Journal of Photochemistry & Photobiology A: Chemistry 367 (2018) 162–170

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Journal of Photochemistry & Photobiology A: Chemistry

journal homepage: www.elsevier.com/locate/jphotochem

Rapid Escherichia coli inactivation in visible light by Fe/Zn-α-NiMoO4 T

nanorod
⁎ ⁎
Schindra Kumar Raya, , Ramesh Prasad Pandeyb, Sanghoon Jeonga, Soo Wohn Leea,
a
Department of Environmental and Bio-chemical Engineering, Sun Moon University, Chungnam, 31460, Republic of Korea
b
Department of BT-Convergent Pharmaceutical Engineering, Sun Moon University, Chungnam, 31460, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: The microwave hydrothermal synthesized Fe and Zn doped α-NiMoO4 nanorod was characterized by various
Microwave hydrothermal techniques. The doping of metal ions into the lattice of α-NiMoO4 was verified by HRTEM, SAED, and EDS
α-NiMoO4 analysis. The Fe and Zn doped α-NiMoO4 photocatalyst completely inactivated the Escherichia coli in aqueous
Nanorod medium under visible light irradiation within 30 min and 45 min, respectively. The extending of absorption
Escherichia coli
towards the visible light region or reduce in band gap, formation of new energy level in valance band and
Photocatalytic disinfection
conduction band, trapping of generation of electron-hole pairs, oxygen vacancy, and efficient separation of
electron-hole make the enhancement of photocatalytic disinfection by doped photocatalyst. Furthermore, the
TEM images suggest the destruction of bacteria cell. The TEM elemental mapping of bacteria reveals that there is
no release of toxic elements into the bacteria cell from the photocatalyst. So, these results demonstrated that the
doped efficient photocatalyst can be applied for rapid inactivation of pathogens in infected waste water.

1. Introduction photocatalyst applied for efficient bacterial inactivation. However,

The waterborneinfection is also a major problem especially in de-
veloping countries due to lack of poor sanitation. The millions of peo-
ples died by waterborne diseases every year. Pathogens are responsible
for waterborne diseases [1]. The Gram-negative bacteria, Escherichia
coli (E. coli) is waterborne bacterial Pathogen. This bacteria is also
called the indicator organisms and used to determine pathogen levels in
water sources [2]. E. coli is considered as the causative agent for acute
diarrhea and bloody diarrhea because of irrigation in farms by con-
taminated water [3]. Also, it causes severe health problems like blood
stream infection, central nervous system diseases, peritonitis, colitis,
bacteremia, infant mortality, and urinary tract infections [4,5]. Various
processes, such as advanced filtration processes, ultraviolet (UV) ra-
diation, ozonation, and chemical treatment by chlorine dioxide are
employed for removal of pathogens from contaminated water sources.
However, most of these methods suffer high cost with huge consump-
tion of chemicals or energy [6]. So, the potential green technology,
utilization of natural sunlight by semiconductor materials is best way to
destroy the pathogens in aqueous solution via advanced oxygen pro-
cesses (AOPs) [5,7–10].
For efficient bacterial inactivation, efficient visible light driven
photocatalyst is the perfect choice because it can utilize the high per-
centage of solar spectrum. In recent years, the silver modified
silver is expensive metal. So, cheap efficient visible light driven pho-
tocatalytic materials is still searching in the scientific community for
efficient removal of pathogens from water. So, Nickel molybdate
(NiMoO4) photocatalyst is suitable choice because it has several good
features such as absorption in visible light, 2.8 eV band gap, low cost,
stable at room temperature, and environmentally friendly. The NiMoO4
consists of low temperature α-phase and high temperature β-phase. So,
the α-phase NiMoO4 is chosen which has monoclinic structure, C2/m
space group, and octahedral coordination of Mo6+ and Ni2+ ions with
edge sharing oxygen atom. The α-NiMoO4 photocatalyst has low pho-
tocatalytic performances due to fast recombination of electron-hole
pairs even it has a narrow band gap [7,9–12]. Nowadays, morphology
tuned and doped techniques are applied to enhance the photocatalytic
disinfection tendency of α-NiMoO4 [9,11]. Among them approaches,
doping of transition metal ions is good option for enhancing the pho-
tocatalytic activity due to favorable crystal structure. The doping of
transition metals makes effective interfacial electron transfer rate, ex-
tending of absorption towards the visible light spectrum or decrease in
band gap, creation of new energy level in valance band and conduction
band, inhibiting the recombination of electron-hole pairs, generating
the electron-hole trapping sites, and forming oxygen vacancy in the
host photocatalyst [7,11]. It also produces higher amount of reactive
oxygen species (ROSs) that can destroy the cell organelles of bacteria

