Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

Design of experiment for optimization of

nitrophenol reduction by green synthesized
silver nanocatalyst

Shanku Denrah, Mitali Sarkar ∗

Department of Chemistry, University of Kalyani, Kalyani 741 235, West Bengal, India

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

Article history: Phenol derived molecules are considered as critical pollutants in the environment and need
Received 8 August 2018 to be decontaminated to safeguard our mother Earth. This may sometimes be achieved
Received in revised form 26 by degradation using nanomaterials. Plant mediated biosynthesis of nanoparticles is truly
December 2018 encouraging for environmental safety as well as easy availability of precursor materials.
Accepted 14 February 2019 The present report demonstrates the catalytic reduction of 4-nitrophenol using silver
Available online 23 February 2019 nanoparticle, synthesized from rhizome of Cyperus Rotundus. It is characterized by UV–vis
and FTIR spectra, DLS, SEM-EDS, AFM, FESEM and TEM. The size of the particle is estimated to
Keywords: be in the range of 10–40 nm. Degradation pathway using NaBH4 and silver nanoparticle cat-
Green synthesis alyst is followed under visible light. The influence of variables such as time, dose of NaBH4 ,
Silver nanoparticle 4-nitrophenol (4-NP) and silver nanoparticle was investigated following response surface
DOE methodology. A mathematical model is built up to correlate the interactive influences of
Catalytic reduction the significant variables and the reduction. The mutual interactions of these variables are
Kinetics mapped in the design space by response surface and contour plots. The process follows a
pseudo first-order kinetic model and the activation energy was evaluated to be 53.3 kJ mol−1 .
The conversion of 4-NP–4-AP was confirmed from NMR studies.
© 2019 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.

1. Introduction
Development of green material/ process is one of the fundamental
issues of nanotechnology research. Nanoparticles, in this context, play
some key role governing the pollutants degradation for environmental
protection. Metal nanoparticles exhibit unique chemical and physical
properties due to large surface/volume ratio, and find wide range of
applications in various fields such as biomedical, pharmaceutical, cos-
metic, environmental, energy storage, catalysis, electronics etc (Saha
et al., 2017; Suvith and Philip, 2014). Generally, nanoparticles synthe-
sized via physical and chemical methods cannot avoid use of toxic
agents and/ or generation of toxic byproducts. Hence, there is a growing
need to develop eco-friendly green process and/or material that min-
imize environmental problems and offers a cost effective, eco-benign
and energy efficient alternative pathway. Synthesis of nanoparticles
using bio-resources such as microorganism (Das et al., 2014; Ali et al.,
2012), fungi (Raliya and Tarafdar, 2013; Xue et al., 2016), yeast (Niknejad
et al., 2015; Sowbarnika et al., 2018) and plant extract (Dubey et al., 2010;
Gan and Li, 2012) becomes a topic of current research.
The present work demonstrates primarily green synthesis of silver
nanoparticle (AgNp) using aqueous rhizome extract of Cyperus Rotun-
dus, characterization of the synthesized nanoparticle and optimization
of nitrophenol reduction using AgNp as catalyst. Cyperus Rotundus com-
monly known as “Nagarmotha” belongs to the Cyperaceae family and
is extensively used in India, China, Japan and Korea as a medicine
for arthritis (Halliwell et al., 1992), dysmenorrhoea, menstrual irreg-
ularities (Kilani et al., 2008), spasms, stomach disorders, candidacies,
malarial fever, inflammatory diseases (Duarte et al., 2005), as well as
in food and confectionary industries (Kumar and Khanum, 2013). The
plant extract, in nanoparticle formation, may function as reducing and
capping agent.
Nitroaromatic compounds are widely used in the synthesis of
pharmaceuticals, pesticides, explosives, dyes, industrial chemicals
(Emmanuel et al., 2014) and are the most common organic pollu-

