods such as ozonation, ionic exchange, oxidative process, photo-
catalysis and adsorption [10,18–21]. Of these methods, the adsorption
is considered one of the most promising and effective on the removal of
dyes [1]. Besides, its low cost and easy operation; simple design and
high efficiency are another advantages versus other methods [6,12]. In
this method have been used different adsorbents for the removal of dyes
such as activated carbon [6], carbon nanotubes [22], zeolites [18], si-
lica gel [23], clays [24], among others.

⁎
Corresponding author.
E-mail address: cylaura@gmail.com (C. Velasco-Santos).

https://doi.org/10.1016/j.diamond.2020.108002
Received 29 April 2020; Received in revised form 23 June 2020; Accepted 10 July 2020
Available online 23 July 2020
0925-9635/ © 2020 Elsevier B.V. All rights reserved.
M. de la Luz-Asunción, et al.
Due to their characteristics of small size and higher surface area,
nanomaterials have gained a lot of attention for their use on the re-
moval of dyes. Carbon nanomaterials with graphitic structure have
shown interesting results on the removal of dyes [25–27]. Graphene
oxide, two-dimensional material considered as a functional form of
graphene containing oxygen groups has shown good performance in the
dyes removal [1,12,26,28,29]. The amount of surface oxygenated
groups is an important parameter in the adsorption of dyes. High ad-
sorption efficiencies have been achieved according to the nature of the
dye [25].
Other carbon nanomaterial that due to their structural character-
istics and no toxicity have a promising future in the environmental
remediation are the graphene quantum dots (GQDs) [30]. This zero-
dimensional material can be obtained using graphene oxide as pre-
cursor. GQDs have generated the interest from the scientific community
due to their interesting optical properties; however, the use of this
carbon nanomaterial in the adsorption process for the removal of pol-
lutants of water has been barely studied. Ying et al. [31] employed the
GQDs as stabilizer of graphene for the removal of aromatic dyes im-
proving the adsorption capacity of graphene.
Due to the similarity in structure (sp2 hybridization), but differences
in dimension between graphene oxide and graphene quantum dots,
dyes adsorption should be achieved by these materials with variations,
due to it have been demonstrated that parameters such as: dimension,
surface area and functional groups at surface, play an important role in
adsorption yield [1,25,28]. Thus, in this work is investigated and
compared the performance as adsorbent of different graphene oxides
and graphene quantum dots on an anionic dye (RR2) at two different
pH values. The amount of KMnO4 was modified in the oxidation reac-
tion in order to know the influence of this parameter on the removal of
RR2. Besides, a new methodology for the obtaining of graphene oxide
in a one-step was used and evaluated with the aim to modify the
quantity of functional groups at materials´ surface and to reduce the
time of obtaining. The experimental data adsorption was adjusted to
non-linear kinetic models in order to obtain information of the ad-
sorption process.
2. Experimental section
2.1. Materials
For the experimental development a graphite powder (GT) from
MEYER Company was acquired. This graphite is technical grade and is
considered as low oriented graphite. Reactive red 2 dye was obtained
from Sigma-Aldrich Company. Nitric acid (HNO3, 70%, Sigma-Aldrich),
Sulfuric acid (H2SO4, 98%, J. T. Baker), Hydrochloric acid (HCl, 37%,
Sigma-Aldrich), Sodium Hydroxide (NaOH, Sigma-Aldrich), Sodium
Nitrate (NaNO3, > 99.0%, Sigma-Aldrich), Potassium permanganate
(KMnO4, > 99.0%, Sigma-Aldrich), Hydrogen peroxide (H2O2, 30%, J.
T. Baker), and N,N-dimethylformamide (DMF, 99.8%, Sigma-Aldrich)
were used as received.
2.2. Characterization
For the infrared spectroscopy (IR) analysis was employed a Bruker
Tensor 37 spectrometer with a resolution of 1 cm−1. Powder samples
were analyzed in ATR mode. The Raman spectroscopy was realized in a
Witec, Alpha 300R equipment. The samples were also analyzed in
powder. The removal of RR2 was monitored through an HACH DR 5000
spectrophotometer to wavelength of 538 nm. The pHPZC of all materials
was obtained using the methodology used by de la Luz-Asunción et al.
