Applied Surface Science 449 (2018) 617–630

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Applied Surface Science

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Full Length Article

Investigations of visible light driven Sn and Cu doped ZnO hybrid

nanoparticles for photocatalytic performance and antibacterial
activity
Shanmugam Vignesh, Jeyaperumal Kalyana Sundar ∗
Materials Science Laboratory, Department of Physics, Periyar University, Salem - 636 011, Tamilnadu, India

a r t i c l e i n f o a b s t r a c t

Article history: In the present work, demonstrate an effectual and facile synthesis of ZnO nanoparticles and investiga-
Received 26 September 2017 tions of structural, optical and photocatalytic performance are established with bi-metal (Sn and Cu)
Received in revised form doped nanoparticles (Sn:Cu:ZnO NPs) have been successfully synthesized by microwave assisted ultra-
14 November 2017
sonicated precipitation process. The XRD pattern appearance of undoped and doped ZnO nanoparticles
Accepted 20 November 2017
Available online 28 November 2017
conserve in a hexagonal wurtzite structure. Highly efficient TEM and SAED were used to determine the
particle size, shape with lattice imperfections, hence the particle size is observed as 38 nm. FTIR spectra
agrees that analysis of presenting a functional group of synthesized samples. SEM images confirm that
Keywords:
Sn-Cu co-doped ZnO pure and Sn:Cu:ZnO NPs have a smooth surface in their morphologies and the presence of elements has
Hybrid nanoparticles been confirmed by EDX analysis. XPS analysis confirms that chemical composition of Sn:Cu:ZnO NPs.
Photocatalyst General, optical measurements of as grown Sn:Cu:ZnO NPs show the optical bandgap tunability of red
Antibacterial activity shift from 3.22 eV to 2.68 eV as the Cu2+ and Sn2+ ion content have been enhancing the near-band-edge
(NBE) of ZnO optical lattices. In order to understand the band structure of ZnO nanomaterials, the photo-
luminescence (PL) spectra at room temperature were studied and their bands appear around ∼590 nm,
while this green-yellow emission suggests zinc vacancy, so it should valid for color LEDs. Chiefly, the
Sn:Cu:ZnO nanoparticles has favourable photocatalyst activity in MB dye compared to pure ZnO. It com-
pletely degrades the dye after 180 min in the Sn:Cu:ZnO photocatalyst under visible-light-driven by
interfacial of photo generated electron-hole pairs will enhances the charge transfer progression and its
photo degradation rate is 2.6 times faster than that of undoped ZnO. Also, the photocurrent response has
exposed to development of photocatalytic properties and more charge carrier ability. Further identifica-
tions of existing residues of photocatalytic process were analysed by mass spectroscopy. The antibacterial
activity is well exposed towards inactivation of bacterial strain including pathogens which are S. aureus
(G+ ) and E. coli (G− ) bacteria by the standard disc diffusion method.
© 2017 Elsevier B.V. All rights reserved.

1. Introduction bandgap (Eg = 3.37 eV) material with a high exciton binding energy
(60 meV), wurtzite crystal structure, piezoelectric property, a chief
Semiconductors metal oxides have reputable a great deal of photocatalyst primarily motivated by its nontoxicity and more
attention due to its potential for commercialization towards the potential applications in multi light emitting diodes, photochem-
environmental purification, micro-organisms treatment, and opti- ical solar cells, optoelectronic devices, water treatment and food
cal applications [1]. Most of TiO2 , ZnO, SiO2 , SnO, ZnWO4 and CuO backing in fields [1–4]. The bandgap energy of ZnO is close to that
NPs have been applied to much more environmental applications. of TiO2 , the most used and standard photocatalytic material, when
Most of them are highly active under UV/visible irradiation and they will occurring some defects which could be ascribed to the reduc-
are effective in the photocatalytic activity. The choice of ZnO as a tion in the bandgap of ZnO. The photocatalytic activities of various
representative II–VI group semiconductor, because of it has wide photocatalysts have been tested using aqueous solutions of sev-
eral dyes and other environmental pollutants. In many cases, ZnO
has been reported to be more efficient than other photocatalysts
∗ Corresponding author. [2–5]. High photosensitivity, excellent mechanical characteristics
E-mail address: jksundar50@[Link] (K.S. Jeyaperumal). and environmentally safe nature together make ZnO as suitable

[Link]
0169-4332/© 2017 Elsevier B.V. All rights reserved.
618 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630

