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Manganese disulfide-silicon dioxide nano-material: Synthesis, characterization, photocatalytic, antioxidant and antimicrobial studies
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
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Manganese disulfide-silicon dioxide nano-material: Synthesis, characterization, photocatalytic, antioxidant and antimicrobial studies
T
Muhammad Aqeel Ashrafa,b,g, , Wan-Xi Penga, Ali Fakhric, , Mojgan Hosseinid, ⁎⁎⁎ Hesam Kamyabe,f, , Shreeshivadasan Chelliapane ⁎
⁎⁎
a
School of Forestry, Henan Agricultural University, Zhengzhou 450002, China Department of Geology Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia c Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran d Department of Science, Islamshahr Branch, Islamic Azad University, Sayad Shirazi St. Islamshahr, Tehran, Iran e Engineering Department, Razak Faculty of Technology and Informatics, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100 Kuala Lumpur, Malaysia f Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA g School of Environmental Studies, China University of Geosciences, 430074 Wuhan, China b
ARTICLE INFO
ABSTRACT
Keywords: Silicon dioxide MnS2 Photocatalytic Biological data
The sol-gel/ultrasonically rout produced the novel MnS2-SiO2 nano-hetero-photocatalysts with the various ratio of MnS2. Prepared nano-catalyst were investigated in the photo-degradation of methylene blue under UV light illumination. Structural and optical attributes of as-prepared nano-catalysts were evaluated by X-ray diffraction and photoelectron spectroscopy. The morphological were studied by scanning electron microscopy-EDS, and dynamic light scattering. The diffuse reflectance spectroscopy was applied to examine the band gap energy. The Eg values of SiO2, MnS2-SiO2–0, MnS2-SiO2–1, and MnS2-SiO2–2 nanocomposites are 6.51, 3.85, 3.17, and 2.67 eV, respectively. The particle size of the SiO2 and MnS2-SiO2–1 nanocomposites were 100.0, and 65.0 nm, respectively. The crystallite size values of MnS2-SiO2–1 were 52.21 nm, and 2.9 eV, respectively. MnS2-SiO2 nano-photocatalyst was recognized as the optimum sample by degrading 96.1% of methylene blue from water. Moreover, the influence of pH of the solution, and contact time as decisive factors on the photo-degradation activity were investigated in this project. The optimum data for pH and time were found 9 and 60 min, respectively. The photo-degradation capacity of MnS2-SiO2–2 is improved (96.1%) due to the low band gap was found from UV–vis DRS. The antimicrobial data of MnS2-SiO2 were studied and demonstrated that the MnS2SiO2 has fungicidal and bactericidal attributes.
1. Introduction Nowadays, the energy and environmental pollutant acmes are the world's significant difficulties in a confrontation by humanity. With the development of several crafts, many types of pollutants were abandoned in the environment [1–5]. Organic compound dyes considered as chemical contaminants are deeply venomous and a menace to human health. Hence, eliminating them from water is significant. Hitherward, several methods have been applied to decompose this type of contaminant, such as filtration, Fenton process, ozone reaction, adsorption, etc. Recently, applying of semiconductors nano-powders as a nano-
photocatalyst to obviate energy and environmental acmes have possessed an excellent deal of attention due to the free and unique usage of the light energy to decompose contaminants [6–20]. Among the semiconductors, TiO2, SnS2 and ZnO have been investigated widely due to its low cost, non-toxic and chemical and optical stability. Despite, this catalyst due to its excellent energy band gap, can only weak work in the light irradiation [21–25]. Silicon dioxide (SiO2) has significant attention due to high chemical stability, low costs, nil toxicity and effective as photocatalysts. There is main method to plan and apply impressive semiconductors in the light area [26–28]. The Polarization is vital to solve of suppressed recombination, and the macroscopic polarization of
Correspondence to: M.A. Ashraf, School of Forestry, Henan Agricultural University, Zhengzhou 450002, China. Correspondence to: A. Fakhri, Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran. Correspondence to: H. Kamyab, Engineering Department, Razak Faculty of Technology and Informatics, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100 Kuala Lumpur, Malaysia. E-mail addresses: [email protected] (M.A. Ashraf), [email protected] (W.-X. Peng), [email protected] (A. Fakhri), [email protected] (H. Kamyab). ⁎
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https://doi.org/10.1016/j.jphotobiol.2019.111579 Received 18 May 2019; Received in revised form 21 July 2019; Accepted 24 July 2019 Available online 25 July 2019 1011-1344/ © 2019 Elsevier B.V. All rights reserved.
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
M.A. Ashraf, et al.
silica component was studied in previous studied and shows it is enormous influence in photocatalysis process [29]. The method is to modify semiconductor oxides using one of heterojunction with other semiconductors, such as metal sulfide [30,31]. Sajad Talebi and et al. were presented the new catalyst ZnS/TiO2 for photo-degradation of a textile dye [32]. Ch. Venkata Reddy and et al. were reported the CdS/ SnO2 for the decomposition of dye compound [33]. The many SiO2 photocatalysts as hybrid or mono components were synthesized as the AgBr–TiO2/SiO2@Fe3O4 [34], the ZnO-coated SiO2 [35], the Fe-Ni@ SiO2 [36], the SiO2@TiO2 [37] the CdS-Ta2O5-SiO2 [38], the Fe3O4/ SiO2/TiO2 [39], the S-TiO2/SiO2 [40], and the NiS/SiO2 [21] for the decomposition of organic compound under source light irradiation. Therefore, we presented the MnS2-SiO2 nanocomposites as nano-catalysts of for decompose of a dye as a pollutant target under UV light irradiation. The prepared catalyst was used for antimicrobial studies.
concentration was measured using a UV–visible spectrometry (UV1650PC, SHIMADZU, λm = 633 nm) [41–51]. The UV light source distance from the MB solution surface in the test was 2.00 cm.
