- Email: [email protected]
Fe3O4 nanocomposite by red water and Caesalpinia gilliesii flower extract
Accepted Manuscript Catalytic reduction of organic pollutants using biosynthesized of Ag/C/Fe3O4 nanocomposite by red water and Caesalpinia gilliesii flower extract Akbar Rostami-Vartooni, Abolfazl Moradi-Saadatmand, Mohammad Mahdavi PII:
S0254-0584(18)30691-6
DOI:
10.1016/j.matchemphys.2018.08.026
Reference:
MAC 20869
To appear in:
Materials Chemistry and Physics
Received Date: 4 February 2018 Revised Date:
15 June 2018
Accepted Date: 10 August 2018
Please cite this article as: A. Rostami-Vartooni, A. Moradi-Saadatmand, M. Mahdavi, Catalytic reduction of organic pollutants using biosynthesized of Ag/C/Fe3O4 nanocomposite by red water and Caesalpinia gilliesii flower extract, Materials Chemistry and Physics (2018), doi: 10.1016/ j.matchemphys.2018.08.026. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
AC C
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT
Catalytic reduction of organic pollutants using biosynthesized of Ag/C/Fe3O4 nanocomposite by red water and Caesalpinia gilliesii flower extract Akbar Rostami-Vartooni,*,a Abolfazl Moradi-Saadatmanda and Mohammad Mahdavib
b
Department of Chemistry, Faculty of Science, University of Qom, Qom 3716146611, Iran
RI PT
a
Department of Chemistry, Malek-ashtar University of Technology, Shahin-shahr P.O. Box 83145/115, Islamic Republic of Iran
Abstract
SC
In this study, a facile synthesis of porous carbon and its Fe3O4 nanocomposite were synthesized via carbonization of red water and co-precipitation reaction, respectively. Then, an aqueous extract of
M AN U
Caesalpinia gilliesii flower was used for reduction of the Ag+ ions to Ag nanoparticles (Ag NPs) and their stabilization on the surface of carbon supports. The formation of the Ag NPs occurs at room temperature within a few minutes. The synthesized porous carbon and its nanocomposites were characterized by FTIR, Raman, XRD, FESEM, EDS, elemental mapping, TEM, BET, and VSM
TE D
techniques. According to the FESEM and TEM images, the average size of the Ag NPs on the surface of porous carbon and C/Fe3O4 was below 35 nm. The magnetically recoverable Ag/Fe3O4/C nanocomposite demonstrated favorable catalytic activity on the reduction of methyl orange (MO) and
AC C
in its activity.
EP
4-nitrophenol (4-NP). In addition, the catalyst can be reused at least 3 times without considerable loss
Keywords: Green synthesis; Ag/Fe3O4/C nanocomposite; Red water; C. gilliesii; Catalytic Reduction
*
Corresponding authors: A. Rostami-Vartooni (E-mail: [email protected] and [email protected]).
1
ACCEPTED MANUSCRIPT
1. Introduction In one of the steps of toluene nitration process, the aqueous Na2SO3 solution was used to remove
RI PT
unwanted products and less stable isomers. The sellite waste solution in this purification process is known as red water which is a toxic waste product. The real composition of pollutants in red water is unknown. This wastewater contains aromatic compounds such as 1,3,5-trinitrobenzene, mono, di and 2-methyl-3,5-dinitrophenol,
5-methyl-2-nitrophenol,
3-methyl-2-nitro-phenol,
SC
trinitrotoluene,
unidentified S-containing compounds, etc [1-3]. The removal of these pollutants and other
M AN U
environmental contaminants such as toxic and carcinogenic dyes from wastewaters is one of the problems of human society [4-10]. In this field, advanced oxidation process (AOPs) [11-21], wet oxidation [22], catalytic adsorption [23,24], ice crystallization [25], vacuum distillation [26] and reduction process with heterogeneous catalysts and NaBH4 [27,28] can be used as efficient methods for the removal of such pollutants.
