Journal of Environmental Management 316 (2022) 115292

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Journal of Environmental Management

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

The identification of byproducts from the catalytic reduction reaction of

4-nitrophenol to 4-aminophenol: A systematic spectroscopic study
Naveen Kumar Reddy Bogireddy a, **, Yetzin Rodriguez Mejia b, Tejraj M. Aminabhavi c, d,
Victor Barba e, Raul Herrera Becerra a, A. David Ariza Flores f, Vivechana Agarwal g, *
a
Instituto de Física, Universidad Nacional Autónoma de México (UNAM), Ciudad de México, C.P., 04510, Mexico
b
Facultad de Química, Universidad Autónoma Del Estado de México, Paseo Colón esq, Paseo Tollocan s/n, Toluca, Estado de México, C.P., 50120, Mexico
c
School of Advanced Sciences, KLE Technological University, Hubballi, Karnataka, 580031, India
d
School of Engineering, University of Petroleum and Energy Studies, Dehradun, Mohali, 248 007, India
e
Centro de Investigaciones Químicas-IICBA, Universidad Autónoma Del Estado de Morelos, Av. Universidad 1001, Col. Chamilpa, Cuernavaca, Morelos CP, 62209,
Mexico
f
CONACyT-Universidad Autónoma de San Luis Potosí, Karakorum 1470, Lomas 4ta Secc, San Luis Potosí, S.L.P., 78210, Mexico
g
Centro de Investigación en Ingeniería y Ciencias Aplicadas, UAEM, Av. Univ. 1001, Col. Chamilpa, Cuernavaca, Morelos, 62209, Mexico

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

Keywords: Acetaminophenol, commonly recognized as paracetamol (considered safer than aspirin) is formed by nitration of
4-Nitrophenol phenol (4-nitrophenol (4-NP)) for its conversion to 4-aminophenol (4-AP), followed by the acetylation for the
Benzoquinone final product. As 4-NP is an intermediate product in acetaminophenol (paracetamol) production from phenol the
Hydroquinone
dynamic analysis of acetylation of amine group is important. This study focuses on the feasibility of spectroscopic
Sodium borohydride
Green synthesis
studies to monitor the removal of 4-NP using sodium borohydride (NaBH4) probe reaction in the presence of
Bimetallic nanoparticles silver, gold, and bimetallic Ag/Au nanoparticles. UV–visible absorbance and fluorescence spectroscopy mea­
surements reveal the formation of 1,4-benzoquinone (BQ), hydroquinone (HQ), and phenol (Ph) as the final
products, in addition to the formation of typically reported 4-AP. The intermediates of NaBH4 seem to play a
significant role in the formation of BQ, which converts to HQ in the basic medium followed by the formation of
phenol in an acidic medium. Complete kinetic analysis with respect to spectroscopic studies of the standard
compounds is presented. Similar results were obtained with 4-NP spiked river and seawater samples. The present
findings may lead to catalytic benchmarking that can differ from most of the current practices and highlight the
importance of adopting a holistic approach towards the fundamental understanding of 4-NP catalytic reduction
that must take into account the concentration of NaBH4 and pH interdependencies.

1. Introduction well as pharmaceuticals such as analgesics and antipyretics. (Bogireddy

In recent days, proper purification of contaminated water with
several industrial effluents has been one of the major topic of research all
over the world (Hadi et al., 2020, 2021a, 2021b; Taheri et al., 2020;
Khajeh et al., 2021; Amin et al., 2021; Rafiei et al., 2021). Among several
nitro group contaminants, 4-Nitrophenol (4-NP) and its derivatives have
been widely used to manufacture the synthetic dyes, paints, corrosion
inhibitors, wood preservatives, herbicides and insecticides (Hadi et al.,
2021a, 2021b; Shen et al., 2017; Neal et al., 2019; Xiong et al., 2019), as
et al., 2020; Abd Razak and Shamsuddin, 2020) Unfortunately, high
concentrations (>60 μg/L, as per U.S. Environmental Protection Agency
(EPA)) of 4-NP in drinking water can cause irreversible damage to the
environment and human health due to its toxicity and refractory
pollutant nature. (Neal et al., 2019; Zhang et al., 2014) The reduction of
4-NP to 4-aminophenol (4-AP) has a significant implication from the
view point of pollution reduction as 4-AP is a compound with a rela­
tively low degree of toxicity (Neal et al., 2019; Abd Razak and Sham­
suddin, 2020).

Abbreviations: 4-NP, 4-nitrophenol; 4-AP, 4-aminophenol; NP, Nanoparticle; Ag, Silver; Au, Gold; BQ, 1,4-benzoquinone; HQ, Hydroquinone; Ph, Phenol; NaBH4,
Sodium borohydride; 4-NP–, 4-nitrophenolate ion; IT, Induction time; CIT, Citrate capped; EPA, Environmental Protection Agency; CAS, Coffea arabica seed powder.
* Corresponding author.
** Corresponding author.
E-mail addresses: naveenbogireddy@fisica.unam.mx (N.K. Reddy Bogireddy), vagarwal@uaem.mx (V. Agarwal).

