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.1 s2.0 S1010603018308256 Main
.1 s2.0 S1010603018308256 Main
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.
⁎
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. Journal of Photochemistry & Photobiology A: Chemistry 367 (2018) 162–170
2.2. Characterization
Fig. 2. FESEM of samples. (a) NM, (b) NM-Zn, and (c) NM-Fe.
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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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S.K. Ray et al. Journal of Photochemistry & Photobiology A: Chemistry 367 (2018) 162–170
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.
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Fig. 6. Raman spectra of samples. Fig. 8. Inactivation of E. coli by various samples (0.2 mg/mL) in visible light.
TEM grid (Lot#211114# 01801 F/C 200 mesh Cu). Furthermore, it was uniform distribution of Ni. Mo, O, and Fe elements. The HRTEM image
allowed to dry for few minutes and placed in the sample holder of TEM of nanorod is shown in Fig. 4h. The measured lattice spacing of 0.22 nm
instrument. 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
3. Results and discussion rings are seen in selected area electron diffraction (SAED) patterns that
is good agreement with XRD patterns and lattice spacing of HRTEM
3.1. Characterization of as-prepared photocatalyst 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
Fig. 1 revealed the XRD spectra of different samples. The observed indicate the existence of Fe3+ in the lattice position of α-NiMoO4.
XRD peaks were well indexed to monoclinic structure of pure α- X-ray photoelectron spectroscopy (XPS) tests were implemented to
NiMoO4 and matched with JCPDS card No. 086-0361. Also, a new peak analyze the elemental composition and their electronic state in sample
was seen at 2θ of 26.76° that suggests the presence of trace amounts of NM-Zn and NM-Fe (Fig. 5). According to the Fig. 5a and e, the Ni 2p3/2
β-NiMoO4 (JCPDS card No. 012- 0348) in samples. The XRD spectra and Ni 2p1/2 peaks were observed in the sample NM-Zn (857.62 eV and
reveals the good crystallinity of samples. The Zn doping causes the 875.29 eV) and NM-Fe (855.53 eV and 873.11 eV). In addition, the sa-
slight increase of crystallinity whereas Fe doping slightly decreases the tellite peaks of Ni 2p3/2 and Ni 2p1/2 were found in NM-Zn (863.58 eV,
crystallinity because of different dopant size. and 881.20 eV) and NM-Fe (861.51 eV and 880.01 eV). The binding
From the FESEM images in Fig. 2(a–c), it can be seen that samples energy of Ni 2p with satellite peaks proved the electron correlation
have nanorod like morphology that consists of size 5–100 nm in width system and interaction of Ni/NiO6 octahedral in α-NiMoO4 [7,10–12].
and 40–200 nm in length. The FESEM elemental mapping of NM In Fig. 5b and f, the presence of Mo6+ oxidation state in the sample was
(Fig. 3a–e), NM-Zn (Fig. 3f–k), and NM-Fe (Fig. 3l–q) as well as EDS analyzed by Mo 3d5/2 and Mo 3d3/2 spectra in NM-Zn (232.38 eV and
analysis (Fig. 3r–t) suggest the uniform distribution of Ni, Mo, O, Fe, 235.08 eV) and NM-Fe (232.62 eV and 233.64 eV) [8,14]. The peaks
and Zn elements in samples. Fig. 4a represents the TEM image of NM-Fe centered at 1024.45 eV and 1047.84 eV were ascribed to 2p1/2 and 2p3/
