Arabian Journal of Chemistry (2020) 13, 7490–7503

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Noble metallic nanoparticles from waste Nypa

fruticans fruit husk: Biosynthesis, characterization,
antibacterial activity and recyclable catalysis
Van-Dat Doan a, Minh-Tan Phung a,b, Thi Lan-Huong Nguyen c, Thanh-Chi Mai d,
Thanh-Danh Nguyen b,d,*

a
Faculty of Chemical Engineering, Industrial University of Ho Chi Minh City, Ho Chi Minh City, Viet Nam
b
Institute of Research and Development, Duy Tan University, Da Nang City, Viet Nam
c
Institute of Biotechnology and Food Technology, Industrial University of Ho Chi Minh City, Ho Chi Minh City, Viet Nam
d
Institute of Chemical Technology, Vietnam Academy of Science and Technology, 1 Mac Dinh Chi Street, District 1, Ho Chi
Minh City, Vietnam

Received 2 July 2020; accepted 22 August 2020

Available online 29 August 2020

KEYWORDS Abstract Biogenic synthesis of noble metal nanoparticles is particularly interested due to the effec-
Nypa fruticans fruit husk; tive applications for plasmonic catalysis and bioactivity. In this work, aqueous extract of waste
Waste; Nypa fruticans (NF) fruit husk was utilized to synthesize silver nanoparticles (NF-AgNPs) and gold
Reduction; nanoparticles (NF-AuNPs). The effected parameters on the green reduction of metallic nanoparti-
Nitrophenol; cles (MNPs) were investigated. Under optimum conditions of concentration, temperature and time,
Antibacterial; the biosynthesized NF-AgNPs and NF-AuNPs showed spherical nanoparticles with average size of
Recyclable catalysis 10–15 nm and 15–20 nm, respectively. The presence of AgCl in NF-AgNPs has been demonstrated
by X-ray diffraction analysis. The elemental components of all samples confirmed the presence of
anions and cations come from the aqueous extract. The biosynthesized nanoparticles were evalu-
ated bacterial activity against three bacterial strains. NF-AgNPs exhibited selective antibacterial
activity against Bacillus cereus but no activity against Staphylococcus aureus and Salmonella typhi-
murium at all tested concentrations. The recyclable catalysis activity of the biosynthesized nanopar-
ticles was evaluated for the reduction of nitrophenols in the presence of sodium borohydride which
possessed good catalytic performance in six running numbers. Additionally, AgCl played role as a
source supplying AgNPs has been demonstrated in catalytic reduction of p-nitrophenol. For study

* Corresponding author at: Institute of Chemical Technology, Vietnam Academy of Science and Technology, 1 Mac Dinh Chi Street, District 1,
Ho Chi Minh City, Vietnam.
E-mail addresses: [email protected], [email protected] (T.-D. Nguyen).
Peer review under responsibility of King Saud University.

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https://doi.org/10.1016/j.arabjc.2020.08.024
1878-5352 Ó 2020 The Author(s). Published by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Noble metallic nanoparticles from waste Nypa fruticans fruit husk 7491

of catalytic kinetic, NF-AgNPs possessed higher rate constant in comparison with NF-AuNPs
whereas TOF values of NF-AuNPs was determined to be higher than those of NF-AgNPs.
Ó 2020 The Author(s). Published by Elsevier B.V. on behalf of King Saud University. This is an open
access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction utilized to manufacture vinegar, toddy or sugar and the fruit

