Professional Documents
Culture Documents
a r t i c l e i n f o a b s t r a c t
Article history: Nanocrystalline anatase titanium dioxide (TiO2 ) nanoparticles doped with nickel ions (1.0–3.0 mol%) were
Received 7 June 2014 synthesized by sol–gel method. XRD and XPS showed the proper substitutions of the few sites of Ti4+ ions
Received in revised form 25 July 2014 by Ni2+ ions in titania host lattice. Particle size was estimated from TEM analysis and found in the range of
Accepted 31 July 2014
10–12 nm. UV–vis diffuse reflectance absorption measurement of doped titania nanoparticles shows the
Available online 9 August 2014
optical absorption in the visible region; which also confirms the incorporation of nickel ions in TiO2 crystal
lattice. For photocatalytic inactivation four common bacterial pathogens, Staphylococcus aureus, Bacillus
Keywords:
subtilis, Escherichia coli, and Salmonella abony were illuminated with nickel doped-TiO2 nanoparticles.
Ni-TiO2 nanoparticles
XPS
This shows a substantial decrease in bacterial numbers. The decrease in photoluminescence intensity
Antibacterial activity with increasing dopant content reveals the higher photocatalytic inactivation and lower recombination
E. coli rate of photogenerated charge carriers. The survival number of all bacteria species is not affected in dark
S. aureus with nanoparticles and in light condition without nanoparticles.
© 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jphotochem.2014.07.024
1010-6030/© 2014 Elsevier B.V. All rights reserved.
H.M. Yadav et al. / Journal of Photochemistry and Photobiology A: Chemistry 294 (2014) 130–136 131
2. Experimental
2.1. Preparation of Ni-TiO2 photocatalyst Fig. 1. XRD patterns of undoped TiO2 and Ni-TiO2 nanoparticles.
The Ni-TiO2 photocatalysts were prepared with the modified of Industrial Microorganisms), National Chemical Laboratory
sol–gel method, which was reported previously [9]. In the prepara- (NCL), Pune, India while B. subtilis is purchased form American
tion, titanium (IV) isopropoxide was mixed with glacial acetic acid Type Culture Collection (ATCC), India.
and magnetically stirred for 5 min, and then aqueous solution of For all experiments, a suspension of each bacterial species with a
sodium dodecyl sulfate was added and again stirred for 1 h. To get concentration of 1 × 106 cfu/mL (identified by UV–vis spectropho-
the desired concentration of Ni2+ ion as a dopant (1.0–3.0 mol%) tometer) was used. For photocatalytic inactivation experiment, a
in TiO2 , required stoichometric amount of aqueous solution of multilamp borosilicate glass reactor having eight fluorescent tubes
NiSO4 (H2 O)6 was then added to the mixture and stirred vigorously (Philips 8 W WW T5, > 400 nm) was used [10]. All samples were
for 2 h. The pH of the resulting solution was adjusted to 10 by adding exposed to a light intensity of ∼0.5 mW cm−2 . For all experiments
ammonia. The solution was further stirred at 60 ◦ C for 3 h and then 1 mg Ni-TiO2 nanoparticles were suspended in 5 mL saline (0.9%
filtered. The catalyst was washed with 50 mL of ethanol. After dry- of NaCl at pH 7.0) containing bacterial suspension and exposed to
ing at 110 ◦ C in oven, the catalyst was calcinated in air at 500 ◦ C visible light. 100 L of bacterial suspension was pipetted at regu-
for 5 h. The color of these Ni-TiO2 nanoparticles is yellowish. The lar time intervals and spread on freshly prepared Mueller–Hinton
various samples such as 1.0 mol% Ni-doped TiO2 , 2.0 mol% Ni-doped agar plates and incubated at 37 ◦ C for 24 h. Then the grown colonies
TiO2 , and 3.0 mol% Ni-doped TiO2 are denoted as Ni1-TiO2 , Ni2-TiO2 were counted. During all these experiments, control tests were
and Ni3-TiO2 , respectively. performed under the same irradiation conditions without nanopar-
ticles and a dark experiment with nanoparticles without light
2.2. Characterizations exposer was carried out simultaneously. Each set of experiments
was performed in triplicate.