∗
Corresponding author.
E-mail address: msarkar@klyuniv.ac.in (M. Sarkar).
https://doi.org/10.1016/j.cherd.2019.02.021
0263-8762/© 2019 Published by Elsevier B.V. on behalf of Institution of Chemical Engineers.
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504
tants found in wastewaters. Removal of such pollutants from aquatic
environment can be achieved following microbial, photocatalytic and
electro Fenton degradation, adsorption, microwave-assisted catalytic
reduction, electro coagulation and electrochemical treatment (Chiou
et al., 2013; Chang and Chen, 2009). However, high cost, low degradation
efficiency and slow kinetics make their use limited for large scale appli-
cation. In this regard hydrogenate reduction of 4-nitrophenol (4-NP) to
4-aminophenol by NaBH4 using nanoparticle as a catalyst is a feasible
option to control environmental degradation. 4-aminophenol (4-AP) is
relatively less toxic and can be easily removed via mineralization com-
pared to 4-NP (Shen et al., 2014). Moreover, it may be considered as
renewable resource as it acts as potent intermediate in manufacture
of many analgesic/antipyretic drugs and can be used as photographic
developer, corrosion inhibitor, anticorrosion lubricant and hair-dyeing
agent (Saha et al., 2010).
Several authors have demonstrated catalytic reduction of some
organic pollutants viz. nitrophenol, 2,6 DNP, picric acid and dyes using
the metallic nanoparticles (Bakhsh et al., 2018; Ali et al., 2018, Ali et al.,
2017a, 2017b, 2017c, Ali et al., 2017d; Ismail et al., 2018a,b,c; Kamal
et al., 2017a, 2017b, 2016a, 2016b. Further the biosynthesized mono and
bi-metallic nanoparticles are reported to have also the bacterial proper-
ties (Khan et al., 2018, 2017; Ismail et al., 2018a, 2018b, 2018c; Gul et al.,
2017; Ali et al., 2017a, 2017b, 2017c, 2017d). The potential of AgNp as
a colorimetric sensor for Cr(VI) and ammonia in aqueous solution is
demonstrated by Ismail et al. (2018a, 2018b, 2018c) in a recent report.
Response surface methodology (RSM), a highly efficient statistical
tool, is employed for optimization of the present catalytic reduction.
RSM generally consists of two steps viz. factorial design and central
composite design. The prominent variables are evaluated from the for-
mer and optimization of prominent/significant variables is made in the
later. It is found that among the operational variables, dose of both 4-
NP and NaBH4 as well as time are significant while dose of AgNp is not.
The reduction condition was optimized as: dose of 4-NP: 100 ␮L, dose
of NaBH4 : 300 ␮L, time: 10 min at the fixed dosing of AgNp. A math-
ematical model correlating the simultaneous as well as cooperative
influences of the significant variables and the reduction extent was
developed. The reduction extent is found to be close to that predicted
and thus favors the derived model. The response surface and contour
plots represent the interactive influences of the significant variables.
The process follows pseudo first order kinetics with activation energy
53.3 kJ mol−1 .
2. Experimental section
2.1. Materials
Anal R grade silver nitrate (AgNO3 ), sodium borohydride
(NaBH4 ), 4-nitrophenol (4-NP) and methanol were purchased
from Merck, India. Milli-Q SP ultra-pure-water (Nihon Milli-
pore Ltd., Tokyo) is used for analytical work. Glass wares are
carefully washed with acid and Millipore water.
2.2. Protocol for silver nanoparticle synthesis
Rhizome extract of crude Cyperus Rotundus was used as a
reducing/ capping agent for the AgNp synthesis. Briefly, 10 g of