is used as local desserts or made into alcoholic beverages
Metallic nanoparticles (MNPs) have found many applications (Hamilton and Murphy 1988; Phetrit et al. 2020). As a result,
in various fields such as optics, medicine, biology, catalysis and abundant amount of the fruit husk is eliminated to the envi-
water treatment (Ly and Joo, 2020; Nam, et al. 2020; ronment as a waste source. The major chemical components
Darabdhara et al. 2019; Nguyen et al., 2018a,b; Hui et al. of fruit husk have been determined to include inorganic com-
2019; Khan et al. 2020). Amongst them, silver and gold pounds, cellulose, hemicellulose, lignin, protein and others
nanoparticles have been particularly considered due to their (Tamunaidu and Saka, 2011). In this study, we used aqueous
excellent biocompatibility, physicochemical properties and cat- extract of waste Nipa palm fruit husk as reducing and stabiliz-
alytic efficiency. On the other hand, green synthesis of MNPs ing agents for biosynthesis of AgNPs and AuNPs. The opti-
has paid increasing attention over chemical and physical meth- mized nanoparticles were well characterized by analytic
ods. The green approaches using bio-sources such as fungi, techniques and applied as antibacterial agents and recyclable
bacteria and plants possess many advantages such as eco- catalysts for reduction of o-, m-, p-nitrophenols.
friendliness, low-cost, availability and simple technique
(Vetchinkina et al. 2019; Abdelghany et al. 2018; Kalantari 2. Experimental
et al. 2019; Jamila et al., 2020). During the past decades, the
biosynthesis of MNPs using plant extract has been an impor- 2.1. Materials
tant topic in nanotechnology due to improvement in bioactiv-
ity, human health and environmental issues (Burlacu et al. All chemicals for synthesis were purchased from Acros (Bel-
2019; Nasrollahzadeh et al. 2019; Sharma et al. 2019; Das gium) in analytical grade and used without further purifica-
et al. 2018). It is approved that bioactive molecules with tion. Distilled water was used throughout. The Nypa
water-soluble polyol components are responsible in reduction fruticans fruit husk was collected in HoChiMinh City,
and stabilization of biogenic MNPs. In recent years, the bio- Vietnam.
genic AgNPs and AuNPs with high antimicrobial activity have
been important materials widely applied for agricultural and 2.2. Preparation of Nypa fruticans fruit husk extract
pharmaceutical fields (Rafique et al. 2017). Most of the studies
on the biosynthesis of MNPs use the fresh plant as a reducing
The NF fruit husk was washed completely with distilled water
source. However, the use of waste source gains considerable
to remove any medium components and dried in an oven dur-
economic benefits. Several recent reports have utilized effec-
ing 48 h at 80 °C. The dried powder of NF fruit husk was
tively waste parts generated from agricultural sources which
obtained after grounding process using an electronic blender.
contain the high contents of secondary metabolites responsible
The dried powder (10 g) was refluxed with 100 mL of the water
for synthesis of MNPs (Vishwasrao et al. 2019; Dodevska et al.
for 2 h. The aqueous solution was filtered under reduced pres-
2019; Agnihotri et al. 2018; Song et al. 2019).
sure and added with water to obtain 100 mL of solution. The
On the other hand, the biogenic MNPs are well known to
extract was stored at 4 °C in the refrigerator. The resultant
be effective catalysts for the complete degradation of toxic
solution was used as reducing and capping agents for biosyn-
effluents and hydrogenation of nitroaromatic compounds
thesis of metallic nanoparticles. The crude solid obtained from
(Singhal and Gupta, 2018; Ghasemi et al. 2020; Vinay et al.
concentrated process of the extract in a rotary vacuum was
2020; Khan et al. 2017; Francis et al. 2017). The later reaction
used for relating characterizations of the extract.
is an important key in organic chemistry and pharmaceutical
applications. Amino-based derivatives which are enormously
2.3. Biosynthesis and optimization of nanoparticles
used as a potent intermediate for manufacturing of many
drugs have been synthesized from hydrogenation of nitro
group (Zhu et al. 2019). However, very few reports on recycla- In a typical procedure for the biosynthesis of noble MNPs, fil-
bility of the biogenic MNPs used as a heterogeneous catalyst in trate of NF extract (1 mL) was mixed with aqueous solution of
aqueous medium have been carried out (Veisi et al. 2018; metallic ions under vigorous stirring in dark. In all experi-
Wang et al. 2019). ments, the volume of NF extract (1 mL) was kept constant.
Nypa fruticans, Nipa palm is a monoecious palm that grows The formation of nanoparticles was associated with changes
in river estuary and brackish water. Nipa palm thrives abun- in colors of the solutions. After completing reaction, the
dantly in Ryukyu Islands, southward to north Queensland biosynthesized nanoparticles were centrifuged at 10,000 rpm
and Southeast Asia (Uhl 1972). In Vietnam, Nipa palm is for 30 min and washed thrice with distilled water. The samples
planted popularly to curb coastal erosion in Mekong Delta were dried in the oven for 24 h. The optimization process was
(Fagherazzi et al. 2017). Nowadays, various use of its produc- carried out toward the best morphology and size of nanopar-
tion contributes to develop agricultural field in coastal commu- ticles. The effect of principle parameters including metallic
nities. For instants, the sap containing 14–17% sucrose is ion concentration, reaction temperature and reaction time
was investigated to reach optimum condition of the biosynthe-
7492 V.-D. Doan et al.

sis. For optimization process, UV–vis method scanned in ated by plots of ln(At/A0) versus the reaction time, t is the reac-
range of 300–700 nm was used to recognize changes in tion time (s), A0 and At are the amount of nitrophenol
nanoparticles concentration and morphology. The absorbance absorbance at time zero and t, respectively. For the reusability
of NF-AgNPs and NF-AuNPs was measured in ranges of 400– of catalysts, the nanoparticles were washed with distilled water
435 nm and 520–540 nm, respectively. and ethanol several times before reused.

