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Green and gentle synthesis of Cu2O

nanoparticles using lignin as reducing
and capping reagent with antibacterial
properties
a a a
Peipei Li , Wei Lv & Shiyun Ai
a
College of Chemistry and Material Science, Shandong
Agricultural University, 271018, Daizong Street 61, Taian,
Shandong, P.R. China
Published online: 03 Mar 2015.

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To cite this article: Peipei Li, Wei Lv & Shiyun Ai (2015): Green and gentle synthesis of Cu2O
nanoparticles using lignin as reducing and capping reagent with antibacterial properties, Journal of
Experimental Nanoscience, DOI: 10.1080/17458080.2015.1015462

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 Journal of Experimental Nanoscience, 2015
http://dx.doi.org/10.1080/17458080.2015.1015462

Green and gentle synthesis of Cu2O nanoparticles using lignin as reducing and
capping reagent with antibacterial properties
Peipei Li, Wei Lv* and Shiyun Ai*

College of Chemistry and Material Science, Shandong Agricultural University, 271018, Daizong Street
61, Taian, Shandong, P.R. China
(Received 21 October 2014; final version received 31 January 2015)

In this work, Cu2O nanoparticles of a particular shape were prepared by an eco-

Downloaded by [Universite Laval] at 04:37 04 March 2015

friendly, gentle and low-cost synthetic method using lignin as a reducing and
capping reagent. Structure and morphology of the Cu2O nanoparticles were
characterised by high-resolution transmission electron microscopy, X-ray
photoelectron spectroscopy, X-ray diffraction (XRD) and Fourier-transform
(FT-IR) spectroscopy. The results established that Cu2O nanoparticles coated by
lignin showed a particular shape. The morphology of Cu2O nanoparticles
presented as some loose accumulation of particles just like broccoli, and the
particle size range was between 100 and 200 nm. And, the XRD revealed the
structure of crystalline of the Cu2O nanoparticles. In addition, the sterilisation of
Cu2O nanoparticles on Staphylococcus aureus (S. aureus) and Escherichia coli (E.
coli) was also investigated. The Cu2O nanoparticles showed effective bactericidal
activity against E. coli and S. aureus. The antibacterial rate could get 100% after
30 min with 4.0 g/L Cu2O nanoparticles. Furthermore, the Cu2O nanoparticles
were confirmed to have low cytotoxicity.
Keywords: Cu2O nanoparticles; lignin; antibacterial; Escherichia coli;
Staphylococcus aureus

1. Introduction
Nowadays, Cu2O nanoparticles, as an excellent p-type semiconductor with a band gap of
2 eV,[1] have attracted considerable attention. And, Cu2O nanoparticles have been widely
used in various fields based on their unique magnetic, electronic and optical properties,
such as CO oxidation,[2] gas sensing,[3] photodegradation,[4] photocatalyst [5] and so on.
It is known that the sizes, structures and shapes which can influence the potential
applications are dependent on the synthesis conditions and methods.[6 8] Numerous
literatures have reported the synthesis methods of Cu2O nanoparticles. The commonly
used methods include long-chained alcohol reduction, electro-deposition, sol gel,
solution phase and also chemical reduction.[9,10] Some synthesis methods were more or
less having some shortcomings. For example, large quantities of organic matter being used
in the long-chained alcohol reduction method are harmful to the environment and difficult
to handle, and also the method needs the condition of high temperature. And the electro-
deposition, sol gel, solution phase are not suitable for mass production. Therefore, the
most frequently used method is the chemical reduction, reducing Cu (II) ions to Cu (I)

*Corresponding authors. Emails: lw83825@yahoo.com.cn; ashy@sdau.edu.cn

Ó 2015 Taylor & Francis

 2 P. Li et al.

ions, followed by the stabilisation step for the Cu2O nanoparticles in the solution.
However, the common reducing reagents, such as polyols,[11] sodium citrate,[12] sodium
borohydride [13] or other organic matters, may present biological hazards or
environmental toxicity. As the global environment is facing with mounting challenges
caused by human activity, it is desirable taking into account to use renewable, nontoxic
materials and reagents.
Some papers have reported the green and convenient synthesis of Au, Ag, Cu, Pt and Pd
nanoparticles reducing and stabilizing by natural products, like silk fibroin, cellulose, starch,
humic acid, carbohydrates, lignin and so on.[14 18] Among them, lignin is a waste product
which comes from the wood pulp industry, and it is the second-most abundant on earth, just
second to cellulose. Lignin is a noncrystalline and heterogeneous polymer with a network
structure, widely existing in higher plant cells.[19] And, lignin is the only kind of biomass
constituent that belongs to the aromatic compounds. Structurally, it contains many aliphatic
and aromatic hydroxyls, several aromatic methoxyls, carboxyls, carbonyls and ethereal
moieties.[20] As lignin has many aliphatic hydroxyl groups, it can be used in reduction of
Downloaded by [Universite Laval] at 04:37 04 March 2015

