Journal of Environmental Chemical Engineering 9 (2021) 106590

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Journal of Environmental Chemical Engineering

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Kinetic analysis of nitrophenol reduction and colourimetric detection of

hydrogen peroxide based on gold nanoparticles catalyst biosynthesised
from Cynomorium songaricum
Van-Dat Doan a, Quoc-Huy Pham a, Bao-An Huynh a, Thi-Lan-Huong Nguyen b,
Anh-Tien Nguyen c, Thanh-Danh Nguyen d, e, *
a
Faculty of Chemical Engineering, Industrial University of Ho Chi Minh City, 12 Nguyen Van Bao, Ho Chi Minh City, Vietnam
b
Institute of Biotechnology and Food Technology, Industrial University of Ho Chi Minh City, 12 Nguyen Van Bao, Ho Chi Minh City, Vietnam
c
Faculty of Chemistry, Ho Chi Minh City University of Education, 280 An Duong Vuong, Ho Chi Minh City, Vietnam
d
Institute of Chemical Technology, Vietnam Academy of Science and Technology, 1A, TL29, Thanh Loc Ward, District 12, Ho Chi Minh City, Vietnam
e
Graduate University of Science and Technology, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Cau Giay District, Hanoi, Vietnam

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

Editor: Despo Kassinos The pseudo-first-order reaction kinetics of metallic nanocatalyst for the model reaction of nitrophenols/NaBH4
were early reported on low reaction temperatures. Here, we investigated reduction of nitrophenols in a wide
Keywords: range of reaction temperature with gold nanoparticles (AuNPs) catalyst that was fabricated via a low-cost and
Nitrophenol reduction effective method using aqueous extract of Cynomorium songaricum (CS). The biosynthesised CS-AuNPs were well
Kinetic
characterised by the analytic techniques such as X-ray diffraction (XRD), transmission electron microscope
Colourimetric detection
(TEM), scanning transmission electron microscopy (STEM). The TEM images showed multiple shapes and size in
Catalysis
Hydrogen peroxide a range of 3–30 nm with an average size of 16 nm. The colloidal solutions were stored at the room temperature
Gold nanoparticles for 30 days with a stability of 63%. The kinetic study of the NiPs reduction showed that the reaction occurred via
Langmuir–Hinshelwood mechanism with a half-order kinetic model for all tested reaction temperatures (30–70
◦
C). The thermodynamic parameters including activation energy, enthalpy, entropy and Gibbs free energy were
calculated. The activation energies in the reduction of 2-nitrophenol and 3-nitrophenol were found to be as low
as 4.88 kJ mol− 1 and 8.66 kJ mol− 1, respectively. Moreover, CS-AuNPs were used as a nanozyme for the
detection of hydrogen peroxide (H2O2) via peroxidase-like reaction with 3,3′ ,5,5′ -tetramethylbenzidine (red-
TMB) that found the lowest limit of detection (LOD) of 2.25 µM.

1. Introduction
Metallic nanoparticles have gained great interest due to the nano­
particles possessing special physicochemical properties with large
number of active positions, which can significantly enhance their cata­
lytic activity [1–3]. Gold nanoparticles (AuNPs) with a high specific
surface area is less prone to self-poisoning which can make them very
active in the catalytic applications [4]. In the recent years, green
approach utilising the biosources such as fungi [5], bacteria [6], plant
embryos [7], plants [8,9] and waste biomass [10] has frequently
investigated. The biosynthesised nanoparticles can improve biocom­
patibility and stability as well as possess a low toxicity due to coating
them with bioactive agents [11,12]. Among these natural precursors,
plant extract as abundant sources is attracted particular attention due to
enabling the scalable and cheap synthesis of AuNPs [13–15].
Catalytic reduction of nitrophenols (NiPs) to relative aminophenols
(APs) has been explored widely as a model reaction for evaluating cat­
alytic activity of metallic nanoparticles since NiPs exhibit high stability
and toxicity in water, causing harm to living environment. Notably, the
product of NiPs reduction, APs, are well known to be important in­
termediates in the fabrication of several antipyretic and analgesic drugs
[16,17]. In the industrial applications, APs are also used as
anticorrosion-lubricating agents in fuels, corrosion inhibitors in paints
and dyeing agents for fur and feathers [18,19]. Thus, several research

* Corresponding author at: Institute of Chemical Technology, Vietnam Academy of Science and Technology, 1A, TL29, Thanh Loc Ward, District 12, Ho Chi Minh
City, Vietnam.
E-mail address: ntdanh@ict.vast.vn (T.-D. Nguyen).