[32]. The energy dispersive X-ray spectroscopy (EDS), Bruker, and Field
Emission Scanning Electron Microscopy (FESEM) analysis was carried
out in a Hitachi SU5000 FESEM; 5 mg of sample was placed in a vial
and 10 mL of ethyl alcohol were added; then, that was sonicated for
10 min in an ultrasonic bath. A drop of the dispersion was placed on a
2
Diamond & Related Materials 109 (2020) 108002
double-sided carbon tape and placed on an aluminum stub. The mor-
phology of the carbon nanostructures was analyzed by Transmission
Electron Microscopy (TEM) using a microscope JEOL JEM-1010. For
analysis, 2 mg of carbon nanomaterial were dispersed in 10 mL of ethyl
alcohol in a bath ultrasonic by 10 min. After, with a capillary tube an
aliquot of the dispersion was taken and deposited in a copper grid with
formvar. The surface area values were obtained using N2 adsorption-
desorption isotherms in a BELSORP-minill BEL JAPAN.
2.3. Graphene oxide synthesis
Graphene oxide was obtained through Modified Hummers Method
[25]. First, in a 3-neck flask were deposited 46 mL of H2SO4 and cooled
at 0 °C in an ice bath. Immediately the temperature is reached, 2 g of
graphite were deposited and after 6 g of KMnO4 were added slowly. The
reaction system was placed inside a bowl containing water which was
heated with a hot place until to reach the 35 °C. The system was
maintained at 35 °C ± 3 for 2 h under magnetic stirring (125 rpm).
After of 2 h, 92 mL of distillated water were added slowly (aliquot of
5 mL at room temperature), to the flask content and the solution was
magnetically stirring without heating by 15 min. Immediately, were
prepared the diluted solutions of HCl and H2O2 (270 mL of distillated
water and 10 mL of HCl and H2O2, respectively). First, the H2O2 solu-
tion was added to the content of flask and all solution was shaken by
10 min and later was added the HCl solution. The solution was cen-
trifuged and the precipitate using distillated water until to reach the
neutral pH was washed. The solid was dried by 24 h at 65 °C. The
sample was ground and employed for the graphene oxide obtaining. For
this, an aqueous dispersion of the ground sample with a concentration
of 10 mg/mL was prepared, and bath-sonicated by 3 h at 40 KHz. Dis-
tillated water was evaporated and the solid was dried to 60 °C for 24 h.
The final product was graphene oxide and was labeled as OGE-1. For
the OGE-0.5 sample obtaining, the same procedure previously de-
scribed was employed, but only 3 g of KMnO4 were used, instead of 6 g
in the oxidation process.
The third sample of graphene oxide (OGE-US) was also synthesized
by the modified Hummers method and in similar form to OGE-1.
However, the 2 h of magnetic stirring were replaced by a treatment in
the ultrasonic bath with a frequency of 40 KHz with the aim to obtain a
graphene oxide in a one-step, which reduce the synthesis time of this
nanomaterial. The temperature was controlled to 35 °C ± 3 adding
manually ice cubes. The temperature was monitored with a thermo-
meter.
2.4. Graphene quantum dots synthesis
The methodology for graphene quantum dots obtaining was based
in the method reported by Rajender et al. [33]. 100 mg of OGE-1
sample were deposited in a vessel and 12 mL of DMF were added. Later,
the solution was bath-sonicated by 15 min and immediately was added
to autoclave (100 mLTeflon-lined stainless steel), which was heated to
200 °C and maintained to constant temperature by 8 h. After of reaction
time, the solution was filtered in a Buchner funnel and washed using
distillated water until obtaining neutral pH. The solid was dried by 4 h
to 65 °C. The powder obtained was labeled as GQD-1. A summary of
complete description of the whole samples is included in Table 1.
2.5. Batch kinetic adsorption experiments
Kinetic study is key point for the design of adsorption systems and
for determining of the controlling step [34]. Batch kinetic experiments
were carried out to study the interaction between graphenic materials
and RR2. The adsorption experiments of RR2 onto carbon nanomater-
ials were carried out at room temperature (25 °C, using a thermostatic
bath) in a 100 mL beaker, containing 50 mL of RR2 solution with a
concentration of 30 mg/L and adsorbent concentration of 0.75 g/L.
M. de la Luz-Asunción, et al. Diamond & Related Materials 109 (2020) 108002

