Environmental Pollution 302 (2022) 119033

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

Fabrication of activated carbon supported modified with bimetallic-platin

ruthenium nano sorbent for removal of azo dye from aqueous media using
enhanced ultrasonic wave☆
Züleyha Bingül Reçber a, Hakan Burhan b, Ramazan Bayat b, Mehmet Salih Nas a, c,
Mehmet Harbi Calimli a, c, Özkan Demirbas d, Fatih Şen b, Karimi-Maleh Hassan e, *
a
Department of Civil Engineering, Engineering Faculty, Igdir University, Igdir, Turkey
b
Faculty of Science, Department of Biochemistry, Dumlupınar University, Kütahya, Turkey
c
Igdir University Research Laboratory Application and Research Center (ALUM), Igdir, Turkey
d
Faculty of Science and Literature, Department of Chemistry, University of Balikesir, Balikesir, Turkey
e
School of Resources and Environment, University of Electronic Science and TechnTechnology China, China

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

Keywords: Herein, activated carbon supported modified with bimetallic-platin ruthenium nano sorbent (PtRu@AC) was
Kinetics synthesized by a thermal decomposition process and used in the removal of methylene blue (MB) from aqueous
Methylene blue solutions. The synthesized nano sorbents were characterized by X-ray Diffraction (XRD), Transmission Electron
Nano adsorbent
Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS) spectroscopic techniques. The data obtained
Thermodynamics
Wastewater
from characterization studies showed that PtRu@AC nano sorbent was highly crystalline and in a form of PtRu
alloy with a monodispersed composition. The results indicated that the maximum adsorption capacity (qemax)
for the removal of MB with PtRu@AC under optimum conditions was detected to be 1.788 mmol/g (569.4 mg/g).
The experimental kinetic results of the study revealed that the adsorption of methylene blue was found to be
more compatible with the false second-order model compared to some tested models. Calculations for thermo­
dynamic functions including enthalpy change (ΔHo), entropy change (ΔSo), and Gibbs free energy change (ΔGo)
values were performed to get an idea about the adsorption mechanism. As a result, the synthesized PtRu@AC
nano adsorbent was detected as a highly effective adsorbent material in the removal of MB from aquatic
mediums.

1. Introduction 2018; Karaman et al., 2021; Kunz et al., 2010). As an azo and cationic
dye, methylene blue is widely used in the textile field such as cotton,
As a result of many processes carried out in industrial areas and paper, wool, and temporary hair dye. However, methylene blue can be
especially in the textile industry, a large amount of wastewater is the main cause of permanent eye injuries to humans and animals (Patra
released into the environment. A wide variety of different impurities et al., 2016). As stated in many studies, Rhodamine, which is a cationic
present in these wastewaters such as pesticides, starches, surfactants, dye like methylene blue, can be caused by liver and thyroid damage as a
biocides, polyvinyl, and dyes. Dyes are comprised of a stable structure result of ingestion (Jain et al., 2003; Patra et al., 2016). Furthermore,
that remains in the wastewater for a long time (Hao et al., 2010; Kale methylene blue can easily penetrate the cell due to the negatively
and Kane, 2018; Karimi-Maleh et al., 2021). The color intensity in the charged cell surface. Due to such negative effects, the removal of
exposed textile wastewater is the main cause of a serious problem for the methylene blue from aqueous environments has been an important
natural environment. Azo-based commercial dyes can cause the forma­ research topic (Huang et al., 2017; Tang et al., 2019). Hitherto, many
tion of aromatic compounds. Therefore, these dyes cause quite negative methods such as ion exchange, electrolysis, ozone treatment, photo­
effects on plant and animal metabolism (Chen, 2002; Kale and Kane, catalytic degradation, chemical precipitation, and adsorption have been

☆
This paper has been recommended for acceptance by Dr. Jörg Rinklebe.
* Corresponding author.
E-mail address: [email protected] (K.-M. Hassan).