https://doi.org/10.1016/j.jece.2021.106590
Received 1 September 2021; Received in revised form 30 September 2021; Accepted 13 October 2021
Available online 16 October 2021
2213-3437/© 2021 Elsevier Ltd. All rights reserved.
V.-D. Doan et al.
groups have explored the catalytic kinetic of NiPs reduction using
NaBH4 in the presence of the metallic nanocatalyst [20–22]. In these
studies, the kinetic analysis indicates that the reaction, which was
almost performed around room temperature, following a
pseudo-first-order rate law via Langmuir-Hinshelwood model for het­
erogeneous catalyst. Recently, Fedorczyk et al. [23] showed that cata­
lytic reduction of 4-NiP with excessive amount of borohydride was
followed by either pseudo-zero-order or pseudo-first-order kinetics,
depended on concentrations of 4-NiP. Meanwhile, Li and Chen [24]
found a wide range of the reaction orders (1.5–6.7) for the reduction of
4-NiP in the presence of metallic nanoparticles coated on poly(allyl­
amine hydrochloride)/poly(glycidyl methacrylate) composite. The re­
action orders depended on the coated metallic nanoparticles coverage.
Thus, it is clear that the kinetic model of NiPs reduction is strongly
affected by the reaction conditions.
H2O2 is used in various fields, including the manufacture of dis­
infecting and cleaning agents, and antibacterial agents [25,26]. Due to
high stability in abiotic environments at ambient condition and neutral
pH, H2O2 is popularly environmental toxins which can kill rapidly ani­
mal cells by producing highly-reactive hydroxyl radicals [27]. More­
over, many enzyme-catalysed reactions such as xanthine oxidase,
5-lipoxygenase, and NADPH oxidases, generate H2O2 as the
by-product. In inflammation behaviour, when oxidative degradation
and modification of base pairs of DNA occur in cells, H2O2 molecules can
accumulate locally, leading to inflammation [28]. Thus, accurate
detection of H2O2 level has been the subject of particular attention by
the researchers. Among numerous techniques, chromogenic red-TMB
can be effectively used for detection of H2O2. In this system, red-TMB is
oxidised by H2O2 in the presence of peroxide-like nanocatalyst such as
noble metallic nanoparticles (AgNPs, AuNPs, PdNPs, etc.) to afford a
blue oxidised TMB form (ox-TMB) [29].
Cynomorium songaricum is a popular plant species living in the
mountainous regions of Vietnam and also found in China, Northern
Africa and the Mediterranean region. C. songaricum possesses various
bioactivity such as antioxidant, immunity-improving and improving
physiological status in men. Moreover, C. songaricum contains many
important ingredients such as flavonoids, phenolic, steroid, protein,
lignans and polysaccharides which can be responsible for reduction and
stabilisation of metallic nanoparticles [30–33]. For instance, the hy­
droxyl group of flavonoids in the plant plays a principal role as a
reductant because the tautomeric transformation of enol form into keto
form may result reactive hydrogen atoms that can reduce metallic ions
to metallic nanoparticles [34]. To the best of our knowledge, the extract
of C. songaricum (CS) has not yet been used in the biosynthesis of
nanoparticles.
In this study, we synthesised AuNPs using CS extract as an eco-
friendly reducing and stabilising agent. The synthetic conditions of
AuNPs were optimised to determine the best effective reaction condi­
tion. Physicochemical properties were investigated by analytic tech­
niques. For their applications, AuNPs were evaluated for catalytic
kinetics of the nitrophenols reduction in a wide range of reaction tem­
peratures and their peroxidase-like activity was used to detect H2O2
levels via an H2O2-TMB sensing system.
2. Materials and methods
2.1. Materials and chemicals
All chemicals used were of analytical grade and utilised without
further purification. Chemicals including hydrogen tetrachloroaurate
(III) hydrate (HAuCl4.3H2O), 2-nitrophenol (2-NiP), 3-nitrophenol (3-
NiP), Glacial acetic acid (CH3COOH), sodium acetate (CH3COONa),
H2O2 solution 30% and red-TMB were purchased from Acros Co
(Belgium). The distilled water was used thoroughly in all experiments.
For the preparation of CS extract, harvested C. songaricum was dried.
The CS powder (2.5 g) was boiled in distilled water (300 mL) for 1 h. The
2
Journal of Environmental Chemical Engineering 9 (2021) 106590
obtained solution was filtered with Whatman filter paper No.1 to
remove the solid, and the extract was stored in a refrigerator at 4–10 ◦ C
for further studies.
2.2. Synthesis of biogenic AuNPs
CS extract as a green reducing and stabilising agent for the synthesis
of AuNPs was added into HAuCl4 solution under dark condition. The
optimal parameters including concentration of gold ions (0.50–1.25
mM), temperature (40–80 ◦ C) and time (15–75 min) were investigated
using UV-Vis measurements (UV-Vis Evolution 300 spectrophotometer).
The change in physicochemical property and concentration of the
nanoparticles was determined by change in absorbance values and
characteristic of surface plasmon resonance (SPR) absorption peaks. The
CS-AuNPs biosynthesised under the optimal condition were used for the
further studies. The solid CS-AuNPs were centrifuged for 30 min at 4000
rpm, washed and dried overnight at 60 ◦ C.
2.3. Characterisation of biogenic AuNPs
Fourier transform infrared spectroscopy (FTIR) spectra of solid
samples were recorded in range of 4000–500 cm− 1 on a Bruker Tensor
27 (Germany) for identification of possible functional groups present in
the CS extract and CS-AuNPs. Crystalline structure of CS-AuNPs was
analysed for powder XRD on the Shimadzu 6100 X-ray diffractometer
(Japan) operating at the voltage of 40 kV, the current of 30 mA with
CuKα radiation at the wavelength of 1.5406 nm, scanning speed of
0.05◦ /s and step size of 0.02◦ in the range 2θ from 10◦ to 80◦ .
Morphological characterisation, size distribution and crystal property of
CS-AuNPs were evaluated by TEM and high resolution transmission
electron microscope (HR-TEM), STEM-EDX mapping and the selected
area electron diffraction pattern (SAED) (JEOL JEM-2100, Japan).