The X-ray diffraction patterns (XRD) of the samples were
recorded on a Bruker AXS D8-Advance X-ray diffractometer with 3. Results and discussion
Cu-K␣ radiation of wavelength 1.5406 Å in 2 range from 20◦ to 80◦ .
X-ray photoelectron spectroscopy (XPS) was used for determining 3.1. X-ray diffraction
the surface compositions of the photocatalysts, using a Physical
Electronics 5600 Multi-technique System with monochromatic Al Fig. 1 shows the XRD patterns of undoped TiO2 and Ni-TiO2
K ␣ radiation. UV–vis diffuse reflectance absorbance spectra of nanoparticles. The diffraction peaks at 2 = 25.07, 37.59, 47.98,
all samples were obtained using a UV–visible spectrophotome- 53.72, 54.86, 62.58, 68.54, 70.05, 75.05, and 82.65 corresponds to
ter (UV3600, Shimadzu, Japan) in the range of 200–800 nm. TEM the (101), (004), (200), (105), (211), (204), (116), (220), (215), and
image of the samples were recorded on a Tecnai F30 field emission (224), respectively for plane of tetragonal anatase TiO2 (JCPDS 21-
transmission electron microscope operating at 300 kV. Elemental 1272). There were no peaks corresponding to rutile phase or oxide
composition was determined from EDS analysis. The photolumi- of the dopant metal ions. The crystallite size was calculated using
nescence (PL) spectra of the sample were recorded by using JASCO Debye–Scherrer formula:
F.P.-750 Model, (Japan) spectrofluorometer.
0.9
D= (1)
ˇ cos
2.3. Photocatalytic bactericidal activity
where D is the crystallite size, is the wavelength of the X-ray
All solutions and reagents were prepared with distilled and radiation (CuKa = 0.15418 nm), is the diffraction angle and ˇ is the
deionized water. All glassware was washed with distilled water full width at half maximum (FWHM). The calculated crystallite sizes
and autoclaved at 121 ◦ C for 20 min prior to use. All experiments are 11.47 nm, 9.67 nm, 8.59 nm, and 7.96 nm for 0.0 mol%, 1.0 mol%,
were performed under sterile conditions. 2.0 mol% and 3.0 mol% doping of Ni2+ in TiO2 , respectively. It can
For the photocatalytic inactivation test, four common be seen that, with increasing dopant concentration the crystallite
pathogenic bacteria, Gram-positive Staphylococcus aureus NCIM size decreases. The decrease in crystallite size can be correlated to
2654, Bacillus subtilis ATCC 6633 and Gram-negative Escherichia coli increase in structural defects that prevent particle growth [15]. The
NCIM 2066, Salmonella abony NCIM 6017 were used. The S. aureus, ionic radius of Ni2+ ion is different from that of Ti4+ ion. Doping of
E. coli and S. abony were purchased from NCIM (National Collection Ni2+ generates oxygen vacancies in the lattice of TiO2 to maintain
132 H.M. Yadav et al. / Journal of Photochemistry and Photobiology A: Chemistry 294 (2014) 130–136
Fig. 2. XPS for the Ni3-TiO2 (a) survey; (b) Ti 2p; (c) O 1s configuration; and (d) Ni 2p configuration.
charge neutrality. In this work, the nickel dopant is incorporated by in the gas phase [19]. The Ni 2p3/2 peak position at 853.69 eV is
replacing few Ti4+ ions in TiO2 crystal lattice. These results clearly quite different from that of metallic Ni (852.7 eV), NiO (853.8 eV)
confirm the successful substitution of few Ti4+ ions by Ni2+ ions. and Ni2 O3 (856.7 eV). The binding energy difference between Ni