https://doi.org/10.1016/j.envpol.2022.119033
Received 17 December 2021; Received in revised form 22 January 2022; Accepted 17 February 2022
Available online 22 February 2022
0269-7491/© 2022 Elsevier Ltd. All rights reserved.
Z. Bingül Reçber et al. Environmental Pollution 302 (2022) 119033

applied in the removal of methylene blue. Among these methods, adsorbents at 200–900 nm. The morphological structure of PtRu@AC
adsorption is more advantageous compared to others because of is nano adsorbents was elucidated in tapping mode with the Nano­
economical, easy, and flexible (Dragan and Apopei Loghin, 2013; Yang magnetic Ins. AFM devise. The chemical composition and surface
et al., 2018). In the removal of contaminants from natural sources, structure of PtRu@AC nano sorbents were clarified by applying char­
various materials have been used and fabricated so far (Calimli et al., acterization studies. The surface composition of platinum and ruthe­
2020; Çalımlı et al., 2019; Nas et al., 2019). The fabrication novel nium metals on activated carbon and the mean particle size of the nano
method based on low cost, available, and nontoxic nanoparticles as nano adsorbents were identified by TEM analyses. The XRD analyses of
adsorbents are highly selected in removing pollutants from aqueous PtRu@AC nano adsorbents were utilized to reveal the crystalline
sources. Nanoparticles exhibit some unique features like large surface structure and XPS analyses were applied for the determining of metal
area containing a lot of reactive sides, besides semi-metallic and metallic compositions on activated carbon.
properties caused improving interaction reactive groups with functional
groups for the targeted molecules (Aygun et al., 2022; Ghaedi et al., 2.3. Fabrication procedure of PtRu@AC nano adsorbent
2013; Hyder et al., 2022; Yang et al., 2004). Activated carbon (AC) is
one of a component of these materials and is widely used as an adsorbent The fabrication of PtRu@AC nano adsorbents was conducted as
for the removal of different pollutants. AC consisted of a large surface described elsewhere [23]. Briefly, a 5 mL ethanol solution containing
area and porous structure, additionally, it is non-toxic and low-cost 0.25 mmol PtCl4 and 0.25 mmol RuCl3 was prepared and stirred for 10
material. In literature, utilizing nanoparticles by loading on activated min, and then 100 mg activated carbon was transferred into the
carbon has been widely utilized in the treatments due to its good per­ resulting solution. This solution was stirred at room temperature for 2 h,
formance, so recently the fabrication of nanoparticles consisting of AC and thereafter 1 mmol super hydride was added on. The solution color
has taken much interest (Arikan et al., 2021; Ghaedi et al., 2013; Göksu changed from brown to black brown showed the stabilizing of metals on
et al., 2020; Kamaraj et al., 2020; Khosravi et al., 2018; Sathishkumar AC. This mixture was filtered, and the solid sample was dried at 80 ◦ C in
et al., 2012). Many materials based on AC and different metal/metal a vacuum oven at overnight.
oxide including silver-palladium, gold, ZnO, CoO, CuO, and Fe3O4
(Ghaedi et al., 2012; Nguyen et al., 2019; Prajapati and Mondal, 2020;
2.4. Experiments of removal MB using PtRu@AC nano adsorbent
Roosta et al., 2014) have been developed for the removal of methylene
blue (MB). In this paper, we address the fabrication and characterization
Experimental setup of adsorption of MB composed of a glass water
of PtRu alloy nanoparticles loaded on activated carbon (PtRu@AC) nano
bath and a round glass balloon kept in the water bath. Initially, a 2.0 ×
sorbents for the removal of methylene blue from an aqueous solution.
10− 5 mol/L− 1 and 100 mL solution of MB including 16 mg PtRu@AC
The fabricated PtRu@AC nano sorbents were characterized by spectro­
nano adsorbent was prepared in a round glass balloon. Using NaOH and
scopic methods like UV–Vis spectrophotometry, XRD, TEM, XPS. The