photocatalyst to treat water from a number of organic pollutants 2. Materials and methods
and solving environmental pollution problems. In their many liter-
ature, the undoped ZnO exhibits low photocatalytic efficiency due All of the chemical reagents used in this work, including zinc
to the quick recombination of charge carriers, and comparatively nitrate hexahydrate (Zn(NO3 )2 ·6H2 O, Molechem Co., Ltd., 99%),
low charge separation [2–7]. A number of methods to improve Stannous Chloride (SnCl2 ·2H2 O, SRL Co., India Ltd., 97%), Copper
the efficiency of heterogeneous photocatalysis systems have been (II) nitrate trihydrate (Cu(NO3 ), Merck Co., Ltd., 99%), ethanol abso-
developed, including the loading noble metals, such as SnO and CuO lute (CH3 CH2 OH, 99.9%), Deionised (DI) water, sodium hydroxide
etc [2]. The wide band gap semiconductor materials assisted pro- (NaOH, Merck Co., Ltd., 95%) and source dye used for the photocat-
cesses, for their activation, demand higher photon energy, which alytic activities (Methylene blue - MB) was of A.R grade and used
could be near-UV or in visible range. Besides the efficient control without further purification.
over the structural properties of photocatalyst themselves, the elec-
tron transfer from semiconductor metal oxides nanoparticles can
occur, will enhances the electron sinks which can decrease the 2.1. Synthesis of undoped and Sn:Cu:ZnO nanoparticles
number of electron/hole recombination events, and improve the
photocatalytic performance of semiconductor oxide-based cata- Bottom-up mechanisms of given NPs with fitting should have
lysts [3–7]. high performance functionalities in the significant for worthable
Since, diversity of conversant metal oxides has been broadly applications [14]. In this paper, the ZnO: Sn: Cu nanomaterials
used as photocatalysts for their wide bandgap and valid potentials were prepared by the oxidation-reduction reactions which takes
of the valence band for actual photocatalytic replies. Numerous place between the metal sources has a facile precipitation pro-
efforts have been carried on the development of semiconductors cess. The Sn and Cu doped ZnO nanoparticles were prepared in
such as MgO, WO3 , ZrO2 , TiO2 , and non-metallic elements (e.g., microwave assisted precipitation method. For synthesizing ZnO:
S, C, and N) has been considered to reduce the bandgap of wide- Sn2+ , 1 M of zinc nitrate and 0.05 M of stannous chloride were
bandgap semiconductors. They have used as a photocatalyst owing taken in 40 ml of deionised water dissolved through continuous
to their high catalytic movement, high stability, low toxicity and stirring for 8 h at 40 ◦ C. Simultaneously, 2.5 M of NaOH has been
cost-effective, etc [8,9]. Single sector semiconductor photocata- dissolved into 30 ml of ethanol absolute and then added drop wise
lyst have a numerous disadvantageous, however they are useful to the precursor solutions, with resulting in a white solution for
because of low light harvesting, high electron-hole pairs recombi- which the pH value was conserved at 11. The concluding solu-
nation rate, strict to separate the catalyst and recycle performances. tion was allowed to cool at room temperature and aged overnight.
Ultimately, the photocatalytic activity of ZnO is primarily trust- This solution was heated by microwave oven in 600 W for 10 min.
ing to the electrons and holes which are formed by proposed light After cooled the prepared material it has been ultrasonicated for
absorption [10]. Some effort has been devoted to reducing recom- 30 min, then centrifuged and washed numerous times with abso-
bination of photogenerated electron-hole pairs and to improve the lute ethanol and water in order to remove unnecessary impurities.
consumption of sunlight in the UV/visible light region by doping, The obtained product was placed in a hot air oven at preheated
deposition of metals, and the combination of another semicon- into 160 ◦ C for 6 h to complete redox reactions. Finally, the sample
ductor. Due to the rapid recombination of photoexcited electrons was annealed by furnace in air at 500 ◦ C for 2 h for oxidation with
and hole pair, the energy band structure of ZnO is modified which stability of ZnO nanostructures [15]. A related procedure was fol-
deteriorates its photocatalytic efficiency [11]. lowed for the synthesis of all the varying contents of 1 M: ZnO with
Doping of metal oxide with transition metal ions have enhances Sn and Cu as denoted into ((Sn-0M: Cu-0M: ZnO (Pure: ZnO), Sn-
the crystal defects and also affects the optical properties by shifting 0.05M + Cu-0M:ZnO (Sn:ZnO), Cu-0.05M + Sn-0M: ZnO (Cu:ZnO),
the optical absorption towards the solar region, when photocat- Sn-0.05M + Cu-0.05M: ZnO (Sn:Cu:ZnO) nanoparticles.
alytic degradation process is analysed through UV and visible
region of light irradiation. Tin (Sn) is the most familiar candi-
date due to its photocatalytic activity with ZnO nanoparticles by 2.2. Characterization techniques
trapping the photoinduced charge carriers by means of numerous
charge recombination process [12]. The Sn has very expensive cat- Crystal structure and phase composition of prepared samples
alytic behaviours which are obtained by co-doping of copper (Cu) were studied by powder X-ray diffraction using Rigaku miniflex
with ZnO, which is also an alternative way to modify absorption and II and analysed to confirm the wurtzite structure (space group
emission in the visible and nearly UV region. Copper ions can attain P63mc, 186) with primary structural parameters taken from the
into the ZnO lattice substitutions because it has deep acceptors in ICDD database (JCPDS card file: 36-1451). Further functional groups
agent with neighbouring effective vacancy [13]. were studied by FTIR analysis. The obtained products surface struc-
However, the photocatalytic efficiency usually depends on the tures were studied using scanning electron microscopy (SEM -
interaction of ZnO with the light, creation of electron-hole (e− /h+ ) JEOL Model JSM 6390LV, also attached with EDAX (JEOL Model JED
pairs, and efficient charge separation. Subsequently the existence 2300) used to estimate the elemental configurations. Particle size
of human society, is affected by many kinds of bacteria which leads is analysed by transmission electron microscopy (TEM - Jeol/JEM
to seriously and even deadly infections. Hence, the photogenerated 2100, source of LaB6). Chemical composition and surface analysis
electron-hole pairs play a crucial role in determining the chemical were calculated using X-Ray Photoelectron Spectroscopy ESCA 3
and bio-reactivity. Mark II Spectrometer. Optical absorptions, reflectance and bandgap
The existing work reports the structural, optical, photocatalytic properties were analysed using UV–vis Diffuse Reflectance Spec-
and anti-bacterial properties of Zn1−x Snx Cux O nanomaterials syn- troscopy (DRS) by Ocean Optics USB4000 spectrometer. The
thesized by precipitation method. High photocatalytic efficiency of photoluminescence (PL) measurements were carried out at room
the synthesized nanomaterials has been studied for the degrada- temperature with a Perkin Elmer LS45 spectrometer. The photocat-
tion of MB dye under UV/visible light irradiation and well associated alytic degradation measurements were done UV–vis Spectroscopy
with the active luminescence yield. Moreover, the anti-bacterial by Perkin Elmer Lambda 25 spectrometer. Identification to the exit-
properties of the Zn1−x Snx Cux O nanoparticles were investigated ing residues of after degraded photocatalyst samples were analysed
by disc diffusion method. using (JEOL GCMATE II GC–MS) mass spectroscopy. The photo-
electronic performance was carried out by CHI-760 electrochemical
 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630 619