2. Experimental
2.5. Antioxidant Activity
2.4. Antimicrobial Analysis The evolution curves of microbial cells studied the influences of prepared materials on fungal and bacteria growth; (T. veride, and A. flavus; E. coli and S. pyogenes). Concisely, 100 ml of Luria Bertani and potato dextrose agar was applied for bacteria and fungal mounting on agar plates. Each culture was incubated in an incubator 37 °C for one day. Subsequently, an aliquot from above was added to 50 μL of suspension (1 mM) of prepared nanomaterials. Agar plate without prepared nanomaterial was used as a regulator. The experiment was performed with three replication [52,53].
1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assay was analyzed for evaluation antioxidant activity [54]. Different concentrations (50–1000 μg/ml) of prepared nanomaterial and ascorbic were prepared. 3 ml of DPPH (0.2 mM) solution was augmented to 4 ml of the prepared solutions. The mixture was stirred and kept in the dark condition for 30 min. Shimadzu UV-1650PC spectrophotometer was applied in test at 517 nm. Ascorbic acid was applied as a standard solution.
The materials were used in this study from Merck CO., Germany. 2.1. Silicon Dioxide and MnS2-SiO2 Catalyst Preparation The silicon dioxide nanoparticles were synthesized as provided in our recent work with the hydrolysis process [21]. The 11 mL of tetraethyl orthosilicate was augmented to in 10 mL H2O. Then, 50 mL of ethanol and 25 mL of ammonia (27%) solution was augmented to the TEOS and H2O solution. The prepared solution locates to pulse sonicator (Misonix S-4000) with a pulse: 5 s, power: 300 W and frequency: 50 kHz and the suspension was stirred for 4 h at 40 °C. The silicon dioxide was dried at 120 °C for 2 h, and at 400 °C for 3 h. The SiO2 nano-catalyst was dispersed in acetone under ultra-sonic bath illumination. Then, the 50 ml of MnCl2.4H2O (0.5 M) and the 50 ml of thioacetamide (C2H5NS) (0.5 M) were propagated to the prepared suspension. The prepared solution locates to pulse sonicator (Misonix S-4000) with a pulse: 5 s, power: 300 W and frequency: 50 kHz, and the suspension was stirred for 1 h at 50 °C under illumination. The final MnS2-SiO2 was collected after drying at 170 °C for 4 h and at 550 °C for 5 h. Three ratios of MnS2 to SiO2 were synthesized with different ratio and labelled as MnSi-0, MnSi-1, and MnSi-2, respectively.
3. Results and Discussion 3.1. Nano-Catalyst Characterization The morphologies of the pure SiO2 and MnS2-SiO2 nano-photocatalysts were studied by using SEM, illustrated in Fig. 1. From Fig. 1A, the morphological of prepared SiO2 samples are spheres with the high size of particles. The SEM image of MnS2-SiO2 nanocomposites demonstrates the agglomerated nanoparticles, which confirms the MnS2 nanoparticles coated on SiO2 nanoparticles surfaces (Fig. 1B). The Energy Dispersive Spectroscopy (EDS) was analyzed for evaluation the presence of all elements in the MnS2-SiO2 nanocomposites framework. EDS analysis shows the Silicon (Si, 32%), Manganese (Mn, 32%), Oxygen (O, 17%), and sulfur (S, 19%). Dynamic light scattering (DLS) is a study in physics that can be used to specify the size values of nanoparticles. The DLS curve of the SiO2 and MnSi-1 are revealed in Fig. 1C. The particle size of the SiO2, and MnSi-1 nanocomposites were 100.0, and 65.0 nm, respectively. The XRD patterns in Fig. 2 shows the crystalline phases of the SiO2, and MnSi-1 nanocomposites, respectively. As can be seen, the diffraction curve of SiO2 indicates the amorphous crystallinity (Fig. 2A) [21]. The MnSi-1 nanocomposites has four distinct diffraction peaks, at 2θ of 30.5°, 34.8°, 42.9°, 54.0°, 55.9°, and 63.0° are ascribed to the (210), (211), (220), and (221) planes, which that shows the crystalline phases of cubic structure of MnS2 (JCPDS card No. 25–0549) [55]. The crystallite size [55] was distinguished to be 52.21 nm for MnSi-1 nanocomposites. In order to further specify the chemical states of elements in the MnSi-1 nanocomposites, their XPS spectra were indicated in Fig. 3. In the status of the Si 2p spectrum (Fig. 4a), the peak at 106.6 eV binding energy well shows Si 2p1/2, and the peaks of Si 2p3/2 identified at 102.2 eV binding energies are corresponding to a spin-orbit splitting specification, respectively [56]. The peaks of Mn 2p clear at a binding energy of 640.2 (Mn 2p3/2) and 652.9 eV (Mn 2p1/2), demonstrating Mn state exists in the MnSi-1 nanocomposites [45]. The O 1 s peaks at 530.41 eV, are certain to lattice oxygen-binding SieO and the water molecules surface hydroxyl group [56]. The S 2p peak appears at 161.4 eV and reports binding energies of Sulfur in MnS2 [45]. For the comparative investigation, the optical properties of SiO2, MnSi-0, MnSi-1, and MnSi-2 are shown in Fig. 4. Spectra in Fig. 4A indicates that the pure SiO2 possess UV–vis absorption spectra, while
2.2. Characterization Devices X-ray diffraction (XRD) study was identified using by Philips X'Pert diffractometer for evaluation of MnS2-SiO2 nanocomposites. The dynamic light scattering (Zetasizer Nano Series Malvern) was applied for the study of MnS2-SiO2 nanocomposites. The morphological of MnS2SiO2 nanocomposites study were identified using by scanning electron microscopy (Model: SU-800, Hitachi). The surface composition and elemental data of MnS2-SiO2 nanocomposites were studied by applying the X-ray photoelectron spectroscopy study (Model: Kratos Axis Ultra DLD; The XPS study was describes as two spectra, spectra with the function of energy and Gaussian and Lorentzian) device. The optical properties of MnS2-SiO2 nanocomposites was investigated by UV–vis (JASCO V-630) spectrophotometer. 2.3. Photo-Decomposition Study Investigation of degradation of MB by the prepared MnS2-SiO2 nanocomposites performed under UV light irradiation (11-W UV lamp irradiation). For this scope, 0.02 g of the prepared nano-catalyst was augmented to 25 ml of the MB solution (10 mg/L). Next, the system solution was kept in the dark condition for 30 min under continuous vigorous stirring to attain absorption and desorption equilibrium reaction. Thereupon, the degradation reactor was exposed to light irradiation. Then, the nano-catalyst was separated, and the residual of MB 2
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
M.A. Ashraf, et al.