HCl solution, the pH of the resultant solution was adjusted to 7 while
developed nano adsorbent was applied to the removal of methylene blue
stirring at 400 rpm. Initial experiments were carried out to determine
at different experimental parameters of temperature, pH, nano adsor­
the adsorption equilibrium. It was found that 40 min was sufficient for
bents, methylene blue concentration, and contact time of nano adsor­
the adsorption equilibrium with the initial experiments. The latest so­
bents with MB dye.
lution reached the adsorption equilibrium was centrifuged. Then, the
absorbance measurements of MB using PtRu@AC nano adsorbent were
2. Materials and methods
performed by taking 4 mL samples from 100 mL solution at different
time intervals in the UV spectrophotometer. The measurements of
2.1. Chemicals
UV–Vis absorbance were performed until reaching non-observing any
change of absorbance. The mass balance was used to calculate the
PtCl4, RuCl3, activated carbon, methylene blue, super hydride,
quantity of dye adsorbed at any time t and qt (Eq. (1)) (Alkan et al.,
dimethylamine borane, NaOH, and HCl were purchased from Sigma-
2008).
Aldrich. These chemicals used in the experiments were of analytical
grade and utilized without any prior purification. Deionized water (Co − Ct).
qt = V (1)
filtered with a Milli Q-pure device was used to clean all lab items and m
glassware.
3. Results and discussion
2.2. Characterization instruments utilized in the structural studies
3.1. Characterizations of PtRu@AC nano adsorbent
TEM analyses of PtRu@AC nano sorbents were conducted by a TEM
instrument of JEOL operating at 200 eV. A suspension sample of 0.5 mg Characterization studies for PtRu@AC nano adsorbent were con­
nano adsorbents present in 3 mL ethanol was prepared in ultrasonic ducted by applying some advanced analytical techniques such as TEM,
conditions. This solution was dropped on a surface composed of carbon XRD, and XPS to determine morphological and surface features of the
with a copper grid (400 mesh). The calculation particle size of PtRu@AC prepared nanoparticles. TEM analyses (Fig. 1.) of PtRu@AC nano sor­
nano sorbents was calculated by counting more than 300 particles in bent were studied to detect the morphology, composition, and particle.
TEM patterns. XPS analyses of PtRu@AC nano adsorbents were con­ As can be seen in Fig. 1, the PtRu@AC nano sorbent shows a good dis­
ducted by the Thermo scientific spectrometer consisting of an X-ray tribution. Also, some agglomeration in the distribution of metal particles
source with Kα lines of Mg operating 10 mA, 1253.6 eV. In taking XPS was observed as seen in patterns of TEM analyses of PtRu@AC nano
patterns, 1s line of carbon at 284.6 Ev was selected as a reference value. adsorbent. Using TEM images, the mean particle size of PtRu@AC nano
The XPS data of PtRu@AC nano adsorbents were fitted by applying adsorbent was calculated and found to be 3.34 ± 0.69 nm. The particle
Gaussian/Lorents method. Sample preparation of XPS of PtRu@AC nano size of the nanoparticles was calculated by counting more than 100
adsorbents was done by deposition the nano adsorbents on cupper tape particles in TEM patterns.
having a double side. XRD analyses of PtRu@AC nano sorbents were XRD analyses for Pt@AC and PtRu@AC nano sorbent were studied to
conducted by a Panalytical Empyrean diffractometer consisting of an X- determine the crystalline structure. Fig. 2. illustrates XRD patterns of
ray source with k = 1.54056 Å, Cu K∞ radiation operation at 40 kV and PtRu@AC nano adsorbent and as seen in this figure some evident peaks
40 mA. PerkinElmer Lambda UV–Vis spectrophotometer was used in intensified at 2θ = 25.13◦ that corresponded to carbon atoms in the
UV–Vis absorbance data of the adsorption of MB using PtRu@AC nano composition of AC. The other peaks for PtRu at 40.33◦ , 46.80◦ , 68.19◦ ,

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Z. Bingül Reçber et al. Environmental Pollution 302 (2022) 119033

be 2.70 nm using the Debye-Scherer method.