⁎
Corresponding authors.
E-mail addresses: schindrakumarray@gmail.com (S.K. Ray), swlee@sunmoon.ac.kr (S.W. Lee).

https://doi.org/10.1016/j.jphotochem.2018.08.031
Received 12 June 2018; Received in revised form 20 August 2018; Accepted 21 August 2018
Available online 24 August 2018
1010-6030/ © 2018 Elsevier B.V. All rights reserved.
S.K. Ray et al.
Fig. 1. XRD patterns of samples.
[13].
In this paper, we demonstrate the synthesis of Zn and Fe doped α-
NiMoO4 photocatalyst by microwave hydrothermal process. The
morphologies and optical properties of doped photocatalyst were in-
vestigated. The photocatalytic inactivation of E. coli was analyzed
under visible light illumination. Furthermore, the TEM and elemental
mapping images are used to observe the photocatalytic effect in E. coli.
2. Materials and methods
2.1. Synthesis of Fe/Zn-α-NiMoO4 photocatalyst
All the chemicals were obtained from Sigma-Aldrich of analytical
grade. At first, 40 ml of NiCl2⋅6H2O (2 × 10−2 mole) aqueous solution
and 40 ml of H2MoO4 (2 × 10−2 mole) aqueous solution were placed in
the separate beaker. FeCl3⋅6H2O (4 wt. %) and Zn(NO3)2⋅6H2O (3 wt.
%) were used for doping Fe and Zn in host, respectively. Both the do-
pant chemicals were placed in NiCl2⋅6H2O aqueous solution which was
mixed drop-wise by continuous magnetic stirring with aqueous
H2MoO4 solution to form pale yellow precipitate. The pH of the solution
was maintained to 7 by using aqueous ammonia (30%). The pre-
cipitated solution was magnetically stirred up to 5 h. Then, the resulting
suspension followed the microwave hydrothermal treatment (150 °C/
60 min/200 W) by using Microwave reactor (Eyla MWO-1000 wave
Magic). After that, the obtained precipitated was washed several times
with water and ethanol. Furthermore, it was dried (70 °C) and calcined
in air (500 °C/5 h). For convenience, the samples were coded as NM,
NM-Zn, and NM-Fe for host, Zn doping, and Fe doping, respectively.
Fig. 2. FESEM of samples. (a) NM, (b) NM-Zn, and (c) NM-Fe.
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Journal of Photochemistry & Photobiology A: Chemistry 367 (2018) 162–170
2.2. Characterization
X-ray diffraction (XRD) patterns were measured on a Rigaku, D/
MAX 2200HR in a 2θ range of 10-70° at scan rate 4° per minute. The
morphologies were investigated by field-emission scanning electron
microscopy (FESEM). After FESEM, transmission electron microscopy
(TEM), high-resolution transmission electron microscopy (HRTEM),
and selected area electron diffraction (SAED) were applied to analyze
the morphology and lattice fringe of sample. The FESEM images of
sample was observed by JSM-6700 F whereas TEM, HRTEM, and SAED
of samples were measured by Titan cubed G2 60-300. The energy-dis-
persive X-ray spectroscopy (EDS) and elemental mapping were carried
out by using Oxford Instruments, X-MaxN50 and Titan cubed G2 60-
300. The TEM and elemental mapping of bacteria was taken from FEI
Tecnai G2-F20. The multilab system (Al Kα source/15 kV/200 W) was
used to analyze the X-ray photoelectron spectroscopy (XPS) of samples.
The Raman spectra was measured on LabRam, Horiba, France at excited
wavelength (λex) 530 nm. The UV–vis diffuse reflectance spectra (DRS)
of samples was measured by V 570, Jasco International Co. Ltd. The
photocatalytic Inactivation of bacteria was carried out by using solar
simulator (portable solar simulator PEC-L01, 150 W short-arc Xe lamp,
100 mW/cm2, Pecell, Am 1.5 G) as a light source. For visible light, UV
cut-off filter (λ < 420 nm) was placed in solar simulator.
2.3. Photocatalytic inactivation of bacteria
The spread-plate (colony counts on agar) technique is used for ob-
serving the bacteria viability in visible light. For determining the E. coli
DH5α (New England Biolabs® Inc., USA) inactivation by samples in
visible light, bacteria was incubated in LB broth at 37 °C for 12 h
shaking and centrifuged at 3000 rpm. After that, the cell pellet was
washed by phosphate buffer saline, PBS (0.2 × 10−3 M, pH = 7.2) and
centrifuged (3000 rpm). The concentration of photocatalyst consists of
0.2 mg/mL. The bacteria concentration was 108 CFU/ml. During the
visible light irradiation period, 10 μL aliquot was immediately taken
and diluted. Then, 100 μL from the diluted suspension was plated on the
LB agar plate with triplicate plating. The aliquot was taken in every
15 min time intervals and the CFU/mL (average/standard deviation)
was calculated. About 12 cm distance was maintained between lamp
and aqueous medium of bacteria.
For TEM and elemental analysis of damaged bacteria, the bacterial
suspension was collected in different Eppendorf tube after irradiation of
visible light by using different samples. After that, the bacterial sus-
pension was centrifuged for 5 min with 4000 rpm. It was washed by
phosphate buffer (pH: 7.4 and concentration: 0.2 M) and centrifuged for
2 min thrice. In addition, it was treated with Glutaraldehyde (2%) for
one hour and washed/centrifuged for five times with phosphate buffer.
The dehydration process was carried out by using various concentration
of ethyl alcohol (50%, 60%, 70%, 80%, 90%, 95%, and 100%). Then, it
was treated with tert-butyl alcohol for 30 min. About 100 μL of the
bacterial suspension was taken into the micropipette. With the help of
micropipette, the bacterial suspension (4 μL) was transformed into the
S.K. Ray et al. Journal of Photochemistry & Photobiology A: Chemistry 367 (2018) 162–170