workstation. Antibacterial activities have been measured by disc

diffusion method at room atmosphere.

2.3. Photocatalytic activity measurements

To investigate the photocatalytic activity of the as-prepared

pure ZnO, Sn: ZnO, Cu: ZnO and Sn:Cu:ZnO nanoparticles they
are taken as a catalyst and measurements as taken. The photocat-
alysts of 0.1 g is added into a 100 mL solution containing in the
20 ppm MB dye degradation process takes place under visible light
exposure. A 500 W high-pressure halogen lamp with the biggest
emission wave of 365 nm was used as the light source. The above
pH-controlled dye solution and the suspension [16] was stirred to
achieve an absorption-desorption equilibrium state and the solu-
tion was kept in the dark before light irradiation. The reaction
container was provided with an outside jacket for water circulation
to maintain the reaction mixture at room temperature. Then the
container was placed under a halogen lamp for irradiation under Fig. 1. XRD patterns of (a) Pure ZnO, (b) Sn doped ZnO, (c) Cu doped ZnO and (d)
continuous stirring. The 2.5 ml of suspension was centrifuged and Sn:Cu doped ZnO nanoparticles.
analyzed with a UV–vis absorption spectrometer at regular time
intervals. The concentration of MB dye degradation was estimated
from the decrease in intensity of its characteristic broad absorption
at 664 nm. By doing the same degradation process for few cycle to
the same catalyst, their stability will be studied.

2.4. In vitro antibacterial studies of undoped and Sn:Cu:ZnO

nanomaterials

The antibacterial activities of the synthesized Pure ZnO, Sn: ZnO,

Cu: ZnO and Sn:Cu:ZnO samples were tested against gram-positive
bacteria (Staphylococcus aureus) and gram-negative bacteria
(Escherichia coli) by adopting the disc diffusion method to deter-
mine their ability as a potential antimicrobial agent. The prepared
medium was poured into petri plates and fresh bacterial cultures
were spread over the plates to ensure homogeneous distribution.
The chosen concentration range was 10, 25 and 50 ␮g/ml in which
the activity was determined by measuring the zone of inhibition.
The plates were incubated at 35 ◦ C for 24 h. After the incubation
period, the diameter of the inhibition zone formed around the paper
discs was measured and expressed in mm. The effect of photo catal-
ysis is also reflected in circular zone growth concentration [17]. Fig. 2. FTIR spectra of (a) Pure ZnO, (b) Sn doped ZnO, (c) Cu doped ZnO and (d)
Sn:Cu doped ZnO nanoparticles.

3. Results and discussion

increases of crystallite size is observed in mono doped nanoparti-
3.1. Structural characterization (XRD analysis) of synthesized cles
nanoparticles
3.2. FTIR analysis
Fig. 1 shows the XRD pattern of undoped, Sn, Cu doped and co-
doped ZnO NPs synthesized in the existing work. XRD spectra show The FT-IR spectra of different samples are shown in Fig. 2. Several
narrow and sharp peaks at the specified positions of 31.54◦ , 34.20◦ , absorption peaks appear in all the prepared samples have been pre-
36.03◦ , 56.41◦ and etc., which are in good agreement with the stan- dicted to their functional groups. All the samples demonstrated the
dard ZnO (JCPDS Card file 36-1451, a = b = 3.2598 Å, c = 5.2323 Å) and set of peaks in the range from 3100 to 3500 cm−1 are assigned to the
indexed as the hexagonal wurtzite structure of ZnO having space stretching vibrational modes of primary O H stretching of solvent.
group P63mc. Furthermore, it can be seen in all doping percent- A series of peaks are observed at 1388, 1410, 1425 and 1397 cm−1 ,
ages of Sn:ZnO, Cu:ZnO and Sn:Cu:ZnO, exchanges of ZnO has been which are consistent with stretching modes of C—H bond [19].
present [18]. Some new peaks in the XRD spectra correspond to Additionally, the characteristic peaks at 835 and 858 cm−1 are
(101) and (111) matched with standard JCPDS data at SnO (85- attributed to the typical bending vibration of C H bond. The dis-
0423) and CuO (89-5895) respectively. An obvious decrease in the tinctive absorption peaks at 608, 545, 556 and 571 cm−1 are clearly
intensity of the above-mentioned to reflections and the appearance observed for ZnO ions, which are accompanied with the Sn O and
of additional reflections are confirmed the addition of SnO and CuO. Cu O stretching vibration at 535 and 542 cm−1 .
The crystallite size was estimated using Scherrer’s formula for the
most prominent X-ray diffraction peaks. 3.3. Morphology and microstructure analysis
The calculated lattice and unit cell values are given in Table 1.
There is no drastic change in the lattice strain. Interestingly, the Scanning electron microscopy (SEM) is one of the prominent
decreases in the crystalline size is observed in co-doping, whereas method to study the morphology of nanostructured materials
620 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630

Table 1
Structural parameters of undoped and doped ZnO nanoparticles.