2.4. Characterization of nanoparticles 3. Results and discussion

Fourier transform infrared (FT-IR, Bruker, Tensor 27, Ger- 3.1. Biosynthesis of the nanoparticles
many) was registered with the wavelength ranging from 500
to 4000 cm 1. Morphology and size of the biosynthesized Biomolecules such as phenolics and proteins contained in the
MNPs were determined by microscopy such as scanning elec- extract play a principle role in reducing metallic ions and sta-
tron microscopy (SEM, S-4800 HI-9057-0006) and transmis- bilizing nanoparticles. In mechanism of this reduction, unsta-
sion electron microscopy (TEM, JEOL JEM-1400). The ble phenoxyl radicals formed from the oxidation of phenolic
crystallinity of MNPs was determined by various techniques groups consistently reduce the metallic ions and the metal nu-
including powder X-ray diffraction (XRD, 6100 X-ray diffrac- clei produced from flocculation (Mosaviniya et al. 2019). The
tometer Shimadzu, Japan) and high resolution transmission biosynthetic process and structure of MNPs are also well
electron microscopy (HRTEM, Tecnai G2 20 S-TWIN, FEI known significant dependence on the ionic components pre-
set at 200 kV) with measuring selected area electron diffraction sented in the plant extract (Doan et al. 2020). These composi-
(SAED) patterns. An analyzer Horiba (EMAX Energy EX- tions can be included in nanoparticles product which can
400) was used to analyze energy dispersive X-ray spectroscopy induce changes in their property and activity. Thus, ionic con-
(EDX) of the powder nanoparticles. tents in the extract should be investigated before the fabrica-
tion of MNPs. In this study, content of anions including
2.5. Antibacterial activity of nanoparticles Cl , Br , NO3 , SO24 , PO34 is determined by ion chromatog-
raphy technique while content of cations Na+, K+, Mg2+,
The antibacterial activity of the biosynthesized MNPs was Ca2+ is determined by ICP-MS technique. Results are shown
tested against two Gram-positive bacterial strains (Bacillus cer- in Fig. 1. The concentration of Cl (79 mM) is very much
eus, Staphylococcus aureus) and Gram-negative bacterial strain higher than concentration of the others. In comparison with
(Salmonella typhimurium) by the disk diffusion method. the corn-cob extract reported previously, content of ion Cl
Briefly, each aliquot (50 mL) was added to 6 mm-diameter presented in NF fruit husk extract is double while content of
paper disks. Mueller Hinton agar was served as medium for anions NO3 , SO24 , PO34 is significantly lower (Doan et al.
the bacterial growth which was taken in the Petri plates with 2020). Dominance of chloride ions in the aqueous solution
bacterial culture of brain-heart infusion (100 lL, 106 CFU/ can form crystalline chloride salt of metallic ions such as
mL). The tested samples were prepared by dissolving the Ag+ during formation process of the biosynthesized nanopar-
nanoparticle solutions to the required concentrations. The ticles. For investigation of cations, concentration of ion Ca2+
NF-AgNPs solutions were diluted at various concentrations presented in the extract is not very significant while the other
of 0.62, 1.24, 2.48 and 4.96 lg/mL and The NF-AuNPs solu- ions possess high concentrations in order of K+ (83 mM),
tions were diluted at various concentrations of 1.12, 2.24, Na+ (39 mM), Mg2+ (6 mM). The presence of the inorganic
4.48, and 8.96 lg/mL. The agar plates were incubated at components in the aqueous extract is supported by the powder
37 °C/24 h. The antibacterial activity of synthesized nanoparti- EDX analysis of NF fruit husk as reported previously
cles was evaluated by the zone of incubation around the well. (Tamunaidu and Saka, 2011).
The route for biogenic synthesis of AgNPs and AuNPs is
2.6. Catalytic activity of nanoparticles illustrated in Fig. 2. The fruit husk was treated to remove
unwanted components before refluxed with distilled water to
The performance of NF-AgNPs and NF-AuNPs was investi- obtain yellow NF extract. The extract is utilized to reduce
gated toward the catalytic reduction of nitrophenols including metallic ions and stabilize nanoparticles. The formation of
o-, m-, p-nitrophenol at the room temperature. An excess MNPs can be confirmed by relating color changes. The differ-
amount of NaBH4 was used as a reducing reagent. For the
reduction, 2.5 mL of each nitrophenol (0.1 mM) and 0.5 mL
A B
of NaBH4 solution (0.1 M) were put into the cuvette and 120
Concentration (mM)

recorded its spectrum. Then 3 mg of catalysts were added to

the reaction mixture. Performance of the reduction was deter- 80
mined by UV–Vis measurements. A rapid decrease of absor-
bance at the corresponding peaks could be observed for the
40
respective nitrophenols. For study of kinetics, because the con-
centration of NaBH4 used was much greater than concentra-
tion of nitrophenols, it was expected that the reduction 0
Cl Br NO3 PO4 SO4 Na K Mg Ca
would proceed according to the pseudo-first-order reaction. Anions Cations
Thus, kinetics of the reduction can be described by the equa-
tion ln (At/A0) = kt, where k is the reaction rate constant Fig. 1 Content of anions (A) and cations (B) presented in the
(s 1) which can be found from slope of the straight line gener- aqueous extract of waste Nypa fruticans fruit husk.
Noble metallic nanoparticles from waste Nypa fruticans fruit husk 7493

Fig. 2 Schematic illustration for study of NF-AgNPs and NF-AuNPs biosynthesized from waste Nypa fruticans fruit husk extract.

ence in size and morphology of MNPs can induce deviation in increased over time which means the increasing yield of
their activity. Thus, the biosynthesis process should be investi- AgNPs.
gated parameters to find optimum reaction conditions The biosynthesis of NF-AuNPs also based on similar con-
(Nguyen et al. 2020). UV–Vis spectroscopy are used to deter- ditions of NF-AgNPs synthesis. The results show that the
mine the formation of the nanoparticles. NF-AgNPs and trend is observed differently from the biosynthesis of NF-
NF-AgNPs showed absorption peaks of surface plasmon reso- AgNPs (Fig. 4). Regarding the effect of gold ion concentra-
nance (SPR) at 418 nm and 532 nm, respectively while there is tions on the biosynthesis of AuNPs, there are no SPR peaks
no absorption peak of the extract in range of 280–600 nm. The appeared at low concentration (<0.5 mM) and high concen-
biosynthesized MNPs at optimized conditions are purified and trations (>1mM). A maximum absorbance was found at con-
followed physicochemical characterizations. The biogenic centration of 0.5 mM. Great amount of gold precipitate was
nanoparticles are applied for antibacterial assay and catalytic observed at range of high gold ion concentrations, explained
reduction of nitrophenols. the disappearance of SPR band. It can be because biomole-
cules presented in the extract are not enough to stabilize
3.2. Optimization of reaction parameters AuNPs generated from the reduction.
For study of reaction temperature, the reduction of AuNPs
The change in reaction condition can affect the reducing abil- is easier in comparison with AgNPs formation. The SPR band
ity of the bioactive molecules presented in the waste NF fruit at around 540 nm was appeared at range of low temperatures
husk extract. Hence, the formation of MNPs strongly depends (even 25 °C). As seen in Fig. 4C, the effect of reaction temper-
on the reaction conditions. In this work, the effects of various ature on the formation of AuNPs was not so significant. The
factors such as the concentration of silver, reaction tempera- increase of reaction temperature induces no change of absor-
ture and time on the biosynthesis were investigated. Fig. 3 bance values of the SPR band.
shows absorbance spectra of NF-AgNPs dependent on the Fig. 4E & 4F showed that reduction of AuNPs induces slow
reaction parameters. The appearance of SPR peaks at low con- increase of nanoparticles concentration in solution with reac-
centration of AgNPs (0.1 mM) indicated the formation of tion time. The conversation of AuNPs achieved a maximum
AgNPs. The increase of absorbance at the SPR bands along value in 20 min.
with gradually concentrated solutions around 0.1–10 mM is For further studies on characterization and application,
observed. The highest yield of the nanoparticles is obtained The MNPs were fabricated at optimized reaction conditions.
at Ag+ concentration of 3.0 mM. For influence of reaction
temperature, the reduction of NF-AgNPs was carried out in 3.3. Characterizations
range of 30–90 °C and the formation yield of AgNPs is
observed with increase of temperature (Fig. 3C and 3D). Inten- 3.3.1. FTIR spectroscopy
sive SPR peaks are not found at range of the low temperature FTIR spectroscopy was used to determine functional groups in
(below 60 °C). At higher temperatures, the absorption peaks the biosynthesized MNPs which acted as the capping agents in
appear clearly and the absorbance values increase rapidly with the extract during the synthesis. Fig. 5 showed the FTIR spec-
growth of the temperature. tra of the NF extract and the final products of nanoparticles.
To study the effect of reaction time on the biosynthesis of Accordingly, spectra of the extract revealed major bands at
NF-AgNPs, the mixture was stirred at 90 0C for 90 min and 3417, 1620, 1520, 1444, 1377, 1257, 1144 cm 1. The broad
the reaction was monitored for each interval of 30 min. Upon band at 3417 cm 1 relates to the OH stretching vibration of
the completing heating process, the appearance of absorption alcohol, phenolic, carbohydrate compounds and carboxylic
peaks is observed and the absorbance value is gradually acids. The sharp peak at 1630 cm 1 is assigned to C‚C and
7494 V.-D. Doan et al.