Fig. 1. The Scanning electron microscopy of SiO2 (A), MnSi-1 nanocomposites (B), and Dynamic light scattering plot (C) of SiO2 (a), MnSi-1 nanocomposites (b).
that of the MnS2-SiO2 nanocomposites has strong UV region spectra. With enhances doping MnS2, the absorption intensity of composite was increased due to charge transfer transition was enhanced [57,58]. The absorption spectra of SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites with the equation (??ℎν)1/2 =??(ℎν) (kubelka-munk equation) [38], which distinguishes the Eg (band gap) data (Fig. 4B). The Eg values of SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites are 6.51, 3.85, 3.17, and, 2.67 eV, respectively.
and reaction time were analyzed to study the performance of the photocatalyst on dye removal. The Dye adsorption was carried out in a dark medium by SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites in 30 min to achieve the adsorption-desorption balance. The results showed, among of prepared samples, the MnSi-2 nanocomposites have significant adsorption of dye about 17.5%, due to the catalyst structure and surface area modified for the removal capacity. The photocatalytic capacity of SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites was done by using MB molecule. From Fig. 5A, the photocatalytic degradation values of methylene blue over SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites are about 53.1, 63.1, 83.1, and 96.1% within the 60 min under UV light illumination, respectively. This enhanced photo-degradation performance of MnSi-2 nanocomposites is generally due to the forming of p-n nanoheterojunction structural
3.2. Photo-Catalytic Assessment The capability of SiO2 and MnS2-SiO2 nano-photocatalysts to decompose dye was studied through its application for photo-degradation of MB under UV light irradiation. Combinations of different levels of pH 3
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
M.A. Ashraf, et al.
Fig. 2. The X-ray diffraction spectra of SiO2 (A), MnSi-1 nanocomposites (B).
Fig. 3. The X-ray photoelectron spectra of MnSi-1 nanocomposites.
which modifies the separation of the e−/h+ pairs and decrease the recombination of the e−/h+ pairs excited, and the low band gap of MnSi-2 was found from UV–vis DRS [59–61]. To identify the influence of pH solution on the photo-degradation of methylene blue over SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites, experiments were done at the pH = 5, 7 and 9 that are indicated in Fig. 5B. As can be obvious, the photocatalytic activity of the prepared samples were high values in basic region. Therefore, the pH influence can be described using pHpzc. The charge zero points of SiO2, and MnS2–SiO2 were determined to be about 4.0, and 6.7, respectively. At pH solution values higher than pHpzc; the surface charge of prepared nano-photocatalyst is negative due to the absorption of OH−. Moreover, methylene blue is a cationic surface charge dye. Herewith, the formation of the electrostatic force between the negative surface charges of the nano-catalyst and the MB positive surface charge, makes the great photo-degradation of MB from water [62].
Fig. 4. The UV–visible spectra (A) and the kubelka-munk plot (B) of SiO2 (a), MnSi-0 (b), MnSi-1 (c), and MnSi-2 nanocomposites (d).
photocatalyst under UV light irradiation, as an essential factor, were studied by five cycles to degradation of MB. As indicated in Fig. 5C, after the five reaction cycle, MB photo-degradation performance decreases from 96.1 to 88.1%. The 8.3% decrease in photo-degradation performance can correspond to MnSi-2 nanocomposites inactivation, slight loss of MnSi-2 nanocomposites during the recycling progress.
3.3. Reusability Study The
stability
and
reusability
of
MnSi-2
nanocomposites 4
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
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Fig. 5. (A) MB photo-decomposition under UV light irradiation at various time (pH 9, nano-photocatalyst dose: 0.1 g/l); (B) MB photo-decomposition under UV light irradiation at various pH (time: 60 min, nano-photocatalyst dose: 0.1 g/l), (C) Reusability of prepared composites.
3.4. Mechanism of Photo-Degradation of Dye
- Conversion of adsorbed oxygen to superoxide radical.
MnS2
The proposed mechanism for MnS2-SiO2-catalyzed photocatalytic removal of MB contains five-stage [63]:
MnS2
SiO2 + h
MnS2
SiO2 (e
cb
+
O2 – + H+
b)
MnS2
SiO2
b)
+ H2 O
MnS2
SiO2 (h+ b) + OH–
H+
+ O2
O2 –
HO2
- Degradation of MB by radicals.
OH, HO2 , O2 – + MB
- Generation of OH% radical
(h+
cb)
- Neutralization of %O2– to %HO2 by protonation
- Excitation of e−/h+ pair under the photo.
h+
SiO2 (e
+ OH
OH 5
Dioxide carbon + water
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
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3.6. Antioxidant Activity
Table 1 Antifungal and antibacterial activity of the prepared nano-catalyst.