https://doi.org/10.1016/j.jenvman.2022.115292
Received 29 September 2021; Received in revised form 20 April 2022; Accepted 9 May 2022
Available online 20 May 2022
0301-4797/© 2022 Elsevier Ltd. All rights reserved.
N.K. Reddy Bogireddy et al.
The catalyst mediated reduction of 4-NP to 4-AP using sodium
borohydride (NaBH4) has emerged as an essential model reaction for
evaluating the catalytic activity in aqueous media (Zhang et al., 2014;
Zhao et al., 2015). Its importance is due to the ease in real-time moni­
toring of the reaction through the real-time spectroscopic changes in
signal decay during absorbance of 4-NP (400 nm) and appearance of a
new peak (300 nm) corresponding to 4-AP (Neal et al., 2019; Aditya
et al., 2015). However, the use of other reducing agents has also been
reported, which includes ascorbic acid (Li et al., 2015), formic acid
(Pradhan et al., 2002), hydrogen gas, and tetramethyl disiloxane,
(Fountoulaki et al., 2014) of which only formic acid and tetramethyl
disiloxane could reduce 4-NP (Strachan et al., 2020).
Recently, several attempts have been made to reduce 4-NP to 4-AP,
employing metal nanoparticles as catalysts, such as Pd (Menumerov
et al., 2016; Islam et al., 2018), Ag (Arora et al., 2018; Khan et al., 2020),
Pt, (Bogireddy et al., 2020; Pandey and Mishra, 2014) Cu (Jiang et al.,
2018), and Au (Shen et al., 2017; Neal et al., 2019; Bogireddy et al.,
2018) obtained via chemical and green synthesis techniques (Rath et al.,
2018; Nasrollahzadeh et al., 2018a, 2018b, 2018c; Xu et al., 2020).
Although the reaction with NaBH4 has been widely used to compare the
4-NP reduction reaction time of the catalysts, better insights are needed
about the mechanisms, due to different interpretations of the induction
time (IT) and reaction mechanism. (Strachan et al., 2020; Menumerov
et al., 2016) Pal et al. (Pradhan et al., 2002), used the chemically syn­
thesized AgNPs to reduce 4-NP using NaBH4. The authors attributed the
IT to the surface re-reduction of AgNPs, in addition to the observation
that IT in oxygen atmosphere is higher than the reaction subjected to N2
atmosphere. Although Neretina et al. (Menumerov et al., 2016) dis­
agreed to this approach, it was affirmed that the dissolved oxygen is
responsible for IT and forms an additional 4-nitrophenolate ion (4-NP–)
when the dissolved oxygen increased. They further defined IT as the
time interval necessary for the dissolved oxygen level to fall below a
critical value (Ccr). It was shown that the end of IT corresponds to the
time when the dissolved oxygen content decreases below Ccr and the
catalyst is independent of BH−4 concentration as the rate at which BH−4
scavenges dissolved oxygen determines the duration of IT (Neal et al.,
2019). However, the proposed hypothesis involved the forward and
reverse reactions competing between 4-NP– and 4-AP with the backward
predominant response through oxidation of 4-AP to 4-NP– until the
dissolved oxygen reaches Ccr, and these studies did not achieve complete
understanding of the mechanism. Neretina et al. (Menumerov et al.,
2018) evidenced that leaching of supported catalysts leads to the for­
mation of heterogeneous unsupported catalysts with considerably high
catalytic activity toward the reduction of 4-NP by BH−4 . Another re­
ported factor is the strong effect of NP ligands on 4-NP reduction and is
mainly due to the inclination of BH−4 to displace ligands on the catalytic
surfaces whose impact depends on the presence of the dissolved oxygen
in the aqueous reagents. In addition, it has been shown that tightly
bound ligands give rise to an IT-like feature that is only observable when
the reagents are free of dissolved oxygen (Neal et al., 2020). Several of
the proposed mechanisms do not consider intermediates, side reactions,
or by-products formed during and after the reaction. Hence, in order to
establish better understanding of the mechanism, there is a need to focus
on the NaBH4 intermediates and their interaction with 4-AP along with
the possible concentration of boron present in the final reaction product.
Real time measurements for the determination of percentage conversion
of 4-NP to 4-AP at different intervals can provide additional information
about the reaction kinetics.
On the other hand, bimetallic nanoparticles composed of two
different metals exhibit improvement over monometallic nanoparticles
by showing the enhancement in catalytic properties. The addition of the
second metal allows control of stability, catalytic activity, and selectivity
of the catalyst (Can, 2011). The addition of another metal causes al­
terations in the electron density of the system and metal–metal bond
length that may lead to improved catalytic activity, including geometry
effects (Can, 2011; Chu et al., 2019; Li et al., 2021; Wang et al., 2021).
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Journal of Environmental Management 316 (2022) 115292
Herein, we present the results of an investigation that delineates the
influence of two widely used techniques, such as chemical (Turkevich)
and green (used Coffea arabica seed powder (CAS) bagasse) synthesis for
the catalytic reduction of 4-nitrophenol. It is shown that citrate-capped
bimetallic nanoparticles (CIT-AuAgNPs) showed the faster catalytic
reduction of 4-NP to 4-AP than CAS bimetallic nanoparticles (CAS-
