Author’s Accepted Manuscript

Microwave irradiation synthesis of silver

nanoparticles using cellulose from Eichhornia
crassipes plant shoot

Oluwatobi. S. Oluwafemi, Tanki Mochochoko,

Anyik John Leo, Sneha Mohan, Denis.N. Jumbam,
Sandile. P. Songca
www.elsevier.com

PII: S0167-577X(16)31412-4
DOI: http://dx.doi.org/10.1016/j.matlet.2016.08.116
Reference: MLBLUE21400
To appear in: Materials Letters
Received date: 28 June 2016
Revised date: 16 August 2016
Accepted date: 24 August 2016
Cite this article as: Oluwatobi. S. Oluwafemi, Tanki Mochochoko, Anyik John
Leo, Sneha Mohan, Denis.N. Jumbam and Sandile. P. Songca, Microwave
irradiation synthesis of silver nanoparticles using cellulose from Eichhornia
crassipes plant shoot, Materials Letters,
http://dx.doi.org/10.1016/j.matlet.2016.08.116
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Microwave irradiation synthesis of silver nanoparticles using cellulose from Eichhornia

crassipes plant shoot

a,b
Oluwatobi. S. Oluwafemi * Tanki Mochochokoc, Anyik John Leo a,b
, Sneha Mohana,

Denis.N.Jumbamc and Sandile. P. Songcac.

a
Centre for Nanomaterials Science Research, University of Johannesburg, Johannesburg,

South Africa.
b
Department of Applied Chemistry, University of Johannesburg, P.O. Box 17011,

Doornfontein 2028, Johannesburg, South Africa.

c
Department of Chemistry and Chemical Technology, Walter Sisulu University, Mthatha

Campus. Private bag XI, Mthatha 5117, Eastern Cape, South Africa.

* Corresponding author: oluwafemi.oluwatobi@gmail.com. Tel: +27765110322

Abstract

We herein report a simple, microwave-assisted synthesis of silver nanoparticles (Ag-NPs)

using cellulose extracted from Eichhornia crassipes (water hyacinth) plant shoot as reducing

and capping agents. The observation of brown colouration with characteristic surface

plasmon resonance (SPR) band of silver in the absorption spectra indicated the formation of

Ag-NPs. The electron microscope results showed that the as-synthesised Ag-NPs are highly

monodispersed, small, and spherical in shape with the average particle diameter of 2.17 ±

0.40 nm. The high resolution electron microscope image confirmed the crystallinity of the

material while the surface chemistry of the as-synthesised Ag-NPs studied using Fourier

transform infrared spectroscopy confirmed successful capping by cellulose.

Keywords: Water hyacinth; Silver nanoparticles; cellulose; microwave; capping agent;

reducing agent

1
1. Introduction

Research involving the synthesis, characterization and applications of metal nanoparticles

especially noble metal nanoparticles such as platinum, gold and silver nanoparticles has been

the subject of enormous interest in recent years [1, 2]. This is due to their distinct and

excellent physical, chemical, electrical and optical properties [3-6]. Hence, they are ideal for

a broad range of applications in various fields like catalysis, medicine, optics,

optoelectronics, fabrication of nanodevices, chemical or biochemical sensing, and water

purification [1-6]. Good optical properties of these noble metals resulted from their strong

absorption in the visible region caused by the collective excitation of free-electron gas –

surface plasmon resonance (SPR). Silver nanoparticles, in particular, have drawn much

attention due to their dynamic application in nonlinear optics, solar energy absorption,

biolabeling, electrical batteries (as intercalation materials), optical receptors, and catalysts for

many chemical reactions [7]. Furthermore, they show strong antimicrobial properties against

various microorganisms which widens their scope of application even further to areas such

as water treatment, treatment of burns, stainless steel materials coating, elimination of

microorganisms on fabrics, and prevention of bacteria colonization on medical devices,

dental materials etc [8-10].