SiO2 MnSi-1 Standard antibiotic
SiO2 MnSi-1 Standard antibiotic
A. flavus
T. veride
6.12 ± 0.12 21.31 ± 0.55 11.34 ± 0.11
4.21 ± 0.31 16.75 ± 0.11 8.44 ± 0.12
E. coli
S. pyogenes
6.51 ± 0.21 20.22 ± 0.12 22.23 ± 0.11
9.14 ± 0.21 28.51 ± 0.32 26.54 ± 0.30
Fig. 6 demonstrates the DPPH radical scavenging activity of MnSi-1 nanocomposites. By getting H+ or e− from donor atom DPPH free radical is reduced [54]. The odd electron of DPPH accepts the H atom from the antioxidants and changes to identical hydrazine [54]. DPPH is a fast method to study antioxidant performance [54]. The radical scavenging performance of MnSi-1 nanocomposites was enhanced. A great data was observed at 200 μg/ml, which is a slightly less than ascorbic acid as standard. Similar result indicated that nanoparticles could enhance the antioxidant activity [54]. 4. Conclusions The novel MnS2-SiO2 photocatalysts with the various ratio of MnS2 produced via the sol-gel/ultrasonically rout. This study confirms that the MnS2 could be improved the photocatalyst properties and reusability of nano-catalyst in UV light photo-decomposition of MB. The photo-degradation activity of MnS2-SiO2 nano-catalyst was firmly higher than SiO2 nanoparticles. Moreover, the influence of solution pH and reaction time on the photo-degradation activity was evaluated, and the optimum operating conditions were found pH: 9 and time: 60 min. The biological investigation shows the Cr2S3-SiO2 nanocomposites has excellent antimicrobial and antioxidant activity. Acknowledgements The researchers are thanking for the patronage of this project by the Islamic Azad University of Science and Research Branch Tehran. Hesam Kamyab is a researcher of UTM under the Post-Doctoral Fellowship Scheme (PDRU Grant) for the project: “Enhancing the lipid growth in algae cultivation for biodiesel production” with vote number: Q. J130000.21A2.03E95 and Research Grant University UTM with vote number: Q.K130000.2540.20H05. References [1] A. Mittal, J. Mittal, A. Malviya, V.K. Gupta, Removal and recovery of Chrysoidine Y from aqueous solutions by waste materials, J. Colloid Interface Sci. 344 (2010) 497–507. [2] L. Yin, Y. Ji, Y. Zhang, L. Chong, L. Chen, Rotifer community structure and its response to environmental factors in the Backshore Wetland of Expo Garden, Shanghai, Aquaculture and Fisheries 3 (2018) 90–97. [3] Tawfik A. Saleh, Vinod K. Gupta, Photo-catalyzed degradation of hazardous dye methyl orange by use of a composite catalyst consisting of multi-walled carbon nanotubes and titanium dioxide, J. Colloid Interface Sci. 371 (2012) 101–106. [4] Hadi Khani, Mohammad Kazem Rofouei, Pezhman Arab, Vinod Kumar Gupta, Zahra Vafaei, Multi-walled carbon nanotubes-ionic liquid-carbon paste electrode as a super selectivity sensor: Application to potentiometric monitoring of mercury ion (II), J. Hazard. Mater. 183 (2010) 402–409. [5] V.K. Gupta, R. Kumar, A. Nayak, T.A. Saleh, M.A. Barakat, Adsorptive removal of dyes from aqueous solution onto carbon nanotubes: a review, Adv. Colloid Interf. Sci. 193–194 (2013) 24–34. [6] R. Saravanan, Elisban Sacari, F. Gracia, Mohammad Mansoob Khan, Vinod Kumar Gupta, et al., J. Mol. Liq. 221 (2016) 1029–1033. [7] R. Manoj Devaraj, R.D. Saravanan, V.K. Gupta, S. Jayadevan, Fabrication of novel shape Cu and Cu/Cu2O nanoparticles modified electrode for the determination of dopamine and paracetamol, J. Mol. Liq. 221 (2016) 930–941. [8] R. Saravanan, S. Joicy, V.K. Gupta, V. Narayanan, A. Stephen, Visible light induced degradation of methylene blue using CeO2/V2O5 and CeO2/CuO catalysts, Mater. Sci. Eng. C 33 (2013) 4725–4731. [9] R. Saravanan, S. Karthikeyan, V.K. Gupta, G. Sekaran, A. Stephen, Enhanced photocatalytic activity of ZnO/CuO nanocomposite for the degradation of textile dye on visible light illumination, Mater. Sci. Eng. C 33 (2013) 91–98. [10] X. Ge, S. Deng, L. Zhu, Y. Li, Z. Jia, Y. Tian, L. Tang, Response of nitrogen mineralization dynamics and biochemical properties to litter amendments to soils of a poplar plantation, Journal of Forestry Research 29 (2018) 915–924. [11] Nourali Mohammadi, Hadi Khani, Vinod Kumar Gupta, Ehsanollah Amereh, Shilpi Agarwal, et al., J. Colloid Interface Sci. 362 (2011) 457–462. [12] Tawfik A. Saleh, Vinod K. Gupta, Synthesis and characterization of alumina nanoparticles polyamide membrane with enhanced flux rejection performance, Sep. Purif. Technol. 89 (2012) 245–251. [13] R. Saravanan, N. Karthikeyan, V.K. Gupta, E. Thirumal, A. Stephen, ZnO/Ag nanocomposite: an efficient catalyst for degradation studies of textile effluents under
Fig. 6. Antioxidant activity plot of SiO2, and MnSi-1 nanocomposites.