Table 1 qt = kid t 0.5 + C (5)

Complete description and nomenclature of the whole samples. 0.5
where kid is the intraparticle diffusion rate constant (mg/g h ), qt is
Nomenclature Description the adsorption capacity (mg∙g−1) at t time (hours), and C denotes the
GT Precursor graphite
layer surrounding the adsorbent (mg/g).
OGE-1 Graphene oxide obtained with 6 g of KMnO4 When the plot of qt vs t0.5 intercepts the origin, the intraparticle
OGE-0.5 Graphene oxide obtained with 3 g of KMnO4 diffusion is the controlling step. Elovich's equation, is employed in
GQD-1 Graphene quantum dots derivate from the sample OGE-1 chemical adsorption processes and it is appropriate for describing the
OGE-US Graphene oxide obtained with 6 g of KMnO4 and ultrasonic bath
kinetics of systems with heterogeneous surfaces [42]. This equation
does not propose a definite mechanism for adsorbate–adsorbent system;
Before the adsorption experiment, the solution was ultrasonicated for this only provides information about the nature of the adsorption
1 min using an ultrasonic bath (40 KHz). The beakers were covered and process. Elovich's model [43], expressed in its differential form is:
the solutions were kept in continuous agitation (235 rpm) by means of a dqt
= αe−βqt
Teflon-coated stirring bar driven by a magnetic stirrer for 8 h. Several dt (6)
aliquots of dye solution were taken in order to know the concentration
This model generally is represented as:
of dye at t time, which was compared with the initial concentration; the
volume of each aliquot was of 1 mL and taken 11 aliquots in the kinetic 1
qt = ln (1 + αβt )
experiment. Before analysis, samples were centrifuged at 12000 rpm for β (7)
15 min, and the supernatant was taken for the measurement. The
where qt is the adsorption capacity (mg/g) at t time, α is the initial
sample was analyzed at 538 nm wavelength in a UV–Vis spectro-
adsorption rate (mg/g · hr) β is the desorption constant (g/mg) and the t
photometer. Each experiment was carried out twice and the adsorption
time in minutes [44]. The constant α represents the initial velocity since
values presented are the average. The adsorption efficiency was cal-
dqt/dt ⟶ α qt ⟶ 0. To simplify the Elovich's equation [36,43], it can
culated using the Eq. (1), where Co y Ct are the initial concentration and
be assumed that βt > > 1, in this way, the equation becomes:
the dye concentration at t time, respectively. To calculate the adsorp-
tion capacity (qt) of the different adsorbents the Eq. (2) was employed, 1
qt = ln (αβt )
where m is the mass of the adsorbent and V is the volume of the RR2 β (8)
solution [35]. Ordering the previous equation results as follows [45]:
C − Ct ⎞ 1 1
Adsorption (%) = ⎛ 0 ⎜ ⎟ qt = ln (αβ ) + ln (t )
⎝ C0 ⎠ (1) β β (9)

C0 − Ct ⎞ Replacing t with tref and qt with qref in the Eq. (9), it is obtained:
qt = ⎛ V
⎝ m ⎠ (2) 1 1
qref = ln (αβ ) + ln (tref )
β β (10)