Metal loading Lattice parameters (Å)

Samples Unit Cell volume (Å3 ) Lattice strain Crystallite size (nm)
(M %)

Sn Cu a=b c c/a

Pure ZnO 0 0 3.2598 5.2300 1.6043 48.129 0.0027 40.94

Sn: ZnO 5 0 3.2580 5.2313 1.6056 48.091 0.0029 42.03
Cu: ZnO 0 5 3.2616 5.2391 1.6062 48.269 0.0027 41.70
Sn:Cu:ZnO 5 5 3.2601 5.2290 1.6039 48.141 0.0028 38.29

Fig. 3. SEM images of (a) Pure ZnO and (b) Sn:Cu:ZnO nanoparticles.

[20]. Fig. 3 represent the micrographs of pure ZnO and Sn:Cu:ZnO 3.4. X-ray photo-electron spectroscopy (XPS) studies
nanoparticles. These images demonstrated that grown nanoparti-
cles were almost spherical shaped and smooth surface is observed XPS designates the statistical information of binding energy,
in Sn:Cn:ZnO NPs (Fig. 3b) compared to Pure ZnO nanoparticles electronic structure, the oxidation state of each element as well as
(Fig. 3a). It is seen that the nanoparticles are mono-dispersed, the composition of the surface functionalization in Sn:Cu:ZnO NPs.
homogeneously distributed and grown in moral density in nature. Fig. 6(a) in high resolution XPS spectra of Sn:Cu:ZnO, indexed peaks
EDX spectrum exhibit well-defined peaks which confirm the correspond to Zn (2p), O (1s), Sn (3d) and Cu (2p) for all the doped
presence of Zn, Sn, Cu and O2 in the catalyst (Fig. 4a and b). Here Cu nanomaterials. The spectra confirm the strong spin orbit coupling
and Sn ions finely replace the zinc elemental composition and indi- moment and where Zn (2p) signal splits into two symmetrical peaks
cate the nominal doping percentage (insert of Fig. 4). The presence such as Zn (2p3/2 ) and Zn (2p1/2 ) core levels, likewise these peaks
of Cu and Sn increase the absorption of light in the entire visible (Fig. 6b) are placed at 1022 eV and 1045.2 eV respectively, and ver-
region. This EDX inspect has strongly suggest that due to conse- ifying with existing of Zn2+ [22]. The broadening binding energy
quent of the reduction reactions of counter ions, (due to dopant ions level of O (1s) at 531 eV has (Fig. 6c) associated with interactions
and their precursors) there is no impurity is added in the present of Zn-O structure [23]. Furthermore, the Fig. 6(d) shows the bind-
nanoparticles. ing energy peaks of Sn (3d) at 487.3 and 495.8 eV correspond to
The morphology, surface and particle size can be explored by 3d3/2 and 3d5/2 spin moments. Sn ions are displaced in high energy
TEM analysis. This image (Fig. 5) has represented the average par- level compared to the normal values in ZnO lattice which may be
ticle size (∼41 nm) matches well with crystalline size supported by caused by the addition of Cu2+ ions. Besides, the peaks correspond
the XRD data. The TEM analysis data proved that no agglomerations to 2p3/2 and 2p5/2 of Cu ions were detected at 933.8 and 953.58 eV
of any other particles, is observed. Also, the observed hexago- are attributed to metallic copper (Cu-O) present in the catalyst [24].
nal structure has defect free linear lattice planes. The selected The obtained peaks of Sn 3d3/2 and Cu 2p5/2 of the present spec-
area electron diffraction patterns (SAED) is shown in Fig. 5(d), tra has low energy than the symmetric peak indicates the existence
which was well-defined circular fringes with dots represents the of mixed valence state on the surface of Sn:Cu:ZnO nanomaterials.
good single crystalline nature of nanoparticles and the regular- The difference in the ionic radius between Zn2+ , Sn and Cu2+ leads
ity of phase without any mis-arrangements [21,22]. TEM analysis to formation of stress in the lattice, and fact that the interaction
revealed well-determined fine lattice fringes with d spacing cor- between Sn and Cu ions and ZnO heterostructure of quantum con-
responding to the (101) plane of hexagonal wurtzite phase. The finement can have medium bonds [25]. Consequently, it’s being
observation of regular lattice fringes explicit the good crystalline chief evidenced that all doped ions are fine bonded and have most
nature of the synthesized nanoparticles. reasonable charge transferring factors with Zn2+ ions.
 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630 621

Fig. 4. EDAX analysis of (a) Pure ZnO and (b) Sn:Cu:ZnO nanoparticles.

Fig. 5. (a–c) TEM images of Sn:Cu:ZnO NPs (d) selected area electron diffraction.
622 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630

Fig. 6. XPS Spectra of Sn:Cu:ZnO nanoparticles.

3.5. Optical properties and bandgap-engineering of pure and doped ZnO NPs causes a red shift in the absorption edge ∼250 nm.
doped ZnO NPs This red shifted absorption spectra are interpreted as possible evi-
dence for good interaction between Zn, Sn, and Cu species. The red
To study the optical response, Ocean Optics UV–vis diffuse shifting behaviour or narrowing in the bandgap for all the samples
reflectance spectrophotometer is used at room temperature and is may be caused by 3d-4s and 4d-5s orbital electrons interactions
the spectra for the prepared samples as shown in Fig. 7. The co- which decrease the electron density. Obviously, the broad visi-
 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630 623

Fig. 7. UV- DRS spectra of synthesized samples.

