Key Engineering Materials Vols 645-646 (2015) pp 1314-1319 Submitted: 2014-12-09

© (2015) Trans Tech Publications, Switzerland Accepted: 2014-12-23

doi:10.4028/www.scientific.net/KEM.645-646.1314 Online: 2015-05-18

Facile Preparation of Cu/TiO2 Nanocomposite via Photocatalysis and

Their Antibacterial Performance
Boxi She 1,a, Junbiao Long1,b, Yuanming Deng 1,c, Xuejuan Wan1,d,
Kejun Zhu2,e, Jiaoning Tang*,1,f
1
Shenzhen Key Laboratory of Special Functional Materials, College of Materials Science and
Engineering, Shenzhen University, Shenzhen 518060, P. R. China.
2
Guangzhou Mente Nanometer Technology Co., Ltd,Guangzhou 511400,P. R. China.
a
147080505@qq.com, bcbill.long@gmail.com, cymdeng@szu.edu.cn, dwanxj@szu.edu.cn,
e
keke5501@126.com, ftjn@szu.edu.cn

Keywords: photocatalysis; hydrophilic aluminum foil; Cu/TiO2 nanocomposite; antibacterial

properties.

Abstract. Cu/TiO2 nanocomposite was first prepared by photocatalytic reduction according to

optimal processing condition selected via orthogonal test: 2.0% of glucose, 0.25% of TiO2, 0.3% of
CuCl2 and reaction time of 12 h. Multiple characterization methods were utilized to confirm the
structure of Cu/TiO2 nanocomposite, and its antibacterial property against Escherichia coli (E.coli)
was then investigated in detail. The obtained Cu/TiO2 (ca. 50 nm) was composed of elemental copper,
TiO2 and a small amount of unreacted CuCl2. EDTA titration and XRF indicated that solid content of
Cu was about 61.68%. Antibacterial test showed that the inhibition zone diameter of Cu/TiO2 with
1% solid content is 15.77 mm and the minimum bactericidal concentration (MBC) of which is 5
mg/mL. Furthermore, Cu/TiO2 (1.0 wt%) was added into a super-hydrophilic coating for the
aluminum cooling fin of air conditioner. The antibacterial ability of the fin can be significantly
improved without obvious changes of hydrophilicity, which can reach the national standard (grade I).

Introduction
As a representative photocatalytic nano-antibacterial agent, TiO2 nanoparticles [1] possesses
advantages such as broad spectrum antibacterial property, good antibacterial endurance and safety,
high stability and good adsorbability, which endows it with tremendous application potential
[2,3,4,5]. Though TiO2 nanoparticles has plenty of merits, there are obvious shortcomings and
deficiencies as well. Photocatalytic reactive oxygen has a relatively short time, and meanwhile,
photocatalytic antibacterial material will lose the bacteriostatic and bactericidal capacity in the dark
because the photocatalytic reaction can not occur without the stimuli of UV-light. To solve these
problems, two-component antibacterial complexes which combine TiO2 with silver, copper and other
antimicrobial metal ions have been widely studied [6,7,8]. Based on the great development prospect
of these kinds of antibacterial materials, a nano-antibacterial composite Cu/TiO2 was prepared to
prevent the breeding of bacteria and molding in air conditioning heat exchanger. The application of
Cu/TiO2 nano-antibacterial agents in the heat exchanger cooling films can not only achieve the
purification of air, but also maintain the hydrophilicity of the super-hydrophilic acrylic coatings,
which may prevent mildewing and reproduction of germs. By combining the advantages of the metal
iron antibacterial and photocatalytic antibacterial property, the antibacterial and mould proof effect
can be well- improved[9], and the cost is low. Besides, the slow release of Cu2+ ion from the
nano-scale Cu/TiO2 composite can guarantee the long-lasting antibacterial capacity and low side
effect. What’s more, the TiO2 substrate can effectively increase the surface area of copper particles,
thus the utilization rate of copper can be significantly improved. The gradual formation of Cu2O
oxidation layer on the nanocomposite can further enhance the contact-antibacterial properties. In this
paper, Cu/TiO2 nanocomposite was added into a super-hydrophilic acrylic coating and coated
uniformly onto an aluminum cooling fins. The obtained fins exhibited significantly improved
antibacterial capacity and well-maintained hydrophilicity.