3.5. Antimicrobial Assessment The influence of synthesized SiO2 and MnS2–SiO2 morphologies against E. coli and S. pyogenes were analyzed using well diffusion method as shown in Table 1. The antibacterial inhibition performance of gram-positive and negative bacteria was purposeful by using SiO2, and MnS2–SiO2 nanocomposites and nitrofurantoin was used as the standard. The results showed that the antibacterial properties of MnS2–SiO2 nanocomposites was higher than SiO2 nanoparticles against E. coli and S. pyogenes, respectively. The influence of SiO2 and MnS2–SiO2 on antifungal progress was investigated with T. veride, and A. flavus fungal. As can be seen from Table 1, the antifungal attributes of MnSi-1 nanocomposites vs. T. veride, and A. flavus was higher than another prepared catalyst, SiO2, and MnSi-1 nanocomposites [64]. The high relative surface area of MnSi-1 nanocomposites facilitated the adsorption of target bacteria and fungal, accelerating the rate of the antibacterial and antifungal reaction [64,65]. 6
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Journal of Photochemistry & Photobiology, B: Biology journal homepage: www.elsevier.com/locate/jphotobiol
Manganese disulfide-silicon dioxide nano-material: Synthesis, characterization, photocatalytic, antioxidant and antimicrobial studies
T
Muhammad Aqeel Ashrafa,b,g, , Wan-Xi Penga, Ali Fakhric, , Mojgan Hosseinid, ⁎⁎⁎ Hesam Kamyabe,f, , Shreeshivadasan Chelliapane ⁎
⁎⁎
a
School of Forestry, Henan Agricultural University, Zhengzhou 450002, China Department of Geology Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia c Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran d Department of Science, Islamshahr Branch, Islamic Azad University, Sayad Shirazi St. Islamshahr, Tehran, Iran e Engineering Department, Razak Faculty of Technology and Informatics, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100 Kuala Lumpur, Malaysia f Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, 845 West Taylor Street, Chicago, IL 60607, USA g School of Environmental Studies, China University of Geosciences, 430074 Wuhan, China b
ARTICLE INFO
ABSTRACT
Keywords: Silicon dioxide MnS2 Photocatalytic Biological data
The sol-gel/ultrasonically rout produced the novel MnS2-SiO2 nano-hetero-photocatalysts with the various ratio of MnS2. Prepared nano-catalyst were investigated in the photo-degradation of methylene blue under UV light illumination. Structural and optical attributes of as-prepared nano-catalysts were evaluated by X-ray diffraction and photoelectron spectroscopy. The morphological were studied by scanning electron microscopy-EDS, and dynamic light scattering. The diffuse reflectance spectroscopy was applied to examine the band gap energy. The Eg values of SiO2, MnS2-SiO2–0, MnS2-SiO2–1, and MnS2-SiO2–2 nanocomposites are 6.51, 3.85, 3.17, and 2.67 eV, respectively. The particle size of the SiO2 and MnS2-SiO2–1 nanocomposites were 100.0, and 65.0 nm, respectively. The crystallite size values of MnS2-SiO2–1 were 52.21 nm, and 2.9 eV, respectively. MnS2-SiO2 nano-photocatalyst was recognized as the optimum sample by degrading 96.1% of methylene blue from water. Moreover, the influence of pH of the solution, and contact time as decisive factors on the photo-degradation activity were investigated in this project. The optimum data for pH and time were found 9 and 60 min, respectively. The photo-degradation capacity of MnS2-SiO2–2 is improved (96.1%) due to the low band gap was found from UV–vis DRS. The antimicrobial data of MnS2-SiO2 were studied and demonstrated that the MnS2SiO2 has fungicidal and bactericidal attributes.
1. Introduction Nowadays, the energy and environmental pollutant acmes are the world's significant difficulties in a confrontation by humanity. With the development of several crafts, many types of pollutants were abandoned in the environment [1–5]. Organic compound dyes considered as chemical contaminants are deeply venomous and a menace to human health. Hence, eliminating them from water is significant. Hitherward, several methods have been applied to decompose this type of contaminant, such as filtration, Fenton process, ozone reaction, adsorption, etc. Recently, applying of semiconductors nano-powders as a nano-
photocatalyst to obviate energy and environmental acmes have possessed an excellent deal of attention due to the free and unique usage of the light energy to decompose contaminants [6–20]. Among the semiconductors, TiO2, SnS2 and ZnO have been investigated widely due to its low cost, non-toxic and chemical and optical stability. Despite, this catalyst due to its excellent energy band gap, can only weak work in the light irradiation [21–25]. Silicon dioxide (SiO2) has significant attention due to high chemical stability, low costs, nil toxicity and effective as photocatalysts. There is main method to plan and apply impressive semiconductors in the light area [26–28]. The Polarization is vital to solve of suppressed recombination, and the macroscopic polarization of
Correspondence to: M.A. Ashraf, School of Forestry, Henan Agricultural University, Zhengzhou 450002, China. Correspondence to: A. Fakhri, Young Researchers and Elites Club, Science and Research Branch, Islamic Azad University, Tehran, Iran. Correspondence to: H. Kamyab, Engineering Department, Razak Faculty of Technology and Informatics, Universiti Teknologi Malaysia, Jalan Sultan Yahya Petra, 54100 Kuala Lumpur, Malaysia. E-mail addresses: [email protected] (M.A. Ashraf), [email protected] (W.-X. Peng), [email protected] (A. Fakhri), [email protected] (H. Kamyab). ⁎
⁎⁎
⁎⁎⁎
https://doi.org/10.1016/j.jphotobiol.2019.111579 Received 18 May 2019; Received in revised form 21 July 2019; Accepted 24 July 2019 Available online 25 July 2019 1011-1344/ © 2019 Elsevier B.V. All rights reserved.
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
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silica component was studied in previous studied and shows it is enormous influence in photocatalysis process [29]. The method is to modify semiconductor oxides using one of heterojunction with other semiconductors, such as metal sulfide [30,31]. Sajad Talebi and et al. were presented the new catalyst ZnS/TiO2 for photo-degradation of a textile dye [32]. Ch. Venkata Reddy and et al. were reported the CdS/ SnO2 for the decomposition of dye compound [33]. The many SiO2 photocatalysts as hybrid or mono components were synthesized as the AgBr–TiO2/SiO2@Fe3O4 [34], the ZnO-coated SiO2 [35], the Fe-Ni@ SiO2 [36], the SiO2@TiO2 [37] the CdS-Ta2O5-SiO2 [38], the Fe3O4/ SiO2/TiO2 [39], the S-TiO2/SiO2 [40], and the NiS/SiO2 [21] for the decomposition of organic compound under source light irradiation. Therefore, we presented the MnS2-SiO2 nanocomposites as nano-catalysts of for decompose of a dye as a pollutant target under UV light irradiation. The prepared catalyst was used for antimicrobial studies.
concentration was measured using a UV–visible spectrometry (UV1650PC, SHIMADZU, λm = 633 nm) [41–51]. The UV light source distance from the MB solution surface in the test was 2.00 cm.