sample which has nanorod morphology. It has 10–40 nm in length and 2+
2, respectively that suggests the existence of Zn ions in the NM-Zn
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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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
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 The Raman spectra of doped and undoped samples are shown in
transformed into the two different peaks, the chemisorbed or dis- Fig. 6. In sample NM, NM-Zn, the intense Raman peak was seen at
sociated oxygen species (527.50 eV) and O2− species in the lattice 932.67 cm−1 that indicates the symmetric stretching modes. The peaks
(531.60 eV). However, the O 1 s peak (Fig. 5g) was deconvoluted into centered at 877.22 and 810.99 cm−1 were assigned to asymmetric
three peaks, the chemisorbed or dissociated oxygen species stretching modes. Moreover, these modes suggest the presence of Mo]
(536.50 eV), O2− species in the lattice (529.32 eV), and oxygen defects O bond, distorted MoO6 octahedral, and pure α-NiMoO4 in sample NM
or vacancy (532.27 eV) [15]. The doping of Fe3+ in α-NiMoO4 host and NM-Zn. The peak at 700.32 cm−1 was assigned to NieOeMo
creates the oxygen vacancy which is beneficial for photocatalytic en- symmetric stretch. The bending modes of MoeO (279.83 and
hancement. In NM-Fe sample, the peaks at 712.83 eV, 717.03, 336.43 cm−1), deformation modes of MoeOeMo (141.42 cm−1 and
724.04 eV, 730.58 eV, and 736.38 eV were assigned to the Fe2+ 2p3/2, 176.71 cm−1), and lattice mode (79.78 cm−1) were found [9–12]. By
Fe3+ 2p3/2, satellite Fe3+ 2p3/2, Fe3+ 2p1/2, and Fe2+ 2p1/2, respec- doping Zn in α-NiMoO4 host, the Raman peaks were not shifted.
tively (Fig. 5h) [16]. So, the XPS observation of sample shows the ex- However, the Raman peaks were depressed and shifted towards the
istence of Ni, Mo, O, Zn2+, Fe2+, and Fe3+. higher wavenumber by Fe doping in α-NiMoO4 host. The symmetric
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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 transfer from 3d orbitals of the Ni2+ ions (occupied) to Mo-5d orbital of
modes (887.07 and 814.20 cm−1), the bending modes of MoeO MoO4− (unoccupied antibonding) with 3A2g(F) → 3T1g(P) of the Ni2+
(280.98 cm−1), and deformation modes of MoeOeMo (146.92 cm−1) ions (d-d transitions) in octahedral coordination. The Ni2+ (Oh) species
were observed in NM-Fe. The shifting of Raman peaks towards high was observed at 710–850 nm [7,10–12]. Interestingly, the Fe doped α-
wavenumber by Fe doping may be associated with effect of dopant ions NiMoO4 has the red shift with increase in visible light absorption.
and electronegative difference between the ions (Ni2+ and Fe3+) to- However, the Zn doped doesn’t increase the visible light absorption in
wards the oxygen atoms bonding that makes the change in vibration α-NiMoO4. The Kubelka-Munk functions versus the band gap energy
frequency between the cluster (MoO4/NiO8/FeO8/FeO8) and bond plot was used to observe the band gap of NM, NM-Zn, and NM-Fe
strength (OeNieOeMoeOeNieO, OeNi-OeMoeOeFeeO, and Oe- samples that reveal the 2.95, 2.94, and 2.64 eV, respectively (Fig. 7b).
FeeOeMoeOeFeeO) [7,11]. The result suggests that doping of Fe has more has tendency to reduce
The UV–vis diffuse reflectance spectroscopy of as-synthesized sam- the band gap of α-NiMoO4 than Zn doping.