Different methods of preparation have been developed for the synthesis of silver

nanoparticles (Ag-NPs) [11-15]. However, many of these methods still involve the use of

aggressive reductant, passivating agents, and non-aqueous solvents which are costly and not

environmentally benign. As part of the quest to integrate principles of “green chemistry" into

nanosynthesis, we report a microwave-assisted synthesis of Ag-NPs using cellulose extracted

from water hyacinth (WH) shoot as both reducing and capping agents and water as a solvent.

Water hyacinth is a deadly aquatic weed, known for causing environmental havocs which

include, blocking of river waters and canal, clogging irrigation and hydropower systems [16,

2
17]. Thus, huge amount of money have been devoted in many countries for the removal of

this weed using chemical, biological, and mechanical methods. Though the presence of this

weed brings many problems, recent studies have shown that this weed can also be useful as it

contains high fibre content and high percentage of cellulose in its shoot and roots [18,19].

Based on these, we reported the first synthesis of Ag-NPs using the cellulose extracted from

this plant via a conventional heating method and we investigated the effect of pH on the

morphological properties [20]. The issue of monodispersity and long-time stability especially

with ultra small sizes ≤ 5 nm has always been a primary challenge for nanomaterials. This

was also a big challenge under the conventional method we used. Hence, there is need for an

alternative method of synthesis that will improve the monodispersity at a reduced reaction

time. In this work, cellulose extracted from water hyacinth plant shoot was used in

conjunction with microwave irradiation to synthesise smaller sized, monodispersed Ag-NPs.

2. Experimental

2.1 Materials

The cellulose was extracted from water hyacinth plant shoot collected from a local river in

the Mthatha area, Eastern Cape Province, South Africa (supporting info 1). Toluene (Sigma-

Aldrich), ethanol (Shalom Lab Supplies cc), sodium hydroxide pellets, hydrogen peroxide

and silver nitrate (Sigma-Aldrich) were all of analytical-grade and were used as purchased

without further purification.

2.2 Synthesis of cellulose-capped silver nanoparticles

Cellulose solution was prepared by dissolving 0.5 g of the extracted cellulose in 100 mL of

distilled water and homogenised at 60 0C for 1 h. The pH of the solution was adjusted to 11

using 1 M NaOH and 2.5 mL of 1 M AgNO3 solution was added to the solution. This was

3
then treated in a microwave oven operating at 200 W and 75 oC. Aliquots were taken at

different reaction time followed by characterizations.

2.3 Characterization

The absorption analysis was carried out by using Perkin Elmer lambda 25 UV/Vis

spectrophotometer. The surface chemistry was investigated by using a Perkin Elmer

spectrum, one FTIR spectrometer equipped with the universal ATR sampling accessory. The

XRD analyses were carried out using XRD – a Bruker aXS D8 Advance diffractometer with

Cu Kα radiation (λ=1.5406˚ A) operated at 40 kV and 40 mA. The electron microscope

images were recorded using a JOEL JEM 2100 operating at the voltage of 200 KV.

2. Results and Discussions

In this synthesis, microwave irradiation was used because it provides uniform heating for the

preparation of metallic nanoparticles and aid the digestive ripening of these materials without

aggregation. It also provides, faster reaction rate, reduced reaction time, homogenous

nucleation and saves energy [8, 21, 22]. Water was used as the dispersing solvent because it

has a large dipole moment and thus suitable solvent for microwave heating while cellulose

extracted from water hyacinth shoot acted as both reducing and stabilising agent. The fast and

distinctive formation of a brown coloured solution at the beginning of the reaction which

intensified to dark brown as the reaction continued indicated the formation of Ag-NPs

(supporting info 2).

Figure 1A shows the absorption spectra of the Ag-NPs synthesized at different reaction times

under microwave irradiation. The obtained cellulose –capped Ag-NPs (C-Ag-NPs) displayed

absorption maxima peaks characteristic of silver surface plasmon resonance (SPR) band.