dried and crushed rhizome (collected from fertile land of West
Bengal, India) was treated with 50 mL of methanol in an Erlen-
meyer flask. This yields a yellow extract which was filtered
(Whatman No. 1) and stored in a refrigerator (4 ◦ C) for sub-
sequent uses. Aqueous AgNO3 (8 mL, 1 mM; negative control)
was added to a portion of the rhizome extract (2 mL; positive
control) and kept at room temperature in the dark for 24 h.
The solution turned to reddish brown. It was centrifuged and
the sediment was collected in a watch glass. It was allowed
to dry in an air oven (60 ◦ C) whereby the crystalline particles
appeared.
495
2.3. Characterization of silver nanoparticle
The optical properties of silver nanoparticle were studied
using Fourier transformed infrared spectroscopy (FTIR; Perkin
Elmer L120–000A) and UV–vis (Shimadzu UV-2401PC) spectral
analysis. The morphological, structural as well as chemi-
cal composition was evaluated employing scanning electron
microscopy-energy dispersive x-ray spectroscopy (SEM-EDX;
FEI QUANTA FEG 250 and EVO LS 10). Hydrodynamic size,
poly-dispersity index (PDI) and zeta potential were estimated
from dynamic light scattering (DLS; Malvern, Nano-ZS) mea-
surement. The shape as well as size of the nanoparticle was
studied from atomic force electron microscopy (AFM; Veeco,
Innova), field emission scanning electron microscopy (FE-SEM;
JEOL, JSM 6700F) and transmission electron microscopy (TEM;
JEOL-JEM-2100-HR with EELS).
2.4. Catalytic activity of silver nanoparticle
Catalytic activity of AgNp was tested for the reduction of 4-NP
using NaBH4 as the reducing agent. 2 mL of aqueous solu-
tion containing 100 ␮L (5 mM) of 4-NP and 0.3 mL (0.1 M) of
NaBH4 was taken in a standard quartz cuvette. AgNp solution
(100 ␮L) was subsequently added to it. In the control experi-
ment AgNp solution was replaced with an equal amount of
Millipore water. The reaction was studied following the time-
dependent absorbance at 400 nm (corresponding to phenolate
ion) at room temperature.
2.5. Statistical design for optimization of 4-NP
reduction
In order to study the simultaneous effects of all the experi-
mental variables on the reduction and subsequently optimize
the reaction condition response surface methodology (RSM)
was applied. The protocol followed is experimental design,
modeling and optimization. The model though provides a
complex response function through combinations of variables
requires a relatively lesser experimental runs (Toles et al.,
1997). In the present report a 24 full factorial design (FFD, to
identify significant variables) and central composite design
(CCD, for optimization of significant variables) using Design-
Expert 8.0 software was employed.
The assumption for FFD is that the interaction effects
among the variables (three or more) are small compared
to the main effects and two-variables interaction effects
(Candioti et al., 2006). However, due to only two levels fac-
torial design model is somewhat restricted. Therefore, an
improved second-order model (the response surface design)
that accounts also the orthogonality function, for location of
an optimum set of experimental condition, is undertaken.
CCD comprising of variables (levels higher than two), star
points and at least one point at the center of the experimental
region (Box and Wilson, 1992) represents a good choice for its
high efficiency (Candioti et al., 2006). At the optimized condi-
tion a polynomial equation (Eq. (1)) may be built to predict the
response.