Fig. 3. FESEM elemental mapping (NM: a–e, NM-Zn: f–k, and NM-Fe: l–q) and EDS (r–t) of samples.

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Fig. 4. (a and b) TEM image, (c–g) elemental mapping, (h) HRETM image, (i) SAED pattern of rectangular area of (h), and (j) EDS analysis of NM-Fe.

Fig. 5. XPS of samples. (a–d) NM-Zn and (e–h) NM-Fe.

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S.K. Ray et al.
Fig. 6. Raman spectra of samples.
TEM grid (Lot#211114# 01801 F/C 200 mesh Cu). Furthermore, it was
allowed to dry for few minutes and placed in the sample holder of TEM
instrument.
3. Results and discussion
3.1. Characterization of as-prepared photocatalyst
Fig. 1 revealed the XRD spectra of different samples. The observed
XRD peaks were well indexed to monoclinic structure of pure α-
NiMoO4 and matched with JCPDS card No. 086-0361. Also, a new peak
was seen at 2θ of 26.76° that suggests the presence of trace amounts of
β-NiMoO4 (JCPDS card No. 012- 0348) in samples. The XRD spectra
reveals the good crystallinity of samples. The Zn doping causes the
slight increase of crystallinity whereas Fe doping slightly decreases the
crystallinity because of different dopant size.
From the FESEM images in Fig. 2(a–c), it can be seen that samples
have nanorod like morphology that consists of size 5–100 nm in width
and 40–200 nm in length. The FESEM elemental mapping of NM
(Fig. 3a–e), NM-Zn (Fig. 3f–k), and NM-Fe (Fig. 3l–q) as well as EDS
analysis (Fig. 3r–t) suggest the uniform distribution of Ni, Mo, O, Fe,
and Zn elements in samples. Fig. 4a represents the TEM image of NM-Fe
sample which has nanorod morphology. It has 10–40 nm in length and
5 nm in width. The TEM mapping (Fig. 4b–f) of NM-Fe indicates the
Fig. 7. (a) UV–vis DRS spectra and (b) Kubelka-Munk plot for band gap energy of samples.
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Fig. 8. Inactivation of E. coli by various samples (0.2 mg/mL) in visible light.
uniform distribution of Ni. Mo, O, and Fe elements. The HRTEM image
of nanorod is shown in Fig. 4h. The measured lattice spacing of 0.22 nm
and 0.27 nm correspond to (040) and (−222) crystal plane, respec-
tively that is well agreement with monoclinic structure of α-NiMoO4
(JCPDS card No. 086-0361). Moreover, a set of well-defined diffraction
rings are seen in selected area electron diffraction (SAED) patterns that
is good agreement with XRD patterns and lattice spacing of HRTEM
image. The EDS reveals the existence of Ni, Mo, Fe, and O in NM-Fe
sample (Fig. 4j). Hence, the XRD, HRTEM, and SAED pattern analysis
indicate the existence of Fe3+ in the lattice position of α-NiMoO4.
X-ray photoelectron spectroscopy (XPS) tests were implemented to
analyze the elemental composition and their electronic state in sample
NM-Zn and NM-Fe (Fig. 5). According to the Fig. 5a and e, the Ni 2p3/2
and Ni 2p1/2 peaks were observed in the sample NM-Zn (857.62 eV and
875.29 eV) and NM-Fe (855.53 eV and 873.11 eV). In addition, the sa-
tellite peaks of Ni 2p3/2 and Ni 2p1/2 were found in NM-Zn (863.58 eV,
and 881.20 eV) and NM-Fe (861.51 eV and 880.01 eV). The binding
energy of Ni 2p with satellite peaks proved the electron correlation
system and interaction of Ni/NiO6 octahedral in α-NiMoO4 [7,10–12].
In Fig. 5b and f, the presence of Mo6+ oxidation state in the sample was
analyzed by Mo 3d5/2 and Mo 3d3/2 spectra in NM-Zn (232.38 eV and
235.08 eV) and NM-Fe (232.62 eV and 233.64 eV) [8,14]. The peaks
centered at 1024.45 eV and 1047.84 eV were ascribed to 2p1/2 and 2p3/
2+
2, respectively that suggests the existence of Zn ions in the NM-Zn
S.K. Ray et al. Journal of Photochemistry & Photobiology A: Chemistry 367 (2018) 162–170

Table 1
Comparison of E. coli inactivation efficiency of different photocatalyst with Fe/Zn-α-NiMoO4 photocatalyst.
Photocatalyst Dose Morphology E. coli Inactivation efficiency in visible light Reference

Ag/AgBr-CNT – – Complete inactivation within 40 min [18]

Ag/AgBr/ZnFe2O4 1 mg/mL Irregular particles Complete inactivation within 120 min [19]
BiVO4 200 mg/L Nanotube Complete inactivation within 5 h [20]
Ag/BiVO4 2 mg/mL Octahedron Complete inactivation within 3 h [21]
Ag/AgCl/TiO2 1 mg/mL Nanoparticles Complete inactivation within 40 min [22]
Ag@MOF-5 – Irregular particles 91% inactivation within 70 min [23]
g-C3N4/TiO2 30 mg in 50 mL Hollow completely inactivated within 180 min [24]
Nano sphere/ nanorod
Ag-BaMoO4: Er3+/Yb3+ 0.2 mg/mL Octahedron completely inactivated within 60 min [5]
Zn-α-NiMoO4 0.2 mg/mL Nanorod completely inactivated within 45 min Our work
Fe-α-NiMoO4 0.2 mg/mL Nanorod completely inactivated within 30 min Our work

Fig. 9. TEM images of E. coli (108 CFU/mL) with samples in visible light. (a) Control, (b) NM, (c) NM-Zn, and (d) NM-Fe.