2.6. Kinetic models Subtracting Eq. (10) from Eq. (9) and dividing both sides of the
resulting equation by qref, it is obtained, the following expression:
Kinetic parameters are often obtained through linear regression qt 1 t
methods that require the linearization of the original non-linear equa- = ln ⎛⎜ ⎞⎟ + 1
qref qref β ⎝ tref ⎠ (11)
tions, which can lead to erroneous regression results [36]. In this study,
non-linear regression with Levenberg-Marquardt algorithm was used Eq. (11) is the dimensionless Elovich's equation [42]. If, it is sub-
with all kinetic equations. stituted RE = 1/qrefβ, which is approaching equilibrium factor it is ob-
Some non-linear kinetic models such as, pseudo-first order (PFO), tained:
pseudo-second order (PSO), Elovich and intraparticle diffusion (ID)
were fitted to the kinetic adsorption data with the purpose to know qt t
= RE ln ⎜⎛ ⎟⎞ + 1
more information about of the adsorption process of RR2 dye onto the qref ⎝ tref ⎠ (12)
four carbon adsorbents (OGE-1, OGE-0.5, OGE-US and GQD-1).
The non-linear form of the pseudo-first order model can be ex- The approaching equilibrium factor (RE) was used to describe the
pressed as [37,38]: characteristic curves of adsorption kinetics of the Elovich's equation.

qt = qe (1 − e−k1 t ) (3) 3. Results and discussion

−1
where k1 (min ) is known as the adsorption constant of pseudo-first
3.1. Infrared spectroscopy
order, while qt y qe are the adsorption capacity (mg∙g−1) at t time (min)
and equilibrium, respectively.
The IR spectra of the carbon nanomaterials obtained and used as
On the other hand, the Eq. (4) shows the non-linear form of the
adsorbents of RR2 dye are showed in Fig. 1. Graphite show two bands
pseudo-second order model, where qt y qe have the same meaning as
to 974 cm−1 and 904 cm−1 due to the stretching vibrations of oxyge-
before, the constant of pseudo-second order is designated as k2 and is
nated groups (CeO) and the graphitic structure (skeletal CeC vibra-
expressed in (g∙(mg∙min)−1) and the t time in minutes [38–40].
tions), respectively. After of the oxidation of graphite, in OGE-0.5 and
k2 qe2 t OGE-1 samples can be observed and shift slightly of the CeO band
qt =
1 + k2 qe t present in graphite at around of 985 cm−1 and the change on the in-
(4)
tensity is evident. Besides, two new bands appear to 1620 cm−1 and
Several stages are present in the adsorption process, within which 1719 cm−1 corresponding to stretching of carbonyl groups (C=O) in
are the transport of the adsorbate molecules to the surface of the ad- quinones and carboxylic acids, respectively [46–48]. At ~3200 cm−1 is
sorbent and the diffusion of the adsorbate molecules into the pores, found the band attributed to stretching vibration of hydroxyl groups
which is generally a slow process. The intraparticle diffusion model is (OH) [46,49]. The sample OGE-US shows a similar spectrum that the
given by Eq. (5) [41]: OGE-0.5 and OGE-1 samples, indicating that the sample OGE-US is also

