Applied Water Science (2018) 8:32

https://doi.org/10.1007/s13201-018-0676-z

ORIGINAL ARTICLE

Novel biosynthesized silver nanoparticles from cobweb as adsorbent

for Rhodamine B: equilibrium isotherm, kinetic and thermodynamic
studies
Luqmon Azeez1 · Agbaje Lateef2 · Segun A. Adebisi1 · Abdulrasaq O. Oyedeji3

Received: 20 December 2016 / Accepted: 30 January 2018 / Published online: 8 February 2018
© The Author(s) 2018. This article is an open access publication

Abstract
This study has investigated the adsorption of Rhodamine B (Rh-B) dye on novel biosynthesized silver nanoparticles (AgNPs)
from cobweb. The effects of contact time, initial pH, initial dye concentration, adsorbent dosage and temperature were studied
on the removal of Rh-B and they significantly affected its uptake. Adsorption isotherms were evaluated using Langmuir,
Freundlich, Temkin and Dubinin–Radushkevich isotherm models. The adsorption process was best described by Langmuir
isotherm with R2 of 0.9901, indicating monolayer adsorption. The maximum adsorption capacity (qmax) of 59.85 mg/g showed
that it has relatively high performance, while adsorption intensity showed a favourable adsorption process. Pseudo-second-
order kinetics fitted best the rate of adsorption and intra-particle diffusion revealed both surface adsorption and intra-particle
diffusion-controlled adsorption process. Negative values of thermodynamic parameters (∆H°, ∆S° and ∆G°) indicated an
exothermic and spontaneous adsorption process. The mean sorption energy (E) and activation energy (Ea) suggested the
uptake of Rh-B onto AgNPs was chemical in nature (chemosorption).

Keywords Biosynthesized AgNPs · Chemosorption · Adsorption isotherm · pH point of zero charge · Spontaneity of
adsorption · Wastewater

Introduction et al. 2015). Most of these wastes have detrimental effects

on environment, human health, agricultural produce, aquatic
Demand for developmental strides and industrialization has lives and are also known to be genotoxic (Bakare et al. 2003;
led to more toxic effluents being discharged with little or Lateef et al. 2007). Dyes are examples of such wastes and
no treatment into the environment especially water bodies. are increasingly being used in pharmaceutical, paint, tex-
Quality water is indispensable and essential to life (Fawole tile industries and laboratories as indicators. They are non-
et al. 2002) but meeting the quality for different purposes biodegradable pollutants that affect water quality by causing
has been a huge task because of loads of wastes received by foul odour, preventing light penetration, increasing chemi-
it from domestic, municipal and industrial sources (Lateef cal oxygen demand, decreasing dissolved oxygen level, and
2004; Adewoye and Lateef 2004; Pal and Deb 2014; Azeez eventually leading to death of aquatic lives. They have been
found to be nephrotoxic and also induce toxicity on repro-
ductive system (Das et al. 2006, 2008; Baskaran et al. 2011;
* Luqmon Azeez
azeez012000@yahoo.com Chen et al. 2012; Ramalingam et al. 2015; Tan et al. 2015).
Rhodamine B (Rh-B) belongs to xanthene dyes and is
1
Department of Chemical Sciences, Osun State University, highly soluble in water. It has high fastness and possesses
Osogbo, Osun State, Nigeria fluorescent property. These characteristics have made it to be
2
Nanotechnology Research Group (NANO+), Laboratory widely applicable in textile, glass, paint, paper, and leather
of Industrial Microbiology and Nanobiotechnology, dyeing (Das et al. 2006, 2008; Satapathy et al. 2013). How-
Department of Pure and Applied Biology, Ladoke Akintola
University of Technology, PMB 4000, Ogbomoso, Oyo State, ever, it is carcinogenic causing hypothalamic cell apoptosis
Nigeria leading to hormonal imbalances. It has also been reported to
3
Department of Science Laboratory Technology, Federal cause eyes, skin, and respiratory tract irritations (Satapathy
Polytechnic Ilaro, Ilaro, Ogun State, Nigeria et al. 2013; Pal and Deb 2014; Bhattacharyya et al. 2014;