sample (Fig. 5d). In NM-Zn sample, the O1 s spectrum (Fig. 5c) was
transformed into the two different peaks, the chemisorbed or dis-
sociated oxygen species (527.50 eV) and O2− species in the lattice
(531.60 eV). However, the O 1 s peak (Fig. 5g) was deconvoluted into
three peaks, the chemisorbed or dissociated oxygen species
(536.50 eV), O2− species in the lattice (529.32 eV), and oxygen defects
or vacancy (532.27 eV) [15]. The doping of Fe3+ in α-NiMoO4 host
creates the oxygen vacancy which is beneficial for photocatalytic en-
hancement. In NM-Fe sample, the peaks at 712.83 eV, 717.03,
724.04 eV, 730.58 eV, and 736.38 eV were assigned to the Fe2+ 2p3/2,
Fe3+ 2p3/2, satellite Fe3+ 2p3/2, Fe3+ 2p1/2, and Fe2+ 2p1/2, respec-
tively (Fig. 5h) [16]. So, the XPS observation of sample shows the ex-
istence of Ni, Mo, O, Zn2+, Fe2+, and Fe3+.
The Raman spectra of doped and undoped samples are shown in
Fig. 6. In sample NM, NM-Zn, the intense Raman peak was seen at
932.67 cm−1 that indicates the symmetric stretching modes. The peaks
centered at 877.22 and 810.99 cm−1 were assigned to asymmetric
stretching modes. Moreover, these modes suggest the presence of Mo]
O bond, distorted MoO6 octahedral, and pure α-NiMoO4 in sample NM
and NM-Zn. The peak at 700.32 cm−1 was assigned to NieOeMo
symmetric stretch. The bending modes of MoeO (279.83 and
336.43 cm−1), deformation modes of MoeOeMo (141.42 cm−1 and
176.71 cm−1), and lattice mode (79.78 cm−1) were found [9–12]. By
doping Zn in α-NiMoO4 host, the Raman peaks were not shifted.
However, the Raman peaks were depressed and shifted towards the
higher wavenumber by Fe doping in α-NiMoO4 host. The symmetric