0.20 0.20
0.1 mM
A B

Absorbance (a.u.)
0.5 mM

Absorbance (a.u.)
0.15 1.0 mM 0.15
3.0 mM
10.0 mM
0.10 0.10

0.05 0.05

0.00 0.00
350 400 450 500 0 5 10
Wavelength (nm) Concentration (mM)
0.4 0.4
30oC
C 45oC D
Absorbance (a.u.)

Absorbance (a.u.)
0.3 60oC 0.3
75oC
90oC
0.2 0.2

0.1 0.1

0.0 0.0
350 400 450 500 60 70 80 90
Wavelength (nm) Temperature (oC)
0.4 0.4
40 min
E 50 min F
60 min
Absorbance (a.u)

Absorbance (a.u.)

0.3 70 min 0.3

90 min

0.2 0.2

0.1 0.1

0.0 0.0
350 400 450 500 40 60 80 100
Wavelength (nm) Time (min)

Fig. 3 UV–vis spectra (left) and plots of parameters versus absorbance (right) of NF-AgNPs: Concentration (A & B), reaction
temperature (C & D) and reaction time (E & F).

C‚O groups related to aromatic compounds and carbonyl 3.3.2. X-ray diffraction (XRD)
group of protein molecules. The peak at 1377 cm 1 confirmed The crystalline nature and size of biosynthesized MNPs can be
the presence of CAH group of carbohydrate compounds. The confirmed by the analysis of XRD patterns as shown in Fig. 6.
bands at 1257 cm 1 showed the in-plane bending vibration of The Bragg reflections of NF-AuNPs were observed at 2h val-
OH groups of phenolic compounds (Odeniyi et al. 2020; ues 38.22°, 44.04°, 64.68°, and 77.36° which correspond to
Hamedi and Shojaosadati 2019; Adebayo-Tayo et al. 2019). the face-centered cubic (FCC) planes of gold indexed as
Comparison of the FTIR spectra between the NF extract (1 1 1), (2 0 0), (2 2 0), and (3 1 1), respectively (card no. 00-
and the biosynthesized nanoparticles showed minor difference 004-0784). The XRD pattern of NF-AgNPs showed small
in the wavelength numbers as well as intensity of observed peaks at 2h values of 38.32°, 44.42°, 64.82° and 77.82° assigned
peaks. The spectra of NF-AgNPs and NF-AuNPs show corre- to (1 1 1), (2 0 0), (2 2 0), and (3 1 1) FCC planes of AgNPs crys-
sponding wavenumbers at 3408, 1629, 1546, 1384, 1265, talline, respectively (card no. 00-004-0783). The strong peaks
1109 cm 1 and at 3188, 1610, 1515, 1438, 1278, 1103 cm 1, at 27.84°, 32.28°, 46.24°, 54.80°, 57.44° and 67.30° correspond
respectively. These bands of the extract shifting new positions to reflections from (1 1 1), (2 0 0), (2 2 0), (3 1 1), (2 2 2), and
can relate to interactions between biomolecules and the MNPs. (4 2 0) planes of crystallite AgCl, respectively (card no. 00-
As a result, the biomolecules presented in the extract are 001-1013) (Vo et al. 2019). The presence of AgCl crystalline
proved as reducing and stabilizing agents during the biosyn- in the NF-AgNPs can be due to the reaction of Ag+ ion with
thesis of MNPs.
Noble metallic nanoparticles from waste Nypa fruticans fruit husk 7495

0.1 mM
0.6 A 0.5 mM 0.6 B

Absorbance (a.u.)
Absorbance (a.u.)
1 mM
3 mM
5 mM
0.4 0.4

0.2 0.2

0.0 0.0
400 450 500 550 600 650 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Wavelength (nm) Concentration (mM)

0.6
C 0.6
D
Absorbance (a.u.)

Absorbance (a.u.)
0.4 0.4

25 oC
40 oC
0.2 0.2
60 oC
80 oC
100 oC
0.0 0.0
400 450 500 550 600 20 40 60 80 100
Wavelength (nm) Temperature (οC)

0.6 E 0.6 F
Absorbance (a.u.)

Absorbance (a.u.)