13
Vol.:(0123456789)
32 Page 2 of 12 Applied Water Science (2018) 8:32

Sulistina et al. 2014; Shen et al. 2015; Mahmoud et al. 2015; to be toxic to human lung alveolar epithelial cells, neurons
Huang et al. 2016). Wastewater containing Rh-B, therefore, as well as animal cells (Choi and Choy 2009; Lu et al.
needs to be effectively, efficiently and qualitatively treated 2009; Zhao et al. 2009). Carbon nanotubes are reported to
before being discharged into the environment (Inyinbor et al. be toxic to human dermal fibroblast cells. This might not
2015, 2016a, b). be unconnected with their methods of preparation which
Several studies have reported different methods for dye are chemical/reduction methods (Patlolla et al. 2010). To
removal from aqueous solutions such as photochemical deg- avoid toxicities arising from physical and chemical-based
radation, biological degradation, coagulation–flocculation, synthetic routes, green (biological) synthesis of nanopar-
chemical oxidation, adsorption, membrane separation pro- ticles which does not involve the use of hazardous chemi-
cess, electrochemical, reverse osmosis, aerobic and anaero- cals provides effective route for non/less toxic and eco-
bic microbial degradation, but their shortcomings have friendly nanoparticles (Vanaja et al. 2014; Adelere and
limited their applications (Majumdar et al. 2015; Das et al. Lateef 2016; Lateef et al. 2016d, e; Pavya et al. 2016;
2013; Sadaf and Bhatti 2014; Sadhukhan et al. 2014; Shen Shukla and Iravani 2017).
et al. 2015). Adsorption has proved to be the most effective In this study, novel eco-friendly silver nanoparticles bio-
physicochemical method in removing dye from effluents synthesized from extracts of cobweb (as source of biomol-
with activated carbon as the most widely used adsorbent. ecules that serve as reducing agents in reducing ­Ag+ to zero-
Activated carbon has been found useful, and effective in valent ­Ag0 to form AgNPs) were used for the adsorption of
dye removal but high cost of preparation and regeneration Rhodamine B from aqueous solution.
maintenance have made its use economically burdensome
(Tan and Hameed 2010; Giwa et al. 2015; Santhi and Kumar
2015). This has led to the use of effective alternative adsor-
bents such as hen feather (Mittal et al. 2007), cassava pel- Materials and methods
lets (Okewale et al. 2013), perlite (Vijayakumar et al. 2012),
Rhizopus oyrzae biomass (Das et al. 2006, 2008), Mucor Biosynthesis and characterization of AgNPs
rouxii (Majumdar et al. 2015) Raphia hookeri epicarp (Iny-
inbor et al. 2016a), Chitosan (Inyinbor et al. 2016b), silk AgNPs used in this study were biologically synthesized
(Jiwalak et al. 2010), phosphoric acid-modified rice husk from cobweb as earlier described (Lateef et al. 2016f). The
(Dada et al. 2012) and sawdust of Parkia biglobosa (Giwa scheme of the synthesis is shown in Fig. 1. Cobweb extract
et al. 2015) for the removal of dyes. However, as micropar- was prepared through hydrolysis of 0.1 g of washed and air-
ticles, these materials will require long time for maximum dried cobweb with 10 ml of 0.1 M NaOH at 90 °C for 1 h.
adsorption. The resulting liquid was centrifuged at 4000 rpm for 30 min
Presently, the applications of metal nanoparticles as to obtain the crude cobweb extract. Biosynthesis was carried
adsorbents have been on increase due to their morphol- by reacting 1 ml of cobweb extract with 40 ml of ­AgNO3
ogy such as highly reactive sites, controlled size and high under ambient condition. The biosynthesized AgNPs were
surface area. Multi-walled carbon nanotube (Yang and characterized by UV–Vis spectroscopy, Fourier transform
Xing 2010), MgO (Li et al. 2012; Mahmoud et al. 2015), infrared spectroscopy (FTIR) and transmission electron
chitosan–zinc oxide (Salehi et al. 2010), zero-valent iron microscopy (TEM) as previously described by Lateef et al.
(Satapanajaru et al. 2011), silver (Satapathy et al. 2013), (2016f).
gold (Xu, 2010), NiO (Samiey and Farhadi 2013), ­TiO2
(Hsiao et al. 2014; Lyu et al. 2014) nanoparticles have
been employed in wastewater purification and have proved pH point of zero charge ­(pHpzc)
to be faster in action and more effective in performance.
Also, catalytic degradation of dyes has been achieved The pH point of zero charge (pHpzc) was determined as
using nanoparticles (Bogireddy et al. 2015; Han et al. previously reported (Giwa et al. 2015; Inyinbor et al. 2015).
2013; Kumari and Philip 2015; Lateef et al. 2016a, b, c; A weighed amount (0.1 g) of AgNPs was added to 50 ml of
Ojo et al. 2016; Oladipo et al. 2017). Despite the excel- 0.1 M NaCl with predetermined pH in 250-ml conical flask.
lent adsorptive capacity of nanoparticles, toxicity aris- The pH of the resultant solution was adjusted between pH 2
ing from their use has been of great concern. Nano-TiO 2 and 10 with either 0.1 M NaOH or HCl. The conical flasks
has limited adsorption affinity for anionic dyes, and was were sealed and shaken in an orbital shaker (Stuart SSLI,
reported to cause unusual sedimentation, haemagglutina- Barlword Scientific Ltd Britain) for 24 h, after which the
tion, haemolysis of erythrocytes in humans and physical final pH values were measured. The difference between the
changes to aquatic ecosystem (Li et al. 2008; Canesi et al. initial and final pH was calculated and plotted against the
2010). Nano-Fe3O4, nano-ZnO and nano-MgO were found

13
Applied Water Science (2018) 8:32 Page 3 of 12 32

Fig. 1  Scheme for the biosyn-

thesis of AgNPs using cobweb
extract

Cl (Uniscope water bath shaker) at 30 °C, agitated at 150 rpm

for 30 min. The solution was centrifuged at 1500 rpm.
(C2H6)2N O N(C2H6)2 The pH was measured with Jenway 3505 pH meter. The
concentration of unadsorbed dye was determined using a
C Jenway 6405 UV–Visible spectrophotometer (Buch Scien-
tific Inc. USA) at 554 nm. Percentage removal and quantity
COOH adsorbed at a given time t were calculated using the follow-
ing equations:
( )
Ci − Cf × 100
% Removal = (1)
Ci
Fig. 2  Structure of Rhodamine B (Rh-B) dye (Inyinbor et al. 2015)

(Ci − Ct )V
initial pH. ­pHpzc was obtained from the point of intersection qt = (2)
M
with pH axis.
where qt is the amount of dye adsorbed per unit mass of
Adsorbate characteristics and preparation adsorbent (mg/g), Ci is the initial dye concentration (mg/l),
Cf is the final dye concentration (mg/l), Ct is the residual
The dye Rhodamine B (Fig. 2) with molecular formula concentration at time t, V is the volume of dye solution (l)
­C28H31N2O3Cl, λmax 554 nm was purchased from Sigma- and M mass of adsorbent (g).
Aldrich (Germany) and was used without further purifica-
tion. All other reagents were of analar grade. A stock solu- Adsorption isotherms
tion of Rhodamine B (Rh-B) was prepared by dissolving
0.1 g in 1000 ml deionized–distilled water. Adsorption isotherms were studied on the adsorption of
Rh-B on AgNPs with Langmuir (Eqs. 3 and 3a), Freundlich
Adsorption studies (Eq. 4), Tempkin (Eqs. 5 and 5a) and Dubinin–Radushk-
evich (Eqs. 6, 6a and 6b) adsorption models.
Effects of initial solution pH (1–9), contact time (5–60 min), The Langmuir isotherm is a monolayer type of adsorp-
AgNPs dosage (0.2–1 g/l), initial Rh-B concentration of dye tion which assumes that adsorption process takes place
(10–50 mg/l) and temperature (303–333 K) on the adsorp- uniformly within the adsorbent surface and with uniform
tion of Rh-B on AgNPs were studied in batches. The pH of distribution of energy level (Langmuir 1918). Freundlich
the Rh-B solution was adjusted with 0.1 M HCl or 0.1 M isotherm explains the heterogeneous nature of adsorp-
NaOH. 1 g/l of AgNPs was weighed and added to 100 ml tion sites having non-uniform distribution of energy level
of 50 mg/l Rh-B solution in a 250-ml conical flask. The (Freundlich 1906). Tempkin isotherm explains the influ-
flask was shaken in a thermostat-regulated water bath shaker ences of indirect adsorbate/adsorbent interactions on

13
32 Page 4 of 12 Applied Water Science (2018) 8:32

adsorption isotherms and also explains the interactions by AgNPs. A linear graph of ln qe against ɛ gives a slope
of these with the heat of adsorption (Tempkin and Pyzhev of β and intercept of ln qo.
1940). The Dubinin–Radushkevich model explains the
relationship between energy of adsorption and type of Adsorption kinetics
adsorption process involved (Dubinin and Radushkevich
1947). Adsorption kinetics were studied with pseudo-first-order
(Eq. 7), pseudo-second-order (Eq. 8), Elovich kinetic models
Ce Ce 1
= + (3) (Eq. 9) and intra-particle diffusion model (Eq. 10). Adsorp-
qe qmax qmax KL
tion kinetics were validated with non-linear Chi-square test
(Eq. 11) and correlation coefficient. Boyd model (Eqs. 12 and
1 13) was used to further confirm rate controlling step of adsorp-
RL =
1 + KL Co (3a)
tion process.