k 
k 
k

k
Y = ˇ0 + ˇi xi + ˇij xi xj + ˇii xi 2 + ε (1)
i=1 i=1 j=1 i=1
where, Y is the response (reduction percent of 4-NP), xi and xj
are variables (i and j range from 1 to k), ˇ0 is the model intercept
496 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504
Fig. 1 – (a) Solution color, (b) UV–vis, (c) FTIR and (d) Raman
spectrum.
coefficient, ˇi , ˇii and ˇij are the interaction coefficients of the
linear, quadratic and second-order terms, respectively, and ε
is the error.
3. Results and discussion
3.1. Characterization of silver nanoparticle
Formation of silver nanoparticle was primarily indicated by
the color change of the solution mixture which was subse-
quently confirmed by UV–vis spectral study. The observed
color change (Fig. 1a) is due to excitation of the surface
plasmon resonance (SPR) at a specific wavelength (Sustry
et al., 1997). The SPR absorbance is extremely sensitive
to nature, size and shape of the particles formed as well
as the inter particle distance and the surrounding media.
The SPR band appears at 458 nm in the present case
(Fig. 1b).
FTIR spectral analysis was carried out to identify the proba-
ble biomolecules of the plant extract responsible for reduction
of Ag+ ions and capping of the bio reduced silver nanopar-
ticles. In Fig. 1c absorption peaks identified at 3383 cm−1 is
attributed to the OH stretching of water available in the
crude extract. Moreover, the bands at 2923 and 2853 cm−1
are assigned for C H stretching vibration. The peaks at 1626
and 1739 cm−1 are attributed to C O stretching vibration of
keto and carboxylic group of the biomolecules (polyphenols,
flavonols, proteins and ascorbic acid residue) in CRR extract
(Sharma and Singh, 2011). Furthermore, absorption peaks at
1356 and 1056 cm−1 correspond to C C bond stretching and
C O H bending vibrations respectively. During AgNp forma-
tion the IR peaks (Fig. 1c) corresponding to the biomolecule
functionalities of CRR extract has been found to be somewhat
shifted. This may be an indication of the participation of the
functional groups for capping with silver ions. Additionally,
two new peaks appeared at 761 and 600 cm−1 indicating the
presence Ag N and Ag O binding in AgNp (Goudarzi et al.,
2016). Raman spectrum of both CRR extract and synthesized
nanoparticle was further studied (Fig. 2d) in order to find the
possible functional groups of capping agents associated in
stabilization of AgNp. The Raman spectrum of CRR extract
shows that functional groups present in the biomolecules
give characteristics strong and sharp peak at 1018 cm−1 due
to C O C stretching and C O H bending mode of vibra-
tion while the peak at 1444 cm−1 is due to C H bending and
CH2 scissoring vibration. The peaks (weak) in the region of
1630–1770 cm−1 could be attributed to C O stretching vibra-
tion of keto and carboxylic group, while those at 2934 and
2824 cm−1 may correspond to the C H stretching vibration.
Interestingly in case of AgNp the Raman peak intensities
are less. This is possibly due to strong participation of the
functional groups of the CRR extract during stabilization of
AgNp. It is also observed that the two former peaks in the
region of 1630–1770 cm−1 are shifted to the left and merged
into one in the region of 1600–1630 cm−1 indicating the par-
ticipation of C O group. A weak peak that appears in the
region of 140–170 cm−1 indicates the Ag O bond forma-
tion.
The SEM image is analyzed to study the morphology and
estimate the nanoparticle size. Fig. 2a indicates that the parti-
cles are spherical in shape with an average diameter in the
range 35–50 nm. EDX reveals the presence of different ele-
ments capped in AgNp (Fig. 2b). The strong signal around at
3 keV indicates the presence of silver. Signals corresponding to
Cl, O, N and C suggest that the silver nanoparticles are bonded
with phyto constituents of the extract. The hydrodynamic size,
PDI and zeta potential of the silver nanoparticle was obtained
from the DLS measurement. The histogram of particle size dis-
tribution is shown in Fig. 2c. It is assessed that more than 99%
particles have average size below 45 nm and only less than
1% has higher than 90–100 nm. The low poly dispersity index
(PDI) of 0.28 indicates good dispersion of the particles. Fig. 2d
represents the zeta potential of nanoparticles using water as
the dispersant. The zeta potential was found to be −33 mV.
The sign indicates that the surface is negatively charged and
magnitude signifies good stability of the synthesized particles
(Raja et al., 2015). AFM image of the AgNp (Fig. 2e) supports its
spherical nature and size approximately of 40 ± 5 nm. How-
ever, FE-SEM indicates the particles of different sizes ranging
from a few nanometers to higher values (Fig. 2f).
The TEM images at different magnifications (50, 20 and
10 nm) are shown in Fig. 3a–c. The spherical nature of sil-
ver nanoparticle was further confirmed. The average particle
diameter of about 10 ± 2 nm is obtained from TEM. The image
of selected areas of electron diffraction (SAED) pattern for sin-
gle particle shows concentric rings favoring highly crystalline
nature of the nanoparticles (Fig. 3d).
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504 497

Fig. 2 – (a) SEM, (b) EDX, (c) DLS, (d) Zeta potential, (e) AFM and (f) FE-SEM.