3
M. de la Luz-Asunción, et al.
Fig. 1. Infrared spectra of carbon materials used as adsorbents.
oxidized and the characteristic oxygenated functional groups of gra-
phene oxide above mentioned are present. Considering intensity of
these signals in OGE-US, it is supposed a higher oxidation degree,
confirmed in next sections by other techniques. In GQD-1 can be ob-
served the loss of the oxygenated groups, especially hydroxyl groups,
due to the thermal treatment with DMF to which graphene oxide is
subjected [50].
3.2. Raman spectroscopy
Raman spectroscopy is a very used technique in the study of carbon
materials where the G and D bands play an important role. G band is a
first order band attributed to the E2g mode and is associated with the
graphitic order [47,51]. On the other hand, D band is associated to the
disorder in the graphitic structure caused by edges, defects, ripples,
amorphous carbon, among others [46,52]. The Fig. 2 shows the Raman
spectra of the carbon nanomaterials. In the samples OGE-0.5, OGE-1,
GQD-1 and OGE-US can be observed a blue shift respect to the graphite
precursor, which is associated to the structural changes in graphitic
structure due to the chemical treatments [47]. The ID/IG ratio is related
to the structural changes in the graphitic/graphenic structure. This ID/
Fig. 2. Raman spectra of samples of carbon materials obtained.
4
Diamond & Related Materials 109 (2020) 108002
IG ratio increases with the formation of sp3 carbon atoms and defects as
edges, vacancies, heptagons, wrinkles, among others [53–56]. OGE-0.5,
OGE-1 and GQD-1 show a similar value of ID/IG ratio, which is higher
than the value for graphite, indicating that the whole of samples are
chemically modified in the oxidation process (sp3 hybridization), which
corroborate the results obtained by infrared analysis. GQD-1 presents
the highest ID/IG ratio value of all samples and it is attributed to the
reduction of size, which generates an increase in the amount of edges
and therefore in curved zones.
3.3. Transmission Electron Microscopy
The morphology of the whole carbon samples employed as ad-
sorbents can be seen in Fig. 3. In Fig. 3a and b are shown the sheets of
the OGE-0.5 and OGE-1 samples, respectively. In both samples of gra-
phene oxide can be observed few sheets which present the character-
istics wrinkles due to presence of functional groups [57]. The obtaining
of Graphene Quantum Dots is corroborated with the Fig. 3c, where is
observed the circular form of GQDs with an average size of 24 nm, si-
milar to the size obtained by Ying et al. [31]. Fig. 3d correspond to the
sample OGE-US, where is observed a similar behavior of the graphene
sheets respect to the samples of OGE-0.5 and OGE-1, indicating that the
modification in the oxidation process can be useful and practical for
reducing the time of the synthesis of graphene oxide; additionally,
generating significant cost savings.
3.4. Field Emission Scanning Electron Microscopy/Energy Dispersive X-ray
spectroscopy
The results of carbon and oxygen content in the carbon samples can
be seen in Table 2. OGE-0.5 shows higher oxygen content than OGE-1,
which indicates that in this graphite is not necessary the use of the
major amount of KMnO4 to obtain a major oxidation. The minor con-
tent of oxygenated groups in OGE-1 sample is attributed to the strong
exothermic reaction caused in the moment of 92 mL of water were
added. At that time, was observed an increase in gases generation re-
spect to the observed in the synthesis of OGE-0.5 sample, which is as-
sociated with the formation of CO2 derivative of the elimination of
amorphous carbon, oxygenated groups created during the oxidation
process and the breakdown of the graphene network due to strong
exothermic reaction [58]. After of the oxidation reaction were re-
covered 2.25 g of OGE-0.5 and 1.7 g of OGE-1 (considering, that, both
samples start with 2 g of precursor), this latter, corroborate the differ-
ences in the synthesis of OGE-0.5 and OGE-1 samples. OGE-US shows a
better oxidation that OGE-1 indicating the ultrasound waves generated
by the ultrasonic bath improve the oxidation process of graphite. The
oxygen content in GQD-1 sample decreased respect to OGE-1, which is
used as precursor. The oxygen loss in this sample is attributed to the
action of DMF, which acts as reducing agent, eliminating part of the
oxygen content [50], confirming the result obtained in the IR analysis.
It is important to mention that the amount of oxygen groups can be
determinant on the adsorption results.
On the other hand, in order to corroborate the presence of RR2 dye
onto the carbon nanomaterials is presented an elemental analysis in
mapping mode to the samples after of the adsorption process and the
results can be observed in Fig. 4. In the three samples were identified
the elements S, Cl, N and Na, which are part of the RR2 structure, in-
dicating the presence of the RR2 dye onto the surface of the carbon
nanomaterials used as adsorbents.
3.5. Surface properties of carbon nanomaterials
Results obtained by BET analysis indicates surface areas of the
samples OGE-0.5, OGE-1, GQD-1 and OGE-US, with the values of 55.2,
80.9, 120 and 34 m2/g, respectively. The highest value of surface area
of the whole samples is obtained by GQD-1, which is atributted to the
M. de la Luz-Asunción, et al. Diamond & Related Materials 109 (2020) 108002

Fig. 3. TEM micrographs of carbon nanomaterials: a) OGE-0.5, b) OGE-1, c) GQD-1 and d) OGE-US.