1 ln(qe − qt ) = ln qe − K1 t (7)
log qe = log Ce + log Kf (4)
n t 1 t
qt
= +
K2 q2e qe (8)
qe = B ln A + B ln Ce (5)
1 1
B = RT∕b (5a) qt = ln (αβ) + ln t (9)
𝛽 𝛽

ln qe = ln qo − 𝛽𝜀2 (6) qt = Kdiff t1∕2 + C (10)

( )
1
𝜀 = RT ln 1 + (6a) n
∑ (qexp − qcal )2
Ce 2
X = (11)
i=1
qcal
√1
E= ∕2𝛽 (6b) qt
F= (12)
where Ce is the equilibrium concentration of Rh-B dye qe
(mg/l), qe is the quantity of Rh-B dye adsorbed onto the
AgNPs at equilibrium (mg/g), qmax is the maximum mon- Bt = −0.4977 − ln(1 − F) (13)
olayer adsorption capacity of adsorbent (mg/g) and KL is the where qe is the quantity adsorbed at equilibrium (mg/g) and
Langmuir adsorption constant (l/mg). qt is the quantity absorbed at time t (mg/g) and K1 is the
A graph of Ceqe
against C e should give a straight line rate constant for the pseudo-first-order sorption in m ­ in−1
obtained from the plot of ln (qe − qt) against t, t is time for
graph with the slope 1 q and q 1 K as intercept. The
/
max max L adsorption in min.
value of RL is in the range 0 < RL < 1 indicating whether K2 is the rate constant of the pseudo-second-order kinetic
the adsorption is favourable or not: unfavourable (RL > 1), model in g/mg/min obtained for the plot of qt aganist t . Kdiff
linear (RL = 1) or irreversible (RL = 0).
t

is the rate constant of intra-particle diffusion (mg/g min−1/2).

K f and n are Freundlich constants corresponding to
α and β are constants depicting chemosorption rate and the
adsorption capacity and adsorption intensity or surface
extent of surface coverage respectively, which are obtainable
heterogeneity, respectively. They are obtained from linear
from the plot of qt against ln t.
plot of log qe versus log Ce with the slope 1∕n and inter-
F is the fraction of solute adsorbed at any time t. Bt is a
cept log Kf.
mathematical function of F.
A (l/g) and B are Tempkin isotherm and Tempkin con-
stants, respectively, which are obtained from the plot of
qe against ln Ce. The value of b (J/mol) which is related
Adsorption thermodynamics
to the heat of absorption is calculated using Eq. (5a), T
Thermodynamic parameters that explain spontaneity, ener-
is the absolute temperature (K), and R is the gas constant
getics and the nature of adsorbate–adsorbent interactions are
(8.314 J/mol/K).
calculated using the following equations:
The value of E in Dubinin–Radushkevich (D–R) model
gives information about the type of adsorption whether ΔSo ΔH o
chemical or physical involved during the uptake of Rh-B ln Ko = − (14)
R RT

13
Applied Water Science (2018) 8:32 Page 5 of 12 32

tremendous activities; including antimicrobial (Lateef

ΔGo = −RT ln Ko (15) et al. 2016f), desulphurization (Olajire et al. 2017), hydro-
Ea∕ gen peroxide scavenging, anticoagulant and thrombolytic
S∗ = (1 − 𝜃)e− RT (16) applications (Lateef et al. 2017). However, until now, there
is no report on the use of cobweb-mediated AgNPs for the
Ce removal of dyes.
𝜃 =1− (17)
Co
Effect of initial pH on the adsorption of Rh‑B
Ko is calculated from qe C , T is temperature (K), R is on AgNPs
/
e
gas constant. ΔSo is change in entropy and ΔH o is change
in enthalpy obtained from the plot of ln Ko against T1 . ΔGo , Effect of various pH on adsorption of Rh-B on AgNPs is
change in free energy is calculated using Eq. (15). Ea is presented in Fig. 4. Adsorption process is dependent on pH
activation energy which is obtained from the plot of where a change would either increase or reduce percent-
(1 − θ) against T1 . S* is the sticking probability which is a age adsorption. pH influences the charge on the surface of
function of adsorbate–adsorbent system and its value adsorbent and mobility of adsorbate (Majumdar et al. 2015;
ranges between 0 < S∗ < 1. Das et al. 2013; Giwa et al. 2015). Percentage removal of
Rh-B increased from 72 to 78% with increase in pH from
pH 2 to 3.4 where maximum adsorption was observed.
This decreased to the minimum (55%) at pH 9. At a pH
Results and discussion below 7.82 ­(pHpzc for AgNPs), the surface of AgNPs was
highly cationic, while Rh-B surface at pH less than 3.22
Biosynthesized AgNPs was also cationic, thus caused repulsion between adsorbent
and adsorbate resulting in poor rate of adsorption. But as
The pH of biosynthesized AgNPs was 6.72 and p­ Hpzc was the pH increased especially at pH 3.4 (which is above 3.22
7.82 (Fig. 3) which was fairly neutral. p­ Hpzc is a parameter for Rh-B), the surface of Rh-B became anionic, therefore,
used to express the degree of adsorbent surface ionization. resulting to high rate of adsorption. This could be due to
At a pH below ­pHpzc of the adsorbent, the surface of the electrostatic interaction between cationic adsorbent and
adsorbent is positively charged and attracts anions while anionic adsorbate leading to favourable adsorption of Rh-B
at pH above it, the surface of the adsorbent is negatively (Majumdar et al. 2015; Das et al. 2013). With increase in
charged and attracts cations (Giwa et al. 2015; Torres et al. pH, the surface of AgNPs became less cationic as it was
2007). Earlier data revealed that cobweb extract-mediated nearing its pHpzc and thereafter became anionic at pH above
AgNP biosynthesis gave dark brown nearly spherical crys- it. This was responsible for reduction in rate of adsorp-
talline AgNPs with surface plasmon resonance obtained at tion obtained at pH above 7.82. Similar trends have been
436 nm. The polydispersed particles having size range of
3–50 nm were formed due to the activities of proteinous
80
materials in the cobweb extract (Lateef et al. 2016f).
The AgNPs mediated by cobweb extract have shown
75

70
% Rh-B adsorbed

2.5
65
2

1.5
60
pH inial - pH final

0.5 55

0
0 2 4 6 8 10 12 50
-0.5 0 2 4 6 8 10
pH
-1

-1.5 pH inial
Fig. 4  Effect of different pH on the adsorption of Rh-B on AgNPs.
1 g/l of AgNPs in 100 ml of 50 mg/l Rh-B, agitation speed 150 rpm,
Fig. 3  pH point of zero charge (pHpzc) agitation time 30 min, temp. 303 K