2p3/2 and Ni 2p1/2 core level is 18.65 eV, which is different from
3.2. X-ray photoelectron spectroscopy the value of metallic Ni (17.27 eV) and NiO (17.49 eV) [16,20,21].
The change in the Ni2p peak and a shift of Ti2p peaks corresponds
The valance state, substitution and contents of all these nickel- to the rearrangement of Ti4+ ions and Ni2+ ions. These results give
doped TiO2 nanoparticles were examined by XPS analysis as shown evidence that a few of the Ti4+ ions are successfully substituted by
in figure. The XPS survey scan spectrum of the Ni3-TiO2 sample Ni2+ ions without forming any detectable impurity phase, such as
shows the existence of Ni, O and Ti ions in an almost stoichio- Ni, Ni2 O3 and NiO. Moreover, XPS results are correlated with the
metric composition (Fig. 2a). Fig. 2b shows the core level Ti 2p EDS results, confirming Ni2+ ions are doped up to 3.0 mol% into TiO2
spectra of Ni-TiO2 sample. For TiO2 , Ti 2p3/2 and Ti 2p1/2 , peaks host lattice.
are observed at 457.21 and 462.94 eV, respectively. The splitting
between the Ti 2p1/2 and Ti 2p3/2 is 5.73 eV, demonstrating a nor- 3.3. UV–vis diffuse reflectance spectroscopy
mal state of Ti4+ ion in the sample [16]. Fig. 2c shows the XPS spectra
of O 1s configuration. The binding energies at 531.47 eV, 529.44 eV Fig. 3 shows the UV–vis absorption spectra in the range of
reveal the existence of surface hydroxyl groups and O 1s electron 300–700 nm for undoped TiO2 and Ni-TiO2 nanoparticles. The
binding energy arising from titanium lattice, respectively [17]. The absorption spectra of the doped samples show a stronger visi-
XPS spectrum shows complex structure 853.69 eV, 861.08 eV for Ni ble light absorption indicating the band gap was decreased upon
2p3/2 , and 872.34 eV, 877.96 eV for Ni 2p1/2 , respectively and these doping. This visible light absorption ascribed the fact that there is
are attributed due to the multiplet splitting (Fig.2d). The peak at a new energy level for Ni2+ /Ni+ below the conduction band and
861.08 eV is due to the O 2p → Ni 3d charge transfer transitions above the valance band edge of TiO2 [22]. Such new energy lev-
[18]. The binding energy of a Ni atom is deduced to be 853.69 eV els and oxygen vacancies generated by metal doping, induce the
on TiO2 host lattice and which is 7.39 eV smaller than atomic Ni bathochromic shift in the band gap transition and the visible light
H.M. Yadav et al. / Journal of Photochemistry and Photobiology A: Chemistry 294 (2014) 130–136 133
Fig. 3. UV–vis diffuse reflectance spectra of undoped TiO2 and Ni-TiO2 nanoparti- 3.5. Photoluminescence spectroscopy
cles.
The PL spectra show broad emission peaks in the region of
440–600 nm. These emission signals are due to the surface defects
and the charge transfer transition from an oxygen vacancy trapped
absorption through a charge transfer between a dopant and con- electron [24]. Interestingly, the PL spectra of Ni-TiO2 show a gradual
duction or valance band or a d–d transition in the crystal field decrease in the peak intensity with increasing nickel concentration
according the energy level [3,8,23]. The calculated band gap energy in TiO2 . The surface defects reduce the recombination rate of pho-
for TiO2 ,Ni1–TiO2 , Ni2–TiO2 , and Ni3–TiO2 , are 3.21, 2.95, 2.58, and togenerated charge carriers. The excited electrons are trapped by
2.36 eV, respectively. After doping with nickel metal ions in TiO2 , the oxygen vacancies and holes are trapped by dopant metal ions.
the absorption shifted the in visible light region due to introduction Additionally, the excited electrons can migrate from the valance
Fig. 4. (a) TEM image; (b) SAED pattern; and (c) EDS spectrum of Ni3-TiO2 nanoparticles.
134 H.M. Yadav et al. / Journal of Photochemistry and Photobiology A: Chemistry 294 (2014) 130–136
Fig. 5. The PL spectra of Ni-TiO2 nanoparticles. Fig. 6. Inactivation of S. aureus as function of time.