2. Experimental
2.5. Antioxidant Activity
2.4. Antimicrobial Analysis The evolution curves of microbial cells studied the influences of prepared materials on fungal and bacteria growth; (T. veride, and A. flavus; E. coli and S. pyogenes). Concisely, 100 ml of Luria Bertani and potato dextrose agar was applied for bacteria and fungal mounting on agar plates. Each culture was incubated in an incubator 37 °C for one day. Subsequently, an aliquot from above was added to 50 μL of suspension (1 mM) of prepared nanomaterials. Agar plate without prepared nanomaterial was used as a regulator. The experiment was performed with three replication [52,53].
1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging assay was analyzed for evaluation antioxidant activity [54]. Different concentrations (50–1000 μg/ml) of prepared nanomaterial and ascorbic were prepared. 3 ml of DPPH (0.2 mM) solution was augmented to 4 ml of the prepared solutions. The mixture was stirred and kept in the dark condition for 30 min. Shimadzu UV-1650PC spectrophotometer was applied in test at 517 nm. Ascorbic acid was applied as a standard solution.
The materials were used in this study from Merck CO., Germany. 2.1. Silicon Dioxide and MnS2-SiO2 Catalyst Preparation The silicon dioxide nanoparticles were synthesized as provided in our recent work with the hydrolysis process [21]. The 11 mL of tetraethyl orthosilicate was augmented to in 10 mL H2O. Then, 50 mL of ethanol and 25 mL of ammonia (27%) solution was augmented to the TEOS and H2O solution. The prepared solution locates to pulse sonicator (Misonix S-4000) with a pulse: 5 s, power: 300 W and frequency: 50 kHz and the suspension was stirred for 4 h at 40 °C. The silicon dioxide was dried at 120 °C for 2 h, and at 400 °C for 3 h. The SiO2 nano-catalyst was dispersed in acetone under ultra-sonic bath illumination. Then, the 50 ml of MnCl2.4H2O (0.5 M) and the 50 ml of thioacetamide (C2H5NS) (0.5 M) were propagated to the prepared suspension. The prepared solution locates to pulse sonicator (Misonix S-4000) with a pulse: 5 s, power: 300 W and frequency: 50 kHz, and the suspension was stirred for 1 h at 50 °C under illumination. The final MnS2-SiO2 was collected after drying at 170 °C for 4 h and at 550 °C for 5 h. Three ratios of MnS2 to SiO2 were synthesized with different ratio and labelled as MnSi-0, MnSi-1, and MnSi-2, respectively.
3. Results and Discussion 3.1. Nano-Catalyst Characterization The morphologies of the pure SiO2 and MnS2-SiO2 nano-photocatalysts were studied by using SEM, illustrated in Fig. 1. From Fig. 1A, the morphological of prepared SiO2 samples are spheres with the high size of particles. The SEM image of MnS2-SiO2 nanocomposites demonstrates the agglomerated nanoparticles, which confirms the MnS2 nanoparticles coated on SiO2 nanoparticles surfaces (Fig. 1B). The Energy Dispersive Spectroscopy (EDS) was analyzed for evaluation the presence of all elements in the MnS2-SiO2 nanocomposites framework. EDS analysis shows the Silicon (Si, 32%), Manganese (Mn, 32%), Oxygen (O, 17%), and sulfur (S, 19%). Dynamic light scattering (DLS) is a study in physics that can be used to specify the size values of nanoparticles. The DLS curve of the SiO2 and MnSi-1 are revealed in Fig. 1C. The particle size of the SiO2, and MnSi-1 nanocomposites were 100.0, and 65.0 nm, respectively. The XRD patterns in Fig. 2 shows the crystalline phases of the SiO2, and MnSi-1 nanocomposites, respectively. As can be seen, the diffraction curve of SiO2 indicates the amorphous crystallinity (Fig. 2A) [21]. The MnSi-1 nanocomposites has four distinct diffraction peaks, at 2θ of 30.5°, 34.8°, 42.9°, 54.0°, 55.9°, and 63.0° are ascribed to the (210), (211), (220), and (221) planes, which that shows the crystalline phases of cubic structure of MnS2 (JCPDS card No. 25–0549) [55]. The crystallite size [55] was distinguished to be 52.21 nm for MnSi-1 nanocomposites. In order to further specify the chemical states of elements in the MnSi-1 nanocomposites, their XPS spectra were indicated in Fig. 3. In the status of the Si 2p spectrum (Fig. 4a), the peak at 106.6 eV binding energy well shows Si 2p1/2, and the peaks of Si 2p3/2 identified at 102.2 eV binding energies are corresponding to a spin-orbit splitting specification, respectively [56]. The peaks of Mn 2p clear at a binding energy of 640.2 (Mn 2p3/2) and 652.9 eV (Mn 2p1/2), demonstrating Mn state exists in the MnSi-1 nanocomposites [45]. The O 1 s peaks at 530.41 eV, are certain to lattice oxygen-binding SieO and the water molecules surface hydroxyl group [56]. The S 2p peak appears at 161.4 eV and reports binding energies of Sulfur in MnS2 [45]. For the comparative investigation, the optical properties of SiO2, MnSi-0, MnSi-1, and MnSi-2 are shown in Fig. 4. Spectra in Fig. 4A indicates that the pure SiO2 possess UV–vis absorption spectra, while
2.2. Characterization Devices X-ray diffraction (XRD) study was identified using by Philips X'Pert diffractometer for evaluation of MnS2-SiO2 nanocomposites. The dynamic light scattering (Zetasizer Nano Series Malvern) was applied for the study of MnS2-SiO2 nanocomposites. The morphological of MnS2SiO2 nanocomposites study were identified using by scanning electron microscopy (Model: SU-800, Hitachi). The surface composition and elemental data of MnS2-SiO2 nanocomposites were studied by applying the X-ray photoelectron spectroscopy study (Model: Kratos Axis Ultra DLD; The XPS study was describes as two spectra, spectra with the function of energy and Gaussian and Lorentzian) device. The optical properties of MnS2-SiO2 nanocomposites was investigated by UV–vis (JASCO V-630) spectrophotometer. 2.3. Photo-Decomposition Study Investigation of degradation of MB by the prepared MnS2-SiO2 nanocomposites performed under UV light irradiation (11-W UV lamp irradiation). For this scope, 0.02 g of the prepared nano-catalyst was augmented to 25 ml of the MB solution (10 mg/L). Next, the system solution was kept in the dark condition for 30 min under continuous vigorous stirring to attain absorption and desorption equilibrium reaction. Thereupon, the degradation reactor was exposed to light irradiation. Then, the nano-catalyst was separated, and the residual of MB 2
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
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Fig. 1. The Scanning electron microscopy of SiO2 (A), MnSi-1 nanocomposites (B), and Dynamic light scattering plot (C) of SiO2 (a), MnSi-1 nanocomposites (b).