Colloidal solution was used to determine zeta potential at the sliding
plane and the size distribution of the particles using dynamic light
scattering (DLS) (nanoPartica Horiba SZ-100, Japan).
2.4. Reduction of nitrophenols
To evaluate the catalytic activity, the hydrogenation of 2-NiP and 3-
NiP was carried out by using excess amount of NaBH4 in the presence of
the solid CS-AuNPs. Briefly, a mixture of NiP (2.5 mL, 0.1 mM) and
NaBH4 (0.5 mL, 0.1 M) was prepared in a cuvette with a length of 1.0
cm. Then, the CS-AuNPs catalyst (3 mg) was added into the solution. The
catalytic performance via kinetic studies were investigated using UV-Vis
spectroscopy at the wavelength of 410 nm for 2-NiP and 390 nm for 3-
NiP and thermodynamic parameters were calculated via reactions per­
formed at wide range of temperatures (30–70 ◦ C).
2.5. Peroxidase-like activity and detection of H2O2
Peroxidase-like activity of CS-AuNPs was based on the reaction be­
tween red-TMB and H2O2 that was carried out as follows: 200 μL of red-
TMB + 300 μL of H2O2 + CS-AuNPs mixed with acetate buffer in a 2 mL-
Eppendorf and left for 30 min. Then, the mixture was transferred to a
standard cuvette with a 1 cm length for measurement of UV-Vis spectra.
The colourimetric detection conditions were explored by keeping
three factors and changing the other. The pH values, reaction temper­
ature, volume of CS-AuNPs solution and red-TMB concentrations were
investigated in the ranges of 1–8, 20–80 ◦ C, 10–80 μL and 0.5–3.5 mM,
respectively. The reaction performance was evaluated via the absor­
bance values at the peak 654 nm in UV-Vis spectra.
For the detection of H2O2, the reaction was performed in 2 mL-
Eppendorf as follows: 200 μL of red-TMB (5.0 mM) + 60 μL of CS-AuNPs
+ 1 mL of acetate buffer at pH 5.0. After that, 300 μL of different H2O2
concentrations (10–400 μM) were added and kept for 30 min at 50 ◦ C.
Then, UV–Vis spectra were recorded and the absorbance values at 654
V.-D. Doan et al.
Fig. 1. Schematic illustration for the biosynthesis of CS-AuNPs and their applications.
nm were evaluated to determine linear curve and LOD value calculated
via a formula 3σ/s where s denotes the slope of linearity and σ represents
the standard deviation, respectively.
3. Results and discussion
3.1. Biosynthesis of CS-AuNPs
The phytochemicals of C. songaricum showed the presence of
numerous active organic compounds such as flavonoids, fatty acids,
phenolic acids, polysaccharides [35,36] that can be responsible in the
green synthesis of metallic nanoparticles without the toxic reagents
used. The formation of the metallic nanoparticles in colloidal solution
can relate to the mechanism involved three different stages [37,38]: (1)
the conversion of metallic ions into metallic nanoparticles occurs via an
oxidoreduction process by the organic reductants present in the plant
which can be affected by redox potential of organic compositions and
metal. (2) The metallic nanoparticles are clustered via an aggregation
process that can be strongly affected by the diffusion model. (3) The
growth of the nanoparticles is carried out via the combination of the
clusters. The growth rates can affect the geometry of metal nano­
particles. In general, the reducing and stabilising agents are principal
factors inducing the difference in their physicochemical properties and
catalytic activities. In this work, we utilised the CS extract as a green
source to biosynthesise AuNPs for catalytic and sensing applications
(Fig. 1). The dried CS was refluxed with the distilled water, affording a
light yellow solution after the filtration process. Due to geometry and
size of AuNPs strongly affected their catalytic activity [39,40], the re­
action conditions including concentration of gold ion, temperature and
time were optimised for the production of CS-AuNPs. The changes in the
solution colour from yellow to pink and absorption intensity at SPR band
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Journal of Environmental Chemical Engineering 9 (2021) 106590
of around 540 nm in UV-Vis spectra confirmed good conversion of gold
ions to CS-AuNPs. The physicochemical properties and structures of the
nanoparticles were well characterised using analytic techniques. Their
applications involved catalytic activity for reduction of NiPs and
peroxidase-like activity for colourimetric detection of H2O2 levels.
In order to gain insight of AuNPs formation, optimal parameters of
the reduction including concentration of gold ion, temperature and time
were explored with the aid of UV-Vis measurement. Changes in the
absorbance and λmax values at the SPR band can provide important in­
formation on size, morphology and yield for the formation of CS-AuNPs.
The absorption results showed that the formation of CS-AuNPs was
strongly dependent on all of the investigated parameters as can be
obviously seen in the different trends (Fig. 2).
Higher gold ion concentrations (0.5–1.25 mM) induce increased the
formation of CS-AuNPs. An increase in absorbance values was observed
in the range 0.5–1.0 mM, indicating that the concentration of the
nanoparticles in the colloidal solution increases with concentration of
gold ions and achieved a maximum value at 1.0 mM. In addition, λmax
values were almost no change in increase of gold ion concentrations that
confirmed stable morphology of the colloidal solution in range of the
investigated concentrations. Thus, the most effective CS-AuNPs forma­
tion was found at a gold ion concentration of 1.0 mM.
For study on the effect of temperature, the reduction was carried out
at a range of 40–80 ◦ C. The formation of CS-AuNPs was observed at all
investigated temperatures that the SPR band of CS-AuNPs appeared at
536–540 nm. The result shows that absorbance values increased rapidly
with increasing temperature and λmax values were stable at region of
high temperature (> 60 ◦ C), indicating that the yield and morphology of
CS-AuNPs formed is highly dependent on the reaction temperature. The
most effective reduction of gold ions was determined to take place at
70 ◦ C.
V.-D. Doan et al. Journal of Environmental Chemical Engineering 9 (2021) 106590