metal salt to metal nanoparticles.[21] The formation of palladium nanoparticles using lignin
as both reducing and stabilising reagents has been investigated.[22] However, copper salt
reduced by lignin to Cu2O nanoparticles has not been reported.
In our work, an eco-friendly, convenient and gentle approach for synthesising Cu2O
nanoparticles had been developed using lignin by a chemical reduction method. The route was
shown in Scheme 1. The following chemical reaction equation can be written for the process.

(1)

(2)

Lignin can dissolve in alkali solution. In alkali solution, the copper hydroxide was
formed. The massive aliphatic hydroxyl groups of lignin have excellent reduction
properties.[22,23] Cu (II) ions were reduced to Cu (I) oxide (Cu2O) nanoparticles. The
aliphatic hydroxyls were oxidised into carbonyls. As lignin has many oxygenous groups, it
has good adsorption properties for metal ions.[24] Therefore, the lignin can also be used as
stabilising agent.
In our case, the antibacterial activity of Cu2O nanoparticles was also investigated. The
results indicated that Cu2O nanoparticles can be an efficient antibacterial material. And,
we have demonstrated that the Cu2O nanoparticles exhibit low cytotoxicity. Moreover,

Scheme 1. Schematic illustration of the synthesis of Cu2O nanoparticles coated with lignin.
 Journal of Experimental Nanoscience 3

Cu2O nanoparticles are quite cheaper than the traditional sterilising materials like silver
nanoparticles.[25 27] Therefore, Cu2O nanoparticles may have a wide range of
applications in agriculture, medicine and many other fields.

2. Experimental
2.1. Materials and reagents
The lignin samples were a gift from Quan Lin Paper Co., Ltd. (China). The lignin samples
need to be purified before being used. All other chemicals reagents including
CuSO4¢5H2O, NaOH and HCl were of analytical reagent grade and used without further
purification. CuSO4¢5H2O, NaOH, HCl, cell counting kit-8 (CCK-8), nutrient broth and
nutrient agar (NA) were obtained from Reagent Company (China). Escherichia coli was
selected from Gram-negative bacteria and Staphylococcus aureus was selected from Gram-
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positive. The cells used in the tests are HeLa cells. All the bacteria and cells were obtained
from the College of Animal Science and Technology, Shandong Agricultural University
(China). All glassware was autoclaved prior to be used in the bacterial tests.

2.2. Purification of lignin

The lignin is directly derived from papermaking waste liquid, so before being used, the
lignin needs to be purified. Lignin sample (50.0 g) was placed in 250 mL of distilled water,
and then the mixture was centrifuged at 12,000 rpm for 5 min, remove the insoluble
impurities. The obtained lignin solution was adjusted to pH 2»3, and then centrifuged
again at 12,000 rpm for 5 min, remove the supernatant. Repeat the step (dissolve the lignin
precipitation with 200 mL of distilled water and centrifuge at 12,000 rpm for 5 min and
remove the supernatant.) three times to get a pure lignin sample. The lignin precipitation
was air-dried at room temperature for further experiments. This method does not adopt
toxic reagents like ionic liquids, it is a green approach.

2.3. Preparation and characterisation of Cu2O nanoparticles

0.15 g pure lignin was dissolved in 5 mL of distilled water, and then the lignin solution was
adjusted to pH 10. 5 mL of lignin solution was mixed with 5 mL of 0.02 mol/L CuSO4
solution in a capped round-bottom flask and stirred for 2 h at 90  C. Finally, the solution
was centrifuged at 12,000 rpm for 5 min. The precipitation was the final product.
The morphology, size and crystallinity of Cu2O nanoparticles were determined by high-
resolution transmission electron microscopy (HRTEM), carried out on an H-7650 TEM
with an acceleration voltage of 200 kV. X-ray diffraction (XRD) pattern of Cu2O
nanoparticles was performed at D/MAX X-ray diffractometer (Rigaku, Japan) with Cu
Ka radiation. X-ray photoelectron spectroscopy (XPS) spectra were recorded with the Mg
Ka source (hn D 1253.6 eV). Fourier-transform (FT-IR) spectra in transmission mode
were recorded using a Nicolet Impact 400 D FTIR spectrometer (4000 400 cm, 4 cm
resolution, KBr pellet).
 4 P. Li et al.