AuAgNPs). Apart, CAS-AuAgNPs produces more 4-AP (30.6%)
compared to CIT-AuAgNPs (24.2%). Further, the intermediates of
NaBH4 influence the conversion of 4-AP to 1,4-BQ later HQ. The ob­
tained final products demonstrate that the mechanistic of NaBH4 in­
termediates influence, and mimicking experiments were performed to
understand role of pH using standard chemical compounds.
2. Experimental section
2.1. Materials
In this work, Coffea arabica seed powder was bought from local su­
permarket, Oaxaca state, Mexico. Sodium citrate, gold chloride
(HAuCl4.3H2O), silver nitrate (AgNO3), 4-nitrophenol (4-NP, spectro­
photometric grade), 4-aminophenol (4-AP), 1,4-benzoquinone (1,4-BQ),
hydroquinone (HQ), phenol, boric acid and sodium borohydride
(NaBH4, 99.99%) were purchased from Sigma-Aldrich, and utilized as
received.
2.2. Coffea arabica seed powder bagasse extract preparation
For preparing CAS extract, 0.2–16 g/L of the sun-dried CA powder
residue obtained from a solution (in distilled water) of CA seed powder
(10 g/L) was kept at 80 ± 20C for 30 min using agitation-controlled
heating mantle. Further, the CAS extract was cooled down to ambient
temperature and filtered using a syringe filter.
2.3. Synthesis of nanoparticles using Coffea arabica seed powder bagasse
extract
Initially, freshly prepared and filtered CAS extract was kept on a
heating mantle with continuous agitation at 80 ± 2 0C. After reaching
the required temperature, one mM of Ag+ salt solution was added to the
extract in a 1:5 volumetric ratio and kept for 10 min. Gradual reduction
of Ag+ and the formation of AgNPs (CAS-AgNPs) confirmed through
UV–visible absorbance spectrophotometry. A similar procedure was
used to fabricate gold nanoparticles (CAS-AuNPs).
In a similar synthesis for bimetallic (Ag–Au) nanoparticles, 1.0 mL of
1 mM of Ag+ and 0.5 mL of Au+3 (1 mM) salt solution was added
simultaneously to the boiling 7.5 mL of 4 g/L CAS extract solution and
kept for 10 min. Immediate reduction of metal ions and the formation of
CAS-AuAgNPs was visually observed through a gradual color change of
the reaction solution, which turned from light yellow to wine and later
violet. A similar synthesis procedure was used to fabricate citrate sta­
bilized bimetallic nanoparticles (CIT-AuAgNPs) by replacing CAS
extract with 22.0 mg of sodium citrate. The optimization in terms of
synthesis parameters (concentration and relative proportion of CAS
extract/metal salt) was performed to obtain the metal nanoparticles
under optimal conditions (for details refer to ESI (Figs. S1-S3)).
2.4. Characterization
X-ray diffraction (XRD) analysis of the powder samples was carried
out in a Bruker D8 Advance eco diffractometer, using CuKα (λ = 1.5406
Å) radiation. The size, morphology, and composition of the bimetallic
nanoparticles were studied using high-resolution transmission electron
microscopy (HR-TEM) images, acquired using JEOL JEM 2100. UV–vi­
sible absorbance spectra of the colloidal CAS-AgNPs, CAS-AuNPs, CAS-
AuAgNPs, and CIT-AuAgNPs have been recorded in a dual-beam Per­
kin-Elmer Lambda 950 spectrophotometer. The Zeta potential of the
N.K. Reddy Bogireddy et al.
Fig. 1. TEM, HR-TEM and FFT analysis of CAS-AuAgNPs (a) and CIT-AuAgNPs (b), with their respective pictorial representation of the interplanar arrangement in
fabricated bimetallic structure.
nanoparticles was determined using the Malvern zeta sizer (Model Nano
ZS). The surface characteristics of the synthesized nanoparticles were
analyzed through a Varian 660-IR FT-IR spectrophotometer. The same
absorbance and Cary eclipse fluorescence spectrophotometers were
utilized for real-time monitoring of the reduction of 4-nitrophenol using
nanoparticles.
2.5. Catalytic reduction of 4-nitrophenol (4-NP)
Separate sets of experiments were carried out as a function of catalyst
type (CAS-AgNPs, CAS-AuNPs, CAS-AuAgNPs, and CIT-AuAgNPs),
catalyst (300–500 μL), and NaBH4 (10–300 mM) concentrations.
Initially, one mM of 4-NP was dispersed into 2 mL of DI water and mixed
with 1 mL of freshly prepared 10 mM NaBH4 to form a 4-nitrophenolate
ion (4-NP-) mixture solution. Subsequently, added 0.5 mL of a catalyst to
the earlier mixture. The 4-NP- reduction process monitored the change
in the absorption spectra at λmax = 400 nm of the solution.
To monitor the real-time absorbance (λmax = 400 nm) and fluores­
cence (λex = 300 nm) changes during the 4-NP reduction (using fabri­
cated nanoparticles), the procedure stated above is carried out as a
function of the concentration of catalyst and NaBH4 at ambient condi­
tions. For better understanding of final product formation during 4-NP
reduction, the system was studied as a function of the pH of the 4-AP
solution (2.5–10.5).
A similar above-stated procedure was implemented to investigate the
possible reusability of the CAS-AuAgNPs as recovered catalysts after
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Journal of Environmental Management 316 (2022) 115292
removing the 4-nitrophenol in marine water samples. The re-collected
catalyst was washed 3 times by centrifugation using distilled water.
Also maintained the amount of 4-NP and NaBH4 solutions used for the
recyclability tests.
3. Results and discussion
As can be noticed from the TEM, HR-TEM, and FFT images presented
in Fig. 1 (b and c), both CAS extract and modified Turkevich mediated