The time-dependent reduction of gold ions was investigated between
15 and 110 min. Increases in both absorbance and λmax values confirmed
increasing concentration and larger size of nanoparticles in the colloidal
solutions with extended reaction times. The formation of CS-AuNPs
occurred rapidly after 30 min of the stirring, and a stable solution was
afforded at 60 min. It is clear that the presence of organic components in
CS extract reduces gold ions more rapidly than that it does with the
aqueous extract of other plants [41–43]. For further studies on their
physicochemical properties and applications, CS-AuNPs were carried
out under optimal condition with gold ion concentration of 1.0 mM at
70 ◦ C for 60 min.

Fig. 2. UV-Vis spectra (left) and colour change (upper) and plots of investigated parameters versus absorption intensity and λmax values (right): concentration of gold
ion (A and B), reaction temperature (C and D), and time (E and F) for the biosynthesis of CS-AuNPs. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)

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Fig. 3. (A) Zeta potential, (B) DLS distribution of colloidal solution of CS-AuNPs, (C) FTIR spectra of CS extract (a) and CS-AuNPs (b) and XRD patterns of CS-AuNPs.

Fig. 4. (A) TEM images and distribution of particles (inset); (B) HR-TEM and SEAD images (inset); (C) EDX patterns and elemental composition (inset) and (D and E)
STEM-mapping of CS-AuNPs.

3.2. Characterisations of CS-AuNPs showed a monodispersed distribution in range of 20–150 nm with an

To confirm successful biosynthesis of the colloidal solution, CS-
AuNPs solution was used to measure the zeta potential and DLS distri­
bution at 25 ◦ C as shown in Fig. 3A and B. The results showed that the
colloidal solution of CS-AuNPs possesses a good stability with a greatly
negative zeta potential (− 45.9 mV). The size distribution of CS-AuNPs
average hydrodynamic diameter of 45 nm. The data reveals that the
bioactive compounds present in the CS extract well stabilised AuNPs
after the reduction.
The functional groups of the bioactive compositions in the CS extract
responsible as the stabilising agents of CS-AuNPs were identified by
using FTIR measurements and the CS extract was also used as a reference

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Fig. 5. (A) UV-Vis spectra and (B) stability over time of CS-AuNPs.

sample for analysis of CS-AuNPs (Fig. 2C). Similar absorption peaks are
obviously observed from both spectra. The peaks of CS extract centred at
wavenumbers of 3350, 2924, 2850, 1725, 1587, 1405 and 1091 cm− 1,
while the CS-AuNPs peaks are slightly shifted to new positions at 3376,
2922, 2852, 1726, 1559, 1406 and 1043 cm− 1 due to the presence of
metal component. The hydroxyl (OH) and amino (N–H) groups repre­
sent at a broad band of 3350 cm− 1 and – – C–H groups are assigned to
the bands of 2924 and 2850 cm− 1 that can be related to the composition
of flavonoids, polyphenols, polysaccharides and proteins [33,44]. A
shoulder that centred at 1725 cm− 1 is assigned to the C– – O stretching
vibration of ketones or amides. The sharp peaks at 1587 cm− 1 and
1091 cm− 1 corresponded to stretching vibrations of C– – C and C–O,
respectively [45]. The observation indicates that the bioactive com­
pounds in CS extract relate to the stabilising agents of AuNPs.
The crystalline structure of CS-AuNPs was evaluated using XRD
analysis (Fig. 3D). The XRD pattern of CS-AuNPs shows sharp diffraction
peaks at 2θ angles of 38.18◦ , 44.36◦ , 64.59◦ and 77.55◦ correlated to the
face-centred cubic (fcc) structure of AuNPs (1 1 1), (2 0 0), (2 2 0) and (3
1 1), respectively (ICDD PDF card number 00-004-0784). The XRD pa­
rameters calculated are shown in Table S1. The crystal size of AuNPs is
determined using the Debye-Scherrer equation D = 0.9λ/βcosθ, where D
(nm) is the average crystal size, β (radian) is the full width at half
maximum (FWHM), λ (0.1540 nm) is the wavelength of used CuKα X-ray
radiation and ‘θ’ (radian) is the Bragg diffraction angle. The crystal
diameter was estimated to be 25.04, 19.05, 21.28 and 23.85 nm for the
fcc planes of (1 1 1), (2 0 0), (2 2 0), and (3 1 1), respectively and a mean
value was calculated to be 22.30 nm. The mean lattice parameter and
cell volume of AuNPs could be determined from interplanar spacing size
that confirms the presence of AuNPs in the sample with 4.07552 Å and
67.69482 Å3, respectively [46,47].
The morphology and crystal structure of CS-AuNPs were evaluated
by TEM, HRTEM and SAED analysis (Fig. 4A and B). TEM images of CS-
AuNPs indicated an uneven geometry with triangular, pentagonal,
hexagonal and spherical shapes and a narrow size distribution of CS-
AuNPs in a range of 2–30 nm with an average size of 16 nm. The mul­
tiple shapes of formed AuNPs can relate to various phytochemicals of
stabilising agents in the CS extract that is similarly observed in the
previous reports [48,49]. The HRTEM image and SAED pattern showed
the crystalline structure of CS-AuNPs. The HRTEM image revealed a
fringe lattice of the crystalline phase with a spacing of 0.22 nm that
correlates to the (1 1 1) plane of AuNPs. The SAED pattern displayed
bright circular rings corresponding to the (1 1 1), (2 0 0), (2 2 0) and (3 1

Fig. 6. Schematic representation of heterogeneous CS-AuNPs catalyst for the reduction of NiPs via the Langmuir–Hinshelwood mechanism. The abbreviations, kNiP,
kBH4, kde and kapp are rate constants of NiP adsorption, BH4 adsorption, detachment of AP product and apparent kinetic respectively.