0.4 0.4

1 min
0.2 5 min 0.2
10 min
20 min
30 min
0.0 0.0
400 450 500 550 600 0 5 10 15 20 25 30
Wavelength (nm) Time (min)

Fig. 4 UV–vis spectra (left) and plots of parameters versus absorbance (right) of NF-AuNPs: Concentration (A and B), reaction
temperature (C and D) and reaction time (E and F).

chloride ion which presented with a high content in NF composition presented in the samples is analyzed by EDX
extract. spectra represented the vertical axis with the number of X-
The XRD patterns can be used to determine the particle ray counts and the horizontal axis with energy (keV). The
size by calculated from Debye-Scherrer equation d = 0.9k/ results are shown in Figs. 7 and 8. The aqueous NF extract
bcosh, where ‘d’ is the average crystallite size in nm; ‘h’ is played a vital role in capping AgNPs can affect the morphol-
the Bragg angle; ‘k’ is the X-ray wavelength (0.1540 nm) and ogy and elemental composition presented in the sample. The
‘b’ is the line broadening at half of the maximum intensity cal- SEM image of biosynthesized AgNPs reveals that the spherical
culated by (p/180)  FWHM (full width at half maximum). shapes dispersed non-uniformly and formed clusters (Fig. 7A).
Mean size of AuNPs calculated at (1 1 1) FCC plane of XRD For EDX analysis, the strong elemental signal at 3.0 keV con-
pattern is estimated to be about 9.5 nm while mean size of firms the presence of silver in the sample. The presence of car-
AuNPs is calculated to be about 22.9 nm. The mean size of bon and oxygen elements in the spectrum suggests that organic
crystallite AgCl estimated from Debye-Scherrer’s equation is molecules of the NF extract were adsorbed on the surface of
38.1 nm. AgNPs. The appearance of chloride peak at 2.6 keV reveals
the AgCl component which is in agreement of XRD data.
3.3.3. Morphology and elemental analysis The presence of other peaks such as 1.0, 2.1, 2.4 and 3.6 keV
The surface morphologies and size of the synthesized AgNPs was assigned to elemental signals of Na, P, S, and K, respec-
are determined by SEM and TEM analysis. The elemental tively that presented in the aqueous extract of waste NF fruit
7496 V.-D. Doan et al.

tribution of NF-AgNPs. It is clear- that most of the nanopar-

NF extract ticles are in spherical shape and well dispersed. The size of
nanoparticles is distributed from 5 to 30 nm and mean particle
size is found to be 10–15 nm. The HRTEM image of NF-
AgNPs showed that the fringe spacing was 0.24 nm which cor-

1525
1377
1444

1257
related well with the spacing between (1 1 1) plane of FCC sil-

1114
1620
ver. The selected area of electron diffraction (SAED) pattern
3417

reveals bright rings, indicating the presence of crystalline nat-

ure. The bright circular rings correspond to reflection planes of
AgNPs and AgCl as also observed in the previous report
(Doan et al. 2020).
NF-AgNPs SEM images of biosynthesized AuNPs showed that the
particles dispersed well on the surface (Fig. 8A). The EDX
analysis appeared similar peaks in the patterns of NF-
AgNPs (Fig. 8B & 8C). The strong peaks of potassium,
1265
1109
chloride elements relating to their high contents (19% and
1546
1384

27% (w/w), respectively) in the sample were observed. The

1629
3408

data showed three strong signals for gold at 2.1, 8.5 and
9.7 keV. A low content of gold in the samples was observed
approx. 13%. Percentage of carbon (26.5%) is lower than
that of the NF-AgNPs. It can be because NF-AuNPs con-
NF-AuNPs tain different capping agents from NF-AgNPs. TEM images
confirm that most of AuNPs exist in spherical shape and dis-
persed consistently. Their sizes are in range of 5–30 nm with
a mean size of 15–20 nm (Fig. 8D & 8E). HRTEM images
and SAED patterns clearly confirm crystal lattice nature of
1515
1438
1278

NF-AuNPs which are in agreement of XRD data

3188

1103
1610

(Fig. 8F). The lattice fringe corresponding to the (1 1 1) plane

had spacing of 0.22 nm. The bright circular rings in SAED
images relating to (1 1 1), (2 0 0), (2 2 0) and (3 1 1) Bragg’s
4000 3500 3000 2500 2000 1500 1000 500 reflection planes of AuNPs indicated nanoparticles existed
-1 in crystalline nature.
Wavenumber (cm )
Fig. 5 FTIR spectra of NF fruit husk extract, NF-AgNPs and 3.4. Stability of colloidal solutions
NF-AuNPs.
Due to agglomeration of nanoparticles in colloidal solutions
over time which strongly influence on the properties and appli-
* cations, their stability in the solutions should be investigated.
# : AgNPs
* To study stability of nanoparticles, both colloidal solutions
* : AgCl * were exposed to daylight and measured UV–vis spectroscopy
NF-AgNPs #
** # after various times after 3, 7, 14, 21 and 30 days. Stability of
# #
* the colloidal solutions can be determined by decrease of absor-
(111) bance values at the SPR band in UV–Vis spectra. As shown in
Fig. 9, both the nanoparticles began to slightly agglomerate in
(200)
initial 3 days. Decrease of the nanoparticle concentration
(220) (311)
NF-AuNPs (about 7–8%) in the colloidal solutions was estimated. Rapid
decrease in stability of the solutions is observed according to
10 20 30 40 50 60 70 80 the investigated time. Stability of the nanoparticle solutions
was around 70–77% after 14 days of the exposition and
2 theta (degree) remained around 35–46% after 30 days of the exposition.
The NF-AgNPs solution possessed a slightly higher stability
Fig. 6 XRD patterns of biosynthesized NF-AgNPs and NF-
in comparison with NF-AuNPs.
AuNPs.
3.5. Antibacterial assay
husk. From EDX spectra data, average contents of elements in
NF-AgNPs were plotted in Fig. 7C. Result shows that the Antibacterial activity of both the biosynthesized nanoparti-
sample contains about 26% (w/w) of silver and 13% (w/w) cles was tested against three strains including B. cereus, S.
of chloride. The content of carbon which represents organic aureus (Gram-positive) and S. typhimurium (Gram-negative)
compounds in the sample is about 38% (w/w). TEM analysis with various concentrations. The extract and ampicillin were
is used to determine shape and size of metallic nanoparticles. used as the negative and positive controls, respectively. The
Fig. 7D &7E shows the TEM images and the particle size dis- results showed that NF-AuNPs did not exhibit bioactivity
Noble metallic nanoparticles from waste Nypa fruticans fruit husk 7497