Table 2 whole carbon adsorbents. The pHPZC decrease with the increase in the
Carbon and oxygen content of the carbon nanomaterials determined by EDS oxygen content. The pHPZC decrease with the increase in the oxygen
analysis. content; adjusting the pH of the solution to a value below the pHPZC
Sample Carbon content (%) Oxygen content (%) C/O RATIO promotes a positive surface charge on the carbon nanomaterials which
contributes to the electrostatic adsorbent-adsorbate interaction.
OGE-0.5 69.5 30.5 2.28 The graphene oxides have values of pHPZC very close, however, the
OGE-1 84.8 15.2 5.58
sample GQD-1 shows a higher value due to the loss of oxygen in the
GQD-1 88.7 11.3 7.85
OGE-US 75.8 24.2 3.13 reaction with the DMF.

3.6. Adsorption of Reactive Red 2

small size of these particles. In OGE-0.5 and OGE-1 samples, the values
of surface area indicate that KMnO4 amount used in the oxidation re-
In Fig. 5 is shown the performance of the different carbon nanos-
action decrease directly proportional to the surface area of graphene
tructures on the removal of Reactive Red dye at pH = 2 and pH = 5.
oxide. On the other hand, the sample OGE-US shows the lowest value of
The adsorption process is followed by 8 h. When the solution of RR2 is
surface area, indicating the oxidation process in ultrasound bath is not
prepared, the pH solution is 5. Under these conditions, the sample OGE-
enough to generate a better exfoliation of graphene sheets. In order to
0.5 and OGE-1 show the best performance on the removal of dye (see
improve the exfoliation of the graphene sheets, the reaction time in
Fig. 5a). The difference between the adsorption reached by these two
ultrasound bath could be increased. However, more structural damages
samples (~10%) is attributed to the higher oxygenated groups presents
could be produced in the graphene sheets.
in OGE-0.5. The oxygenated groups on surface improve the dispersion
The point of zero charge of the adsorbents is an important para-
of the graphene oxide, generating more interaction between the gra-
meter in the adsorption process, determinating the charge pre-
phene oxide and the RR2 molecules. The sample GQD-1, despite having
dominating on the adsorbents surface according to pH of the immersion
the largest surface area, shows a poor removal of RR2 which it is at-
solution. The values of pHPZC obtained for the samples OGE-0.5, OGE-1,
tributed to the low content of oxigenated groups. Similar removal of
GQD-1 and OGE-US are 3.17, 3.33, 4.82 and 3.19 respectively. These
RR2 is obtained by the sample OGE-US that has the lowest surface area.
values of pHPZC have a relationship with oxygen content found in the
The best results of RR2 adsorption are found when the dye solution