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1) reflection planes of AuNPs. The results are in agreement with the

earlier data of the XRD pattern. The elemental composition of CS-AuNPs
was measured by EDX analysis (Fig. 4C). Strong signals at around 2.2,
9.8, 11.5 and 13.4 keV confirm the presence of elemental gold in the
sample [50] and the appearance of carbon (0.4 keV), oxygen (0.5 keV),
chloride (2.6 keV) can relate to the composition of CD extract. The mean
percentage of gold in CS-AuNPs was estimated to be 17.0% (w/w). The
scanning transmission electron microscopy (STEM) mapping images
(Fig. 4D and E) confirm the presence of well-dispersed AuNPs without
the agglomeration. The results show that the active composition in the
CS extract effectively reduced and stabilised AuNPs.

3.3. Stability

Although the result of zeta potential showed a highly stable colloidal

solution of CS-AuNPs (Fig. 3 A) the agglomeration of nanoparticles over
time can strongly affect their catalytic activity. Thus, their stability
should be investigated over the storage time. The samples were stored in
a vial with a cover at room temperature. UV-Vis spectroscopy of the
colloidal solutions were measured after various times of 3, 7, 10, 14, 17,
20, 24, 27 and 30 days. The stability was determined by decrease of the
absorption intensity at SPR peak (Fig. 5). The result shows that the
nanoparticles rapidly agglomerate in an initial week with decrease in
stability of 20%. However, a slow decrease is observed in longer time
and their stability is remained 66% after 30 days of the exposition. Thus,
the AuNPs biosynthesised from CS extract display higher stability at
room temperature in comparison with that synthesised from the other
extract [51].

3.4. Kinetic modelling

NiPs are known to be a toxic and persistent organic substance that is

emitted from dyes, pesticides and explosives [52]. Hence, the reduction Fig. 7. Changes in concentrations of 2-NiP (left) and 3-NiP (right) as a function
of NiPs into APs using NaBH4 is widely investigated. On earlier reports, of time via various kinetic models: zero-order (A and B), half-order (C and D),
the kinetic model of NiPs reduction in heterogeneous metallic nano­ first-order (E and F), one-half-order (G and H) and second-order (I and J).
particle catalysts under room temperature region was found to be
pseudo-first-order [39,53,54]. However, several recent reports showed by the NiP substrates [24] and the rate equation can be expressed as
the NiPs reduction followed zero-order or nth-order mechanism (n > 1) follows.
that depended on reaction conditions such as initial concentration of
dCNiP
NiPs [23] or coated metallic nanoparticles coverage [24]. In the present rt = − = KSθNiP = kapp CnNiP (1)
dt
work, the conversion of 2-NiP and 3-NiP into corresponding APs was
performed using BH4‾ as a reducing agent in the presence of CS-AuNPs (kNiP CNiP )x
catalyst. The reaction was conducted under a wide range of temperature θNiP = (2)
1 + (kNiP CNiP )x
from 30 to 70 ◦ C. Therefore, the reaction might undergo a reaction order
differing from pseudo-first-order. Where θNiP is the surface coverage value of NiPs, kNiP is the adsorption
With an excess of NaBH4, the catalytic reduction occurred at the constant of NiPs, x refers to the exponent related to the heterogeneity of
surface of AuNPs following Langmuir–Hinshelwood model of hetero­ the sorbent, n is the apparent order of reaction with respect to NiPs, and
geneous catalyst without leaching atom in the solution [55] and both kapp is the apparent kinetic constant which can be identified as follows:
reactants, nitrophenolate and BH4‾ ion, absorbed onto the surface of
KSkxNiP Cx−NiPn
nanoparticles before the NiPs reduction. Several mechanisms have been kapp = (3)
1 + (kNiP CNiP )x
reported for the reduction of NiPs using metal nanocatalyst that includes
surface-mediated hydrogen transfer for catalysts e.g. PdNPs, and bi­
metals [55–57] or surface-mediated electron transfer for catalysts of 3.4.1. Pseudo-zero-order kinetic
AuNPs and AgNPs [24,53,58] or combination of both these mechanisms The reaction rate based on zero-order kinetic can be expressed as
[59]. In this work, the mechanism of NiPs reduction in the presence of follows:
heterogeneous CS-AuNPs catalyst refers to be described via the electron dCNiP
transfer as illustrated in Fig. 6. The reaction mechanism can be assumed rt = − = k0 (4)
dt
via two main stages. In the first stage, the adsorption of BH4‾ ion and
electron transfer into the surface of catalyst. Due to the excess of NaBH4 Where k0 is rate constant of pseudo-zero-order reaction and has units of
used, the BH4‾ ion adsorption is assumed to be an irreversible process. mol s− 1. Integrating Eq. (4), we obtain Eq. (5).
The second stage includes the equilibrated adsorption of nitrophenolate, CNiP0 − CNiP = k0 t (5)
transferring electron from the surface of the nanoparticles into nitro­
phenolate and formation of the product via the detachment of amino­ Thus, a plot of CNiP0 − CNiP as a function of time may give a straight
phenolate. The adsorption of NiPs on the surface of the AuNPs is line, and the slope value can be used to estimate the pseudo-zero-order
reversible and modelled by the Langmuir isotherm. Thus, the reaction rate constant k0.
rate (rt) is mainly dependent on the fraction of catalyst surfaces covered