Fig. 7 (A) SEM image; (B) EDX spectrum; (C) Elemental percent collected from EDX spectrum; (D) TEM and SAED pattern (inset);
(E) particle size distribution; and (F) HRTEM of NF-AgNPs.

Fig. 8 (A) SEM image; (B) EDX spectrum; (C) Elemental percent collected from EDX spectrum; (D) TEM and SAED pattern (inset);
(E) particle size distribution; and (F) HRTEM of NF-AuNPs.

against any bacterial strain even at the highest concentration the sample NF-AgNPs exhibited high antibacterial activity
(8.95 lg/mL) while the sample of NF-AgNPs exhibited selec- against B. cereus but it did not inhibit two strains, S. aureus
tive antibacterial activity against three tested strains. The and S. typhimurium at tested concentration. Moreover, the
results of antibacterial activity for the NF-AgNPs are listed bioactivity is increasing with increase of the biosynthesized
in Table 1. The antibacterial effect of NF-AgNPs was pre- NF-AgNPs concentration. The minimum inhibitory concen-
sented in zone of inhibition and influence of concentrations tration (MIC) value of NF-AgNPs against B. cereus was
on their bioactivity was investigated. The results showed that found to be 1.24 lg/mL.
7498 V.-D. Doan et al.

1.0 1.0 100

Initial Initial
3 days 3 days
Absorbance (a.u.) 0.8 0.8 80

Absorbance (a.u.)
7 days 7 days

Stability (%)
14 days 14 days
0.6 21 days 0.6 21 days 60
30 days 30 days
0.4 0.4 40

0.2 0.2 20 NF-AgNPs

A B C NF-AuNPs
0.0 0.0 0
350 400 450 500 550 600 400 450 500 550 600 650 700 0 5 10 15 20 25 30
Wavelength (nm) Wavelength (nm) Time (days)

Fig. 9 UV–Vis spectra of NF-AgNPs (A) and NF-AuNPs (B) and plot of stability against time (C).

Table 1 Antibacterial effect of NF-AgNPs at various concentrations.

Bacterial strains Zone of inhibition (mm)
Ampicillin Extract Concentration of NF-AgNPs (lg/mL)
0.62 1.24 2.48 4.96
B. cereus 18.5 6 6 7 9 12
S. aureus 24 6 6 6 6 6
S. typhimurium 26 6 6 6 6 6

3.6. Catalytic performance for reduction of nitrophenols tion spectra of the reactions were directly tested from the cuv-
ette. With the addition of NaBH4, the color change was
Organic aromatic substances especially nitrophenols, which observed for all nitrophenols and the maximum peaks of o-,
are extensively used in industrial process, possess highly toxic m- and p-nitrophenols shifted to new positions at 415, 391
effects in aquatic environment. The presence of low concentra- and 400 nm, respectively. The regular decline of the corre-
tion of nitrophenols also poses serious threat to the life envi- sponding peaks and formation of aminophenols with increas-
ronment because it is difficult to degrade in the normal ing absorbance of new peaks were observed upon completing
condition (Gul et al. 2017; Albukhari et al. 2019). Moreover, addition of the catalyst. Due to high amount of NaBH4 (excess
catalytic hydrogenation of nitrophenols into aminophenols 200 times) and very little amount of the nanoparticles (3 mg),
has potential of great pharmaceutical application. the kinetic of nitrophenols reduction follows the pseudo first
The aminophenols are essential precursors for synthesis of order reaction (Nguyen et al. 2020). The recyclable perfor-
numerous drugs such as paracetamol and phenacetin mance of the catalysts was also tested for five reaction recycles.
(Majumdar et al. 2016). In the present work, evaluation of cat- The catalyst was washed with distilled water and then ethanol
alytic performance for reduction of o-, m-, p-nitrophenols in before each reuse process performed.
aqueous medium was performed by catalytic hydrogenation Fig. 10 shows that reduction time of all nitrophenols using
of NaBH4 using UV–vis method as a model reaction. It is well NF-AgNPs was completed in 9 min while the rate constants of
known that reduction of nitrophenols using NaBH4 without the nitrophenols were slightly different. The rate constant val-
catalyst is a thermodynamically favorable reaction but it is ues of o-, m- and p-nitrophenols were found to be 3.54x10 3,
also a kinetically unfavorable reaction due to the kinetic bar- 2.49x10 3 and 2.70x10 3s 1, respectively. The recycling pro-
rier between the BH4 and nitrophenolate ions. In fact, inten- cess showed that the recycle ability of NF-AgNPs is strongly
sity and maximum peaks of nitrophenols in UV–vis spectra dependent on the substrate structure. The catalysis perfor-
remain unchanged over time without the catalyst as reported mance of NF-AgNPs was stable in the reduction of o- and p-
elsewhere (Vo et al. 2020; Nguyen et al. 2019a,b). This barrier nitrophenols without decays after 5 successive recycles
can be overcome by the addition of catalyst such as noble met- (yield > 97%) whereas yield of m-nitrophenol reduction
als that performed via an electron transfer mechanism. In this reduced to 80% after the first recycle. It can be because
mechanism, both borohydride and nitrophenolate ions are adsorbed or/and released process of m-nitrophenol is slower
played roles as donor and acceptor, adsorbed/released on the than the other substrates. However, trend of the nitrophenol
catalyst surface where electrons are transferred from borohy- reduction in the presence of AgNPs was not unique with the
dride to nitrophenolate ion (Nguyen et al. 2019a,b). Therefore, previous study (Doan et al. 2020). It can relate to difference
the catalytic effect is dependent on the property of both of chemical compositions, especially content of AgCl between
reagents and catalyst. Moreover, the reusability of noble metal the catalysts. Although composite Ag@AgCl is well known as
catalysts is particularly necessary to effectively reduce the cost. an effective catalyst for the reduction of nitrophenols
Results for the remediation of nitrophenols in the presence (Konvičková et al. 2018; Attia and Mohamed, 2018; Zhou
of the biosynthesized AgNPs are shown in Fig. 10. The absorp- et al. 2017), the role of AgCl in this reaction has not been eval-
Noble metallic nanoparticles from waste Nypa fruticans fruit husk 7499