5
M. de la Luz-Asunción, et al.
Fig. 4. FESEM-EDS elemental mapping of the samples of carbon nanomaterials
containing RR2 adsorbed: a) OGE-0.5, b) OGE-1 and c) GQD-1.
is adjusted to pH = 2 (see Fig. 5b). In this pH value, the surface of the
carbon nano-adsorbents is positively charged due to that the pH solu-
tion is below of the pHPZC of the carbon nanomaterials, which favors the
electrostatic interaction with the negative charge of the RR2 dye mo-
lecules. According to the pHPZC values of the carbon nanomaterials, the
order of the positive surface charge in the different adsorbents is OGE-
0.5 > OGE-US > OGE-1 > GQD-1. The samples OGE-0.5 and OGE-1
reach a RR2 removal of ~76% and 56%, respectively at pH = 2, which
represent a increase of 33% for OGE-0.5 and 22% for OGE-1 respect to
the RR2 removal at pH = 5. The highest RR2 removal is obtained by the
sample GQD-1 (85%) (at pH = 2), with a increase of 57% and constant
removal increment with time; while the sample OGE-US show the
lowest performance of removal (49%). The whole adsorbents show a
6
Diamond & Related Materials 109 (2020) 108002
major RR2 removal at pH = 2. The high efficiency of the sample GQD-1
is attributed to a combination between the positive surface charge that
favors the electrostatic interactions and its surface area. The samples
OGE-0.5, OGE-1 and OGE-US have major positive charges but minor
surface area which explain the obtained results. Fig. 6 shows the pro-
posed of adsorption mechanisms between the dye and the graphenic
materials. The main parameters involved are the electrostatic interac-
tions, the hydrogen bonding and the π-π interactions. The first is due to
the difference of the surface charge between the adsorbent and ad-
sorbate. The hydrogen bonding is achieved through hydrogen atom
present in the graphenic materials and the nitrogen and oxygen atoms
of the structure of RR2 dye. The π-π interactions is due to the attraction
between the π-electrons present in the aromatic rings of the RR2
structure and the graphitic structure of the graphenic materials.
3.7. Kinetic study
The fit plots of the kinetic models are presented in Fig. 7 (a-d). The
criteria to select the best model is the highest value of R2 and the lowest
value of Δq. In this case, the Elovich's equation is the one that presented
the lowest value of Δq with respect to the whole kinetic models. Si-
milarly, this equation is the one that obtained a value of R2 closest to
the unit (Table 3).
Wu et al. [42] conducted a study of 64 adsorption systems, in which
80% is in the zone of “mild adsorption” and 20% to the zone of “rapid
adsorption”. These researchers propose according to the curvature, four
zones based on RE value: when RE > 0.3 (zone I), the curve rises slowly;
when 0.3 > RE > 0.1 (zone II), the curve rises mildly; when
0.1 > RE > 0.02 (zone III), the curve rises rapidly; when RE < 0.02
(zone IV), the curve instantly approaches equilibrium. It can be seen in
Table 3, the RE values for OGE-0.5 and OGE-1, 0.034 and 0.038, re-
spectively, so these samples belong to zone III; this can be corroborated
in Fig. 7c, in which an almost instantaneous removal is observed in the
first minutes of the adsorption process. On the other hand, the RE values
for GQD-1 and OGE-US are 0.120 and 0.121, respectively, indicating
these materials are in the zone II; in Fig. 7c, we can see that the time to
reach equilibrium is slightly longer than the samples belonging to zone
II.
Table 3 shows the values of α and β which satisfy the condition
mentioned in the Eq. (8) (αβt > > 1). The adsorption process presents
feasibility when α values are higher than β values), representing that
the adsorption rate is greater than desorption [43]. In the case of the
intraparticle diffusion model, any lines do not pass through the origin
(Fig. 7-d), therefore, we can say that this is not the controlling step of
the adsorption process.
The standard deviation (Δq), is applied to verify the accuracy of the
measured and calculated data, which it is evaluated using the following
equation:
∑ [(qt , exp − qt , cal )/ qt , exp ]2
∆q (%) = x100
n−1 (13)
where qt, exp and qt, cal are the experimental and calculated adsorption
capacities, respectively; and n is the number of data points [59].
In Table 3, PFO, followed by PSO, present the highest values of Δq
with respect to the other models; this represents a greater error in the
adjustment of these models, and therefore they are discarded. For the
Elovich and ID models, their Δq values are in a close range; however,
the R2 values for the Elovich model are closer to unity, therefore, this
last model is chosen as the one that best represents the experimental
kinetic data.
4. Conclusions
OGE-0.5 sample showed a major amount of oxygen and yield re-
spect to OGE-1, indicating the KMnO4 amount used in the Hummers
M. de la Luz-Asunción, et al.
Fig. 5. Removal of Reactive Red 2 onto carbon nanostructures at pH = 5 (a) and pH = 2 (b). (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)
Fig. 6. Adsorption mechanisms proposal between RR2 dye and graphenic materials at pH = 2.
method can be modified according to the kind of graphite used. This
could reduce the environmental impact of the oxidation process. Owing
to higher percentage of oxygen on OGE-0.5, is promoted greater ad-
sorbent-adsorbate interaction through hydrogen bonding. Oxygenated
functional groups play a key factor which is reflected in the sample
OGE-0.5 that contains the highest amount of oxygen, reaching a much
faster equilibrium than the rest of the adsorbents.
The graphite oxidation with ultrasound (OGE-US) is a good alter-
native for the graphene oxide synthesis, however, some parameters can
be modified in order to obtain a higher surface area. The samples OGE-
0.5 and GQD-1 showed a high performance on the removal of RR2.
GQD-1 is favored in the removal process due to its greater surface area
compared to the other adsorbents. The removal of RR2 was favored at
pH = 2, due to the electrostatic interaction generated between the
aromatic rings in RR2 dye and the surface charge of the carbon nano-
materiales. The hydrogen bonding and π-π interactions also contribute
in the adsorption process of RR2.
By modifying the pH of the solution, OGE-0.5, OGE-1 and OGE-US
are influenced by their PZC values since, being lower with respect to
GQD-1, these materials generate a greater positive charge on their
surface, which promotes electrostatic interaction with the RR2 dye.
GQD-1 is considered a novel nanomaterial for different fields, it has a
chemical structure similar to graphene oxide. The main difference be-
tween GQD-1 and graphene oxide derived materials is the small size.
7
Diamond & Related Materials 109 (2020) 108002
This parameter could be influencing the removal of the RR2 pollutant
since this generates a greater surface area, which is corroborated with
the aforementioned data. The behavior of the adsorption curve of GQD-
1 indicates that after 8 h, this sample could continue adsorbing mole-
cules of RR2, which is attributed to higher amount of active sites
available for the adsorption due to the its surface area. Elovich's
equation was the best model to fit the experimental kinetics data, since
R2 values were higher than 0.99 for all adsorbents, indicating the
chemical nature of the adsorption process. The adsorption behavior of
the Elovich's equation was classified in zone II y III, the region of “mild
adsorption” and “rapid adsorption”, respectively.
CRediT author statement
Miguel de la Luz-Asunción: Methodology, validation, formal ana-
lysis, investigation, writing-original draft, visualization. Eduardo E.
Perez-Ramirez: Methodology, validation, formal analysis, investigation,
writing-original draft, visualization. Ana Laura Martinez-Hernandez:
Conceptualization, resources, writing – review & editing, supervision,
project administration. Perla E. García-Casillas: review & editing, su-
pervision, Project administration, funding acquisition. Gabriel Luna-
Bárcenas: Resources, review & editing, supervision, Project adminis-
tration, funding acquisition. Carlos Velasco-Santos: Conceptualization,
resources, review & editing, supervision, Project administration,
M. de la Luz-Asunción, et al. Diamond & Related Materials 109 (2020) 108002