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Table 1
Rate constants derived from the kinetic experiments conducted at different reaction temperatures.
Comp. Kinetic model 303 K 313 K 323 K 333 K 343 K
− 3 2 − 3 2 − 3 2 − 3 2 3
kx10 R kx10 R kx10 R kx10 R kx10− R2

2-NP zero 2.86 0.94 3.00 0.93 3.18 0.96 3.29 0.96 3.37 0.92
half 3.32 0.99 3.59 0.98 3.84 0.97 3.96 0.99 4.20 0.98
first 4.27 0.98 4.89 0.97 5.41 0.95 5.72 0.92 6.45 0.95
one-half 6.15 0.91 7.73 0.88 9.24 0.82 10.39 0.76 12.93 0.80
second 9.92 0.80 14.2 0.74 19.12 0.67 23.6 0.61 33.56 0.63
3-NP zero 1.82 0.97 2.05 0.93 2.30 0.96 2.35 0.94 2.39 0.96
half 2.09 0.99 2.42 0.99 2.72 0.99 2.97 0.99 3.09 0.99
first 2.48 0.98 3.02 0.99 3.46 0.98 4.20 0.94 4.53 0.94
one-half 3.06 0.96 4.01 0.95 4.76 0.91 6.79 0.81 7.69 0.81
second 3.92 0.91 5.65 0.87 7.09 0.81 12.52 0.67 15.09 0.67

3.4.2. Pseudo-first-order kinetic times are shown in Fig. 7 and kapp and correlation coefficients (R2) are
The reaction rate based on first-order kinetic with respect to NiPs can summarised in Table 1. The result reveals that the reaction orders more
be expressed as follows: than first (n = 1.5 and 2) possess low correlation coefficients in all
temperatures. Thus, these kinetic models are unsuitable to describe the
dCNiP
rt = − = k1 CNiP (6) reduction reaction of NiPs. It is noteworthy that linear plots of CNiP vs
dt
time with high correlation coefficients at low temperatures (R2
Where k1 is rate constant of pseudo-first-order reaction and has units of = 0.98–0.99) confirm a pseudo-first-order but these values are signifi­
s− 1. Integrating Eq. (6), we obtain Eq. (7). cantly decreased at high temperatures (R2 = 0.92–0.95). It indicates that
model of pseudo-first-order reaction is appropriate to describe the ki­
CNiP0 netic of NiPs reduction at low reaction temperature region as well
ln( ) = k1 t (7)
CNiP known in the literature [53,60,61]. However, this kinetic model is
Thus, a plot of ln(CNiP0 /CNiP ) as a function of time may give a straight inaccurate to be employed under high reaction temperatures that can
line, and the slope value can be used to estimate the pseudo-first-order induce high disorder of NiPs molecules, led to adsorption of nitro­
rate constant k1. phenolate ions on the surface of the catalyst increasing independence of
NiPs concentration. The kinetic model of zero-order reaction shows a
3.4.3. Pseudo-nth-order kinetic low correlation between CNiP vs time whereas the half-order kinetic
The reaction rate based on nth-order kinetic with respect to NiP can indicates a good linearity of CNiP vs time plots for all tested reaction
be expressed as follows: temperatures, confirming that the behaviour of CS-AuNPs catalyst for
reductions of NiPs follows half-order reaction.
dCNiP
rt = − = kn CnNiP (8) Moreover, increasing slopes along with increase of reaction tem­
dt perature can be related to collision theory which described the move­
Where kn is rate constant of pseudo-nth-order reaction and has units of ment of NiPs molecule being more vigorous in high temperature, leading
mol1− n s− 1. Integrating Eq. (8), we obtain Eq. (9). to a better chance for the collision and more rapid reaction rate.
Therefore, this data can be used to calculate the thermodynamic pa­
1
(C(1− n) (1− n)
(9) rameters. Apparent rate constant of 2-NiP and 3-NiP were found in range
NiP0 − CNiP ) = kn t
1− n of 3.32 × 10− 3 to 4.20 × 10− 3 mol1/2 s− 1 and 2.09 × 10− 3 to
Thus, a plot of (1/(1 − n))(C(1− n) (1− n) 3.09 × 10− 3 mol1/2 s− 1, respectively. The significant difference in
NiP0 − CNiP ) with n ∕
= 1, as a function of
time gives a straight line, and the slope value can be used to estimate the reactivity of NiPs can be related to the adsorption ability of their
pseudo-nth-order rate constant kn. different molecular structures.
The apparent reaction order and rate constants can be determined
using a time-dependent manner of NiPs concentration which is moni­
3.5. Thermodynamic parameters
tored by UV-Vis measurement. By fitting the time dependence of the
corresponding NiPs concentration curves using Eqs. (5), (7) and (9), the
The values kapp of half-order reaction at different temperatures was
apparent rate constant could be obtained for corresponding reaction
used to calculate thermodynamic parameters of the hydrogenation re­
orders and an appropriate kinetic modelling could be derived from
action including activation energy (Ea), enthalpy (ΔH‡), entropy (ΔS‡),
comparing among correlation coefficients. The reactions occurred under
and Gibbs energy (ΔG‡).
reaction temperature in range of 303–343 K were confirmed by discol­
The values Ea are calculated via the Arrhenius equation [62,63].
oration of NiPs and decrease in absorbance values at 410 and 390 nm in
the UV–Vis spectra of 2-NiP and 3-NiP, respectively (Table S1). The kapp = Ae(−
Ea
RT 2
)
(10)
results showed the reactions completed in 10 min for all tests.
The value kapp of both 2-NiP and 3-NiP reductions with reaction or­ Or
ders of zero, half, first, one-half and second was calculated for different Ea
reaction temperatures. The plots of the concentrations versus reaction lnkapp = lnA − (11)
RT