4 0.5
A B C

Absorbance (a.u.)

Conversion (%)
0.0 100
3
80

Ln(At/A0)
-0.5

2 -1.0 60
9 min
-1.5 40
1 k = 3.54x10-3 s-1
-2.0 20
R2 = 0.93
0 -2.5 0
300 350 400 450 500 550 600 0 100 200 300 400 500 600 1 2 3 4 5 6
Wavelength (nm) Time (s) Running numbers
4 0.5
D E 100
F
Absorbance (a.u.)

Conversion (%)
0.0
3
80

Ln(At/A0)
-0.5

2 -1.0 60

-1.5 40
9 min
1 k = 2.49x10-3 s-1
-2.0 20
R2 = 0.99
0 -2.5 0
300 350 400 450 500 550 600 200 300 400 500 600 1 2 3 4 5 6
Wavelength (nm) Time (s) Running numbers
4 0.5
G H K
Absorbance (a.u.)

100

Conversion (%)
0.0
3
80
Ln(At/A0)

-0.5

2 -1.0 60
9 min
-1.5 40
1 k = 2.70x10-3 s-1
-2.0 R2 = 0.97 20

0 -2.5 0
300 350 400 450 500 550 600 0 100 200 300 400 500 600 1 2 3 4 5 6
Wavelength (nm) Time (s) Running numbers

Fig. 10 UV–vis spectra (left), first order kinetics (middle) and conversion efficiency for 5 running numbers (right) of o-nitrophenol (A, B,
C), m-nitrophenol (D, E, F) and p-nitrophenol (G, H, I) by NaBH4 in the presence of NF-AgNPs.

4 4
A B

3 3
Absorbance (a.u.)
Absorbance (a.u.)

2 2
5 min 60 min

1 1

0 0
300 350 400 450 500 550 600 300 350 400 450 500 550 600
Wavelength (nm) Wavelength (nm)

Fig. 11 UV–vis spectra of reduction of p-nitrophenol by NaBH4 in the presence of AgCl (A) and reused AgCl (B).

uated. In the present work, we investigated the reduction of 4- values almost were not decreased in 60 min after addition of
nitrophenol in the presence of crystalline AgCl catalyst and its the catalyst, indicating the crystalline AgCl deactivated after
recyclable ability. the first recycle. Therefore, it is supposed that surface of crys-
The reaction was carried out under the same conditions talline AgCl is attached by the other molecules which can
with the presence of crystalline AgCl and recognized by pro- induce deactivation of the catalyst. To study chemical compo-
gressive decrease of the absorbance at 400 nm in UV–vis spec- sitions, the used catalyst was measured XRD spectroscopy.
tra. The results revealed that the crystalline AgCl was an The result shows the XRD pattern of the used catalyst
effective catalyst and the reaction was rapidly completed in appeared peaks at 2h values of crystallite silver similarly to
only 5 min (Fig. 11A). For the recycle process, the catalyst that of the NF-AgNPs sample (Fig. 12). It revealed that the
sample was washed with water and ethanol to remove organic used catalyst was covered by the crystalline silver which could
compounds before reuse. Fig. 11B showed that the absorbance be formed from the reduction of AgCl molecules into crys-
7500 V.-D. Doan et al.

* reduction of reaction time (5 min). The rate constants of

# AgNPs B
NF-AuNPs catalyst for reduction of o-nitrophenol, m-
* AgCl nitrophenol and p-nitrophenol were found to be 2.34  10 3
* s 1, 1.12  10 3 s 1 and 3.42  10 3 s 1, respectively. It
#
*
clearly reveals that the catalytic reduction of nitrophenols is
dependent on both the nanoparticles and reactants due to dif-
#
ferent interaction of nitrophenols and nanoparticle surfaces
* * # *# (Doan et al. 2020). A comparison of catalysis activity with pre-
* * vious reports is shown in Table S1. For recycling process, it is
observed that the recyclable ability of NF-AuNPs is lower
* A than that of NF-AgNPs. The hydrogenation performance of
o-nitrophenol is gradually declined after six running numbers
and achieved 80% at the sixth run while yield of m-
* nitrophenol reduction decreased (about 82%) after the second
* run. The stability of NF-AuNPs catalyst for p-nitrophenol
reduction is very much lower than stability of NF-AgNPs.
* * Catalytic yield of NF-AuNPs reduced to 68% after the second
*
* * run.
In addition to rate constant, turnover number (TON) and
10 20 30 40 50 60 70 80 the turnover frequency (TOF) are important parameters used
2 theta (degree) for comparison of catalyst performance. In this heterogeneous
catalyst, TON is the number of nitrophenol moles that 1 mol
Fig. 12 XRD pattern of AgCl before reduction of p-nitrophenol
of nanocatalyst may convert into aminophenol. TOF value is
(A) and after reduction of p-nitrophenol (B).
simply calculated by TON/time. For NF-AgNPs catalyst,
TOF values for three nitrophenols were found to be
NO2 6.4  10 5 s 1 while higher values were found for NF-
AuNPs catalyst. TOF values are calculated to be 2.1  10 4
s 1 for o- and m-nitrophenol reductions and 6.3  10 4 s 1
NaBH4 for p-nitrophenol reduction in NF-AuNPs catalyst. The high
TOF values of NF-AuNPs catalyst are attributed to a low con-
OH
tent of gold in NF-AuNPs catalyst compared with that of sil-
AgCl Ag0 ver in NF-AgNPs catalyst although reaction time of NF-
AuNPs catalyst is higher.