ples reveals the absorption in UV and visible region (Fig. 7a). The ab-
sorption band 200–415 nm suggests the charge transfer process from
3.2. Photocatalytic inactivation of E. coli
O2− ligand to Mo6+ in MoO4 groups as well as octahedral (Oh) Mo
species. The absorption band, 415–450 nm represents the electron
In Fig. 8, the photocatalytic inactivation of E. coli in aqueous
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medium was analyzed by counting the numbers of CFUs (colony from the unsaturated hydrocarbon of phospholipid layer to generate the
forming units) in terms of Log CFU/mL in visible light up to 45 min of H2O, HO2%, H2O2 and reactive unstable hydrocarbon radical that makes
different samples (0.2 mg mL−1). The control experiment was per- damages in the outer framework of bacteria [11]. The TEM elemental
formed without the presence of photocatalyst under visible light irra- mapping of Fe and Zn doped photocatalyst was shown in Fig. 10. The
diation. Due to production of ROSs by bacteria in visible light, the TEM elemental mapping of the sample with bacteria suggested that
phototoxic effect is occurred [17]. So, there is slightly decrease in mi- there is no release of metal ions such as Ni2+, Fe3+, and Zn2+ from the
crobial count in control for 45 min. After 30 min, the microbial counts photocatalyst into the bacteria cell. It clearly indicates that ROS are
Log CFU/mL were reduced to 4.1, 2.39 and 0 by sample NM, NM-Zn, responsible for inactivation of bacteria but not the toxicity of particles.
and NM-Fe, respectively. In addition, the microbial counts were de- The possible mechanism of enhanced photocatalytic inactivation of
creased to 2.6 and 0 in 45 min by NM and NM-Zn sample, respectively. E. coli in visible light by the Fe/Zn doped α-NiMoO4 photocatalyst was
The results indicate that NM-Fe sample has strong tendency to in- proposed in Fig. 11. Under visible light irradiation, the photocatalyst
activate the E. coli completely within 30 min. Also, the NM-Zn sample generates valance band (VB) and conduction band (CB) as well as the
can deactivate the E. coli within 45 min. The Fe doped sample destroyed holes and excited electrons on the photocatalyst surface. According to
rapidly bacteria than the Zn doped sample. The possible reason for oxidation process in surface of photocatalyst, the holes produce OH% by
increase in photocatalytic disinfection by doping may related with interaction of H2O and OH−. Also, O2%− is produced from O2 by
shifting of absorption edge in the visible region or reduction in band electron accepting which reacts with HO2% to form H2O2 and OH% on
gap. Due to more band gap reduction by Fe doping than Zn doping, Fe the basis of reduction process [7–10]. The Fe/Zn-α-NiMoO4 photo-
doped photocatalyst has more inactivation efficiency than Zn doped catalyst has strong capacity to generate ROSs in visible light with ef-
photocatalyst. Table 1 revealed that doped α-NiMoO4 photocatalyst has ficient separation of electron-hole pair. The doping produces new en-
strong tendency to inactivate E. coli as compared to various visible light ergy band between the VB and CB that acts as a charge trapping site for
driven photocatalyst as well as silver loaded photocatalyst [5,18–24]. preventing electron-hole recombination rate. The doping of Fe gen-
To investigate the membrane deformities with physical changes of erates the oxygen vacancy, which causes the increase in photocatalytic
E. coli in visible light by the various doped and host samples, TEM inactivation process [11]. The existence of Fe3+, Fe2+, and Zn2+ also
technique was used (Fig. 9). In control (without photocatalyst under causes the trapping of electron-hole pairs. The existence of particles
visible light irradiation), E. coli reveals the rod morphology and well- inside and outside the bacterial cell (cell membrane) also causes the
preserved cell wall or intact. The original morphology of E. coli was damaging effect and alteration of membrane permeability. The mod-
damaged in visible light by all samples. The attachment of nanorods to ification of photocatalyst by doping produces the high amount of ROSs
the bacteria cell were seen that causes the damage effect in bacteria. and damages of cellular organelles (protein, DNA, lipids, etc.) [5]. The
The nanorods were found inside the bacteria cell due to penetration of ROSs can disturb the cellular metabolic pathways. It also makes loss of
cell membrane. The cavities were are also observed due to damage of protein motive force and enzyme disruption. Furthermore, the photo-
phospholipid layer present in the bacterial cell membrane and releasing catalytic inactivation causes intercellular out flow of various cell
of cytoplasm. In this process, OH% and O2%− remove the hydrogen atom components [5–7,9,11,25–27].
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