Where A is the pre-exponential factor and R (8.314 J K− 1 mol− 1) is the

Table 2
Thermodynamic parameters derived from Arrhenius and Eyring equations for identical gas constant. The value exp(− Ea/RT2) represents the fraction
kinetic model of half-order reaction. of collisions which have enough energy to overcome the activation
barrier at temperature T(K).
Comp. Ea (kJ mol− 1) ΔH‡ (kJ mol− 1) ΔS‡ (J mol− 1
K− 1) ΔG‡ (kJ mol− 1)
In this work, the reduction of NiPs is proposed as a unimolecular
2-NP 4.88 2.20 -176.83 54.90 reaction. Thus, the other thermodynamic parameters (ΔH‡, ΔS‡ and
3-NP 8.60 5.93 -168.26 56.07
ΔG‡) can be estimated using the Eyring and Gibbs equations.

8
V.-D. Doan et al. Journal of Environmental Chemical Engineering 9 (2021) 106590

the adsorption ability of different molecular structures of NiPs onto the

surface of nanocatalyst [53,64,65]. It also confirms the reduction of NiPs
following the Langmuir–Hinshelwood mechanism. The values Ea are
more comparable than those of AuNPs catalysts reported in the litera­
ture [53,66].
The plot of value ln(kapp/T) vs 1/T showed positive values of ΔH‡ for
the reduction of both NiPs, indicating that the NiPs reduction is endo­
thermic because reaction products, APs, possess higher enthalpy than
that of the reactant, NiPs [59]. The value ΔH‡ for reduction of 2-NiP
(2.2 kJ mol− 1) is much lower than the value of 3-NiP reduction
(5.93 kJ mol− 1) indicated a good correlation with relative activation
energy. The values ΔS‡ provide an insight of the molecularity of the
rate-determining step. The negative value of ∆S‡ indicates that the
transition state possessed a more ordered structure than that of the re­
actants in the ground state which can be attributed to an associative
mechanism of the adsorption process of NiPs and BH4‾ onto the surface
Fig. 8. UV-Vis spectra and corresponding colour (upper photographs) of of AuNPs to form the activated state [67]. The reduction of 2-NiP with a
AuNPs + H2O2; AuNPs + red-TMB; red-TMB + H2O2 and AuNPs + red- more negative ΔS‡ (more ordered structure) confirms better adsorption
TMB + H2O2 incubated for 30 min at 40 ◦ C. (For interpretation of the refer­ ability of 2-NiP in good agreement with value Ea. The Gibbs free energy
ences to colour in this figure legend, the reader is referred to the web version of of activation (ΔG‡) identified the barrier to move from the molecular
this article.) state to the activated state, was calculated at 298 K [68]. The
free-energy was found to be 54.90 kJ mol− 1 and 56.07 kJ mol− 1 for the
Eyring equation: reduction of 2-NiP and 3-NiP, respectively, indicating that reduction of
2-NiP into 2-AP required a slightly lower energy than the conversion of
kapp ∆H ‡ ∆S‡ kB 3-NiP into 3-AP. The result reveals that the reactivity of NiPs is signifi­
ln = − + + ln (13)
T RT R h cantly dependent on the substitution position of hydroxyl group as
Gibbs equation: confirmed from the kinetic data.

∆G = ‡
∆H‡ − T∆S‡
Where kB is the Boltzmann constant (1.38 × 10− 23 J K− 1) and h is
Planck’s constant (h = 6.63 × 10− 34 J s− 1).
The plot of value ln(kapp) vs 1/T can be used to estimate the activa­
tion energy (Ea) and the thermodynamic parameters (ΔH‡ and ΔS‡) are
defined by the slope of linear plot of ln (kapp/T) vs 1/T as described in
Fig. S3. The value ΔG‡ is derived from the Gibbs Eq. (14). The results are
summarised in Table 2. The values Ea were found to be 4.88 kJ mol− 1
and 8.60 kJ mol− 1 for the reduction of 2-NiP and 3-NiP, respectively,
indicating the barrier energy of 2-NiP reduction is lower than that of 3-
NiP. The significant difference in values Ea between NiPs can relate to
(14)
3.6. Peroxidase-like activity of CS-AuNPs nanozyme and detection of
hydrogen peroxide
To evaluate the peroxidase-like activity of the CS-AuNPs nanozyme
in the oxidation of red-TMB using H2O2 as an oxidant, the solutions
containing different components were measured by UV-Vis spectroscopy
as shown in Fig. 8. The solutions containing H2O2 + AuNPs and red-
TMB + AuNPs were colourless without the peak at 654 nm corre­
sponding to ox-TMB absorption while the solution containing red-
TMB + H2O2 was slightly blue with a tiny absorption band at 654 nm,
reflecting that H2O2 slightly oxidises red-TMB into ox-TMB without the

Fig. 9. UV-Vis spectra for peroxidase-like activity of CS-AuNPs and plots of absorbance in changes of (A and B) pH range from 1–8; (C and D) incubation temperature
from 20 ◦ C to 80 ◦ C; (E and F) nanozyme volume from 10 to 70 μL; and (G and H) concentration of red-TMB from 0.5 to 3.5 mM.