NH2 4. Conclusions

In this study, highly efficient and simple synthesis of noble

metal nanoparticles was accomplished by utilization of waste
OH Nypa fruticans fruit husk extract. This method not only offered
a low-cost and reduced-toxic synthesis but also used effectively
Fig. 13 Proposed mechanism of AgCl catalyst for reduction of the waste sources in the agricultural field. The biomolecules in
p-nitrophenol. the aqueous extract acted as capping agent and reducing agent
allowed a transformation of metallic ions to MNPs. The
cations and anions presented in the extract was major reasons
talline silver on their surface by NaBH4. As a result, the estab-
to explain presence of AgCl in the NF-AgNPs and low content
lished crystalline silver played a role as an effective catalyst for
of metallic nanoparticles in the solid samples. Average size of
reduction of p-nitrophenol. Due to the disappearance of sur-
AgNPs and AuNPs is about 10–15 nm and 15–20 nm, respec-
factants, the crystalline silver with large size, which is approved
tively. NF-AgNPs exhibited selective antibacterial activity that
by sharply intense peaks in the XRD pattern, covers on the
showed the strong bioactivity against B. cereus but no activity
AgCl surface led to a low surface area of the catalyst. Thus,
against S. aureus and S. typhimurium at all tested concentra-
the crystalline AgCl is easy to be deactivated in the first recy-
tions. The biosynthesized nanoparticles also demonstrated
cle. A proposed mechanism of the AgCl catalyst can be illus-
potentially recyclable catalysts in reduction of nitrophenols
trated in Fig. 13. It reveals the role of AgCl in NF-AgNPs
into the corresponding aminophenols. The presence of AgCl
sample as a source supplying AgNPs in the catalytic reduction
in NF-AgNPs as a source supplying AgNPs for the reduction
of p-nitrophenol using NaBH4.
reaction. The kinetic studies showed that rate constants of NF-
For the catalytic reduction of nitrophenols in the presence
AgNPs were higher than those of NF-AuNPs. However, TOF
of NF-AuNPs, the results are shown in Fig. 14. A different
values of NF-AuNPs were found to be greater than those of
trend was observed in comparison with the NF-AgNPs cata-
NF-AgNPs. The nanoparticles could be used effectively with
lyst. The significant decrease of catalytic performance for
six running numbers. Hence, the noble nanoparticles biosyn-
hydrogenation of o-nitrophenol and m-nitrophenol can be
thesized from this waste source encompass a wide range of
confirmed by increase of reaction time (15 min) while the per-
applications that can be used for varied scientific domains.
formance of p-nitrophenol hydrogenation is increasing with
Noble metallic nanoparticles from waste Nypa fruticans fruit husk 7501

4 0.5
A B C
Absorbance (a.u.) 0.0 100

Conversion (%)
3
80

Ln(At/A0)
-0.5

2 -1.0 60

15 min -1.5 40
1
-2.0 k = 2.34x10-3 s-1 20
R2 = 0.96
0 -2.5 0
300 350 400 450 500 550 600 0 200 400 600 800 1000 1 2 3 4 5 6
Wavelength (nm) Time (s) Running numbers
4 0.5
D E F
Absorbance (a.u.)

100

Conversion (%)
0.0
3
80

Ln(At/A0)
-0.5
2 -1.0 60

-1.5 40
1 15 min k = 1.12x10-3 s-1
-2.0 R2 = 0.99 20
0 -2.5 0
300 350 400 450 500 550 600 0 200 400 600 800 1000 1 2 3 4 5 6
Wavelength (nm) Time (s) Running numbers
4 0.5
G H I
Absorbance (a.u.)

0.0 100

Conversion (%)
3
80
Ln(At/A0)

-0.5

2 5 min -1.0 60

-1.5 40
1 k = 3.42x10-3 s-1
-2.0 R2 = 0.99 20

0 -2.5 0
300 350 400 450 500 550 600 0 100 200 300 400 1 2 3 4 5 6
Wavelength (nm) Time (s) Running numbers

Fig. 14 UV–vis spectra (left), first order kinetics (middle) and conversion efficiency for 6 running numbers (right) of o-nitrophenol (A, B,
C), m-nitrophenol (D, E, F) and p-nitrophenol (G, H, I) by NaBH4 in the presence of NF-AuNPs.

Declaration of Competing Interest challenges. Colloids Surf A: Physicochem. Eng. Aspects 577, 548–
561.
Attia, Y.A., Mohamed, Y.M.A., 2018. Silicon-grafted Ag/AgX/rGO
No potential conflict of interest was reported by the
nanomaterials (X = Cl or Br) as dip-photocatalysts for highly
authors. efficient p-nitrophenol reduction and paracetamol production.
Appl. Organometal. Chem. 33, e4757.
Appendix A. Supplementary material Burlacu, E., Tanase, C., Coman, N.A., Berta, L., 2019. A Review of
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Boukherroub, S.R., 2019. Ag and Au nanoparticles/reduced
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