13
32 Page 6 of 12 Applied Water Science (2018) 8:32

previously reported in different studies (Giwa et al. 2015; 35

Inyinbor et al. 2015; Ramalingam et al. 2015). Consequently, 30

all batch adsorption experiments were, therefore, carried out
at pH 3.4. 25

qt (mg/g)
20
Effects of initial concentrations of Rh‑B
15

The result of effect of initial dye concentrations on per- 10

centage uptake of Rh-B on AgNPs is presented in Fig. 5.
It was discovered from the plot that percentage removal of 5
4 14 24 34 44 54 64
Rh-B increased with increasing concentration of the dye. Time (min.)
Maximum adsorption of 93% was recorded for highest con-
centration (50 mg/l), while the least adsorption (67%) was Fig. 6  Adsorption capacity of AgNPs for the removal of Rh-B at dif-
obtained for lowest concentration (10 mg/l). This could be ferent contact times. 1 g/l of AgNPs in 100 ml of 50 mg/l Rh-B, agi-
attributed to the increase in the driving force from higher tation speed—150 rpm at 303 K, pH 3.4
concentration which enhances the sorption process as earlier
reported (Inyinbor et al. 2016a, b; Satapathy et al. 2013). from 0.2 to 1 g/l. The increase was from 52 to 87%. The
increase in the percentage removal with adsorbent dosage
Effect of contact time may be adduced to the increase in the nanoparticle’s surface
area available for adsorption. This is in consonance with
Contact time is one of the most effective factors in batch earlier reports (Satapathy et al. 2013; Amuda et al. 2014;
adsorption process and its effect on the adsorption of Rh-B Inyinbor et al. 2016a, b).
on AgNPs is presented in Fig. 6. It is evident from the plot
that the adsorption capacity (qt) at time t increased steadily Effect of temperature
with increase in time until it reached equilibrium at 30 min.
The increase was from 7 mg/g at 5 min to 30.55 mg/g at Temperature influences adsorption capacity and its effect
30 min. This is in agreement with earlier reports (Amuda on the adsorption of Rh-B onto AgNPs is presented in
et al. 2014; Mahmoud et al. 2015) where the noticed action Fig. 8. The temperature dependency of adsorption of Rh-B
could be due to the available surface sites before equilibrium on AgNPs was studied at 303, 313, 323, 333 K, and it was
was reached. observed that percentage removal of Rh-B reduced with
increase in temperature. This phenomenon indicates that
Effect of adsorbent dosage the adsorption process was exothermic in nature and it is
in consonance with earlier reports (Satapathy et al. 2013;
The result of effect of AgNPs dosage on the removal of Rh-B Girish and Murty 2014; Inyinbor et al. 2016a, b).
from aqueous solution is presented in Fig. 7. Percentage
Rh-B adsorbed increased with increase in AgNPs dosage

95 90
90

80
% Rh-B dye adsorbed

% Rh-B Adsorbed

85

80
70
75

70 60
65

60 50
5 15 25 35 45 55 0.1 0.3 0.5 0.7 0.9 1.1
Inal Rh-B dye Concentraon (mg/L) AgNP Dosage (g/L)

Fig. 5  Percentage removal of Rh-B on AgNPs at different concentra- Fig. 7  Effect AgNPs dosage on the adsorption of Rh-B. 50 mg/l
tions. 1 g/l of AgNPs in 100 ml of 50 mg/l Rh-B, agitation speed— Rh-B, agitation speed—150 rpm, agitation time—30 min at 303 K,
150 rpm, agitation—30 min at 303 K, pH 3.4 pH 3.4

13
Applied Water Science (2018) 8:32 Page 7 of 12 32

100 50
45
90
40
% Rh-B adsorbed

80 35
70 30
25

qe
60
20
50 15

40 10
300 305 310 315 320 325 330 335 5
Temp. (K) 0
0 0.5 1 1.5 2 2.5 3 3.5 4
lnCe
Fig. 8  Effect of temperature on the adsorption of Rh-B on AgNPs at
different temperatures. 1 g/l of AgNPs in 100 ml of 50 mg/l Rh-B,
150 rpm 60 min, pH 3.4 Fig. 11  Temkin adsorption isothermal plot for the adsorption of Rh-B
on AgNPs

0.8

0.7 4

0.6 3.5

0.5 3
Ce/qe

0.4 2.5
lnqe
0.3 2

0.2 1.5

0.1 1

0 0.5
0 5 10 15 20 25 30 35
Ce 0
0 200 400 600 800 1000 1200 1400 1600 1800
ε2 x 103
Fig. 9  Langmuir adsorption isothermal plot for the adsorption of
Rh-B on AgNPs
Fig. 12  Dubinin–Radushkevich adsorption isothermal plot for the
adsorption of Rh-B on AgNPs

1.8

1.6
plots of Langmuir, Freundlich, Tempkin and Dubinin–Radu-
shkevich adsorption isotherms, respectively, for the adsorp-
1.4 tion of Rh-B on AgNPs. The parameters obtained from
the plots are presented in Table 1. Correlation coefficient
log qe

1.2
(R2) was used to determine which model best describes the
1 adsorption process. The closer the R2 to unity (1), the bet-
0.8
ter the agreement between experimental data, and model
predicted value and the best fit it is. Comparing R2 of each
0.6 isotherm, Langmuir (0.9901), Freundlich (0.9860), Tempkin
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
log Ce
(0.9740) and Dubinin–Radushkevich (0.9441), it is evident
that Langmuir isotherm best fits the adsorption of Rh-B on
Fig. 10  Freundlich adsorption isothermal plot for the adsorption of AgNPs which indicates monolayer and homogenous adsorp-
Rh-B on AgNPs tion process with all adsorption sites possessing equal affin-
ity for adsorbate (Foo and Hameed 2010). The favourability
of the adsorption process is confirmed if the value of ­RL is in
Adsorption isotherms the range 0 < RL < 1. As obtained in this study (Table 1), RL
is 0.18, confirming that the adsorption process was favour-
For the explicit examination of the relationship between able (Majumdar et al. 2015; Satapathy et al. 2013; Inyinbor
quantity of Rh-B adsorbed and its concentration, Langmuir, et al. 2016a, b).
Freundlich, Tempkin and Dubinin–Radushkevich isothermal The maximum monolayer adsorption (qmax) obtained
models were employed. Figures 9, 10, 11 and 12 show the from Langmuir plot is 59.85 mg/g and when compared with