bimetallic nanoparticles contain well-dispersed particles of average
sizes very close to each other (12 ± 3 nm and 13 ± 3 nm). While the HR-
TEM image of CAS-AuAgNPs shows the presence of two different lattices
(A-Ag and B–Au), the corresponding FFT analysis exhibits the formation
of two distinct crystallinities, which may be due to the formation of
bimetallic NPs as one particle (shown schematically in the inset of the
figure). Further, the measured d-spacing of inter planes values are 0.238
nm (A, upper part in the HRTEM) and 0.251 nm (B, lower part in the
HRTEM), which closely matches with the d-spacing of CAS-AgNPs and
CAS-AuNPs. It confirms the successful formation of bimetallic NPs using
CAS extract. Similarly, HR-TEM imaging and FFT analysis of the fabri­
cated CIT-AuAgNPs exhibited the formation of disordered interplanar
crystal structures.
The d-spacing measurement also proved continuous differences in
the values, confirming the formation of disordered bimetallic structures
(shown in the inset of Fig. 1). The obtained bimetallic systems are found
to be different from the already reported literature on the green
N.K. Reddy Bogireddy et al.
Fig. 2. UV–visible absorption spectra for the reduction of 4-nitrophenol using (a, b) CAS-AuAgNPs and CIT-AuAgNPs at 200x NaBH4 concentration, and (c) the
production of 4-aminophenol from 4-nitrophenol after the reaction completion, (d) time-dependent fluorescence spectra for the production of 4-aminophenol during
the 4-NP reduction reaction.
synthesis of bimetallic Au–Ag nanoparticles using various plant extracts,
such as Silybummarianum, Piper pedicellatum, Solidago canadensis,
Pulicariaundulata and other (Ivar, 1917).
The crystallinity of the fabricated bimetallic nanoparticles using the
CAS and sodium citrate process, analyzed by recorded XRD patterns. As
expected, (Ivar, 1917) apart from similar XRD patterns for both silver
and gold (Fig. S4), the diffraction patterns of the CAS-AuAgNPs revealed
a broad and well-defined peak around 38.2◦ and 44.4◦ which correspond
to the (111) and (220) lattice planes of metallic silver or gold in fcc
phase (JCPDS # 04–0783). The broad pattern indicates the successful
formation of bimetallic (Ag–Au) nanoparticles. Similarly, XRD patterns
of the CIT-AuAgNPs (Fig. S4) revealed diffraction peaks at around 38.2◦
and 46.6◦ , which correspond to the same lattice planes of fcc silver/gold.
The observed slight variations in higher angle shift of the (220) lattice of
the peak position indicate shrinkage or expansion of interplanar spacing
of CIT-AuAgNPs, and it closely matched with the TEM results.
To know the surface functional groups present on the bimetallic
nanoparticles, FT-IR spectroscopy was performed. Similar, spectra were
observed in both CAS-AuAgNPs and CIT-AuAgNPs, as shown in Fig. S5
(a). Various distinctive absorption bands were observed, such as 3650
cm− 1, 2941 cm− 1, 1390 cm− 1, 1287 cm− 1, and 750-920 cm− 1which
refer to the presence of hydroxyl (O–H), C–N stretching vibrations, C– –O
stretching, C–C stretching, and aromatic C–H bending, respectively.
Further, the surface charge of the synthesized nanostructures was
recorded using zeta potential studies (Fig. S5 (b)). The obtained surface
charges for CAS-AgNPs, CAS-AuNPs, CAS-AuAgNPs, and CIT-AuAgNPs
are − 36 ± 2 mV, − 23 ± 2 mV, − 25 ± 3, and 27 ± 2 mV, respectively.
From these results, we can conclude that the obtained nanostructures
were highly stable due to the presence negative surface charge.
4
Journal of Environmental Management 316 (2022) 115292
As per our previous report (Bogireddy et al., 2018), apart from the
presence of phenolic compounds, C– – O and –OH stretching bands are
present in the coffee arabica extract. After the termination of the re­
actions, the intensity of C–
– O stretching and –OH stretching band de­
creases significantly, indicating their active participation in the
reduction and stabilization of gold/silver to form AuAgNPs.
3.1. Effect of freshly prepared NaBH4 concentration in the 4-NP
reduction reaction
The reduction of 4-nitrophenol was tested using CAS-AgNPs, CAS-
AuNPs, CAS-AuAgNPs, and CIT-AuAgNPs by NaBH4. A visual color
change of 4-NP (light yellow) to 4-nitrophenolate ion (4-NP-, bright
yellow) was observed in the presence of NaBH4 along with a redshift of
the absorption peak from 317 (broad) to 400 nm (Fig. S6). Removing H2
by addition of NaBH4 to 4-NP results in the formation of the 4-NP-. On
the other hand, there is no further reaction observed in the absence of
catalyst into the reaction solution, which shows that only NaBH4 does
not take part in the 4-NP reduction process. Fig. 2 (a and b) and Fig. S7
indicate the real-time absorption spectra during the catalytic reduction
of 4-NP in the presence of the four fabricated catalysts by NaBH4 (200
times). As the strong absorption peak of 4-NP- disappears within 90s in
the presence of the Tr-AuAgNPs catalyst (it is faster reaction compared
with other CAS fabricated nanoparticles in this work), a simultaneous
evolution of a new absorption peak corresponding to 4-AP (300 nm)
(Bogireddy et al., 2018) is observed.
Moreover, a blue shift of 28, 30, 31 and 15 nm in the LSPR absor­
bance peak position was observed in CAS-AuNPs, CAS-AuNPs, CAS-
AuAgNPs, and CIT-AuAgNPs due to the surface ligand desorption from
N.K. Reddy Bogireddy et al. Journal of Environmental Management 316 (2022) 115292