XPS analyses (Fig. 3) of PtRu@AC nano sorbent were performed to
determine the oxidation and electronic status of platinum and ruthe­
nium atoms. Peak fittings for PtRu@AC nano sorbent were carried out
using Gaussian/Lorentzian, Shirley’s techniques, and subtraction back­
grounds. Deconvolution for Pt 4f atoms Fig. 3(a) was conducted for three
forms of platinum in the nanoparticles compositions. As seen in XPS
patterns, two peaks correspond to binding energies 71.7 and 75.1 eV
related to Pt(0) atoms. Some slight peaks at 72.7/76.1 eV and 74.1/77.2
eV binding energies related to Pt(II) and Pt(IV) most likely may occur
during XPS sample preparation. The deconvolution of Ru 3p atoms was
performed as seen in Fig. 3(b). two evident peaks at 464.5 and 484.9 eV
that assigned to metallic states of Ru 3p3/2 and Ru 3p1/2. In addition, the
corresponding binding energy levels for Ru(IV) were observed as 465
and 488.4 eV.
The equilibrium time was calculated by studying the MB cationic dye
adsorption with different starting concentrations of PtRu@AC nano
Fig. 1. TEM image of PtRu@AC nano absorbent.
sorbent as a function of contact time. Experimental data obtained from
studies were determined that the adsorbed methylene blue on the sur­
face of the nanocomposite material reached equilibrium for about 35
min. In Fig. 4(a), the amount of dye adsorbed over time is reflected to
understand its effect at the determined dye concentrations. For this
purpose, when the dye concentration was increased by 1.6–2.2.10− 5 M,
there was an increase in the adsorption amount (0.85 mmol/g − 1.26
mmol/g). In optimal removal of PtRu@AC nano sorbent particle MB, the
maximum adsorption capacity (qm) was approximately 1.788 mmol/g
(or 569.4 mg/g). The highest adsorption capacity (qm) of dyes adsorbed
by different adsorbents is shown in Table 1.
The pH as a parameter effect of adsorption of MB dye on the
PtRu@AC nano sorbent surface can be evaluated concerning the surface
load of the adsorbent materials. As seen in Fig. 4(b), the pH of the so­
lution appears to significantly affect the amount of dye adsorbed. It was
determined that dye uptake increased from 1.09 mmol/g to 1.626
mmol/g for an increase from pH 5 to pH 11. In Fig. 4(b), it can be seen
that the amount of adsorption increased with increasing pH due to the
electrostatic attraction between the dyestuff and the PtRu@AC nano
sorbent surface with a negative charge. As the pH value increases from 5
to 11, it can be explained by the increase in the number of ionizable
Fig. 2. XRD image of PtRu@AC nano adsorbent. areas per unit on the PtRu@AC nano sorbent surface. Effective removal
of paint at higher pH can occur for two reasons. The first reason can be
and 82.01◦ are associated with the planes of (111), (200), (220), (311), explained by the loaded surface and an effective electrostatic gravita­
respectively. A slight shift over 2θ shows the formation of an alloy of tional force (Alkan et al., 2007; Erim et al., 2022). It is possible to see the
PtRu metals in the compositions of the nano adsorbent. The average adsorption of methylene blue on different absorbent particles with a
crystalline particle size of PtRu@AC nano adsorbent was determined to similar effect (Alkan et al., 2005; Doǧan et al., 2006). A second reason is

Fig. 3. XPS image of PtRu@AC nano adsorbent.