13
32 Page 8 of 12 Applied Water Science (2018) 8:32

Table 1  Adsorption isotherm parameters for the uptake of Rh-B on Adsorption kinetics
AgNPs at 30 °C
Isotherms Constants Values The rate of removal of Rh-B and its controlling mechanism
were studied as part of kinetics. Pseudo-first-order, pseudo-
Langmuir qmax (mg/g) 59.85
second-order, Elovich kinetic models and intra-particle dif-
KL (l/mg) 0.093
fusion model were employed to describe Rh-B uptake onto
RL 0.18
AgNPs. The parameters obtained for pseudo-first-order,
R2 0.9901
pseudo-second-order, Elovich kinetic models and intra-par-
Freundlich n 1.647
ticle diffusion model are presented in Table 3. Correlation
KF 6.07
coefficient (R2) was used to determine the goodness of fit
R2 0.9860
between experimental and calculated data. R2 of the best fit
Temkin B 12.21
model must be the closest to 1. Also, similarities between
A (l/g) 1.48
experimentally determined and calculated data expressed
b (J/mol) 206.32
using non-linear Chi-square test (χ2) (Eq. 11) must exist. A
R2 0.9740
relatively low (χ2) value indicates the model successfully
Dubinin–Radushkevich qo (mg/g) 42.81
describes the equilibrium kinetics (Al-Meshragi et al. 2008;
β ­(mol2/KJ2) 0.00133
Boulinguiez et al. 2008). Comparison of correlation coef-
E (KJ/mol) 19.38
ficients of pseudo-first-order (R2 = 0.9421), pseudo-sec-
R2 0.9441
ond-order (R2 = 0.9882) and Elovich (R2 = 0.9723) kinetic
models shows that pseudo-second-order best describes the
mechanism and rate of uptake of Rh-B on AgNPs. Equally,
previously published reports in other studies (Table 2), it lower value of χ 2 validates pseudo-second-order as the
shows that AgNPs is a relatively better adsorbent in terms of kinetic model describing the rate of adsorption. This sug-
performance than some previously used adsorbents (Majum- gests that the controlling process of adsorption of Rh-B on
dar et al. 2015; Das et al. 2006; Satapathy et al. 2013; AgNPs may be by chemosorption (Girish and Murty 2014).
Amuda et al. 2014; Inyinbor et al. 2015, 2016a; Mahmoud Many factors control the rate of adsorption, one of which
et al. 2015; Shen et al. 2015). is intra-particle diffusion. The possibility of involvement of
Kf and n were calculated from Freundlich isotherm plot intra-particle diffusion affecting the adsorption process was
with the value of n (1.647) greater than 1 indicating a favour- studied and is presented in Fig. 13. To further investigate
able adsorption of Rh-B on AgNPs and the chemical nature rate controlling step in the adsorption process, the Boyd
of adsorption (Foo and Hameed 2010; Amuda et al. 2014). model as given in Eqs. 12 and 13 was used and the result
Adsorption energy (E) calculated from slope of
Dubinin–Radushkevich plot is 19.38 kJ/mol suggesting
Table 3  Adsorption kinetics of Rh-B on AgNPs
that chemosorption was involved in the uptake of Rh-B
on AgNPs as it was earlier reported (Inyinbor et al. 2015, qe experimental (mg/g) 30.55
2016a, b). Pseudo-first order
qe, calculated (mg/g) 33.44
K1 ­(min−1) 0.096866
R2 0.942067
Table 2  Comparison of monolayer adsorption capacity of Rh-B on χ2 0.249
AgNPs with other adsorbents Pseudo-second order
qe, calculated (mg/g) 31.27
Adsorbent qmax (mg/g) References
K2 (g/mg/min) 0.000152
Lantana camara stem 19.84 Amuda et al. (2014) R2 0.988223
Raw dika nut 212.77 Inyinbor et al. (2015) χ2 0.017
Dika nut char 52.90 (Inyinbor et al. 2016a, b) Elovich
MgO nanocomposite 77.2 Mahmoud et al. (2015) Β (mg/g/min) 0.088
NiO nanoparticle 52.91 Satapathy et al. (2013) Α (g/mg) 19.49
Plant-mediated AgNPs 1.891 Shen et al. (2015) R2 0.972226
Rhizopus oryzae biomass 39.21 Das et al. (2006) Intraparticle diffusion
Mucor rouxii 74.6 Majumdar et al. (2015) Kdiff (mg/g min−1/2) 7.008
Cobweb-mediated AgNPs 59.85 This study C (mg/g) 5.12

13
Applied Water Science (2018) 8:32 Page 9 of 12 32

30 3

25 2.5

20 2

15 1.5
qt

lnK
1
10

0.5
5

0
0 0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325 0.0033 0.00335
2 2.5 3 3.5 4 4.5 5 5.5
t1/2 -0.5
1/T (K-1)

Fig. 13  Intra-particle diffusion of adsorption of Rh-B on AgNPs Fig. 15  Van’t Hoff’s plot for adsorption of Rh-B on AgNPs. 1 g/l of
AgNPs in 100 ml of 50 mg/l Rh-B, 150 rpm 60 min, pH 3.4

(Satapathy et al. 2013). Activation energy (Ea) of the adsorp-

1.5 tion process obtained using Eqs. 16 and 17 is presented in
Table 4. The magnitude of activation energy gives idea about
1 the type of adsorption, which mainly can either be physi-
osorption or chemosorption (Mahmoud et al. 2015).
Bt

0.5 The Ea of the adsorption calculated was 103.273 kJ/mol

which depicts the adsorption process as chemosorption
0 because its range for chemosorption is usually between
0 5 10 15 20 25 30
40 and 800 kJ/mol. (Satapathy et al. 2013; Mahmoud et al.
-0.5
t (min)
2015).
Negative enthalpy (− ∆H°) and entropy (− ∆S°) values
Fig. 14  Boyd plot for adsorption of Rh-B on AgNPs obtained indicate the adsorption process was exothermic in
nature with decreased randomness during adsorption. The
∆G° values calculated at all temperatures were negative
is presented in Fig. 14. The parameters obtained from the indicating the adsorption was spontaneous and feasible.
plot in Fig. 13 are presented in Table 3. A single linear plot The adsorption process became less spontaneous with
obtained for intra-particle diffusion of AgNP–Rh-B did not higher values of ∆G° at higher temperature (Majumdar
pass through the origin and has high correlation coefficient et al. 2015; Inyinbor et al. 2015; Mahmoud et al. 2015).
(R2 = 0.9971) indicating that intra-particle diffusion was
involved in the adsorption but it was not the sole rate-con-
trolling step. This was confirmed by Boyd plot which also
did not pass through the origin. Therefore, surface adsorp- Conclusion
tion and intra-particle diffusion were both concurrently
occurring during adsorption process (Cheung et al. 2007; This study has reported the adsorption of Rh-B onto
Hameed et al. 2008; Abou-Gamra and Medien 2013; Girish AgNPs biosynthesized using cobweb extract. Initial pH,
and Murty 2014). The value of C (intercept) gives the idea contact time, initial dye concentration, adsorbent dos-
about the thickness of the boundary, the larger the value of age and temperature significantly affected the adsorption
C, the greater the boundary layer diffusion effect (Konicki of Rh-B and maximum adsorption was observed at pH
et al. 2013). 3.4. Four adsorption isotherms were used to describe the
adsorption process with Langmuir isotherm suitably fitted
Activation energy and adsorption thermodynamic best. Maximum monolayer adsorption capacity showed a
relatively high performance. Pseudo-second-order kinetics
Thermodynamic parameters (∆G°, ∆H° and ∆S°) calculated best fitted the rate of adsorption which was both controlled
from Van’t Hoff’s plot (Fig. 15) for adsorption of Rh-B on by intra-particle diffusion and surface adsorption. Ther-
AgNPs are presented in Table 4. These parameters give modynamic parameters indicated exothermic spontaneous
information about the spontaneity of adsorption process adsorption process. The adsorption process was found to
be chemical in nature as showed by the values of energy