Fig. 9. Photoluminescence spectrum of the nanoparticles.

ble absorption above 350 nm is enhanced after the deposition of 3.6. Photoluminescence studies
dopants in ZnO ions.
Hence, the substitutions of Sn and Cu ions with their electron Photoluminescence (PL) Spectroscopy is an effective technique
density will lead to higher binding energy. It is observed the absorp- to study the electronic band structure, such as defect and vacancies,
tion edges of doped materials shifted to higher level compared as well as the efficiency of charge carrier trapping, immigration
to pure ZnO [26]. These shifts towards the higher energy wave- and charge transfer can be obtained. Fig. 9 shows the PL spectra
length of UV rays suggesting that the bandgap narrowing in doped of the prepared samples at the absorption wavelength described
compounds is confirmed by the analysis of UV-DR spectroscopic in the UV-DRS measurements, and the broad excitation is 405 nm.
data via tauc plots. The direct transitions of their particular co- All the samples have sharp emission bands around 590 nm and its
ordination have been confirmed to linear fitting of the (␣h␯)2 vs. h␯ emission in green-yellow region due to the emission from band
plot (Fig. 8). (␣h␯)2 = A (h␯ – Eg) Where, ␯ is the frequency of light, to band transition [28]. The excitation wavelength for Pure ZnO,
A is a constant, h is the Planck’s constant, and Eg is energy bandgap Sn: ZnO, Cu: ZnO and Sn:Cu:ZnO NPs were 590, 589, 588 and 589
of the material. respectively. Here, the doped nanoparticles have blue shift of NBE
The Sn2+ and Cu2+ ions are might covalently interact with the emission originates from the Burstein–Moss effect.
zinc ions and reduce the bandgap. The bandgap measured for the Sub-band gap absorption and red emission suggest these nature
pure ZnO, Sn: ZnO, Cu: ZnO and Sn:Cu:ZnO NPs are ∼3.22, 3.03, defects of zinc (Vz) and oxygen vacancy (Vo) and its effects have
2.98, and 2.67 eV are respectively. The present bandgap of ZnO identified a new source of single photons which takes the numerous
nanoparticles corresponds to 3.22 eV has a red shift of about 0.08 eV applications through the sensing and red LEDs.
compared to the bulk bandgap of 3.3 eV due to quantum confine- This is main reason behind the rapid decrease in luminescence
ment effect [27]. intensity with increasing the Sn2+ and Cu2+ of bi-metal doping
and co-doping. The process of PL emission may be due to the
band edge luminescence and/or defect emission [29], when the
electron-hole pair is tightly bound with distance between e− and h+
(HOMO and LUMO) were comparable to the lattice constants and
which are called excitons of Frenkel. Thus, it can be concluded that
decrease in the intensity caused by superior textural properties,
tight bound electron−hole (e− –h+ ) separation and low recombina-
tion rate which are the factors responsible for optoelectronics and
photocatalytic applications.

3.7. Photocatalytic activity

To explore the photocatalytic activity and stability of the as-

prepared promising bandgap semiconductor materials of pure ZnO,
Sn: ZnO, Cu: ZnO and Sn:Cu:ZnO nanoparticles we select some
widely used destructive dye, such as methylene blue (MB) as the
model pollutant. Total concentrations of dye with aqueous solution
were simply determined from the maximum absorption (664 nm)
measurements by UV spectra [30,31]. Since the adsorption of the
dye on pure ZnO photo catalysts is too weak it can be ignored and
the above experiments show that the present prepared materi-
als of effective Sn:Cu:ZnO nanoparticles can be promoted as the
Fig. 8. Bandgap energy (tauc lot) of prepared nanoparticles. well-known photodegradation of the MB dye molecule.
624 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630

The UV–vis absorption spectrum analysis of an aqueous solu-

tion of 20 ppm MB dye with photocatalysts of pure ZnO, Sn: ZnO,
Cu: ZnO and Sn:Cu:ZnO nanoparticles under UV/visible irradiation
is carried out for various time duration. The first step in degradation
involves into adsorption of the dye onto the surface of ZnO nanos-
tructures will leads to generation of electron–hole (e− – h+ ) pairs
in zinc lattices [32]. These photogenerated electrons in the conduc-
tion band of ZnO interact with the oxygen molecules adsorbed on
Sn:Cu:ZnO nanoparticles can indeed to form of superoxide anion
radicals (O2− ). The holes created in the valence band of that remain
on the Sn and Cu ions in the ZnO responds to the surface hydroxyl
groups and it can produce highly reactive hydroxyl radicals (OH)
[33]. These photogenerated holes can lead to dissociation of water
molecules in the aqueous solution, producing radicals.
The extremely reactive hydroxyl radicals (OH) and superoxide
radicals (O2 ) react with MB dye adsorbed on ZnO nanostructures
and lead to its degradation/decoloration resulting in its colorless
form. According to the TEM images, it clear that the Sn:Cu:ZnO
nanostructures were fine traded into Sn and Cu particles can leads
by ZnO lattice. Here, Sn:Cu:ZnO nanoparticles act as a good electron
Fig. 10. C/Co Curves of photocatalytic degradation of MB over different catalysts
trapper would favour for electron transfer and it is best com-
under exposure of UV/visible light.
pared to undoped and other doped ZnO nanoparticles [34,35]. Thus,
an improved separation rate of the photogenerated electrons and
holes in the Sn:Cu:ZnO nanoparticles could be expected hence it
will be influenced. The progress of photocatalytic activity of the
sample with Sn:Cu:ZnO nanoparticles has generally been described
according to the mechanism has illustrated in the equations (1–5).
Primarily, the photons delivered by the UV and the visible irradia-
tion, with some energy equal or higher than the ZnO bandgap, are
released by the semiconductor [36], making possible the existence
of OH radical and O2 radicals can have depends on electrons (e− ) in
the conduction band (CB) and an equal number of holes (h+ ) in the
valence band (VB). The presence of Sn:Cu:ZnO on the surface of ZnO
lattices hence it will favor the formation of the Schottky barriers at
the metal-semiconductor interface.
 