Fig. 7. Adsorption kinetics of RR2 on carbon nanomaterials: (a) Pseudo-first order, (b) Pseudo-second order, (c) Elovich model, and (d) Intraparticle diffusion
(Co = 30 mg/L, T = 25 °C ± 1 °C, pH = 2.0 ± 0.1).

Table 3
Coefficient of determination and standard deviation of the kinetic models.
PFO PSO ELOVICH ID

Δq (%) R2 Δq (%) R2 α β RE Δq (%) R2 Δq (%) R2

OGE-0.5 3.677 0.985 2.513 0.993 6.96 × 1011 0.967 0.034 1.294 0.998 1.042 0.936
OGE-1 3.911 0.984 2.079 0.995 2.07 × 1010 1.157 0.038 1.346 0.997 2.051 0.808
GQD-1 13.669 0.884 8.753 0.951 1492.632 0.243 0.120 3.556 0.991 1.782 0.989
OGE-US 11.858 0.908 7.117 0.965 1409.534 0.435 0.121 2.832 0.992 3.625 0.948

funding acquisition.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgments
The authors are grateful to Ms. Ma. Lourdes Palma Tirado and
Instituto de Neurobiología – Universidad Nacional Autónoma de
México for their assistance in TEM Analysis. To Ms. Hortencia Reyes
Blas of Universidad Autónoma de Ciudad Juárez for her support in the
FESEM-EDX analysis. We also appreciate the support of the CIQA-
LNMG, Dr. Salvador Fernández Tavizón and Mr. Jesus Alfonso Mercado
for their technical assistance in Raman spectroscopy. E.E. Pérez-
Ramírez and M. de la Luz-Asunción are thankful to CONACYT for the
grant in their postdoctoral research.
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