There was no significant shift in the SPR peak position (424 nm) within the first hour of the

4
reaction. However, the absorbance increased with time indicating increase in the

concentration of Ag-NPs present in the solution. After one hour, there was a bathochromic

shift in the SPR peak position from 424 nm to 437 nm. This is attributed to Ostwald ripening

i.e the dissolution of the small particles due to their high surface energy. The C-Ag-NPs

remained well dispersed in water under ambient condition for months without aggregation as

evident by negligible variation in the SPR peak position recorded after 6 months of storage

(Fig. 1 B). This confirms that the silver nanoparticles prepared using the extracted cellulose

from water hyacinth are quite stable.

Figure 2 shows the typical TEM micrograph and size distribution of the as-synthesised Ag-

NPs using cellulose extracted from WH plant shoot. The TEM micrograph indicates that the

particles are small, monodispersed and spherical in shape. The particles are in the range 1.67

to 3.71 nm with mean particle diameter of 2.17 nm and standard deviation of (σ) of 0.40 nm

indicating particle with narrow size distribution. The abundance OH reducing group of the

cellulose and the microwave heating effect breaks the Ag-precursor into smaller particles

while the inter and intramolecular hydrogen bonding network which protracts from the O-H

hydroxyl of one unit to the O ring oxygen of another unit across the glycosidic bond prevent

aggregation of the as-synthesied Ag-NPs and hence monodispersity of the as-synthesised

nanomaterial. The high resolution TEM images (Fig. 2A inset A1) of the as-synthesised C -

Ag-NPs shows the presence of lattice fringe indicating the high crystalline nature of the

material. The lattice spacing (d) of 0.233 nm obtained from the HRTEM micrograph

corresponds to the d(111) spacing for face-centered cubic (fcc) Ag . The crystalline nature

of the as-synthesised C-Ag-NPs was further confirmed by the presence of clear singular

reciprocal points shown by the fast Fourier transform (FFT) patterns (Fig. 2A inset A2).

The typical X-ray diffraction pattern of the as-synthesised C-Ag-NPs (Fig. 3) shows

diffraction peaks at 2θ values of 38.03°, 44.26°, 64.72°, 77.41° corresponding to (111), (200),
5
(220), and (311) crystallographic planes of face centred cubic silver nanoparticles. The

intensity of the (111) peak is the strongest and no peak splitting is detected indicating that the

(111) peak is the predominant orientation. The broadness of the diffraction peaks is attributed

to the nanocrystalline nature of the as-synthesized Ag-NPs. The cellulose passivation of the

as-synthesised C-Ag-NPs was confirmed using FT-IR spectroscopy (supporting info 3). The

bands at 3286 cm-1 and 2970 cm-1 are attributed to the O-H stretching vibrations and C-H

stretching (sp3 carbon) of cellulose respectively. The peak at 1630 cm-1 is due to OH bending

vibration of the absorbed water. The absorption band at 1419 cm-1 is due to the CH2 bending

while the peak at 1201 cm-1 is attributed to OH in plane bending. The peak at 1315 cm-1 and

1103 cm-1 corresponds to CH2 wagging and antisymmetric –in- phase ring stretching

respectively [22]. The presence of these bands confirmed the successful passivation of the

silver nanoparticles surfaces by the extracted cellulose from the water hyacinth shoot.

3. Conclusions

The present study revealed the synthesis of Ag-NPs using cellulose extracted from WH shoot

as both reducing and capping agent under microwave irradiation. The as-synthesied materials

are small, spherical, well dispersed in water, stable and were successfully passivated by the

extracted cellulose. This method offers a cost effective, simple and hazard-free method for

disposing water hyacinth and may be extended for the synthesis of other noble metal

nanoparticles.

Acknowledgements

This work was supported by National Research Foundation (NRF), South Africa under the

Nanoflagship programme (Grant no: 97983).

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 Highlights

 Highly water soluble, stable, small and monodispersed Ag-nanoparticles were

synthesised.
 Cellulose extracted from water hyacinth serves as both reducing and
stabilizing agent.
 The method offers a hazard-free method of disposing water hyacinth plant.

Graphical Abstract

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