Fig. 3. Real-time 4-nitrophenol reduction absorbance spectra as a function of (a) CAS-AuAgNPs concentration, (b) as a function of NaBH4 concentrations 100x, 200x
and 300x denoted as NaBH4_1, NaBH4_2 and NaBH4_3, and the addition of 4-NP and excess of H2O after the reaction starts (4s) the reaction to NaBH4_2 and CAS-
AuAgNPs mixture denoted as NaBH4_2-4-NP and NaBH4_2-H2O.

Fig. 4. Time-dependent UV–visible absorbance studies for the formation of 1,4-benzo quinone from 4-aminophenol (a), reduction of 1,4-BQ (b), conversion of 1,4-
BQ to HQ during the 4-nitrophenol reduction reaction (c), and mimicking reaction with standard 4-aminophenol and aged NaBH4 (d).

the catalyst. Here we observed significant blue shift in the CAS fabri­
cated nanostructures, due to the presence of higher surfactant (higher
zeta potential)from CAS extract than Robert et al. (Neal et al., 2020)
After the complete reduction of 4-NP- to 4-AP, a new broad absorption
peak near 382 nm was observed, which corresponds to the freshly pre­
pared NaBH4 solution in an aqueous medium. This band was much
closer to the SPR band of CAS-AgNPs and CIT-AuAgNPs.
In addition to kinetic rate constants (using pseudo first-order reac­
tion: ln (Ct/C0) = -kapp × t), turnover number (TON) and the turnover
frequency (TOFF) parameters are important to evaluate the catalytic
activity of the reduction of 4-nitrophenol (Bogireddy et al., 2020). TON is
calculated using the number of substrate moles that 1 mol of the catalyst
can convert substrates into products and TOFF is calculated simply by
TON/reaction time. From the above-mentioned calculations obtained
kapp (at 10 mM NaBH4), TON and TOFF are 0.47 × 10− 3 s− 1, 6.02 and 2.41
for CAS-AuAgNPs (at 200 mM NaBH4) (Fig. 2a and S11).