Fig. 3 – TEM at (a) 50, (b) 20, (c) 10 nm and (d) SAED image.
498 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504
Table 1 – Operational variables with symbol and range
for (24 ) FFD.
Variable Range
Real Coded −1 +1
Dose of 4-NP (␮L) A 50 150
Dose of NaBH4 (␮L) B 100 500
Dose of AgNp (␮L) C 50 150
Time (min) D 1 19
Fig. 4 – Pareto chart.
3.2. Optimization of the reaction condition using RSM
3.2.1. Scrutiny of variables from Pareto chart and building
of FFD
The primary consideration of FFD is that it includes all possible
combinations of variables across all the levels [(higher, +1) and
(lower, −1)] and assumes that the sparsity-of-effects principle
is valid. The effects of operating variables (time, dose of 4-NP,
NaBH4 and AgNp) on the reduction efficiency were assessed
from a (24 ) FFD model. The range of operational variables with
symbol/code is selected and is presented in Table 1. The cat-
egory of variables (significant and not significant), through
the main effects, was scrutinized at 95% confidence inter-
val (p = 0.05) from the Pareto chart presented by bar (Fig. 4).
The length of the bar is proportional to the absolute value of
the estimated effects of the variable and indicates the extent
of influence of variable on the response. The bars above the
upper threshold t-limit (Bonferroni) are significant while those
below the lower threshold of the t-limit are insignificant. How-
ever, bars in between Bonferroni limit and the lower t-limit
may possibly be significant. Among the four variables studied
only three i.e., time, dose of NaBH4 and 4-NP are significant
(above upper t-limit 3.78519) and have prominent influence
on the response (reduction percent). The effect of AgNp dose
is not significant (below lower t-limit 2.22814). The hollow bar
represents the influence of single variable and the solid bar
the multiple or combined influences of the variables. Aim-
ing to identify the effect of each single variable the solid bars
are not considered. Moreover the nature of effect (positive
or negative) of each variable on the response (reduction per-
cent) is assessed from the Pareto chart. The dose of NaBH4
and time are found to impart positive effect while the dose
of 4-NP imparts negative effect. As the dose of the reducing
agent increases and the time progresses the extent of reduc-
tion is expected to increase. Similarly with high concentration
of 4-NP and fixed dose of NaBH4 the extent of reduction will
become less.
The percentage contribution of the variables to the
response follows the order: time (D, 65.57%) > 4-NP dose (A:
12.36%) > NaBH4 dose (B: 11.82%) > AgNp dose (C: 2.51%). Thus
D has the most prominent influence while C the least on the
reduction. This signifies the catalytic role of AgNp for initiating
the reduction. Accordingly, the concentration of catalyst was
kept constant for further study (100 ␮L) and the optimization
was performed with time, dose of NaBH4 and 4-NP to achieve
maximum efficiency.
3.2.2. Optimization by CCD
In order to model 4-NP reduction, in the present case, a sec-
ond order CCD matrix is built with three significant variables
keeping the fourth one constant at some predetermined point.
Each variable was coded at five levels [very low (−␣), −1 (low),
0 (central), +1 (high) and very high (+␣)]. The matrix layout is
presented in Table 2a. The design consists of center, axial and
factorial points of significant variables. The total number of
experimental data points (E.D.P) in the design is found to be
20 as evaluated from the Eq. (2),
E.D.P = 2k (factorial) + 2k(axial) + 6(center) (2)
where, k (=3) denotes the number of significant variables.
A second order polynomial in coded terms (Eq. (3)) cor-
relating significant variables and the response (Y) is built
as,
Y = 89.01744 − 9.86666A + 21.79289B + 32.32938D
− 0.015AB − 0.4225AD + 6.765BD − 11.7365A2
− 15.8129B2 − 22.3972D2 (3)
The significance and adequacy of the model was tested
from analysis of variance (ANOVA) and Fisher’s F-parameter
(Dil et al., 2015) and is presented in Table 2b. The F-value
compares between the mean square of the model and the
residuals. The model F-value of 11.19 implies that the present
model is significant suggesting that there is only a 0.07%
chance for the model F-value to occur due to noise. Values
of ‘Prob > F’ less than 0.0500 indicate model terms are signifi-
cant, whereas those greater than 0.0500 are insignificant. Here
the significant model terms are found to be B, D, A2 , B2 and D2 .
Quality of the model developed is determined from R2 (regres-
sion coefficient). The value of R2 is found to be 0.9179, being
close to 1.000 favors the model and suggests 91.79% accuracy.
The adjusted R2 value is found to be 0.8359, which is close to
that of the R2 . Thus the present design model is considered to
be favorable. Moreover, the adequate precision is found to be
10.835. As an adequate precision value (an estimate of the sig-
nal to noise ratio) greater than 4 designate the design model
significant (Asfaram et al., 2015), the present model predict-
ing reduction of 4-NP is well characterized and can be used to
navigate the design space.
The mutual interaction effects between each pair of vari-
ables and their optimum value were elucidated through 3D
surface and contour plots keeping the third parameter static
at the optimum value. Fig. 5(a) and (b) represents interaction
between dose of 4-NP and NaBH4 (time fixed), Fig. 5(c) and
(d) represents the interaction between dose of 4-NP and time
(dose of NaBH4 fixed) and Fig. 5(e) and (f) represents interac-
tion between dose of NaBH4 and time (dose of 4-NP fixed). The
nature of the surface and contour plots suggest some definite
and profound effects of all the three experimental variables
on the reduction of 4-NP. It is also evident from the F-value
(1.44) that the interaction between the dose of NaBH4 and
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504 499