that of the MnS2-SiO2 nanocomposites has strong UV region spectra. With enhances doping MnS2, the absorption intensity of composite was increased due to charge transfer transition was enhanced [57,58]. The absorption spectra of SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites with the equation (??ℎν)1/2 =??(ℎν) (kubelka-munk equation) [38], which distinguishes the Eg (band gap) data (Fig. 4B). The Eg values of SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites are 6.51, 3.85, 3.17, and, 2.67 eV, respectively.
and reaction time were analyzed to study the performance of the photocatalyst on dye removal. The Dye adsorption was carried out in a dark medium by SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites in 30 min to achieve the adsorption-desorption balance. The results showed, among of prepared samples, the MnSi-2 nanocomposites have significant adsorption of dye about 17.5%, due to the catalyst structure and surface area modified for the removal capacity. The photocatalytic capacity of SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites was done by using MB molecule. From Fig. 5A, the photocatalytic degradation values of methylene blue over SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites are about 53.1, 63.1, 83.1, and 96.1% within the 60 min under UV light illumination, respectively. This enhanced photo-degradation performance of MnSi-2 nanocomposites is generally due to the forming of p-n nanoheterojunction structural
3.2. Photo-Catalytic Assessment The capability of SiO2 and MnS2-SiO2 nano-photocatalysts to decompose dye was studied through its application for photo-degradation of MB under UV light irradiation. Combinations of different levels of pH 3
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
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Fig. 2. The X-ray diffraction spectra of SiO2 (A), MnSi-1 nanocomposites (B).
Fig. 3. The X-ray photoelectron spectra of MnSi-1 nanocomposites.
which modifies the separation of the e−/h+ pairs and decrease the recombination of the e−/h+ pairs excited, and the low band gap of MnSi-2 was found from UV–vis DRS [59–61]. To identify the influence of pH solution on the photo-degradation of methylene blue over SiO2, MnSi-0, MnSi-1, and MnSi-2 nanocomposites, experiments were done at the pH = 5, 7 and 9 that are indicated in Fig. 5B. As can be obvious, the photocatalytic activity of the prepared samples were high values in basic region. Therefore, the pH influence can be described using pHpzc. The charge zero points of SiO2, and MnS2–SiO2 were determined to be about 4.0, and 6.7, respectively. At pH solution values higher than pHpzc; the surface charge of prepared nano-photocatalyst is negative due to the absorption of OH−. Moreover, methylene blue is a cationic surface charge dye. Herewith, the formation of the electrostatic force between the negative surface charges of the nano-catalyst and the MB positive surface charge, makes the great photo-degradation of MB from water [62].
Fig. 4. The UV–visible spectra (A) and the kubelka-munk plot (B) of SiO2 (a), MnSi-0 (b), MnSi-1 (c), and MnSi-2 nanocomposites (d).
photocatalyst under UV light irradiation, as an essential factor, were studied by five cycles to degradation of MB. As indicated in Fig. 5C, after the five reaction cycle, MB photo-degradation performance decreases from 96.1 to 88.1%. The 8.3% decrease in photo-degradation performance can correspond to MnSi-2 nanocomposites inactivation, slight loss of MnSi-2 nanocomposites during the recycling progress.
3.3. Reusability Study The
stability
and
reusability
of
MnSi-2
nanocomposites 4
Journal of Photochemistry & Photobiology, B: Biology 198 (2019) 111579
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Fig. 5. (A) MB photo-decomposition under UV light irradiation at various time (pH 9, nano-photocatalyst dose: 0.1 g/l); (B) MB photo-decomposition under UV light irradiation at various pH (time: 60 min, nano-photocatalyst dose: 0.1 g/l), (C) Reusability of prepared composites.
3.4. Mechanism of Photo-Degradation of Dye
- Conversion of adsorbed oxygen to superoxide radical.
MnS2
The proposed mechanism for MnS2-SiO2-catalyzed photocatalytic removal of MB contains five-stage [63]:
MnS2
SiO2 + h
MnS2
SiO2 (e
cb
+
O2 – + H+
b)
MnS2
SiO2
b)
+ H2 O
MnS2
SiO2 (h+ b) + OH–
H+
+ O2
O2 –
HO2
- Degradation of MB by radicals.
OH, HO2 , O2 – + MB
- Generation of OH% radical
(h+
cb)
- Neutralization of %O2– to %HO2 by protonation
- Excitation of e−/h+ pair under the photo.
h+
SiO2 (e
+ OH
OH 5
Dioxide carbon + water
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3.6. Antioxidant Activity
Table 1 Antifungal and antibacterial activity of the prepared nano-catalyst.