SCZ + h␯ → ZnO + e− (CB) + h+ (VB) (1)
.
OH + MB → CO2 + H2 O (2)
+
h + MB → CO2 + H2 O → (3)
+ . +
H2 O + h → OH / H → (4)
+
OH. / h + MB → degradation products + CO2 + H2 O → (5)
Fig. 11. Effect of dye degradation efficiency (Time (min) vs. dye degradation (%)).
The photocatalytic degradation of MB dye under UV also visible
light over different photocatalyst prepared is shown in Fig. 10. From
the graph, can be seen that the Sn:Cu:ZnO nanostructures are highly
As shown in the Fig. 12, the Sn:Cu:ZnO nanoparticles display the
efficient photocatalysts compared to others. The photodegradation
superior photocatalytic activity and around 98.5% to 95% of MB dye
efficiency percentage (Fig. 11) of MB dye for the respective catalysts
molecules can be degraded in five cycles. In the presence of MB dye,
were calculated from the Eq. (6), where Ct and Co are the concen-
Sn:Cu:ZnO nanoparticles has been standing as good photocatalyst
trations of MB at time 0 and t, respectively, and t is the irradiation
and explored a stable catalytic activity for the five cycles.
time in seconds [37].
The separation of electron-hole recombination can be increased
Co − Ct by various intrinsic or extrinsic defects which are created prob-
D (%) = × 100 → (6)
Co abilistic in nature [40,41]. In Sn:Cu:ZnO nanostructures intrinsic
Therefore, the recombination activity of photogenerated elec- defects contain zinc (VZn) and oxygen vacancies (Vo) in nanostruc-
trons and holes is suppressed, leaving more holes and more tured materials itself, because of preparation method and extrinsic
electrons in the Sn:Cu:ZnO of prepared material. Subsequently, the defects are may due to the doping of Sn and Cu ions. Because of their
electron can accumulate on the CB of SnO and CuO nanoparticles possible defects on the surface of catalysts are also responsible for
loaded on the surface of ZnO which reduce the adsorbed O2 rapidly photogenerated electron-hole pairs under visible light exposures.
to superoxide anion radicals (O2 •− ) or h+ . Simultaneously, the pho- The photocatalytic degradation kinetics (C/C0 ) of Sn:Cu:ZnO pho-
togenerated holes in the VB of ZnO react with OH- to form OH• . tocatalysts upto 5th cycle are shown in Fig. 13. It is clearly observed
These highly active species O2 •− and OH• are responsible for the that the Sn:Cu:ZnO sample has higher photocatalytic activity in
degradation of MB [38,39]. all cycles with very low decrease in 5th cycle even for the same
Hereafter, favorable reagent of Sn:Cu:ZnO nanoparticles is taken exposure time. Although, in this degradation process has compared
as photo catalysts for the treatment in 20 ppm of same MB dye and to standard Degussa P25 TiO2 , whereas it has possessed that less
the degradation process has been studied upto cycle 5 upto 15 h. degradation efficiency (38%) than Sn:Cu:ZnO nanoparticles.
 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630 625

Fig. 14. Stability analysis by XRD spectra after photocatalytic process.

Fig. 12. Catalyst reusability of Sn:Cu:ZnO nanoparticles in cyclic photodegradation
of MB dye for five cycles.

Fig. 13. Degradation kinetics of Sn:Cu:ZnO nanoparticles upto cycle 5.

Fig. 15. First order kinetic studies (Ln(Co /Ct)) for the photodegradation of MB over
the photocatalyst.
3.8. Catalyst stability

The dye degradation rate depends on the stability, morphology,

crystallinity of the photocatalysts, large surface area and number
of active sites are stimulated due to the separation efficiency of catalysts as expressed by novel eqn of Ln (Co/C) = Kt. This model is
electron–hole pairs in the kinetics of photocatalytic reactions [42]. largely used for the photocatalytic degradation method if the initial
From the viewpoint of practical applications, the stability of the concentration of pollutant is low, where k is the pseudo-first-order
catalyst was also explored by XRD [43]. Fig. 14 shows the stability rate constant also.
of the catalyst by its structure and there is no obvious structural Fig. 15 shows the linear relationship for ln(C/Co) plotted against
changes observed over all the samples, especially Sn:Cu:ZnO pho- irradiation time. The apparent rate constant K is calculated and it
tocatalyst has good structural stability during all the consecutive being tabulated (Table 2). Kapp value increases (0.0001–0.0103 min
cycle’s. Hence Sn:Cu:ZnO nanoparticles has the successive catalyst −1 ) with the increase in Sn and Cu dopant. The K rate of Sn:Cu:ZnO

with outstanding stability and great potential value in dye removal nanoparticles is 2.64 times greater than Pure ZnO nanoparticles.
for environmental applications. Introduction of good dopant of ions into the ZnO lattice is improved
the photocatalytic activity by increasing the lifetime of charge car-
3.9. Kinetic study riers [45,46]. Even though, the Sn and Cu content is low level, they
are playing vital role in separation efficiency of the electrons/holes
To investigate whether the process obeyed into the decom- excited by visible light irradiation, and they are the key factors in
position of MB could be assigned to a pseudo-first-order kinetics deciding the rete constant. From the table, it is seen that Sn:Cu:ZnO
reaction with a simplified, [44], which is well recognized for organic has very high degradation efficiency compared to other nanoparti-
compound degradation in the occurrence of heterogeneous photo- cles and its withstand for many cycles with same efficiency.
626 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630

Fig. 16. Mass spectra of (a) Pure ZnO, (b) Sn doped ZnO (c) Cu doped ZnO and (d) Sn:Cu doped ZnO nanoparticles after degradation process.