Table 2 – CCD.
(a) Matrix layout

Sl. no. Nature Variable Reduction (%)

Real Coded

4-NP dose NaBH4 dose Time A B D

1 Center 100 300 10 0 0 0 93.56
2 Center 100 300 10 0 0 0 95.25
3 Factorial 150 100 1 1 −1 −1 0.22
4 Factorial 50 500 19 −1 1 1 92.25
5 Factorial 50 500 1 −1 1 −1 31.21
6 Factorial 150 500 19 1 1 1 85.22
7 Factorial 50 100 1 −1 −1 −1 5.60
8 Center 100 300 10 0 0 0 90.56
9 Factorial 150 100 19 1 −1 1 32.52
10 Center 100 300 10 0 0 0 90.23
11 Factorial 50 100 19 −1 −1 1 50.25
12 Factorial 150 500 1 1 1 −1 15.21
13 Axial 100 50 10 0 −1.68 0 20.52
14 Axial 100 300 0.5 0 0 −1.68 2.50
15 Axial 100 300 25.13 0 0 1.68 92.5
16 Center 100 300 10 0 0 0 94.52
17 Axial 200 300 10 1.68 0 0 15.54
18 Axial 100 636.35 10 0 1.68 0 91.56
19 Center 100 300 10 0 0 0 89.25
20 Axial 25 300 10 −1.68 0 0 90.51

(b) ANOVA

Parameter Sum of squares dfa Mean square F-Value p-Value Prob > F

Block 133.373 1 133.373

Model 25552.0 9 2839.12 11.1922 0.0007
A 1291.11 1 1291.11 5.08979 0.0505
B 5574.04 1 5574.04 21.9737 0.0011
D 11271.1 1 11271.1 44.4324 <0.0001
AB 0.001800 1 0.001800 7.10E-06 0.9979
AD 1.42805 1 1.42805 0.005630 0.9418
BD 366.121 1 366.121 1.44330 0.2603
A2 2412.62 1 2412.62 9.51093 0.0131
B2 2521.68 1 2521.68 9.94086 0.0117
D2 4522.79 1 4522.79 17.8295 0.0022
Residual 2283.01 9 253.668
Lack of Fit 2251.56 5 450.313 57.2753 0.0008

a
df = degree of freedom.

time (Fig. 5(e) and (f)) is much stronger than the other two with and without catalyst (silver nanoparticle) with progress
interactions. of time at three different temperatures was presented. The
data was fitted to the first order kinetic plots (Fig. 7b) following
the Eq. (4)
3.3. Catalytic activity of silver nanoparticle