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Z. Bingül Reçber et al. Environmental Pollution 302 (2022) 119033

Fig. 4. Effect of a) initial dye concentration), b) solution pH and c) Zero point charge of PtRu@AC nano adsorbent.

the pH value of at zero load point the adsorbent material used to remove
Table 1
dyes. At several pH ranges (pH = 2–11), 20–25 mg of adsorbent was
Some studies were conducted on MB removal and their adsorption capacities.
added to 50–60 mL sodium nitrate to achieve the zero load point of
Adsorbents Adsorption Adsorption capacity, Reference PtRu@AC nano sorbent (Mongalo et al., 2018). After shaking the pro­
Kinetics mg/g
duced mixture, the final pH values have been reached. In Fig. 4 (c), the
GO-MNP Pseudo Second 1428 Othman et al., related pH change is compared to the original pH values. The pH of zero
Order (2018) point of charge (pHzpc) was found to be 6.61 for PtRu@AC nano sor­
Fe3O4@PPy/ Pseudo Second 270 Bai et al., (2015)
rGO Order
bent. The surface of PtRu@AC nano sorbent is negatively charged when
Ni/PC-CNT Pseudo Second 312 Jin et al., (2018) pH > pHzpc, which favors cationic colorant dye adsorption. The prin­
Order cipal adsorption process is electrostatic interactions between methylene
P-CSCNT Pseudo Second 319 Gong et al., (2015) blue and the adsorbent. As a result, higher affinity to the PtRu@AC nano
Order
sorbent surfaces of methylene blue will be achievable when pH > pHzp
TGC Pseudo Second 195.74 Demirbaş and Nas,
Order (2016) (Mishra et al., 2010).
Diatomite Clay Pseudo Second 128 (Çalımlı et al., Fig. 5(a) shows the absorption capacity of methylene blue (2 × 10− 5
Order 2018) mol/L as initial concentration) overtime at to determine the adsorption
Cotton stalk Pseudo Second 315 Deng et al., (2009) capacity at 298, 303, 310, 317, and 323 K temperatures. Experiments
Order
Waste tea Pseudo Second 554.3 Auta and Hameed,
carried out at different temperatures showed that the removal of
Order (2011) methylene dye increased with a certain level of temperature increase.
Graphite Pseudo Second 599.8 Yan et al., (2014) The viscosity of the solution decreases as the temperature rises, which
Order may be accounted for by an increase in the dye molecules’ diffusion rate
Glycerol Pseudo Second 865 Narvekar et al.,
in the outside boundary layer and inside pores of the nano adsorbent.
Order (2018)
GO@TiO2 Pseudo Second 900 Wang et al., (2016) Also, changing the temperature range may change the balance capacity
Order of the adsorbent for a particular dyestuff (Demirbaş and Alkan, 2011). In
PtRu@AC Pseudo Second 569.4 This study adsorption studies, it is extremely important to investigate the effect of
Order nano adsorbent parameters on dye removal. Several investigations were

Fig. 5. Effect of a) temperature, and b) nanoparticle parameters.

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Z. Bingül Reçber et al. Environmental Pollution 302 (2022) 119033