5
N.K. Reddy Bogireddy et al.
Fig. 5. Real-time spectroscopy measurements: (a, b) UV–visible absorption
studies at 254 nm attributed to 1,4-benzoquinone, 300 nm corresponding to 4-
aminophenol and hydroquinone, and (c, d) fluorescence excitation at 290 nm
(for 1,4-BQ and HQ) and 300 nm (for 4-AP), respectively.
3.2. Production of 4-aminophenol in 4-nitrophenol reduction reaction
As we know, reducing 4-nitrophenol using NaBH4 gained more
attention for the last two decades.17On the other hand, the production of
4-aminophenol using several reducing agents has been investigated for
more than ten decades to the present day (Ivar, 1917). Due to the
importance of 4-AP, in the present study, we also calculated the 4-ami­
nophenol production percentage using the standard 4-aminophenol
calibration curve (Fig. S8 (a and b)). Although CIT-AuAgNPs exhibit a
faster reduction reaction as compared to other green synthesized nano
catalysts, the conversion of 4-NP- to the 4-AP percentage (from absor­
bance intensity) is better (7%) in CAS-AuAgNPs (Fig. 2 (c)). The con­
centration of 4-AP was calculated using Beer-Lamberts law (A = εbc;
A-absorbance, ε-molar absorptivity, b-length of the light path, and
c-concentration) from standard 4-AP solution. There are several reports
in which authors obtained more percentage of 4-aminophenol from
4-nitrophenol using higher concentrations of NaBH4 (Herv é s et al.,
2012).
We also monitored the formation of 4-AP during the 4-NP reduction
process through fluorescence signal intensity with an excitation of 300
nm (Fig. 2 (d)), which shows the evolution of PL signal at 373 nm
attributed from 4-AP. To confirm this, we also measured PL spectra of
standard 4-aminophenol (presented in Fig. S8 (c)).
6
Journal of Environmental Management 316 (2022) 115292
3.3. Effects of catalyst amount and NaBH4 concentration on induction
time (IT)
The real-time absorbance measurements at 400 nm were performed
as a function of catalyst amount in the reaction solution during the
reduction of 4-NP-. Fig. 3 (a) and Fig. S9 show the time-dependent
absorbance studies of all four catalysts, a decrease in the induction
time (IT) from 152 to 46 s was observed with increasing the amount of
CAS-AgNPs catalyst. This IT effect is negligible in other catalysts from
the present study. There are several reported studies on understanding
the IT and ligand desorption during the 4-NP reduction most of them are
using gold nanoparticles and there are insufficient reports on plant ex­
tracts to compare these effects and confirm the effect of IT on green and
chemically synthesized Ag and bimetallic catalyst systems.
To further understand IT, we carried out the following three exper­
iments: the impact of NaBH4 concentration (Fig. S10), altering the
addition of 4-NP and excess of water addition during the 4-NP reduction.
The obtained real-time absorption measurements clearly show the
drastic decrease in the IT with increasing the NaBH4 concentration, due
to the facilitation of faster electron transfer from catalyst to 4-NP.
(Strachan et al., 2020) Similar to above mentioned 4-AP concentra­
tions calculations, here the concentration of 4-NP is calculated from
standard 4-NP solution using the Beer-Lambert law. The change in the
order of 4-NP addition and excess of water, exhibits the additional in­
duction periods due to the post-oxygen administration. The obtained
results are consistent with Strachan et al. (Strachan et al., 2020) and
Neretina et al. (Can, 2011) reports. From these results, we believe that
the induction time is majorly dependent on the concentrations of cata­
lyst and NaBH4 during the reduction of 4-NP.
3.4. Possible boron contamination from NaBH4 in 4-NP reduction
reaction
Although most of the reports are using higher concentrations of
NaBH4 (i.e., more than 100 times to 4-NP concentration) to reduce the
reaction time and to get pseudo-first-order reaction profile in the 4-NP
reduction process, unknowingly, it tends to originate boron contami­
nation through excess of BH−4 ions from NaBH4 (Neal et al., 2020).
Considering the World Health Organization (WHO), and Environmental
Protection Agency (EPA) limits of boron (<2.4 mg/L) (WHO, 2009), we
performed a 4-NP reduction reaction with 189 mg of NaBH4 (i.e., 1.08
mg/L of B) in 50 mL DI water by CAS-AuAgNPs (Fig. S11 (a)). As ex­
pected, the response takes more time (3 h) to reduce the 4-NP to 4-AP,
surprisingly the production of 4-AP concentration increased to 32.4%
(around 2% higher than 200x NaBH4 with CAS-AuAgNPs) (Fig. S11 (b)).
It shows that the slow reduction reaction can improve the conversion of
4-AP from 4-NP. Moreover, we can additionally avoid boron purification
process due to the minimal presence of boron in the solution (less than
WHO and EPA toxic limits).
3.5. Effect of NaBH4 intermediates on formed 4-AP
As mentioned above, the absorbance spectrum around 400 nm is
attributed to NaBH4 solution in an aqueous medium after the formation
of 4-AP from 4-NP. A similar characteristic absorption peak at 400 nm
was observed for freshly prepared and aged NaBH4 (after 24 h) in the
aqueous medium (Fig. S12 (a)). There was an absorption spectrum po­
sition difference from 203 nm to 210 nm in aged NaBH4 solution. Which
indicates the complete elimination of hydrogen from BH−4 . Moreover,
after the reduction of 4-NP to 4-AP there was a shift in NaBH4 absorption
position from 400 nm to 382 nm, which is due to the formation of in­
termediate product of NaBH4. Further, the absorption spectrum of
standard aqueous boric acid was compared with aged NaBH4 (Fig. S12
(b)). Interestingly, there was no notable absorbance peak observed in
standard boric acid. Clarifies that the absence (or significantly less
concentration) of boric acid and presence of other BH−4 such as [B
N.K. Reddy Bogireddy et al.
Fig. 6. UV–visible absorption spectra of 4-aminophenol to phenol formation at pH (a) 2.5, and (b) 5.0, and 4-aminophenol to hydroquinone formation at pH (c) 7.5,
and (d) 10.5 presence of NaBH4.
(OH)4]-, [B3O3(OH)4]- and [B3O3(OH)5]2− intermediates, the solution
pH is recorded as basic (≈10.5). Similar characteristics were observed in
previously published Irina Stepina et al. (Stepina and Kotlyarova, 2018)
report.
After the reduction of 4-NP to 4-AP, there were other reactants
including 4-AP, catalyst, and NaBH4 intermediates from their corre­
sponding absorbance spectra position in the final reaction solution
(Fig. S13). Noteworthy, after some time (it depends on several factors
like concentration of NaBH4, ambient temperature, dimensions of the
vial/cuvette) we observed the evolution of a new absorbance spectrum
around 253 nm attributed to the evolution of 1,4-benzoquinone (1,4-
BQ)and gradual disappearance of the absorption bands corresponding to
4-AP (232 nm and ≈300 nm) with blue shift in the NaBH4 absorption
position around 380 nm (Fig. S13). Still there was a little absorption
band around 300 nm which corresponds to second characteristic peak
position of 1,4-BQ. The formation of 1,4-BQ occurred due to the con­
version of 4-AP in presence of intermediates of NaBH4 or aged NaBH4.
Later, 1,4-BQ tends to decrease the absorption intensity at 253 nm (i.e.,
reduction of 1,4-BQ) with no observable absorption band at 300 nm, and
the intensity of NaBH4 absorption band (≈380 nm) is increased
(Fig. S13), which confirms the complete conversion of 1,4-BQ to 1,4-HQ
in basic medium. The observed kinetic formation of the 1,4-BQ is faster
than 1,4-BQ reduction, which is closely matches with the William et al.
(Senad and Remick, 1957).
Finally, the reduced 1,4-BQ absorbance peak position at 255 nm
shifted to ≈276 nm with a new broad band at 320 nm, meanwhile the
decrease in the absorption band of NaBH4 intermediates observed,
which confirms the formation of hydroquinone (HQ) with NaBH4 in­
termediates complex formation. Meanwhile, the pH of the total reaction
measured and it was around 8.6–9.5 from 4-NP- to HQ formation. This is
7
Journal of Environmental Management 316 (2022) 115292
the first study in the well-established 4-NP model reduction reaction to
encounter the formation of 1,4-BQ, reduction of 1,4-BQ, and then finally
it converts to HQ (Fig. S13).
The NaBH4 concentration-dependent studies were also carried out to
convert 4-AP to 1,4-BQ and 1,4-BQ to HQ by increasing the concentra­
tion of the NaBH4 (from 10x to 300x times higher concentration than 4-
NP) increasing the time to convert 4-AP to 4-BQ (Fig. 4 and Fig. S13).
The immediate conversion of 4-AP to 1,4-BQ is identified using 10x
concentrations of NaBH4 (Fig. 4).
The real-time spectroscopic studies were carried out using UV–vi­
sible absorbance at 254 nm (1,4-BQ) and 300 nm (4-AP and HQ), and the
fluorescence measurements at 290 nm (for 1,4-BQ and HQ) and 300 nm
(4-AP) excitation, respectively (Fig. 5). From the fluorescence studies, it
is observed that after some time (i.e., depends on the concentration of
NaBH4) the PL signal corresponding to 4-AP started quenching due to
the gradual conversion of NaBH4 to their corresponding intermediates.
Interaction of intermediates of NaBH4with 4-AP gives the formation of
1,4-BQ, and later it reduced to HQ similar to UV–visible absorbance
studies.
For further understanding, we carried out several mimicking exper­
iments using standard 4-AP (4-AP (std)) and boric acid, such as 4-AP
(std) in (A) basic pH medium, (B) boric acid, and (C) aged NaBH4
(after 24 h). In reaction A, standard 4-AP (4-APstd) is maintained pH 8
and 11, the complete disappearance of 4-APstd (300 nm) and evolution
of new absorption spectra at 382 nm, which is similar as aged 4-APstd in
an aqueous medium (Fig. S14 (a, b)). Due to its light sensitive property it
tends to oxidize easily in ambient conditions (Fig. S14 (c). Moreover, it
confirms that only the 4-AP is not converting to 1,4-BQ in the basic
medium. In reaction B, the addition of boric acid (10 mM) into 4-APstd
exhibits similar absorption as standard 4-AP, apart from boric acid
N.K. Reddy Bogireddy et al. Journal of Environmental Management 316 (2022) 115292