2.4. Antimicrobial performance and cytotoxicity tests

Antimicrobial tests were conducted according to the procedure described in the literature.[28]
All the target bacteria were harvested by centrifugation, washed with phosphate buffered
saline (PBS; pH D 7.0) and resuspended in PBS with the cell concentration at approximately
6 £ 108 colony forming units mL¡1. 10 mL bacterial suspensions were inoculated into
190 mL Cu2O nanoparticles solution. Inoculate the grown bacterial suspension on NA in
Petri dishes after certain number of sterilisation time. After 24 h cultivation at 37  C, the
number of survived cells was counted. The number of surviving cells was calculated as a
percentage in comparison with no Cu2O nanoparticles experiment. Each experiment was
performed in triplicate. All materials used in the experiments were autoclaved for 30 min at
120  C at 0.1 Mpa.
CCK-8 assays were carried out according to the manufacture’s protocol to evaluate the
cytotoxicity of the Cu2O nanoparticles. The cell viabilities of HeLa cells were tested after
being exposed to Cu2O nanoparticles at different concentrations (0 50 mg/mL). The
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plates were read in an SH-1000 Lab microplate reader at 450 nm.

3. Results and discussion

3.1. Characterisation of Cu2O nanoparticles
Figure 1 shows the XRD pattern of Cu2O nanoparticles sample, which clearly reveals the
structure of crystalline. The peaks in this pattern are sharp and have no significant
scattering background. And all the peaks match well with standard data (JCPDS, No. 05-
0667). The (111) peak at 36.526 (d D 0.2454) is the most strong peak of the pattern, and
(110) peak at 29.661 (d D 0.3015) is the weakest in intensity. The XRD shows the final
product is a pure Cu2O sample.[29]
Figure 2(a) shows an HRTEM image of the synthesised Cu2O nanoparticles. The
obtained Cu2O nanoparticles reveal possessing homogeneous distribution. The
morphology can be observed more clearly in Figure 2(b). As shown in Figure 2(b), the

Figure 1. XRD patterns of Cu2O nanoparticles sample.

 Journal of Experimental Nanoscience 5
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Figure 2. HRTEM images of the synthesised Cu2O nanoparticles.

morphology of Cu2O nanoparticles present as some loose accumulation of particles just

like broccoli. Our imagination could be further confirmed by a TEM image with higher
magnification (Figure 2(c)). The surface of Cu2O nanoparticle seems to have a layer of
transparent material as displayed in Figure 2(c). Probably, the transparent material is the
lignin which played as reducing and supporting agents. The crystal planes of Cu2O
nanoparticles are shown in Figure 2(d), and it is more clearly shown in the inset of
Figure 2(d), parallel and perpendicular to the Cu2O nanoparticle have the spacings of
about 0.21 and 0.15 nm. The lattice spacings correspond to those of (200) and (220)
planes, respectively, which can be proved by XRD (Figure 1). These results indicate that
the Cu2O nanoparticles are of high crystallinity.
XPS is an available technique to probe the valence state and surface modification of the
samples. Figure 3(a) represents the full scan spectrum of Cu2O nanoparticles. There are
four peaks obtained at the binding energies of 933, 533, 401 and 283 eV for Cu 2p3, O 1s,
N 1s and C 1s, respectively. In Figure 3(b), one peak located at 952.3 eV is assigned to
Cu2O, the other peak located at 932.4 eV is Cu2O or Cu metal.[30 32] In contrast to the
XRD pattern (Figure 1), we can conclude that Cu 2p region reveals that the sample is pure
Cu2O nanoparticles. Figure 3(c) depicts the XPS peaks of C 1s, the strong peak is
dominated by three peaks with binding energies of 288.1, 286 and 284.8 eV. Assigned to 1s
carbon, the first peak located at 288.1 eV includes O CHO and CHO. Centred at 286 eV,
the peak includes C O H and C O C. The peak at 284.8 eV is due to the C H
bonding.[33,34] As shown in Figure 3(d), O 1s region is dominated by five components
centred at 533.3, 532.6, 531.9, 531.2 and 530.5 eV, assigned to O 1s, CHO, O C O,
OH, OHC and Cu2O, respectively.[35] Based on the above test results, we can infer the
surface of Cu2O nanoparticles coated a layer of lignin. This conclusion had also been
 6 P. Li et al.
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Figure 3. XPS spectra of Cu2O nanoparticles (a) Survey scan (b) Cu 2p, (c) C 1s (d) O 1s.