SiO2 MnSi-1 Standard antibiotic
SiO2 MnSi-1 Standard antibiotic
A. flavus
T. veride
6.12 ± 0.12 21.31 ± 0.55 11.34 ± 0.11
4.21 ± 0.31 16.75 ± 0.11 8.44 ± 0.12
E. coli
S. pyogenes
6.51 ± 0.21 20.22 ± 0.12 22.23 ± 0.11
9.14 ± 0.21 28.51 ± 0.32 26.54 ± 0.30
Fig. 6 demonstrates the DPPH radical scavenging activity of MnSi-1 nanocomposites. By getting H+ or e− from donor atom DPPH free radical is reduced [54]. The odd electron of DPPH accepts the H atom from the antioxidants and changes to identical hydrazine [54]. DPPH is a fast method to study antioxidant performance [54]. The radical scavenging performance of MnSi-1 nanocomposites was enhanced. A great data was observed at 200 μg/ml, which is a slightly less than ascorbic acid as standard. Similar result indicated that nanoparticles could enhance the antioxidant activity [54]. 4. Conclusions The novel MnS2-SiO2 photocatalysts with the various ratio of MnS2 produced via the sol-gel/ultrasonically rout. This study confirms that the MnS2 could be improved the photocatalyst properties and reusability of nano-catalyst in UV light photo-decomposition of MB. The photo-degradation activity of MnS2-SiO2 nano-catalyst was firmly higher than SiO2 nanoparticles. Moreover, the influence of solution pH and reaction time on the photo-degradation activity was evaluated, and the optimum operating conditions were found pH: 9 and time: 60 min. The biological investigation shows the Cr2S3-SiO2 nanocomposites has excellent antimicrobial and antioxidant activity. Acknowledgements The researchers are thanking for the patronage of this project by the Islamic Azad University of Science and Research Branch Tehran. Hesam Kamyab is a researcher of UTM under the Post-Doctoral Fellowship Scheme (PDRU Grant) for the project: “Enhancing the lipid growth in algae cultivation for biodiesel production” with vote number: Q. J130000.21A2.03E95 and Research Grant University UTM with vote number: Q.K130000.2540.20H05. References [1] A. Mittal, J. Mittal, A. Malviya, V.K. Gupta, Removal and recovery of Chrysoidine Y from aqueous solutions by waste materials, J. Colloid Interface Sci. 344 (2010) 497–507. [2] L. Yin, Y. Ji, Y. Zhang, L. Chong, L. Chen, Rotifer community structure and its response to environmental factors in the Backshore Wetland of Expo Garden, Shanghai, Aquaculture and Fisheries 3 (2018) 90–97. [3] Tawfik A. Saleh, Vinod K. Gupta, Photo-catalyzed degradation of hazardous dye methyl orange by use of a composite catalyst consisting of multi-walled carbon nanotubes and titanium dioxide, J. Colloid Interface Sci. 371 (2012) 101–106. [4] Hadi Khani, Mohammad Kazem Rofouei, Pezhman Arab, Vinod Kumar Gupta, Zahra Vafaei, Multi-walled carbon nanotubes-ionic liquid-carbon paste electrode as a super selectivity sensor: Application to potentiometric monitoring of mercury ion (II), J. Hazard. Mater. 183 (2010) 402–409. [5] V.K. Gupta, R. Kumar, A. Nayak, T.A. Saleh, M.A. Barakat, Adsorptive removal of dyes from aqueous solution onto carbon nanotubes: a review, Adv. Colloid Interf. Sci. 193–194 (2013) 24–34. [6] R. Saravanan, Elisban Sacari, F. Gracia, Mohammad Mansoob Khan, Vinod Kumar Gupta, et al., J. Mol. Liq. 221 (2016) 1029–1033. [7] R. Manoj Devaraj, R.D. Saravanan, V.K. Gupta, S. Jayadevan, Fabrication of novel shape Cu and Cu/Cu2O nanoparticles modified electrode for the determination of dopamine and paracetamol, J. Mol. Liq. 221 (2016) 930–941. [8] R. Saravanan, S. Joicy, V.K. Gupta, V. Narayanan, A. Stephen, Visible light induced degradation of methylene blue using CeO2/V2O5 and CeO2/CuO catalysts, Mater. Sci. Eng. C 33 (2013) 4725–4731. [9] R. Saravanan, S. Karthikeyan, V.K. Gupta, G. Sekaran, A. Stephen, Enhanced photocatalytic activity of ZnO/CuO nanocomposite for the degradation of textile dye on visible light illumination, Mater. Sci. Eng. C 33 (2013) 91–98. [10] X. Ge, S. Deng, L. Zhu, Y. Li, Z. Jia, Y. Tian, L. Tang, Response of nitrogen mineralization dynamics and biochemical properties to litter amendments to soils of a poplar plantation, Journal of Forestry Research 29 (2018) 915–924. [11] Nourali Mohammadi, Hadi Khani, Vinod Kumar Gupta, Ehsanollah Amereh, Shilpi Agarwal, et al., J. Colloid Interface Sci. 362 (2011) 457–462. [12] Tawfik A. Saleh, Vinod K. Gupta, Synthesis and characterization of alumina nanoparticles polyamide membrane with enhanced flux rejection performance, Sep. Purif. Technol. 89 (2012) 245–251. [13] R. Saravanan, N. Karthikeyan, V.K. Gupta, E. Thirumal, A. Stephen, ZnO/Ag nanocomposite: an efficient catalyst for degradation studies of textile effluents under
Fig. 6. Antioxidant activity plot of SiO2, and MnSi-1 nanocomposites.
3.5. Antimicrobial Assessment The influence of synthesized SiO2 and MnS2–SiO2 morphologies against E. coli and S. pyogenes were analyzed using well diffusion method as shown in Table 1. The antibacterial inhibition performance of gram-positive and negative bacteria was purposeful by using SiO2, and MnS2–SiO2 nanocomposites and nitrofurantoin was used as the standard. The results showed that the antibacterial properties of MnS2–SiO2 nanocomposites was higher than SiO2 nanoparticles against E. coli and S. pyogenes, respectively. The influence of SiO2 and MnS2–SiO2 on antifungal progress was investigated with T. veride, and A. flavus fungal. As can be seen from Table 1, the antifungal attributes of MnSi-1 nanocomposites vs. T. veride, and A. flavus was higher than another prepared catalyst, SiO2, and MnSi-1 nanocomposites [64]. The high relative surface area of MnSi-1 nanocomposites facilitated the adsorption of target bacteria and fungal, accelerating the rate of the antibacterial and antifungal reaction [64,65]. 6
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