The reduction of 4-nitrophenol to 4-aminophenol (Fig. 6) was ln(At /A0 ) = k1 t + C (4)

conducted using NaBH4 (reducing agent) and silver nanopar-
ticle as the catalyst. The reduction pathway was monitored
through spectral study in the visible region. Initially 4-
nitrophenol displays a pale yellow color in water having max
at 317 nm. On addition of NaBH4 the peak shifts to 401 nm.
Such red shift of absorption peak is due to the formation of 4-
nitrophenolate ion which displays green color. With progress
of time the peak at 401 nm diminishes with simultaneous
appearance of a new peak at 296 nm (Fig. 6). This is due to the
reduction of a nitrophenolate ion (green color) to aminophenol
(colorless). Addition of silver nanoparticle to the reaction mix-
ture of 4-nitrophenol and NaBH4 prompted the reduction that
completes within 10 min (Fig. 6). In absence of silver nanopar-
ticle the reduction did not take place even after 30 min of
interaction. In Fig. 7a the reduction pattern of 4-nitrophenol
where, At and A0 represent the absorbance at time t and time
t = 0 respectively and C is a constant. The slope of the plot rep-
resents the first order rate constant (k1 ) and is calculated to
be 0.159, 0.293 and 0.323 min−1 at temperature 293, 298 and
303 K respectively. The increase of k1 indicates an accelera-
tion of reaction with increase of temperature. It is suggested
that reduction of 4-nitrophenol occurs due to interaction of
the reactants over the surface of AgNp, that probably acts as
the electron transfer mediator and hydrogen carrier.
The activation energy (Ea ) for the reduction can be calcu-
lated using the well known Arrhenius equation
lnk1 = −Ea /RT + lnA (5)
500 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504

Fig. 5 – (a, c, e) response surface and (b, d, f) contour plots.

Fig. 8 – Correlation of actual and predicted reduction.

Fig. 6 – UV–vis spectral profile. (For interpretation of the
references to color in the text, the reader is referred to the
web version of this article.)
where, R is the universal gas constant (8.314 JK−1 mol−1 ), T
is the reaction temperature and A is Arrhenius parameter. A
plot of ln k1 against 1/T (Fig. 7c) gives a straight line with a
slope equals to –Ea /R. The activation energy for the reduction
is estimated to be 53.3 kJ mol−1 .
3.4. Validation of the experimental results
In order to investigate the model validity the actual (experi-
mental) reduction (AR %) and predicted (model) reduction (PR
%) was compared (Fig. 8). All the values are found to be well cor-
related over the range and the AR (95.5%) is found to be close
to that of PR (120%), again supporting the model validity. Each
experiment was repeated at least thrice and the mean value
was taken. The model value was evaluated from the following

Fig. 7 – (a) Reduction pattern, (b) first order kinetic plots and (c) Arrhenius plot.
 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504
Fig. 9 – 1 H NMR spectra of (a) 4-NP, (b) intermediate and (c) end product.
second order polynomial equation (in real term).
Reduction% = −59.6547 + 0.750524 × 4 − NP + 0.308424
× NaBH4 + 8.088751 × Time + 1.50E-06 × 4-NP × NaBH4
− 0.00094 × 4-NP × Time + 0.003758NaBH4 × Time
− 0.00469 × 4-NP2 − 0.0004 − NaBH4 2 − 0.27651 × Time2 (6)
In an aim to confirm the reduction pathway and identify
the end product 1 H NMR spectral investigation was made.
Fig. 9 indicates the 1 H NMR spectra of (a) 4-NP (parent), (b)
intermediate reaction product after 5 min and (c) end product
purified by silica gel column chromatography. The two dou-
blets appear in the region 6.8–8.3 ppm are due to aromatic
H of 4-NP (a). In the studied region the hydroxyl protons do
not appear in the spectrum. The characteristics peaks at 4.365
and in the region 6.397–6.479 ppm correspond to amine H and
aromatic H respectively of 4-AP in the final product (c). How-
ever, the peaks due to both 4-NP and 4-AP are observed in
the intermediate (b). This confirms the conversion of 4-NP to
4-AP during the catalytic reduction. The conversion yield is
estimated to be around 95%.
501
Finally, the performance of the AgNp as the catalyst
for 4-NP reduction is compared with other reported metal
nanoparticles (Table 3). The performance of the nanoparticle
synthesized in the present method is found to be comparable
and sometimes even better.
4. Conclusion
The silver nanoparticle synthesized using the extract of rhi-
zome of Cyperus Rotundus, a tropical plant is found effective
for catalytic reduction of 4-NP. The particle was characterized
and its nanonature was confirmed by DLS, SEM-EDS, AFM,
FESEM and TEM study. Statistical optimization of the operation
using response surface methodology was made to maxi-
mize the reduction performance. Factorial design shows that
among the different variables time, dose of 4-NP and NaBH4
were found to have significant influence while dose of AgNp
have non-significant influence on the reduction. A model cor-
relating the multiple interactions among the variables and
the reduction extent was built to predict the efficiency of
the process following central composite design. The mutual
and interactive influence of the variables is mapped in the
design space. The reduction data was fitted to the pseudo
first order kinetic equation and activation energy is estimated
502 Chemical Engineering Research and Design 1 4 4 ( 2 0 1 9 ) 494–504