proved by HRTEM image (Figure 2(c)). As we can see the surface of Cu2O nanoparticle
seems to have a layer of transparent material as displayed in Figure 2(c), the transparent
material is lignin. Therefore, lignin has played an important role as reducing and
supporting agents in the process of preparing Cu2O nanoparticles. In addition, further
proof has been made by FT-IR.
Figure 4 shows the FTIR spectrum of Cu2O nanoparticles coated by lignin. The most
representative FT-IR bands of lignin are in the spectral region of 4000 550 cm¡1. The
strong band at 3400 cm¡1assigned to O H stretching vibration is due to the presence of
phenolic and alcoholic hydroxyl groups.[36] The bands at 2925 and 2852 cm¡1 are caused
by the symmetric CH2 and asymmetric CH2 stretching, respectively.[36,37] The absorption
band at 1621 cm¡1 is attributed to carbonyl stretching in g-lactone.[38] The low intensity
of the bands at 1610 1500 cm¡1 indicates that the sample has a small number of aromatic
rings.[37,39] The sharp band at 1100 cm¡1 is attributed to the C O stretching for
methoxyl groups.[40] The peak of 625 cm¡1 is due to cis-CH-swing and the CH, CH2
rock.[29] Above all, it can be inferred that the lignin is bounded to the surface of Cu2O
nanoparticles as indicated in Figure 4.

3.2. Antimicrobial performances of the Cu2O nanoparticles

Figure 5 displays the results of the growth of E. coli and S. aureus incubated in PBS buffer
with different sterilising time or different concentrations of Cu2O nanoparticles. As shown
 Journal of Experimental Nanoscience 7
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Figure 4. FT-IR spectra of Cu2O nanoparticles.

in Figure 5(a), the antibacterial rate against E. coli and S. aureus increased with the
prolonged time. The antibacterial rate against E. coli could get 100% after 28 min. And, it
needs 30 min to kill all the S. aureus. The effect of Cu2O nanoparticles concentrations on
inactivation has also been investigated and the results were illustrated in Figure 5(b), the
antibacterial rate against E. coli and S. aureus could get 100% after 30 min with 4.0 g/L
Cu2O nanoparticles. Figure 5(c) shows the growth of E. coli with Cu2O nanoparticles. The
survived bacteria with Cu2O nanoparticles were significantly less than the control groups.
We have also compared the antibacterial activity of Cu2O nanoparticles with different
kinds of antibacterial materials in Table S1. Taken together, the bactericidal activity of
Cu2O nanoparticles is effective and near to other traditional antibacterial materials.
The cytotoxicity of Cu2O nanoparticles were evaluated by testing cell viability using
CCK-8 assay. The HeLa cells were incubated with different concentrations of Cu2O
nanoparticles (0 50 mg/mL) for 24 h before being explored the viabilities. As shown in
Figure 6, there was no apparent loss of cell viability for the HeLa cells. This result
indicates that the Cu2O nanoparticles have low cytotoxicity.

Figure 5. (a) The antibacterial rates on the time of sterilisation, (b) the antibacterial rates on the
concentration of Cu2O nanoparticles, (c) the growth of E. coli with Cu2O nanoparticles by the plate
count method.
 8 P. Li et al.

Figure 6. Relative viabilities of HeLa cells after being incubated for 24 h with different
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concentrations of Cu2O nanoparticles.

4. Conclusions
In summary, Cu2O nanoparticles wrapped by lignin were prepared through a green and
gentle method. In the synthesis process of Cu2O nanoparticles, lignin played as reductant
as well as stabiliser. The Cu2O nanoparticles were fully characterised by HRTEM, XPS,
XRD and FT-IR. The results showed that the morphology of Cu2O nanoparticles
presented as some loose accumulation of particles with the particle size of about
100 200 nm and distributed homogeneously. The Cu2O nanoparticles exhibited efficient
antibacterial activity and low cytotoxicity. This synthesised nanomaterial has several
advantages in terms of low cost, nontoxic reductant, efficient antibacterial activity and
good stability, which made Cu2O nanoparticles have a broad potential application
prospect.

Disclosure statement
No potential conflict of interest was reported by the authors.

Funding
This work was supported by the National Natural Science Foundation of China [grant number
21375079], [grant number 21105056]; Project of Development of Science and Technology of
Shandong Province, China [grant number 2013GZX20109].

Supplemental data
Supplemental data for this article can be accessed here.

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