conducted at 298 K, pH of 7, and 400 rpm to investigate the adsorption Equation (9) is specified in Table 3, by considering the particle
activity of nanoparticles for this purpose. The numerical data obtained diffusion model, kint (mg (g min-1/2) − 1, the velocity constant in the
are reflected graphically in Fig. 5(b). When using 16 mg PtRu@AC nano intraparticle diffusion model. Fig. 7 shows the graph of qt versus t1/2 for
sorbent at fixed conditions, the maximum dye removal efficiency coef­ MB adsorption to PtRu@AC nano sorbent surface. Fig. 7 shows that the
ficient was obtained. This is expressed by the increase of surface area sorption process tends to walk two stages. In the determined conditions,
depending on the amount of nano adsorbent particles (Çiçek et al., the particle diffusion coefficients, kint,1 and kint,2 are calculated and re­
2007). Methylene blue removal effectiveness decreases somewhat as the flected in Table 3. This step cannot be considered as a speed-limiting
amount of nano-adsorbent added to the solution medium increases. Due step because of its high value for kint,1. However, the slope of the sec­
to the superposition or buildup of active regions on the nanoparticle ond linear part of the graphic part is expressed as the in-particle diffu­
surface, this might have damaged adsorption (Seid et al., 2022; Turan sion parameter kint,2 (mol/(g min0.5)) (Hao et al., 2000; Kannan and
Beyli et al., 2015). Sundaram, 2001).
To test the reusability efficiency of PtRu@AC nano adsorbents, ex­ By utilizing the Arrhenius equation (Eq. (7) to look at the MB
periments were conducted under constant conditions such as 16 mg L− 1 adsorption impact on PtRu@AC nano sorbent, the values of the second-
nano adsorbent, 2.10− 5 mol/L− 1 methylene dye, and pH 9. The drop in order rate constants are utilized to calculate the activation energy. The
nano-adsorbent activity from 96% to 62% as a consequence of five activation energy of the adsorption of methylene blue by PtRu@AC nano
successive trials, as shown in Fig. 6(a), suggests that the nano adsorbent adsorbent was obtained to be 15.2 kJ/mol using the slope of the 1/T
is reusable. The shift in absorption peaks as a result of the interaction graph against lnk2 to determine the Ea. Consequently, low activation
between the PtRu@AC nano sorbent and the MB is shown in Fig. 6(b). energy values indicate that it is a characteristic event for the sorption
Kinetic models were investigated with the data obtained from process studied here and higher activation energy values indicate that
experimental studies to evaluate the control mechanism of the adsorp­ the mechanism occurs as chemisorption (Tekin et al., 2006). Adsorption
tion process. of methylene blue has a potential barrier, according to data collected for
The Pseudo first order and second order equations are expressed x adsorption. The Eyring equation was used to analyze crucial thermo­
using the relationship given below, respectively. (Eqs. (2) and (3)) (Ho dynamic activation functions of the process research, such as ΔH*, en­
and McKay, 1999): tropy ΔSo, and free energy ΔGo. Eq. (8) (Doğan et al., 2004).
ln(qe − qt ) = ln qe − ki t (2) Ea
lnk2 = lnA − (7)
R.T
t 1 1
= + t (3) ΔS ΔH
qe k2 q2e qe ln(k2 / T) = ln(kb / h) + − (8)
R RT
The half adsorption time of the dye is obtained by the equation given
below (Eq. (4)). ΔG∘ = ΔH ∘ − T.ΔS∘ (9)

t1/2 =
1
(4) where kb is defined by the Boltzmann constant expression (1.3807 ×
k2 qe 10− 23 J/K) and the h Planck constant function (6.6261 × 10− 34 J s).
The initial adsorption rate of the reaction mechanism using equation Fig. 8 shows the graph of ln (k2/T) versus 1/T as stated. The Gibbs en­
(5) is expressed by h (mol g− 1 min− 1). ergy difference was achieved at 298 K at 123.7 kJ/mol. The value of
standard enthalpy change thermodynamic function was found as 18.72
h = k2 q2e (5) kJ/mol. This value indicates that adsorption occurs physically as weak
attraction forces in nature, and the adsorption method shows an endo­
k2, qe, t1/2, and h values obtained in the studies are given in Table 2. As thermic event. The low value of ΔH*, on the other hand, suggests that
shown in Table 2. Experimental data indicated that the adsorption the bond between the dye molecules and the nano adsorbent surface is
mechanism is compatible with the pseudo-second-order kinetic weak. Standard entropy change (ΔS *) − 364.5 J/K mol value was ob­
equation. tained. This indicates that the system tends to decrease entropy.
The initial rate of in-particle diffusion is evaluated using the Furthermore, the system’s negative entropy value suggests that the nano
following. (6) (Ho and McKay, 1999). adsorbent’s internal structure does not change much after methylene
qt = k12 c (6) blue adsorption (Gupta et al., 2012). This conclusion does not suggest
that the event happened, but rather that the active force for the

Fig. 6. Effect of a) reusability efficiency and b) process time in MB removal.