Table 3 – Comparison of reduction performance with reported metal nanoparticles.

Nanoparticle Time (min) Rate constant (k1 ) (min−1 ) Reference

AgNp 12 0.159 Muthu and Priya (2017)

Silver/iron oxide composite 10–40 0.185 Chiou et al. (2013)
AuNp 10 0.100 Chang and Chen (2009)
Mono and bimetallic nanoparticles (Pt/Cu, 20a 0.120b Pozun et al. (2013)
Pd/Cu, Pd/Au, Pt/Au, and Au/Cu)
AgNp 400–1500a (1.53–17.04) × 10−3b Kästner and Thünemann (2016)
AuNp 780–1380a (0.33–0.8) × 10-3b Seo et al. (2017)
AuNp 360a 0.59 Shen et al. (2016)
CoNp 8–12 0.210 Mondal et al. (2017)
AgNp 20 – Prasad et al. (2015)
AgNp, AuNp 11 4.06 × 10−3 & 9.2 × 10−3 b Gangula et al. (2011)
AgNp 12 2.21 × 10−3 b Safari et al. (2016)
CS/zinc phthalocyanine (ZnPc-CS) 7–60 0.0238–0.3632 Ali et al. (2017a,b,c,d)
nanocomposite coated with metal ion
AgNp 36 – Bello et al. (2017a,b)
AgNp 4c – Bello et al. (2017a,b)
Chitosan coated cotton cloth supported 10 0.2937 Ali et al. (2017a,b,c,d)
zero-valent nanoparticles
(M◦ = Fe/CC CH)
Cu nanoparticles loaded CS-CMM 12 2.1 × 10−3 b Haider et al. (2016)
(Cu/CS-CMM)
Ni-nanoparticles-CS composite 9–16 – Kamal et al. (2016a,b)
Ag-nanoparticle loaded CH-FP (Ag/CH-FP) 1740a 3.9 × 10−3 Ahmad et al. (2016)
PES-CA-CB spheres supported Cu 60 – Khan et al. (2016)
(Cu@PES-CA-CBspheres) nanoparticles
AgNp 8–10 0.293 This work

a
sec.
b
sec−1 .
c
reaction initiated.

to be 53.3 kJ mol−1 . The conversion of 4-NP to 4-AP was con-
firmed from NMR studies. The performance of the synthesized
nanomaterial is comparable and even better than some of the
reported nanomaterials. The quick reduction time and green
synthetic pathway make the present AgNp catalyst is a good
choice for decontamination of nitrophenol, a potential organic
pollutant from water.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors sincerely acknowledge the assistance received
under UGC-SAP, DST-FIST and DST-PURSE program, Govt. of
India. One of the authors (SD) is thankful to KU for provid-
ing the research fellowship. The authors are thankful to Prof.
Tarakdas Basu, Department of Biochemistry & biophysics, KU
for DLS and AFM studies. Arunangshu Biswas, IIIT, Hyderabad
is duly acknowledged for Raman studies. The instrumen-
tal facilities availed from Nanoscience centre, CU, are duly
acknowledged.
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