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications, www.ttp.net. (ID: 132.239.1.231, University of California, San Diego, La Jolla, USA-06/06/15,03:04:16)
 Key Engineering Materials Vols. 645-646 1315

Experimental Section
Materials and measurements. Cupric chloride (CuCl2·2H2O, AR), and glucose (AR) were
purchased from Sinopharm Chemical Reagent Company and used as received. Titanium dioxide
(TiO2) of ca. 20-65 nm was prepared as literature reported [10]. The surface morphology and particle
sizes of the Cu/TiO2 nanocomposite were observed using a scanning electron microscope (SEM) and
laser particle analyzer. The component of Cu/TiO2 was carried out using an X-ray diffractometer
(XRD). The solid content of Cu was analyzed via EDTA titration test and X-ray fluorescence
spectrometer (XRF).
Synthesis of Cu/TiO2 nanocomposites. Certain amount of CuCl2·2H2O, TiO2 nanoparticle and
glucose were respectively dissolved with 300 mL deionized water. CuCl2 solution was added slowly
into TiO2 suspension with magnetic stirring, followed by the addition of glucose solution. The
reaction mixture was then diluted to 1 L with deionized water, and then placed in a self-made
photocatalytic reaction workstation (Fig. 1) in a specified period of time.

Fig. 1 Photocatalytic reaction workstation.

Antibacterial test. Inhibition zone qualitative test and minimum bactericidal concentration
(MBC) quantitative test against Escherichia coli (E.coli) were adopted. Typical procedure of
inhibition zone test can be described as follows: 1 mL bacterium suspension (~106 CFU/mL) was
dropped onto the surface of a nutrient agar medium in a Petri dish, and then coated equably. Sample
wafers of ca. 6mm were immersed into Cu/TiO2 suspension (1.0 wt%) and glued onto the medium
dispersedly. Blank control was prepared. The diameter of inhibition zone of samples was measured
using vernier calipers for three times after being incubated at 37 for 24 h. MBC test was carried out as
follows: five sample solutions were prepared by mixing 95 mL phosphate buffer (PB), 5 mL
bacterium suspension and varied qualities of Cu/TiO2(1.0 wt%). Blank control sample was prepared
by replacing 5 mL bacterium suspension with 5 mL saline. The obtained sample solutions were
incubated using bed temperature incubator at a sharking rate of 150 r/min at 37 oC for 24 h. 0.1 mL
mixture of the above six samples was diluted to a certain concentration before being coated onto a
plate (with about 20 mL solid medium) separately, and then incubated at 37 oC for another 24 h so as
to figure up sterilizing efficiency by plate counting method. The lowest concentration of
nanoparticles that killed 99.9% of the bacteria was the MBC.
Antibacterial test of the hydrophilic coating on aluminum foil. Different mass fractions of
Cu/TiO2(1.0 wt%) were added into super-hydrophilic acrylic coating, and dispersed by a high-speed
homogenizer. The coating obtained was coated uniformly on an aluminum foil, and the antibacterial
performance of which was evaluated according to GB/T 21866－2008.
1316 Micro-Nano Technology XVI

Results and Discussion

Orthogonal test is the main method to screen out the optimal parameters when there are multiple
factors influence the result. Representative four points and three levels for the preparation of Cu/TiO2
nanocomposite were selected (factor 1: glucose with various qualities of 0, 2.0 and 4.0 wt%; factor 2:
reaction time for 6, 12 and 18 h; factor 3: mass fractions of TiO2: 0.1, 0.25 and 0.5 %; factor 4:
concentration of CuCl2 0.1, 0.3 and 0.6 wt% ).

Fig. 2 The effect of glucose (a), reaction time (b), TiO2 (c) and CuCl2 (d) concentration on particle size
of Cu/TiO2 and the reduction rate of copper.

Orthogonal table L9(34) was studied to determine the preparation process of Cu/TiO2
nanocomposite. The integrated average particle size and copper reduction rate of each factors and
levels were described as Fig. 2. Particle size of Cu/TiO2 and reduction rate of Cu increased with
increasing concentration of glucose (Fig. 2a), as gradually enhanced impairment ability for free
radical ·OH in photocatalytic reduction process could effectively inhibit oxidation reaction, resulting
in improved reduction efficiency of Cu2+ and enlarged particle size. Considering the economic factors,
the concentration of glucose is located at 2.0%. Fig. 2b indicated that copper reduction rate and
particle size also increased with prolonged reaction time, ascribing to the growth in reduction quantity
of copper on the surface of TiO2 nanoparticles. In order to guarantee a certain reduction rate of Cu and
simultaneously smaller particle size, 12 h was adopted as the optimum reaction time. In Fig. 2c, the
reduction rate of Cu exhibited a tendency to decline with the increasing concentration of TiO2, as too
much TiO2 solution would lead to lower pH value of the reaction mixture, thereby reducing the
copper reduction rate and simultaneously decreasing the particle size of Cu/TiO2 nanocomposite.
Considering to obtain smaller particle size and relatively higher Cu reduction rate, mass fraction of
TiO2 was chosen as 0.25%. Fig. 2d demonstrated that Cu reduction rate fell with increasing
concentration of CuCl2 and then gradually stabilized. However, increasing CuCl2 will bring
increasing amount of Cu in solution, resulting in the larger composite site, which indicated that
quality fraction of 0.3% was favorable in the preparation process. Thus, the optimum synthesis
 Key Engineering Materials Vols. 645-646 1317