13
32 Page 10 of 12 Applied Water Science (2018) 8:32

Table 4  Thermodynamic Temperature ∆G° (KJ/mol) ∆H° (KJ/mol) ∆S° (JK/mo) Ea (KJ/mo) S
parameters of Rh-D adsorption (K)
on AgNPs
303 − 6.17 − 62.11 − 184.01 103.273 1.59 × 10−20
313 − 4.54
323 − 2.68
333 − 0.56

of adsorption and activation energy. This study has shown Canesi L, Fabbri R, Gallo G, Vallotto D, Marcomini A, Pojana G
that low-cost and eco-friendly biosynthesized AgNPs with (2010) Biomarkers in Mytilus galloprovincialis exposed to sus-
pensions of selected nanoparticles (Nanocarbon black, C60 fuller-
93% dye removal from aqueous solution possess potential ene, nano-TiO2, nano-SiO2). Aquat Toxicol 100:168–177
adsorbent capacity to remove dye. Chen X, Xue Z, Yao Y, Wang W, Zhu F, Hong C (2012) Oxidation
degradation of Rhodamine B in aqueous by UV/S2O82− treatment
Open Access This article is distributed under the terms of the Crea- system. Int J Photoenergy. https​://doi.org/10.1155/2012/75469​1
tive Commons Attribution 4.0 International License (http://creat​iveco​ Cheung WH, Szeto YS, McKay G (2007) Intraparticle diffusion pro-
mmons​.org/licen​ses/by/4.0/), which permits unrestricted use, distribu- cesses during acid dye adsorption onto chitosan. Bioresour Tech-
tion, and reproduction in any medium, provided you give appropriate nol 98:2897–2904
credit to the original author(s) and the source, provide a link to the Choi SJ, Oh JM, Choy JH (2009) Toxicological effects of inorganic
Creative Commons license, and indicate if changes were made. nanoparticles on human lung cancer A549 cells. J Inorg Biochem
103:463–471
Dada AO, Olalekan AP, Olatunya AM, Dada O (2012) Langmuir,
Freundlich, Temkin and Dubinin–Radushkevich isotherms stud-
References ies of equilibrium sorption of Zn2+ unto phosphoric acid modi-
fied rice husk. J Appl Chem 3:38–45
Abou-Gamra ZM, Medien HAA (2013) Kinetic, thermodynamic Das SK, Bhowal J, Das AR, Guha AK (2006) Adsorption behav-
and equilibrium studies of Rhodamine B adsorption by low cost iour of Rhodamine B on Rhizopus oryzae biomass. Langmuir
biosorbent sugar cane bagasse. Eur Chem Bull 2:417–422 22:7265–7272
Adelere IA, Lateef A (2016) A novel approach to the green synthesis Das SK, Ghosh P, Ghosh I, Guha AK (2008) Adsorption of rhoda-
of metallic nanoparticles: the use of agro-wastes, enzymes and mine B on Rhizopus oryzae: role of functional groups and cell
pigments. Nanotechnol Rev 5:567–587 wall components. Colloids Surf B Biointerf 65:30–34
Adewoye SO, Lateef A (2004) Assessment of the microbiological Das SK, Khan MMR, Paranthamon T, Laffir F, Guha AK, Sekaran G,
quality of Clarias gariepinus exposed to an industrial effluent in Mandal AB (2013) Nano-silica fabricated with silver nanopar-
Nigeria. Environmentalist 24:249–254 ticles: antifouling adsorbent for efficient dye removal, effective
Al-Meshragi M, Ibrahim HG, Aboabboud MM (2008) Equilibrium and water disinfection and biofouling control. Nanoscale 5:5549–5560
kinetics of chromium adsorption on cement kiln dust. In: Proceed- Dubinin MM, Radushkevich LV (1947) The equation of the char-
ings of the World Congress on Engineering and Computer Sci- acteristic curve of the activated charcoal. Proc Acad Sci USSR
ence. WCECS, October 22–24, San Francisco, USA Phys Chem Sect 55:331–337
Amuda OS, Olayiwola AO, Alade AO, Farombi AG, Adebisi SA Fawole OO, Lateef A, Amaefuna M (2002) Microbiological exami-
(2014) Adsorption of methylene blue from aqueous solution using nation of drinking water in Ogbomoso metropolis, Southwest,
steam-activated carbon produced from Lantana camara stem. J Nigeria. Sci Focus 1:16–20
Environ Protect 5:1352–1363 Foo KY, Hameed BH (2010) Insights into the modelling of adsorp-
Azeez L, Salau AK, Adewuyi SO, Osineye SO, Tijani KO, Balogun tion isotherm systems. Chem Eng J 156:2–10
RO (2015) Safety evaluation of Osun river water containing heavy Freundlich HMF (1906) Over the adsorption in solution. J Phys
metals and volatile organic compounds (VOCs) in rats. Niger J Chem 57:385–470
Physiol Sci 30:103–109 Girish CR, Murty VR (2014) Adsorption of Phenol from aqueous
Bakare AA, Lateef A, Amuda OS, Afolabi RO (2003) The aquatic Solution using Lantana camara, forest waste: kinetics, iso-
toxicity and characterization of chemical and microbiological con- therm, and thermodynamic studies. Int Sch Res Notices. https​
stituents of water samples from Oba River, Odo-Oba, Nigeria. ://doi.org/10.1155/2014/20162​6
Asian J Microbiol Biotechnol Environ Sci 5:11–17 Giwa AA, Oladipo MA, Abdulsalam KA (2015) Adsorption of Rho-
Baskaran K, Venkatraman BR, Hema M, Arivoli S (2011) Adsorption damine B from single, binary and ternary dye systems using
kinetics and thermodynamics of malachite green dye onto Calat- Sawdust of Parkia biglobosa as adsorbent: isotherm, kinetics
ropis gigantis bark carbon. J Ind Pollut Control 27:5–13 and thermodynamics studies. J Chem Pharm Res 7(2):454–475
Bhattacharyya KG, SenGupta S, Sarma GK (2014) Interactions of the Hameed BH, Tan IAW, Ahmad AL (2008) Adsorption isotherm,
dye, Rhodamine B with kaolinite and montmorillonite in water. kinetic modeling and mechanism of 2,4,6-trichlorophenol on
Appl Clay Sci 99:7–17 coconut husk-based activated carbon. Chem Eng J 144:235–244
Bogireddy NKR, Anand KKH, Mandal BK (2015) Gold nanopar- Han TH, Khan MM, Kalathil S, Lee J, Cho MH (2013) Simultaneous
ticles-Synthesis by Sterculia acuminata extract and its cata- enhancement of methylene blue degradation and power gen-
lytic efficiency in alleviating different organic dyes. J Mol Liq eration in a microbial fuel cell by gold nanoparticles. Ind Eng
211:868–875 Chem Res 52:8174–8181
Boulinguiez B, LeCloirec P, Wolbert D (2008) Revisiting the determi- Hsiao Y-C, Wu T-F, Wang Y-S, Hu C-C, Huang C (2014) Evaluating
nation of Langmuir parameters application to tetrahydrothiophene the sensitizing effect on the photocatalytic decoloration of dyes
adsorption onto activated carbon. Langmuir 24:6420–6424 using anatase-TiO2. Appl Catal B 148–149:250–257