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Z. Bingül Reçber et al. Environmental Pollution 302 (2022) 119033

Table 2
Kinetic values calculated for MB onto PtRu@AC nano adsorbent.
T/ PtRu@AC dosage pH MB mol./L Pseudo second- qe (cal.) qe (exp.) (mmol. k2 (g.mg R2 h(mol min− 1g− 1) t1/2 (min)
K (mg.L1) 10− 4 order R2 (mmol.g− 1) g− 1). min− 1) 10− 5 104

298 16 7 0.2 0.86 1.260 1.260 0.048 0.99 0.07 16.5

303 16 7 0.2 0.84 1.463 1.463 0.054 0.99 0.11 12.6
310 16 7 0.2 0.85 1.626 1.628 0.066 0.99 0.18 9.31
317 16 7 0.2 0.79 1.788 1.790 0.08 0.99 0.25 7.03
323 16 7 0.2 0.94 1.544 1.552 0.072 0.99 0.17 9.01
298 16 3 0.2 0.90 1.097 1.102 0.024 0.99 0.03 37.9
298 16 5 0.2 0.88 1.178 1.183 0.038 0.99 0.050 22.4
298 16 7 0.2 0.86 1.260 1.260 0.048 0.99 0.07 16.5
298 16 9 0.2 0.86 1.382 1.390 0.056 0.99 0.10 13.1
298 16 11 0.2 0.92 1.626 1.630 0.062 0.99 0.16 9.92
298 10 7 0.2 0.99 1.113 1.116 0.032 0.99 0.04 28.1
298 12 7 0.2 0.89 1.260 1.280 0.037 0.99 0.06 21.5
298 14 7 0.2 0.74 1.463 1.469 0.042 0.99 0.09 16.3
298 18 7 0.2 0.77 1.626 1.650 0.053 0.99 0.14 11.6
298 16 7 0.16 0.95 0.853 0.858 0.058 0.99 0.04 20.3
298 16 7 0.18 0.97 1.097 1.103 0.062 0.99 0.08 14.7
298 16 7 0.22 0.93 0.934 0.938 0.078 0.99 0.07 13.8

adsorption process is the electrostatic interaction between the nano

Table 3
adsorbent (negative surface) and methylene blue (positive charge).
Kinetic values calculated for MB onto PtRu@AC nano adsorbent.
Mass transfer Intraparticle diffusion
4. Conclusions
T/ PtRu@AC pH MB mol. kint,1 R1 2 kint,2 mg R22
K mg. L− 1 min− 1 g− 1 min− 1 In this current study, PtRu@AC nano sorbent was synthesized using a
10− 4 mg.g-
series of thermal decomposition methods. The synthesized nano­
298 16 7 0.2 0.2183 0.92 0.1116 0.88 composite particle was evaluated to remove methylene blue from an
303 16 7 0.2 0.2437 0.88 0.1131 0.84
aqueous medium. The process parameters were examined with different
310 16 7 0.2 0.2639 0.92 0.1134 0.92
317 16 7 0.2 0.2942 0.96 0.1758 0.96 parameters such as pH, contact time, nanoparticle concentration,
323 16 7 0.2 0.2745 0.92 0.1166 0.96 methylene blue dye concentration, and temperature. The synthesis and
298 16 3 0.2 0.2405 0.90 0.1068 0.99 different identity characteristics of nanocomposite particle samples
298 16 5 0.2 0.2782 0.94 0.0651 0.93 were determined by XRD, TEM, UV–Vis spectroscopy, and XPS appa­
298 16 9 0.2 0.2672 0.92 0.1779 0.96
ratus. The mean particle size of PtRu@AC nano adsorbent was found to
298 16 11 0.2 0.2824 0.97 0.1652 0.98
298 10 7 0.2 0.3356 0.96 0.2264 0.95 be 3.34 ± 0.69 nm and its average crystalline particle size was deter­
298 12 7 0.2 0.2743 0.92 0.1142 0.92 mined to be 2.70 nm. Metallic PtRu alloy was successfully obtained and
298 14 7 0.2 0.2876 0.98 0.0741 0.94 decorated on the surface of AC. XPS studies revealed that nearly whole
298 18 7 0.2 0.3026 0.90 0.2235 0.96
Pt and Ru metals were present in metallic states. Kinetic studies showed
298 16 7 0.2 0.1725 0.92 0.0179 0.95
298 16 7 0.18 0.1876 0.94 0.1789 0.95
that the best model for removal MB with PtRu@AC nano adsorbent is the
298 16 7 0.22 0.0665 0.98 0.1784 0.88 Pseudo Second Order model with 569.4 mg/g maximum adsorption
capacity. The enthalpy and standard entropy were found as 18.72 kJ/
mol and − 364.5 J/K, respectively. Furthermore, after five trials, the
synthesized PtRu@AC nano adsorbent was re-tested at defined ideal