3.9.1. Analysis of the exciting residues and their identification of The measurements of mass spectra were investigated under a (+
degraded MB dye products (mass spectroscopy (GC–MS)) ve) signal were very low intermediates have been occurred, which
The photo-generated catalysed samples of MB dye degradation means m/z 81.53, 84.55, 81.53 and 81.52 m/z will correspond to
were analysed through mass analyser (JEOL GCMATE II GC–MS). The the dye molecules. Which is undegraded dye contained nanoparti-
mass spectra (Fig. 16) of Sn, Cu doped and co-doped ZnO nanopar- cles which means intermediates of irradiation time. The spectrum
ticles were recorded by scanning from 30 m/z to 150 m/z. When the gives an important m/z signals at 94.94, 108.86, 79.54 and 93.47 m/z
MB dye degraded with Sn, Cu doped and co-doped ZnO nanoparti- yields the piece ions zinc metal ions along with some methyl
cles are isolated via mass analyser, ions of precursors (MB dye) and (–CH3 ). The compound has the signals at 53.61, 51.75, 53.22, and
the ions of these collisions create some fragmented ions [47,48]. 51.75 m/z of lower angle has referred to the cleavage of a methyl
 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630 627

Table 2
Shadowing the pseudo-first order rate constants (K), R2 values and maximum degradation (%) of the nanoparticles.

Materials K (rate constant) min −1 R2 Maximum Degradation efficiency (%)

Dye without NPs 0.0001 0.9052 1.69

NPs without UV 0.0018 0.9502 3.36
Pure ZnO 0.0039 0.9536 21.29
Sn: ZnO 0.0042 0.9623 50.44
Cu: ZnO 0.0070 0.9668 65.09
Sn: Cu: ZnO 0.0103 (Cycle 1) 0.9680 (Cycle 1) 98.40 (Cycle 1)
0.0102 (Cycle 2) 0.9685 (Cycle 2) 97.86 (Cycle 2)
0.0102 (Cycle 3) 0.9698 (Cycle 3) 97.05 (Cycle 3)
0.0102 (Cycle 4) 0.9726 (Cycle 4) 95.16 (Cycle 4)
0.0100 (Cycle 5) 0.9728 (Cycle 5) 94.35 (Cycle 5)

group (–CH3 ) from the dye molecule. The peak at m/z (95.45) lower
level can be illustrates the decomposition of oxygen molecule and
hydrogen molecule. The peak at m/z 93.94 was derived from the
cleavage of nitrogen molecule from the MB dye of the compound
[49].

3.10. Photo-electronic performance

The photo-electronic performance of synthesized samples was

assessed using a CHI-760 instrument, with the typical three-
electrode system consisting of Pt wire as counter electrode,
sample-coated Indium Tin oxides (ITO) glass as working elec-
trode, Ag/AgCl as reference electrode and chief aqueous solution of
Na2 SO4 (0.1 M) is used as a electrolyte [50]. During the procedure,
the applied voltage can be moved to 10 V for 10 min. When irra-
diation was used in the photocurrent test, with Xe lamp and a UV
filter attained at 0.3 V vs Ag/AgCl, plots were collected at different
frequencies of light in On and OFF positions.
The photocurrent responses of pure ZnO, Sn:ZnO, Cu:ZnO and
Sn:Cu:ZnO NPs were explored in several on-off cycles of light irra-
Fig. 17. Photocurrent responses of prepared nanoparticles under visible light.
diation (Fig. 17). It is well-known that the obtained photocurrent
intensity of Sn:Cu:ZnO nanoparticles has abundant higher than that
of remaining samples, which is good agreement to the develop- trapped into easily [54] by the electrostatic interactions between
ment of photocatalytic properties and more charge carrier ability the appreciated ions and the bacteria’s.
[51]. The spectra also suggest that improved photocatalytic activity From the Fig. 18 the Sn:Cu:ZnO nano-antibacterial material has
can be accredited to the decoration of Sn:Cu:ZnO NPs, which has been exhibit good zone inhibition level compared to pure ZnO,
greatly improved the photo-response of the photocatalyst and the Sn:ZnO and Cu:ZnO. A zone of inhibition is formed in each disc
separation/transfer ability of charge carriers in the composite. loaded with the samples indicates the zones of inhibition are fairly
clean, inside an open circle around the disc (Fig. 18) with dis-
3.11. Effects on antibacterial activities of undoped and Sn:Cu:ZnO tinct variations in the susceptibility of bacteria towards Sn:Cu:ZnO
nanoparticles nanoparticles is maximum at around ∼10–20 mm.
The antibacterial activity of the nanoparticles may be accredited
Antibacterial studies of prepared nanoparticles were studied to to the two probable mechanisms viz, (i) the generation of enhances
explore their utility as a potential material for biological appli- stages of Reactive Oxygen Species (ROS) i.e. corresponds of super
cations, especially nano-antibacterial agent due to their lower oxide anion radical (O2 /h- ), hydroxyl radical (h+ /OH) and hydro-
toxicity, heat resistance and become an alternative for food backing, gen peroxide (H2 O2 ), moreover (ii) the deposition of nanoparticles
long-lasting, and no drug resistance [52,53]. The excellent activ- on surface of the bacteria. The decreased crystallite size of the Sn:
ity of 10, 25 and 50 ␮g/ml of synthesized nanoparticles against Cu: ZnO sample (as confirmed by XRD analysis) is also one of the
the S. aureus (G+ ) and E. coli (G- ), has been observed with good reasons for enhanced bacterial exploit. Besides, the bacterial activ-
bacterial strains by disc diffusion method. Activity towards the G+ ity of the prepared ZnO samples can be described as follows: ZnO
bacteria are more because of the cell wall of G- bacteria is more with crystal defects such as typical vacancies can be triggered by
probable than the G+ bacteria, and ZnO, Sn and Cu ions may get both UV and visible light which means enhances wide absorption