13
Applied Water Science (2018) 8:32 Page 11 of 12 32

Huang Y, Zheng X, Feng S, Guo Z, Liang S (2016) Enhancement of Li X, Xiao W, He G, Zheng W, Yu N, Tan M (2012) Pore size and
rhodamine B removal by modifying activated carbon developed surface area control of MgO nanostructures using a surfactant-
from Lythrum salicaria L. with pyruvic acid. Colloids Surf A templated hydrothermal process: high adsorption capability to azo
489:154–162 dyes. Colloids Surf A 408:79–86
Inyinbor AA, Adekola FA, Olatunji GA (2015) Adsorption of Rho- Lu S, Duffin R, Poland CD, Paul Murphy F, Drost E, MacNee W, Stone
damine B dye from aqueous solution on Irvingia gabonensis V, Donaldson K (2009) Efficacy of simple short-term in vitro
biomass: kinetics and thermodynamics studies. South Afr J assays for predicting the potential of metal oxide nanoparticles to
Chem 68:115–125 cause pulmonary inflammation. Environ Health Perspect 117:241
Inyinbor AA, Adekola FA, Olatunji GA (2016a) Kinetics and iso- Lyu J, Zhu L, Burda C (2014) Considerations to improve adsorption
thermal modelling of liquid phase adsorption of Rhodamine B and photocatalysis of low concentration air pollutants on T ­ iO2.
onto urea modified Raphia hookerie epicarp. Appl Water Sci. Catal Today 225:24–33
https​://doi.org/10.1007/s1320​1-016-0471-7 Mahmoud HR, Ibrahim SM, El-Molla SA (2015) Textile dye removal
Inyinbor AA, Adekola FA, Olatunji GA (2016b) Liquid phase from aqueous solutions using cheap MgO nanomaterials: adsorp-
adsorptions of Rhodamine B dye onto raw and chitosan sup- tion kinetics, isotherm studies and thermodynamics. Adv Powder
ported mesoporous adsorbents: isotherms and kinetics studies. Technol. https​://doi.org/10.1016/j.apt.2015.12.006
Appl Water Sci. https​://doi.org/10.1007/s1320​1-016-0405-4 Majumdar SS, Das SK, Chakravarty R, Saha T, Bandyopadhyay TS,
Jiwalak N, Rattanaphani S, Bremner JB, Rattanaphani V (2010) Guha AK (2015) A study on lead adsorption by Mucor rouxii
Equilibrium and kinetic modelling of the adsorption of indigo biomass. Desalination 251:96–102
carmine onto silk. Fiber Polym 11:572–579 Mittal A, Kurup L, Mittal I (2007) Freundlich and Langmuir adsorption
Konicki W, Sibera D, Mijowska E, Lendzion-Bielun Z, Narkiewicz isotherms and kinetics for the removal of Tartrazine from aqueous
U (2013) Equilibrium and kinetic studies on acid dye Acid Red solutions using hen feathers. J Hazard Mater 146:243–248
88 adsorption by magnetic ­ZnFe2O4 spinel ferrite nanoparticles. Ojo SA, Lateef A, Azeez MA, Oladejo SM, Akinwale AS, Asafa TB,
J Colloid Interf Sci 398:152–160 Yekeen TA, Akinboro A, Oladipo IC, Gueguim-Kana EB, Beu-
Kumari MM, Philip D (2015) Degradation of environment pollutant kes LS (2016) Biomedical and catalytic applications of gold and
dyes using phytosynthesized metal nanocatalysts. Spectrochim silver-gold alloy nanoparticles biosynthesized using cell-free
Acta Part A Mol Biomol Spectr 135:632–638 extract of Bacillus safensis LAU 13: antifungal, dye degradation,
Langmuir I (1918) The adsorption of gases on plane surfaces of anti-coagulant and thrombolytic activities. IEEE Trans Nanobiosci
glass, mica and platinum. J Am Chem Soc 40:1361–1403 15:433–442
Lateef A (2004) The microbiology of a pharmaceutical effluent and Okewale AO, Babayemi KA, Olalekan AP (2013) Adsorption iso-
its public health implications. World J Microbiol Biotechnol therms and kinetics models of starchy adsorbents on uptake
20:167–171 of water from ethanol–water systems. Int J Appl Sci Technol
Lateef A, Yekeen TA, Ufuoma PE (2007) Bacteriology and geno- 3:35–42
toxicity of some pharmaceutical wastewaters in Nigeria. Int J Oladipo IC, Lateef A, Elegbede JA, Azeez MA, Asafa TB, Yekeen TA,
Environ Health 1:551–562 Akinboro A, Gueguim-Kana EB, Beukes LS, Oluyide TO, Atanda
Lateef A, Ojo SA, Folarin BI, Gueguim-Kana EB, Beukes LS OR (2017) Enterococcus species for the one-pot biofabrication
(2016a) Kolanut (Cola nitida) mediated synthesis of silver-gold of gold nanoparticles: characterization and nanobiotechnological
alloy nanoparticles: antifungal, catalytic, larvicidal and throm- applications. J Photochem Photobiol B Biol 173:250–257
bolytic applications. J Clust Sci 27:1561–1577 Olajire AA, Abidemi JJ, Lateef A, Benson NU (2017) Adsorptive des-
Lateef A, Akande MA, Ojo SA, Folarin BI, Gueguim-Kana EB, Beu- ulphurization of model oil by Ag nanoparticles-modified activated
kes LS (2016b) Paper wasp nest-mediated biosynthesis of silver carbon prepared from brewer’s spent grains. J Environ Chem Eng
nanoparticles for antimicrobial, catalytic, anti-coagulant and 5:147–159
thrombolytic applications. 3 Biotech 6:140 Pal J, Deb MK (2014) Efficient adsorption of congo red dye from aque-
Lateef A, Akande MA, Azeez MA, Ojo SA, Folarin BI, Gue- ous solution using green synthesized coinage nanoparticles coated
guim-Kana EB, Beukes LS (2016c) Phytosynthesis of silver activated carbon beads. Appl Nanosci 4:967–978
nanoparticles (AgNPs) using miracle fruit plant (Synsepalum Patlolla A, Patlolla B, Tchounwou P (2010) Evaluation of cell viability,
dulcificum) for antimicrobial, catalytic, anti-coagulant and DNA damage and cell death in normal human dermal fibroblast
thrombolytic applications. Nanotechnol Rev 5:507–520 cells induced by functionalized multiwalled carbon nanotube. Mol
Lateef A, Azeez MA, Asafa TB, Yekeen TA, Akinboro A, Oladipo Cell Biochem 338:225–232
IC, Azeez L, Ojo SA, Gueguim-Kana EB, Beukes LS (2016d) Pavya T, Praseetha PK, RimalIsaac RS (2016) Green synthesis of gold
Cocoa pod husk extract-mediated biosynthesis of silver nano- nanoparticles using plant sources for cancer therapy: a review. Res
particles: its antimicrobial, antioxidant and larvicidal activities. J Pharm Biol Chem Sci 7:472–480
J Nanostruct Chem 6:159–169 Ramalingam B, Khan MMR, Mondal B, Mandal AB, Das SK (2015)
Lateef A, Ojo SA, Elegbede JA (2016e) The emerging roles of Facile synthesis of silver nanoparticles decorated magnetic-
arthropods and their metabolites in the green synthesis of metal- chitosan microsphere for efficient removal of dyes and microbial
lic nanoparticles. Nanotechnol Rev 5:601–622 Contaminants. ACS Sustain Chem Eng 3:2291–2302
Lateef A, Ojo SA, Azeez MA, Asafa TB, Yekeen TA, Akinboro A, Sadaf S, Bhatti HN (2014) Evaluation of peanut husk as a novel, low
Oladipo IC, Gueguim-Kana EB, Beukes LS (2016f) Cobweb cost biosorbent for the removal of Indosol Orange RSN dye from
as novel biomaterial for the green and eco-friendly synthesis of aqueous solutions: batch and fixed bed studies. Clean Techn Envi-
silver nanoparticles. Appl Nanosci 6:863–874 ron Policy 16(3):527–544
Lateef A, Ojo SA, Elegbede JA, Azeez MA, Yekeen TA, Akinboro A Sadhukhan B, Mondal NK, Chattoraj S (2014) Biosorptive removal of
(2017) Evaluation of some biosynthesized silver nanoparticles cationic dye from aqueous system: a response surface methodo-
for biomedical applications: hydrogen peroxide scavenging, anti- logical approach. Clean Technol Environ Policy 16:1015–1025
coagulant and thrombolytic activities. J Clust Sci 28:1379–1392 Salehi R, Arami M, Mahmoodi NM, Bahrami H, Khorramfar S (2010)
Li SQ, Zhu RR, Zhu H, Xue M, Sun XY, Yao SD, Wang SL (2008) Novel biocompatible composite (Chitosan–zinc oxide nanoparti-
Nanotoxicity of T ­ iO2 nanoparticles to erythrocyte in vitro. Food cle): preparation, characterization and dye adsorption properties.
Chem Toxicol 46:3626–3631 Colloids Surf B 80:86–93