Fig. 7. a) Pseudo-first-order kinetics, b) pseudo-second-order, and c) intra-particle diffusion for MB onto PtRu@AC nano sorbent.

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Z. Bingül Reçber et al. Environmental Pollution 302 (2022) 119033

Fig. 8. a) The plot of lnk2 versus to 1/T and b) graph of ln (k2/T) versus 1/T.

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Credit author statement reduced-graphene oxide supported nanoadsorbents. J. Mol. Liq. 309, 113171.
https://doi.org/10.1016/J.MOLLIQ.2020.113171.
Züleyha Bingül, Hakan Burhan, Ramazan Bayat, Mehmet Salih Nas, Calimli, M.H., Demirbas, O., Aygun, A., Alma, M.H., Nas, M.S., Khan, A., Asiri, A.M.,
Sen, F., 2019. Equilibrium, kinetics and thermodynamics of bovine serum albumin
Mehmet Harbi Calimli and Özkan Demirbas: Experimental part, Char­ from carbon based materials obtained from food wastes. Bionanoscience 9, 692–701.
acterization of data and analysis of experimental part. Prof. Hassan https://doi.org/10.1007/S12668-019-00633-Z/TABLES/3.
Karimi-Maleh and Prof. Fatih Şen: Writing- Original draft preparation Calimli, M.H., Demirbas, O., Aygun, A., Alma, M.H., Nas, M.S., Sen, F., 2018.
Immobilization kinetics and mechanism of bovine serum albumin on diatomite clay
and revise of paper. from aqueous solutions. Appl. Water Sci. 8, 1–12. https://doi.org/10.1007/S13201-
018-0858-8/TABLES/5.
Chen, B.Y., 2002. Understanding decolorization characteristics of reactive azo dyes by
Declaration of competing interest Pseudomonas luteola: toxicity and kinetics. Process Biochem. 38, 437–446. https://
doi.org/10.1016/S0032-9592(02)00151-6.
The authors declare that they have no known competing financial Cicek, F., Ozer, D., Ozer, Ahmet, Ozer, Ayla, 2007. Low cost removal of reactive dyes
using wheat bran. J. Hazard Mater. 146, 408–416. https://doi.org/10.1016/J.
interests or personal relationships that could have appeared to influence JHAZMAT.2006.12.037.
the work reported in this paper. Demirbas, O., Alkan, M., 2011. Thermodynamics, kinetics and adsorption properties of
some biomolecules onto mineral surfaces. Thermodyn. - Kinet. Dyn. Syst. https://
doi.org/10.5772/22833.
Acknowledgments Demirbas, O., Nas, M., 2016. Kinetics and mechanism of the adsorption of methylene
blue from aqueous solution onto Turkish green clay. Arch. Curr. Res. Int. 6, 1–10.
H. Burhan and R. Bayat are supported by the Council of Higher Ed­ https://doi.org/10.9734/ACRI/2016/30677.
Deng, H., Yang, L., Tao, G., Dai, J., 2009. Preparation and characterization of activated
ucation (CoHE) with 100/2000 Ph.D. Scholarship. carbon from cotton stalk by microwave assisted chemical activation—application in
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