condition was carried out as follows: quality fraction of glucose, TiO2 and CuCl2 were 2.0 wt% , 0.25
wt% and 0.3 wt% respectively, and reaction time was chosen as 12 h.

Fig. 3 SEM image,diameter distribution(a) and XRD spectrum(b) of Cu/TiO2 nanocomposite .

The morphology of the obtained Cu/TiO2 nanocomposite was studied by SEM analysis, and the
granularity of it was also measured by laser granularity analyzer. It showed that the sample is featured
of homogeneous distribution and regular shape with average size about 50 nm (Fig. 3a). The X-ray
diffraction in Fig. 3b indicated that this sample is composed of elemental Cu, TiO2 and unreacted
CuCl2 by comparison with the standard card. To characterize copper reduction rate of Cu/TiO2
obtained under optimum technological condition, EDTA titration method was adopted to test upper
clear liquid and X-ray fluorescence (XRF) measurement was used to determine lower sediment after
centrifugation of the reaction mixture, and the results were shown in Table 1. The final reduction rate
of Cu reached 61.8%, which is ideal.

Table 1 Reduction rate of copper.

EDTA titration[%] XRF[%] Average rate[%]
60.85 62.51 61.68

Fig. 4 Result of inhibition zone test of blank control (left) and Cu/TiO2 (1.0 wt%, right).

Antibacterial activities of Cu/TiO2 nanocomposite (1.0 wt%) were investigated via inhibition
zone and minimum bactericidal concentration (MBC) tests. Digital image of the inhibition zone result
was shown in Fig. 4. Average diameter of the three inhibition zones was measured to be 15.77 mm
which was much larger than control filter paper (6 mm). Therefore, we can qualitatively determine
that the obtained Cu/TiO2 nanocomposite have excellent bactericidal and bacteriostatic performance.
1318 Micro-Nano Technology XVI

For MBC test, a series of different concentration (1, 2, 3, 5, 10 mg/mL) of Cu/TiO2 (1.0 wt%) samples
were mixed with bacterial suspension and cultivated for 24 h. After that, 0.1 mL of the cultivation
mixture was transferred into a plate, and cultivated for another 24 h. The number of viable bacteria of
samples was compared with the blank control sample in order to calculate the bactericidal rate, and
the result was shown in Table 2. As the concentration of Cu/TiO2 nanocomposite exceeds 5 mg/mL,
the sterilization rate was more than 99.9%. Thus, the MBC of Cu/TiO2 is determined to be 5 mg/mL.

Table 2 Antibacterial rate of Cu/TiO2 nanocomposite with various concentrations.

Concentration of TiO2 [mg/mL]
1 2 3 5 10
Number of colony of control
5.2 ×108 1.6 ×109 3.4 ×108 1.1 ×109 4.2 ×108
sample [CFU]
Number of colony of Cu/TiO2
1.2 ×108 3.1 ×108 2.6×107 6.2 ×105 3.4 ×104
[CFU]
Antibacterial rate [%] 77.71 80.89 92.22 99.94 99.99

Various amount (0%, 2%, 4%, 6%) of Cu/TiO2 (1 wt%) antibacterial agent were then added into
a hydrophilic coating and further coated onto hydrophilic aluminum foil. The sterilization rate of the
foil was investigated against E.coli. According to the national standard, the antibacterial agent was
supposed to reach grade 1 when the sterilization rate exceeds 99%, while 90% for grade 2. The
antibacterial effect of the as-prepared hydrophilic aluminum foil coated with Cu/TiO2 nanocomposite
could meet the first-grade as the quality fraction of Cu/TiO2 was more than 4%, while meet the
secondary-grade when the fraction was more than 2% (Fig. 5), suggesting that the antibacterial
capacity of the Cu/TiO2 nanocomposite can be well-retained in the hydrophilic coatings and endow
the hydrophilic aluminum foil with outstanding antibacterial performance.