Fig. 7. UV–visible absorbance spectra of 4-nitrophenol spiked river water samples (a), reduction of 4-NP (1 mM) using NaBH4 (10 mM) by CAS-AuAgNPs in river
sample A (b), river sample B (c), river sample C (d), their respective 4-aminophenol production (e), and intermediate and final products formation (f), respectively.

protects from oxidation of 4-AP (Fig. S14 (d)). Later, the pH of the so­ the reaction solution, which is confirmed through standard sample
lution containing boric acid and 4-APstd naturally remained constant 10, measurements.
then the formation of 1,4-BQ and HQ was observed (Fig. S14 (e)). In
reaction C, freshly prepared NaBH4 in an aqueous medium was kept for
3.6. Effect of pH of NaBH4 intermediates solution on formed 4-AP
24 h and later named it “aged NaBH4”, in which NaBH4 is converted to
their intermediate forms as mentioned earlier. The addition of aged
After reducing 4-NP to 4-AP using freshly prepared NaBH4 and CAS-
NaBH4 into 4-APstd leads to rapid development with increasing and
AuAgNPs, adjusted the reaction solution pH to 2.5, 5.0, 7.5, 9.5, and
followed by decreasing absorbance spectrum at 253 nm, similar to the
10.5 immediately (Fig. 6). The spontaneous conversion of phenol from
changes observed in the 4-NP reduction probe reaction (Fig. 4 (d)). It
4-APstd in acidic medium (pH ≤ 5.5) with blue shift in the absorption
confirms the involvement of NaBH4 intermediates in converting 4-AP to
positions from 230 to 220 nm, 300 nm–272 nm with decrease in the
1,4-BQ and reducing 1,4-BQ to HQ.
intensity of NaBH4 intermediates at ≈ 380 nm. The LSPR band of AuNPs
To have a deeper insight, we performed PL analysis using obtained
shifted to red side from 504 nm to 515 nm and increased the broad ness
1,4-BQ, HQ with their standards solutions (Fig. S15 (a, b)). Surprisingly,
of the peak due to the lack of –OH groups NPs tends to aggregate at acid
we didn’t observe a PL signal in the reaction solution, further identified
pH. Similar observation was noted at pH 5.0, but still there is an ab­
as the quenching of PL signal in the presence of aged NaBH4 solution in
sorption band related to 4-AP due to lack of more acidic nature in the

8
N.K. Reddy Bogireddy et al.
Fig. 8. UV–visible absorbance spectra of 4-nitrophenol spiked sea water samples (a), reduction of 4-NP (1 mM) using NaBH4 (10 mM) by CAS-AuAgNPs, and their
corresponding intermediate/final products formation (b).
Scheme 1. Represents the possible mechanistic understanding in the reduction of 4-nitrophenol to Hydroquinone and Phenol.
Fig. 9. Re-usability of CAS-AuAgNPs tested up to five successive cycles.
solution. Further, the formation of 1,4-BQ and HQ in basic medium (pH
≥ 7.5) was recorded using UV–visible absorbance spectroscopy. The
obtained absorption spectra were closely matching with standard 1,4-
BQ (≈250 nm and ≈290 nm) and HQ (≈290 nm).
Redshift with a broad peak in the obtained characteristic absorbance
spectrum (around 245 nm–253 nm) compared to standard 1,4-BQ may
9
Journal of Environmental Management 316 (2022) 115292
be due to the complex formation between intermediates of NaBH4 and
1,4-BQ. Similarly, the obtained final product (HQ) absorbance spectra
also show a blue shift with a broad peak compared to standard HQ
(≈290 nm), which may be also due to the complex formation of HQ with
intermediates of NaBH4. Due to the complex formation of 1,4-BQ and
HQ with intermediates of NaBH4, there is quenching in the PL signal
observed (as discussed earlier). On the contrary, the obtained phenol at
2.5 solution pH perfectly matches the standard phenol absorption
spectrum. Further clarifies that the pH of the solution mixture controls
the formation of the final product from 4-AP.
3.7. Identification of final products in 4-nitrophenol reduction using
NaBH4 in river and sea water samples
To check the practical viability and efficiency of the CAS-AuAgNPs,
the 4-NP reduction probe reaction was performed using three river
water samples. Initially, 4-NP and NaBH4 were prepared in the respec­
tive river water solutions (Fig. 7). There were changes in the absorption
spectra of the pure 4-NP was observed in the river solutions as compared
with a laboratory water solution due to the variation in the pH of the
water samples, i.e., river A (7.3), river B (7.5), and river C (6.9). The
complete conversion of 4-NP (317 nm) to 4-NP- (400 nm) was observed
with the addition of freshly prepared NaBH4. The reaction was further
proceeded with the addition of CAS-AuAgNPs into the above reaction
solution, which shows the reduction of 4-NP and formation of 4-AP. The
reaction rate is faster in river A compared to river B and C (Fig. 7(a–d)).
Moreover, the identified 4-AP production 0.316, 0.295 and 0.308 mM
attributed to river A, river B and river C sample values are very close to
N.K. Reddy Bogireddy et al. Journal of Environmental Management 316 (2022) 115292