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S.K. Ray et al.
Fig. 10. TEM elemental mapping of treated E. coli and nanoparticles in visible light.
stretching modes (989.73 and 940.69 cm−1), asymmetric stretching
modes (887.07 and 814.20 cm−1), the bending modes of MoeO
(280.98 cm−1), and deformation modes of MoeOeMo (146.92 cm−1)
were observed in NM-Fe. The shifting of Raman peaks towards high
wavenumber by Fe doping may be associated with effect of dopant ions
and electronegative difference between the ions (Ni2+ and Fe3+) to-
wards the oxygen atoms bonding that makes the change in vibration
frequency between the cluster (MoO4/NiO8/FeO8/FeO8) and bond
strength (OeNieOeMoeOeNieO, OeNi-OeMoeOeFeeO, and Oe-
FeeOeMoeOeFeeO) [7,11].
The UV–vis diffuse reflectance spectroscopy of as-synthesized sam-
ples reveals the absorption in UV and visible region (Fig. 7a). The ab-
sorption band 200–415 nm suggests the charge transfer process from
O2− ligand to Mo6+ in MoO4 groups as well as octahedral (Oh) Mo
species. The absorption band, 415–450 nm represents the electron
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Journal of Photochemistry & Photobiology A: Chemistry 367 (2018) 162–170
transfer from 3d orbitals of the Ni2+ ions (occupied) to Mo-5d orbital of
MoO4− (unoccupied antibonding) with 3A2g(F) → 3T1g(P) of the Ni2+
ions (d-d transitions) in octahedral coordination. The Ni2+ (Oh) species
was observed at 710–850 nm [7,10–12]. Interestingly, the Fe doped α-
NiMoO4 has the red shift with increase in visible light absorption.
However, the Zn doped doesn’t increase the visible light absorption in
α-NiMoO4. The Kubelka-Munk functions versus the band gap energy
plot was used to observe the band gap of NM, NM-Zn, and NM-Fe
samples that reveal the 2.95, 2.94, and 2.64 eV, respectively (Fig. 7b).
The result suggests that doping of Fe has more has tendency to reduce
the band gap of α-NiMoO4 than Zn doping.
3.2. Photocatalytic inactivation of E. coli
In Fig. 8, the photocatalytic inactivation of E. coli in aqueous
S.K. Ray et al.
Fig. 11. Photocatalytic inactivation mechanism of E. coli.
medium was analyzed by counting the numbers of CFUs (colony
forming units) in terms of Log CFU/mL in visible light up to 45 min of
different samples (0.2 mg mL−1). The control experiment was per-
formed without the presence of photocatalyst under visible light irra-
diation. Due to production of ROSs by bacteria in visible light, the
phototoxic effect is occurred [17]. So, there is slightly decrease in mi-
crobial count in control for 45 min. After 30 min, the microbial counts
Log CFU/mL were reduced to 4.1, 2.39 and 0 by sample NM, NM-Zn,
and NM-Fe, respectively. In addition, the microbial counts were de-
creased to 2.6 and 0 in 45 min by NM and NM-Zn sample, respectively.
The results indicate that NM-Fe sample has strong tendency to in-
activate the E. coli completely within 30 min. Also, the NM-Zn sample
can deactivate the E. coli within 45 min. The Fe doped sample destroyed
rapidly bacteria than the Zn doped sample. The possible reason for
increase in photocatalytic disinfection by doping may related with
shifting of absorption edge in the visible region or reduction in band
gap. Due to more band gap reduction by Fe doping than Zn doping, Fe