100
99.62% 99.98%
91.88%
80
Antibacterial Rate [%]

60

40

20

0 1 2 3 4 5 6

Cu/TiO2 [ω/%]

Fig. 5 Antibacterial activities of hydrophilic coating added with various Cu/TiO2.

Table 3 Hydrophilic angle test results of the coating with different concentrations of Cu/TiO2.
Addition of Cu/TiO2
0% 2% 4% 6%
1 [º] <1 <1 <1 <1
2 [º] <1 <1 <1 <2
3 [º] <1 <1 <1 <1
average [º] <1 <1 <1 <2
The hydrophilicity of the obtained antibacterial hydrophilic aluminum foil was determined and
the results of hydrophilic angle test were shown in Table 3. Parallel experiments (three samples) were
 Key Engineering Materials Vols. 645-646 1319

conducted simultaneously, and average value was given. The results suggested that all the samples
performed high hydrophilicity, indicating the addition of Cu/TiO2 nanocomposite exhibited
negligible interference of the hydrophilicity of the coating.

Conclusion
In conclusion, Cu/TiO2 nanocomposite was prepared by photocatalytic reduction and its
antibacterial ability was investigated in detail. The optimal preparation process of Cu/TiO2
nanocomposite was first chosen by orthogonal test and the parameters were shown as followed: 2.0%
of glucose, 0.25% of TiO2, 0.3% of CuCl2 and 12 h of reaction time. Antibacterial tests on Cu/TiO2
indicate that the obtained samples have good antibacterial ability against E.coli. The inhibition zone
diameter of Cu/TiO2 (1.0 wt%) is about 15.77 mm and the minimum bactericidal concentration is 5
mg/mL. Subsequently, nanocomposite Cu/TiO2 (1.0 wt%) was added into a super-hydrophilic
coating and then coated on a aluminum cooling fin. The antibacterial ability of the fin can be
significantly improved without obvious changes of hydrophilicity, which can reach the national
standard (grade I).

Acknowledgements
The authors gratefully acknowledge financial support from National High-Tech Research and
Development Program of China (863 Program, No. 2012AA030312).

References
Reference an article:
[1] J. Sund, J. Palomäki, N. Ahonen, K. Savolainen, et al, Phagocytosis of nano-sized titanium
dioxide triggers changes in protein acetylation, J. Proteomics. 108 (2014) 469-483.
[2] E. Huerta-García, et al, Titanium dioxide nanoparticles induc strong oxidative stress and
mitochondrial damage in glial cells, J. Free. Radical. Bio. Med. 73 (2014) 84-94.
[3] S. Rtimi, et al, Innovative transparent non-scattering TiO2 bactericide thin films inducing
increased E.coli cell wall fluidity, J. Surf. Coat. Tech. 254 (2014) 333-343.
[4] Z.C. Yan, L. Liu, J.L. Tan, Q. Zhou, Z.F. Huang, D.D. Xia, H.G. Shu, X.K. Yang, X.Y. Wang,
One-pot synthesis of bicrystalline titanium dioxide spheres with a core-shell structure as anode
materials for lithium and sodium ion batteries, J. Power. Sources. 269 (2014) 37-45.
[5] M.S. Kim, K.M. Hong, J.G. Chung, Removal of Cu(II) from aqueous solutions by adsorption
process with anatase-type titanium dioxide, J. Water. Res. 37 (2003) 3524-3529.
[6] B.S. Necula, I. Apachitei, F.D. Tichelaar, L.E. Fratila-Apachitei, J. Duszczyk, An electron
microscopical study on the growth of TiO2-Ag antibacterial coatings on Ti6Al7Nb biomedical
alloy, J. Acta. Biomater. 7 (2011) 2751-2757.
[7] B.S. Necula, I. Apachitei, F.D. Tichelaar, L.E. Fratila-Apachitei, J. Duszczyk, Antibacterial
property and characterization of cotton fabric treater with chitosan/AgCl-TiO2 colloid, J.
Carbohyd. Polym. 96 (2013) 326-331.
[8] J. Mungkalasiri, L. Bedel, F. Emieux, A.V.D. Cara, J. Freney, F. Maury, F.N.R. Renaud,
Antibacterial properties of TiO2-Cu composite thin films grown by a one step DLICVD process,
J. Surf. Coat. Tech. 242 (2014) 187-194.
[9] S.G. Chen, Y.J. Guo, H.Q. Zhong, S.J. Chen, J.N. Li, Z.C. Ge, J.N. Tang, Synergistic
antibacterial mechanism and coating application of copper/titanium dioxide nanoparticles, J.
Chem. Eng. J. 256 (2014) 238-246.
[10] Y.F. You, C.H. Xu, S.S. Xu, S. Cao, J.P. Wang, Y.B. Huang, S.Q. Shi, Structural
characterization and optical property of TiO2 powders prepared by the sol-gel method, J. Ceram.
Int. 40 (2014) 8659-8666.
Micro-Nano Technology XVI
10.4028/www.scientific.net/KEM.645-646