Table 3
Antibacterial activity of prepared nanoparticles.

Microorganisms Bacteria’s (size of zones (mm))

E. Coli S. aureus

Synthesized nano-antibacterial materials 10 ␮g 25 ␮g 50 ␮g 10 ␮g 25 ␮g 50 ␮g

Pure ZnO 10 ± 0.5 11 ± 0.5 11 ± 0.5 11 ± 0.5 12 ± 0.5 12 ± 1
Sn: ZnO 13 ± 0.5 15 ± 0.5 15 ± 1 10 ± 0.5 13 ± 1 13 ± 0.5
Cu: ZnO 12 ± 0.5 13 ± 1 13 ± 0 12 ± 0.5 14 ± 1 14 ± 0.5
Sn: Cu: ZnO 16 ± 1 17 ± 0.5 19 ± 1 15 ± 0.5 17 ± 1 19 ± 0.5
628 V. Shanmugam, K.S. Jeyaperumal / Applied Surface Science 449 (2018) 617–630

Fig. 18. Antibacterial activity of prepared samples.

region [55]. When a photon of suitable energy falls on ZnO, an elec- for Sn:Cu:ZnO compared to pure ZnO nanomaterials. The decrease
tron from the valence band is excited to the conduction band exit in bandgap energy is attributed to the incorporation of Sn and Cu
of hole in the valence band. The enhanced electrons in the conduc- ions into the ZnO lattice, which may be attributed to sp-d orbital
tion band react with the softened oxygen molecules were initiating exchange interactions. PL emission intensity was decreased grad-
superoxide anion radicals (O− ). Detailed of probable solution which ually due to the (e− – h+ ) separations and the emission range of
may have the holes in the valence band divided water molecule 590 nm has referred in the green-yellow region whereas applicable
into OH and H+ ions. The superoxide anion radical (O− ) has fur- for colour LEDs. However, the photocatalytic degradation experi-
ther react with the H+ generating HO− radicals. The HO− radical ments indicated that unique Sn:Cu:ZnO nanoparticles possessed
replies with electron and H+ yielding H2 O2 molecule. Commonly strong photocatalytic activity with the degradation 98.5% of MB
the H2 O2 can fluently penetrate to the cell membrane and even- within 180 min and good cycling capability upto 5th cycles with
tually cause the death of the bacteria [56]. While the Sn: Cu: ZnO good stability. The Sn:Cu:ZnO nanoparticles under visible-light-
sample is a good nanomaterial used for this application, and are driven photocatalyst by an interfacial charge transfer process and
better antibacterial agent towards pathogenic bacteria may be due its photodegradation rate is 2.64 times faster than that of undoped
to progress of oxygen species. Hence, the above suggestions the Sn: ZnO. The photocurrent responses revealed that Sn:Cu:ZnO system
Cu: ZnO nanoparticles can penetrate and easily disrupt the mem- where good carrier transport, and active electron−hole separation
branes of bacteria. Fig. 18, clearly shows that Sn: Cu: ZnO sample process. The mass spectra data clearly support owing the photocat-
has much better antibacterial activity compared to pure ZnO, Sn: alytic performance of Sn:Cu:ZnO nanoparticles, which has shown
ZnO and Cu: ZnO samples, with their consistent zone of inhibition that middle of degradation process of MB dye contained nanopar-
are tabularized (Table 3). ticles. The antibacterial evaluations performed against a G+ and G−
bacterial strains show that the Sn:Cu:ZnO nanoparticles possessed
a superior antibacterial effect than undoped ZnO nanoparticles.
4. Conclusion Hence the co-doped ZnO nanomaterials has high stable photocat-
alytic activity and antibacterial activity which is very much useful
Sn and Cu doped ZnO nanoparticles are successfully synthe- for environmental applications.
sized by facile strategy in cost effective, single step route and in
order to understand correlations between the structural, optical
and photocatalytic properties. The hexagonal (wurtzite) crystalline Appendix A. Supplementary data
structure was acknowledged in undoped and doped ZnO through
XRD analysis and confirmed the incorporation of Sn and Cu ions Supplementary material related to this article can be found, in
into the lattice site of Zn2+ ions and the Sn:Cu:ZnO nanoparti- the online version, at doi:[Link]
cles of average crystalline size of ∼40 nm in such cases of lattice 167
parameters are calculated. The presence of all functional groups
was observed from FTIR analysis. Spherical like morphologies are
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