doped photocatalyst has more inactivation efficiency than Zn doped
photocatalyst. Table 1 revealed that doped α-NiMoO4 photocatalyst has
strong tendency to inactivate E. coli as compared to various visible light
driven photocatalyst as well as silver loaded photocatalyst [5,18–24].
To investigate the membrane deformities with physical changes of
E. coli in visible light by the various doped and host samples, TEM
technique was used (Fig. 9). In control (without photocatalyst under
visible light irradiation), E. coli reveals the rod morphology and well-
preserved cell wall or intact. The original morphology of E. coli was
damaged in visible light by all samples. The attachment of nanorods to
the bacteria cell were seen that causes the damage effect in bacteria.
The nanorods were found inside the bacteria cell due to penetration of
cell membrane. The cavities were are also observed due to damage of
phospholipid layer present in the bacterial cell membrane and releasing
of cytoplasm. In this process, OH% and O2%− remove the hydrogen atom
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from the unsaturated hydrocarbon of phospholipid layer to generate the
H2O, HO2%, H2O2 and reactive unstable hydrocarbon radical that makes
damages in the outer framework of bacteria [11]. The TEM elemental
mapping of Fe and Zn doped photocatalyst was shown in Fig. 10. The
TEM elemental mapping of the sample with bacteria suggested that
there is no release of metal ions such as Ni2+, Fe3+, and Zn2+ from the
photocatalyst into the bacteria cell. It clearly indicates that ROS are
responsible for inactivation of bacteria but not the toxicity of particles.
The possible mechanism of enhanced photocatalytic inactivation of
E. coli in visible light by the Fe/Zn doped α-NiMoO4 photocatalyst was
proposed in Fig. 11. Under visible light irradiation, the photocatalyst
generates valance band (VB) and conduction band (CB) as well as the
holes and excited electrons on the photocatalyst surface. According to
oxidation process in surface of photocatalyst, the holes produce OH% by
interaction of H2O and OH−. Also, O2%− is produced from O2 by
electron accepting which reacts with HO2% to form H2O2 and OH% on
the basis of reduction process [7–10]. The Fe/Zn-α-NiMoO4 photo-
catalyst has strong capacity to generate ROSs in visible light with ef-
ficient separation of electron-hole pair. The doping produces new en-
ergy band between the VB and CB that acts as a charge trapping site for
preventing electron-hole recombination rate. The doping of Fe gen-
erates the oxygen vacancy, which causes the increase in photocatalytic
inactivation process [11]. The existence of Fe3+, Fe2+, and Zn2+ also
causes the trapping of electron-hole pairs. The existence of particles
inside and outside the bacterial cell (cell membrane) also causes the
damaging effect and alteration of membrane permeability. The mod-
ification of photocatalyst by doping produces the high amount of ROSs
and damages of cellular organelles (protein, DNA, lipids, etc.) [5]. The
ROSs can disturb the cellular metabolic pathways. It also makes loss of
protein motive force and enzyme disruption. Furthermore, the photo-
catalytic inactivation causes intercellular out flow of various cell
components [5–7,9,11,25–27].
S.K. Ray et al.
4. Conclusions
In conclusion, microwave synthesized Fe/Zn doped α-NiMoO4 na-