Table 1
Performance comparison of tested CAS-AuAgNPs catalyst with the reported literature.
Catalyst Catalyst Amount (mg) C(NaBH4)/C(4- NP)* Kapp ( × 10− 3s− 1) 4-AP confirmation Ref

Pt-EMSiOx 0.24 94 84 Absorbance Bogireddy et al. (2020)

Au/CaCo3 1 0.56 17.9 Absorbance Ding et al. (2020)
AuNPs-NGODs 0.040 100 9.4 Absorbance Bogireddy et al. (2021a)
Au/Ag BMNPs 0.6 7000 6.07 Absorbance Lv et al. (2019)
Pt–Ni (96:4) 0.004 150 1.93 Absorbance Ghosh et al. (2004)
Av-AuNPs 0.009 10 1.55 Absorbance Bogireddy and Agarwal (2019)
SA-PtNPs 0.08 100 0.6 Absorbance Bogireddy et al. (2021b)
CAS-AuAgNPs 0.028 5 0.47 Absorbance and Photoluminescence Present study

the DI water sample (0.328 mM) (Fig. 7e). The small variation in the
reduction time and 4-AP production may be due to the presence of
several unknown moieties in the aqueous river solutions.
Further, the identified observation such as conversion of 4-AP to 1,4-
BQ, and reduction of 1,4-BQ to HQ, in the DI water, were also exhibited
in the river sample of 4-NP reduction reaction solutions (Fig. 7f). The
formation of 4-NP to 4-AP, 4-AP to 1,4-BQ, and 1,4-BQ to HQ, shows the
accordance with obtained products and efficiency of the catalyst prep­
aration, and the identified new products efficient in the river samples.
Similar results in the reduction of 4-nitrophenol to 1,4-hydroquinone in
basic medium and Phenol formation in acidic medium were identified in
the sea water (Fig. 8).
Methodology, Investigation, Writing – original draft, Visualization.
Yetzin Rodriguez Mejia: Writing – original draft. Tejraj M. Ami­
nabhavi: Writing – review & editing. Victor Barba: Methodology. Raul
Herrera Becerra: Supervision. A. David Ariza Flores: Funding acqui­
sition. Vivechana Agarwal: Supervision, Funding acquisition, Writing –
review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.

3.8. Possible understanding of NaBH4 intermediates role in the final Acknowledgement

products
During the 4-NP degradation, the proposed mechanism involves first
the nitrophenolate formation by elimination of the H+ with the
respective H2 evolution, then the 4-AP formation is observed by action
of the NaBH4 within the catalyst as described in several processes. A
prolongated exposition on solution (including the NaBH4 derivatives)
and catalyst leads to oxidation of the 4-AP to 1,4-BQ, this procedure can
be helped by the quinone-imine intermediate formation as proposed by
Senad et al. (Senad and Remick, 1957). Finally, final reduction to form
1.4-hydroquine is attributed because of the basic media solution. In
addition, 4-AP can be transformed into the phenol in acid medium with
the ammonium ion elimination (Scheme 1).
As the practical application of any catalyst depends on its economic
viability, possible scalability and stability, the catalytic reusability of the
fabricated CAS-AgAuNPs was further examined by reducing 4-nitrophe­
nol up to five successive cycles in marine water samples (Fig. 9). How­
ever, after five cycles, the CAS-AgAuNPs catalyst exhibited a 40%
decrease in the 4-NP reduction. The performance comparison of the
tested CAS-AuAgNPs catalyst, with the reported literature, is presented
in Table 1.
4. Conclusions
We present here the successful fabrication of bimetallic plasmonic
(Au–Ag) nanoparticles using both green and chemical synthesis
methods. The obtained nanoparticles were used for understanding and
establishing 4-nitrophenol reduction model reaction. The present study
opens the discussion regarding the importance of induction time, 4-ami­
nophenol production, possible contamination of boron using higher
concentrations of NaBH4, effect of pH and intermediates of NaBH4 in 4-
nitrophenol reduction reaction. Moreover, the simultaneous/subsequent
formation of 1,4-benzoquinone, hydroquinone, phenol advances the
experimental procedure involving the catalytic reduction of 4-NP and
further underlines the importance of NaBH4 intermediates with the
obtained products.
CRediT authorship contribution statement
Naveen Kumar Reddy Bogireddy: Conceptualization,
VA, NKRB and ADAF acknowledge the support from CONACyT Basic
Sciences projects A1-S-30393 and 256243. NKRB acknowledge
Dirección General de Asuntos del Personal Académico (DGAPA) de la
UNAM for postdoctoral fellowship. We express special gratitude to
Margarita I. Bernal-Uruchurtu of CIQ, UAEM for her participation in the
discussions. We thank Jose Juan Ramos-Hernandez and Maura Casales
Diaz of ICF, UNAM for their support in the XRD analyses and providing
sea water.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jenvman.2022.115292.
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