13
32 Page 12 of 12 Applied Water Science (2018) 8:32

Samiey B, Farhadi S (2013) Kinetics and thermodynamics of adsorp- Tempkin MI, Pyzhev V (1940) Kinetics of ammonia synthesis on pro-
tion of fuchsin acid on nickel oxide nanoparticles. Acta Chim moted iron catalyst. Acta Phys Chim USSR 12:327–356
Slov 60:763–773 Torres MA, Beppu MM, Santana CC (2007) Characterization of chemi-
Santhi M, Kumar PE (2015) Adsorption of Rhodamine B from an aque- cally modified chitosan microspheres as adsorbents using standard
ous solution: kinetic, equilibrium and thermodynamic studies. Int proteins (bovine serum albumin and lysozyme). Braz J Chem Eng
J Innov Res Sci Eng Technol 4:497–510 24:325–336
Satapanajaru T, Chompuchan C, Suntornchot P, Pengthamkeerati P Vanaja M, Paulkumar K, Baburaja M, Rajeshkumar S, Gnanajobitha G,
(2011) Enhancing decolorization of Reactive Black 5 and Reac- Malarkodi C, Sivakavinesan M, Annadurai G (2014) Degradation
tive Red 198 during nanozerovalent iron treatment. Desalination of methylene blue using biologically synthesized silver nanoparti-
266:218–230 cles. Bioinorg Chem Appl. https​://doi.org/10.1155/2014/74234​6
Satapathy MK, Banerjee P, Das P (2013) Plant-mediated synthesis of Vijayakumar G, Tamilarasan R, Dharmendirakumar M (2012) Adsorp-
silver-nanocomposite as novel effective azo dye adsorbent. Appl tion, Kinetic, Equilibrium and Thermodynamic studies on the
Nanosci 5:1–9 removal of basic dye Rhodamine-B from aqueous solution by the
Shen J, Wu Y, Zhang B, Li F (2015) Adsorption of Rhodamine B use of natural adsorbent perlite. J Mater Environ Sci 3:157–170
dye by biomimetic mesoporous S ­ iO2 nanosheets. Clean Technol Xu B (2010) Adsorption behaviour of metal cations on gold nanoparti-
Environ Policy 17:2289–2298 cle surfaces studied by isothermal titration microcalometry. J Chin
Shukla AK, Iravani S (2017) Metallic nanoparticles: green synthesis Chem Soc 57:309–315
and spectroscopic characterization. Environ Chem Lett 15:223. Yang K, Xing B (2010) Adsorption of organic compounds by carbon
https​://doi.org/10.1007/s1031​1-017-0618-2 nanomaterials in aqueous phase: Polanyi theory and its applica-
Sulistina DR, Ratnawati R, Wiyasa IA (2014) Rhodamine B increases tion. Chem Rev 110:5989–6008
hypothalamic cell apoptosis and disrupts hormonal balance in rats. Zhao J, Xu L, Zhang T, Ren G, Yang Z (2009) Influences of nanoparti-
Asian Pac J Reprod 3(3):180–183 cle zinc oxide on acutely isolated rat hippocampal CA3 pyramidal
Tan IAW, Hameed BH (2010) Adsorption isotherms, kinetics, ther- neurons. Neurotoxicol 30:220–230
modynamics and desorption studies of basic dye on activated
carbon derived from oil palm empty fruit bunch. J Appl Sci Publisher’s Note Springer Nature remains neutral with regard to
10:2565–2571 jurisdictional claims in published maps and institutional affiliations.
Tan KB, Vakili MT, Horri BA, Poh PE, Abdullah AZ, Salamatinia B
(2015) Adsorption of dyes by nanomaterials: recent developments
and adsorption mechanisms. Separ Purif Technol 150:229–242

13