norod was characterized by various techniques and applied for E. coli
inactivation in aqueous medium. Under visible light irradiation, the Fe
doped photocatalyst destroyed rapidly E. coli within 30 min. Fe doped
photocatalyst shows the more inactivation efficiency than Zn doped
because of higher absorption in the visible region in the solar spectrum.
The TEM images of damaged bacteria reflects the effect of ROSs gen-
eration and penetration of rods into the bacteria cell. There is no release
of heavy elements inside the bacterial cell on the basis of TEM ele-
mental mapping result. The increase in visible light absorption or de-
crease in band gap, presence of ionic species (Zn2+, Fe2+, and Fe3+) in
the lattice, formation of new energy level, and efficient prevention of
electron-hole pair recombination are responsible for enhancement of
bacterial destruction by doping. Therefore, this work represents a
highly efficient visible light driven photocatalyst for rapid inactivation
of E. coli in aqueous solution.
Acknowledgments
This Research was supported by the Global Research Laboratory
Program (Grant Number: 2010-00339) of the National Research
Foundation of Korea (NRF) funded by the Ministry of Education,
Science and Technology (MEST) of Korea.
References
[1] J.P.S. Cabral, Water microbiology. Bacterial pathogens and water, Int. J. Environ.
Res. Public Health 7 (2010) 3657–3703.
[2] P.K. Pandey, P.H. Kass, M.L. Soupir, S. Biswas, V.P. Singh, Contamination of water
resources by pathogenic bacteria, AMB Express 4 (2014) 1–16.
[3] F. Ramírez-Castillo, A. Loera-Muro, M. Jacques, P. Garneau, F. Avelar-González,
J. Harel, A. Guerrero-Barrera, Waterborne pathogens: detection methods and
challenges, Pathogens 4 (2015) 307–334.
[4] Z.D. Blount, The unexhausted potential of E. coli, Elife 4 (2015) 1–12.
[5] S.K. Ray, D. Dhakal, R.P. Pandey, S.W. Lee, Ag-BaMoO4: Er3+/Yb3+ photocatalyst
for antibacterial application, Mater. Sci. Eng. C. 78 (2017) 1164–1171.
[6] O.K. Dalrymple, E. Stefanakos, M.A. Trotz, D.Y. Goswami, A review of the me-
chanisms and modeling of photocatalytic disinfection, Appl. Catal. B Environ. 98
(2010) 27–38.
[7] S.K. Ray, D. Dhakal, Y.K. Kshetri, S.W. Lee, Cu-α-NiMoO4 photocatalyst for de-
gradation of Methylene blue with pathways and antibacterial performance, J.
Photochem. Photobiol. A Chem. 348 (2017) 18–32.
[8] S.K. Ray, Y.K. Kshetri, D. Dhakal, C. Regmi, S.W. Lee, Photocatalytic degradation of
Rhodamine B and Ibuprofen with upconversion luminescence in Ag-BaMoO4:Er3+/
Yb3+/K+ microcrystals, J. Photochem. Photobiol. A Chem. 339 (2017) 36–48.
[9] S.K. Ray, D. Dhakal, C. Regmi, T. Yamaguchui, S.W. Lee, Inactivation of
Staphylococcus aureus in visible light by morphology tuned α-NiMoO4, J.
170
Journal of Photochemistry & Photobiology A: Chemistry 367 (2018) 162–170
Photochem. Photobiol. A Chem. 350 (2018) 59–68.
[10] S.K. Ray, D. Dhakal, S.W. Lee, Insight into malachite green degradation, me-
chanism, and pathways by morphology-tuned α -NiMoO4 photocatalyst,
Photochem. Photobiol. 94 (2018) 552–563.
[11] S.K. Ray, D. Dhakal, J. Kyung, S. Kim, S.W. Lee, Efficient inactivation of
Pseudomonas aeruginosa by Cu/Co-α-NiMoO4 in visible light, Chem. Eng. J. 347
(2018) 366–378.
[12] S.K. Ray, D. Dhakal, S.W. Lee, Rapid degradation of naproxen by AgBr-α-NiMoO4