5. Conclusions
[15] B. Choudhury, A. Choudhury, Structural, optical and ferromagnetic properties [24] J. Yu, L. Qi, M. Jaroniec, Hydrogen production by photocatalytic water splitting
of Cr doped TiO2 nanoparticles, Mater. Sci. Eng. B 178 (2013) 794–800. over Pt/TiO2 nanosheets with exposed(001) facets, J. Phys. Chem. C 114 (2010)
[16] C.D. Wagner, W.M. Riggs, L.E. Davis, J.F. Moulder, G.E. Muilenberg, Handbook 13118–13125.
of X-Ray Photoelectron Spectroscopy, Perkin-Elmer Corp., Physical Electronics [25] H. Tang, H. Berger, P.E. Schmid, F. Lévy, G. Burri, Photoluminescence in TiO2
Division, USA, 1979. anatase single crystals, Solid State Commun. 87 (1993) 847–850.
[17] L. Li, C. Liu, Y. Liu, Study on activities of vanadium (IV/V) doped TiO2 (R) [26] S. Josset, N. Keller, M.C. Lett, M.J. Ledoux, V. Keller, Numeration methods
nanorods induced by UV and visible light, Mater. Chem. Phys. 113 (2009) for targeting photoactive materials in theUV-A – a photocatalytic removal of
551–557. microorganisms, Chem. Soc. Rev. 37 (2008) 744–755.
[18] K.S. Kim, R.E. Davis, Electron spectroscopy of the nickel–oxygen system, J. Elec- [27] K. Sunada, T. Watanabe, K. Hashimoto, Bactericidal activity of copper-deposited
tron Spectrosc. Relat. Phenom. 1 (1972) 251–258. TiO2 thin film under weak UV light illumination, Environ. Sci. Technol. 37 (2003)
[19] K. Godehusen, T. Richter, P. Zimmermann, M. Martins, 2p Photoionization of 4785–4789.
atomic Ni: a comparison with Ni metal and NiO photoionization, Phys. Rev. [28] Y.S. Kim, L.T. Linh, E.S. Park, S. Chin, G.N. Bae, J. Jurng, Antibacterial performance
Lett. 88 (2002) 217601. of TiO2 ultrafine nanopowder synthesized by a chemical vapor condensation
[20] G.H. Yu, L.R. Zeng, F.W. Zhu, C.L. Chai, W.Y. Lai, Magnetic properties and X-ray method: effect of synthesis temperature and precursor vapor concentration,
photoelectron spectroscopy study of NiO/NiFe films prepared by magnetron Powder Technol. 215–216 (2012) 195–199.
sputtering, J. Appl. Phys. 90 (2001) 4039–4043. [29] L.K. Adams, D.Y. Lyon, P.J.J. Alvarez, Comparative eco-toxicity of nanoscale TiO2 ,
[21] Z. Yin, N. Chen, F. Yang, S. Song, C. Chai, J. Zhong, H. Qian, K. Ibrahim, Structural, SiO2 , and ZnO water suspensions, Water Res. 40 (2006) 3527–3532.
magnetic properties and photoemission study of Ni-doped ZnO, Solid State [30] H.A. Foster, I.B. Ditta, S. Varghese, A. Steele, Photocatalytic disinfection using
Commun. 135 (2005) 430–433. titanium dioxide: spectrum and mechanism of antimicrobial activity, Appl.
[22] K. Ubonchonlakate, L. Sikong, T. Tontai, F. Saito, P. aeruginosa inactivation with Microbiol. Biotechnol. 90 (2011) 1847–1868.
silver and nickel doped TiO2 film coat on glass fiber roving, Adv. Mater. Res. [31] L. Caballero, K.A. Whitehead, N.S. Allen, J. Verran, Inactivation of Escherichia coli
150–151 (2010) 1726–1731. on immobilized TiO2 using fluorescent light, J. Photochem. Photobiol. A: Chem.
[23] S.D. Sharma, D. Singh, K.K. Saini, C. Kant, V. Sharma, S.C. Jain, C.P. Sharma, 202 (2009) 92–98.
Sol–gel-derived super-hydrophilic nickel doped TiO2 film as active photo- [32] J.G. Tortora, R.B. Funke, L.C. Case, Microbiology: An Introduction, 10th ed., Per-
catalyst, Appl. Catal. A: Gen. 314 (2006) 40–46. son Education Inc., New York, 2010.