Facile Preparation of Cu/TiO2 Nanocomposite via Photocatalysis and their Antibacterial Performance
10.4028/www.scientific.net/KEM.645-646.1314

DOI References
[1] J. Sund, J. Palomäki, N. Ahonen, K. Savolainen, et al, Phagocytosis of nano-sized titanium dioxide
triggers changes in protein acetylation, J. Proteomics. 108 (2014) 469-483.
http://dx.doi.org/10.1016/j.jprot.2014.06.011
[2] E. Huerta-García, et al, Titanium dioxide nanoparticles induc strong oxidative stress and mitochondrial
damage in glial cells, J. Free. Radical. Bio. Med. 73 (2014) 84-94.
http://dx.doi.org/10.1016/j.freeradbiomed.2014.04.026
[3] S. Rtimi, et al, Innovative transparent non-scattering TiO2 bactericide thin films inducing increased E. coli
cell wall fluidity, J. Surf. Coat. Tech. 254 (2014) 333-343.
http://dx.doi.org/10.1016/j.surfcoat.2014.06.035
[4] Z.C. Yan, L. Liu, J.L. Tan, Q. Zhou, Z.F. Huang, D.D. Xia, H.G. Shu, X.K. Yang, X.Y. Wang, One-pot
synthesis of bicrystalline titanium dioxide spheres with a core-shell structure as anode materials for lithium
and sodium ion batteries, J. Power. Sources. 269 (2014).
http://dx.doi.org/10.1016/j.jpowsour.2014.06.150
[5] M.S. Kim, K.M. Hong, J.G. Chung, Removal of Cu(II) from aqueous solutions by adsorption process with
anatase-type titanium dioxide, J. Water. Res. 37 (2003) 3524-3529.
http://dx.doi.org/10.1016/S0043-1354(03)00227-6
[6] B.S. Necula, I. Apachitei, F.D. Tichelaar, L.E. Fratila-Apachitei, J. Duszczyk, An electron microscopical
study on the growth of TiO2-Ag antibacterial coatings on Ti6Al7Nb biomedical alloy, J. Acta. Biomater. 7
(2011) 2751-2757.
http://dx.doi.org/10.1016/j.actbio.2011.02.037
[7] B.S. Necula, I. Apachitei, F.D. Tichelaar, L.E. Fratila-Apachitei, J. Duszczyk, Antibacterial property and
characterization of cotton fabric treater with chitosan/AgCl-TiO2 colloid, J. Carbohyd. Polym. 96 (2013) 326-
331.
http://dx.doi.org/10.1016/j.carbpol.2013.04.004
[8] J. Mungkalasiri, L. Bedel, F. Emieux, A.V.D. Cara, J. Freney, F. Maury, F.N.R. Renaud, Antibacterial
properties of TiO2-Cu composite thin films grown by a one step DLICVD process, J. Surf. Coat. Tech. 242
(2014) 187-194.
http://dx.doi.org/10.1016/j.surfcoat.2013.08.039
[9] S.G. Chen, Y.J. Guo, H.Q. Zhong, S.J. Chen, J.N. Li, Z.C. Ge, J.N. Tang, Synergistic antibacterial
mechanism and coating application of copper/titanium dioxide nanoparticles, J. Chem. Eng. J. 256 (2014)
238-246.
http://dx.doi.org/10.1016/j.cej.2014.07.006
[10] Y.F. You, C.H. Xu, S.S. Xu, S. Cao, J.P. Wang, Y.B. Huang, S.Q. Shi, Structural characterization and
optical property of TiO2 powders prepared by the sol-gel method, J. Ceram. Int. 40 (2014) 8659-8666.
http://dx.doi.org/10.1016/j.ceramint.2014.01.083