composite photocatalyst in visible light: mechanism and pathways, Chem. Eng. J.
347 (2018) 836–848.
[13] A. Sirelkhatim, S. Mahmud, A. Seeni, N.H.M. Kaus, L.C. Ann, S.K.M. Bakhori,
H. Hasan, D. Mohamad, Review on zinc oxide nanoparticles: antibacterial activity
and toxicity mechanism, Nano-Micro Lett. 7 (2015) 219–242.
[14] S.K. Ray, D. Dhakal, S.W. Lee, Insight into sulfamethoxazole degradation, me-
chanism, and pathways by AgBr-BaMoO4 composite photocatalyst, J. Photochem.
Photobiol. A Chem. 364 (2018) 686–695.
[15] C. Hu, S. Guo, G. Lu, Y. Fu, J. Liu, H. Wei, X. Yan, Y. Wang, Z. Guo, Carbon coating
and Zn2+ doping of magnetite nanorods for enhanced electrochemical energy sto-
rage, Electrochim. Acta 148 (2014) 118–126.
[16] R. Tang, C. Jiang, W. Qian, J. Jian, X. Zhang, H. Wang, H. Yang, Dielectric re-
laxation, resonance and scaling behaviors in Sr3Co2Fe24O41 hexaferrite, Sci. Rep. 5
(2015) 1–11.
[17] A. Lipovsky, Y. Nitzan, A. Gedanken, R. Lubart, Visible light-induced killing of
bacteria as a function of wavelength: implication for wound healing, Lasers Surg.
Med. 42 (2010) 467–472.
[18] H. Shi, G. Li, H. Sun, T. An, H. Zhao, P.K. Wong, Visible-light-driven photocatalytic
inactivation of E. coli by Ag/AgX-CNTs (X=Cl, Br, I) plasmonic photocatalysts:
bacterial performance and deactivation mechanism, Appl. Catal. B Environ.
158–159 (2014) 301–307.
[19] Y. Xu, Q. Liu, C. Liu, Y. Zhai, M. Xie, L. Huang, H. Xu, H. Li, J. Jing, Visible-light-
driven Ag/AgBr/ZnFe2O4 composites with excellent photocatalytic activity for E.
coli disinfection and organic pollutant degradation, J. Colloid Interface Sci. 512
(2018) 555–566.
[20] W. Wang, Y. Yu, T. An, G. Li, H.Y. Yip, J.C. Yu, P.K. Wong, Visible-light-driven
photocatalytic inactivation of E. coli K-12 by bismuth vanadate nanotubes: bac-
tericidal performance and mechanism, Environ. Sci. Technol. 46 (2012)
4599–4606.
[21] A.Y. Booshehri, S. Chun-Kiat Goh, J. Hong, R. Jiang, R. Xu, Effect of depositing
silver nanoparticles on BiVO4 in enhancing visible light photocatalytic inactivation
of bacteria in water, J. Mater. Chem. A Mater. Energy Sustain. 2 (2014) 6209–6217.
[22] J. Zhang, X. Liu, X. Suo, P. Li, B. Liu, H. Shi, Facile synthesis of Ag/AgCl/TiO2
plasmonic photocatalyst with efficiently antibacterial activity, Mater. Lett. 198
(2017) 164–167.
[23] S.R. Thakare, S.M. Ramteke, Fast and regenerative photocatalyst material for the
disinfection of E. coli from water: silver nano particle anchor on MOF-5, Catal.
Commun. 102 (2017) 21–25.
[24] G. Li, X. Nie, J. Chen, Q. Jiang, T. An, P. Keung, Enhanced visible-light-driven
photocatalytic inactivation of Escherichia coli using g-C3N4/TiO2 hybrid photo-
catalyst synthesized using a hydrothermal-calcination approach, Water Res. 86
(2015) 17–24.
[25] J. Cadet, J.R. Wagner, DNA base damage by reactive oxygen species, oxidizing
agents, and UV radiation, Cold Spring Harb. Perspect. Biol. 5 (2013) 1–16.
[26] L. Wang, C. Hu, L. Shao, The antimicrobial activity of nanoparticles: present si-
tuation and prospects for the future, Int. J. Nanomed. (2017) 1227–1249.
[27] W. Wang, G. Huang, J.C. Yu, P.K. Wong, Advances in photocatalytic disinfection of
bacteria: development of photocatalysts and mechanisms, J. Environ. Sci. (China)
34 (2015) 232–247.