9
V.-D. Doan et al.
Fig. 10. (A) UV-Vis spectra of ox-TMB with H2O2 concentration of 10–400 μM with the colour change of the corresponding solutions (upper photographs); and (B)
the linear calibration plot of the absorbance at 654 nm and H2O2 concentrations based on the peroxidase-like oxidation of red-TMB. (For interpretation of the
references to colour in this figure legend, the reader is referred to the web version of this article.)
catalyst. In addition, a strong absorption peak centred at 654 nm was
observed in the sample containing red-TMB + H2O2 + AuNPs, which
confirmed the catalytic activity of AuNPs. It is noteworthy that signifi­
cant decrease in absorbance at peak around 550 nm in the absorption
spectrum of H2O2 + AuNPs in comparison with red-TMB + AuNPs in­
dicates oxidation of Au(0) into Au (I) by H2O2, which play a role as the
active site on AuNPs in the oxidation process of red-TMB into ox-TMB
[69,70]. The result confirms CS-AuNPs behaving as a nanozyme for
peroxidase-like activity with red-TMB.
The catalytic performance of the CS-AuNPs for peroxidase-like ac­
tivity can be affected by changes in reaction conditions. In this work, the
effect of reaction factors including the pH, incubation temperature,
concentration of CS-AuNPs, and concentration of red-TMB was explored
via UV-Vis measurement. For effect of pH values, the reaction was
performed in a range of 1–8. The absorption spectra showed that the
peaks at 654 nm only appeared in pH range of 3–7. The absorbance
values were increased with increase of medium pH and a maximum
value achieved at pH 5 ( Fig. 9A and B). Greater pH values induced a
significant decrease in concentration of ox-TMB, which might relate to
the stability of ox-TMB in these media. The similar trend was observed
for the optimisation of the incubation temperature that was carried out
in a range of 20–80 ◦ C at pH 5. The absorption intensity at 654 nm
increased with high temperature and found a maximum absorbance
value at 50 ◦ C (Fig. 9C and D). Higher temperatures significantly
decreased in absorption intensity of ox-TMB, indicating low thermal
stability of ox-TMB in H2O2 in acidic medium [71]. For the quantity of
catalyst, different volumes of CS-AuNPs nanozyme (10–70 μL) was
added to the solution. The best efficiency of ox-TMB formation was
found at 60 μL of CS-AuNPs solution, which achieved the highest
absorbance value at peak 654 nm (Fig. 9E and F). The optimisation of
the red-TMB concentrations was investigated in a range of 0.5–3.5 mM
(Fig. 9G and H). The absorbance values increased with increase of
red-TMB concentrations and the best catalytic activity was found at
2.5 mM. Therefore, the most effective oxidation of red-TMB in the
presence of CS-AuNPs was at pH 5, temperature of 50 ◦ C, 60 μL of
CS-AuNPs, and red-TMB concentration of 2.5 mM.
Because H2O2 is extensively employed in numerous fields and had
environmental impact and high toxicity, a low-cost and effective sensor
for the detection of H2O2 is particularly considered by research
10
Journal of Environmental Chemical Engineering 9 (2021) 106590
community. Thus, the oxidation of red-TMB in the presence of the CS-
AuNPs catalyst dependent on concentration of H2O2 can be used to
sense H2O2 levels. In this work, various concentrations of H2O2
(10–400 μM) were added to the mixture of CS-AuNPs + acetate buffer
(pH 5) and incubated at 50 ◦ C for 30 min and absorption spectra were
then measured. The result shows that the blue colour of ox-TMB solu­
tions was changed from light to dark, along with increase in absorbance
values at 654 nm in the range of tested concentrations ( Fig. 10). The
plot of ox-TMB absorbance vs H2O2 concentrations from 10 to 400 μM
shows a good linearity with a regression equation of Abs. = 0.0023
CH2O2 + 0.897 and a correlation coefficient of R2 = 0.999. The limit of
detection (LOD) value calculated from straight line of linear calibration
was found to be 2.25 μM, which is better than the previously reported
values [72–74].
4. Conclusions
This work successfully applied a low-cost and effective method for
green synthesis of gold nanoparticles from aqueous extract of Cyn­
omorium songaricum. Gold nanoparticles were formed in multiple shapes
with a mean size of 16 nm which displayed effective catalytic ability in
reduction of nitrophenols. The previous reports showed that the
reduction of nitrophenols using NaBH4 in region of room reaction
temperature via Langmuir–Hinshelwood mechanism was followed by
the pseudo-first-order. However, the finding showed that a suitable
model for the nitrophenol reduction was pseudo-half-order even at high
temperatures. The activation energies in the reaction of 2-nitrophenol
and 3-nitrophenol in the presence of gold nanoparticles were found to
be 4.88 kJ mol− 1 and 8.66 kJ mol− 1, respectively. The thermodynamic
parameters including ΔH‡, ΔS‡ and ΔG‡ were determined from Erying
and Gibbs equations. Gold nanoparticles were successfully investigated
for detection of the hydrogen peroxide with LOD of 2.25 µM.
CRediT authorship contribution Statement
Van-Dat Doan: Conceptualization, Investigation, Writing – original
draft. Quoc-Huy Pham: Investigation, Visualization. Bao-An Huynh:
Investigation, Visualization, Writing – original draft. Thi-Lan-Huong
Nguyen: Visualization. Anh-Tien Nguyen: Visualization. Thanh-Danh
V.-D. Doan et al.
Nguyen: Methodology, Supervision, 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.
Data availability
The data used to support the findings of this study are included
within the article.
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at doi:10.1016/j.jece.2021.106590.
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