TE D
In recent years, carbon materials have obtained from carbonization or pyrolysis of agricultural waste products followed by chemical activation using dehydrating agents (i.e. KOH, H3PO4, H2SO4, ZnCl2) or physical activation in the presence of air, steam or carbon dioxide as oxidizing gases at
EP
temperatures below 700 °C [29-31]. Carbon structures have been used in various applications such as
AC C
catalyst supports and adsorbents for gases or metal species due to singular structure, appropriate electronic conductivity and improved accessibility of compounds to their active sites [32-40]. The Fe3O4/C composites have been employed as absorbents for organic dyes and heavy metal ions removal applications [41-43]. An important property of these materials is easy separation from a reaction mixture using an external magnetic force. Li et al. [44] prepared porous Fe3O4/C and Fe3O4/C/Cu2O composites by calcining iron tartrate precursor and precipitation-reduction methods,
2
ACCEPTED MANUSCRIPT
respectively. These composites exhibited photo-Fenton catalytic performance for removal of dye (methylene blue) under visible light irradiation. Distributing of metal nanoparticles (MNPs) over the surface of magnetic materials and other
RI PT
inorganic supports such as metal oxides [45], zeolites [46], carbon structures [47-52], seashell [53] and perlite [54] lead to lower agglomeration, more reactivity, stability and simple separation of catalyst. Nowadays, plants and their extractives as nontoxic reducing and stabilizing agents are important in
SC
the synthesis of the MNPs [53-55]. This ecofriendly biosynthesis approach is simple and it does not require chemical materials, time-consuming and harsh working conditions. The water soluble phenolic
M AN U
compounds, terpenoids, and alkaloids in the plants extract not only are responsible for the reduction of metal ions into metals, but also act as capping agents in the synthesis of nanoparticles with a welldefined size and morphology.
Caesalpinia gilliesii (bird of paradise) as a shrub in the legume family has health benefits for curing
TE D
cough, sores, and fever, but the seeds and the green seed pods of this plant are toxic which causes vomiting and other abdominal symptoms [56].
Here we report the preparation of porous carbon via carbonization of red water as a low cost and
EP
easy process. Also, the biosynthesized of Ag/C/Fe3O4 nanocomposite was synthesized using C. gilliesii extract. The catalytic efficiency of the Ag/C/Fe3O4 nanocomposite was evaluated through reduction of
AC C
methyl orange (MO), and 4-nitrophenol (4-NP).
2. Experimental
2.1. Chemical substances and instruments All chemical substances were obtained from Merck KGaA, Darmstadt, Germany. The red water soloution was obtanied from an industrial unit of 2,4,6-trinitrotluene (TNT) production. The flowers of C. gilliesii were collected from Vartoon village (Isfahan, Iran). UV-Vis spectral analysis was carried 3
ACCEPTED MANUSCRIPT
out on a double‐beam spectrophotometer (Hitachi, U‐2900). Fourier transform infrared (FTIR) spectra were recorded on Nicolet 370 FT/IR spectrometer (Thermo Nicolet, USA) in the range of wavenumbers 3900-400 cm-1. Raman spectra were obtained using a Takram P50C0R10 spectrometer
RI PT
with a 532 nm Nd: YAG laser. X-ray powder diffraction (XRD) measurements were performed using an XRD PHILIPS powder diffractometer type PW1730 goniometer employing Cu Ka radiation (λ = 1.5418 Å) in the 2θ range from 10 to 90˚. Field emission scanning electron microscope (FESEM) and
SC
elemental mapping images were obtained on Cam scan MV2300 equipped with an energy dispersive X-ray spectroscopy (EDX). TEM images of nanocomposite were obtained on Philips-EM-208S
M AN U
transmission electron microscope operating at 100 kV. Vibrating sample magnetometer (VSM) measurement was performed by using a SQUID magnetometer at room temperature (Quantum Design MPMS XL). The Brunauer-Emmett-Teller (BET) surface area and pore volume of the nanocomposites were measured by a Bell Japan BELSORP mini II apparatus.
TE D
2.2. Preparation of the C. gilliesii flower extract
10.0 g of dried flowers of C. gilliesii were added to 100.0 mL of distilled water and then heated at 70 °C for 20 min. Finally, the aqueous extract was filtered by applying a Whatman No.1 filter paper to
EP
obtain a clear solution of extract.
2.3. Preparation of the porous carbon
AC C
The porous carbon was synthesized from red water as a cheap carbon source. The red water from explosive industries is a byproudt of 2,4,6-Trinitrotoluene (TNT) purification process. The red water has 5.3 w.t% organic materials such as 2,4-dinitrotoluene-3-sulfonate, 2,4-dinitrotoluene-5-sulfonate and other derivatives. About 2000 ml of red water was dried at 90 ºC in an oven under good ventilation of a hood, and then was burned in a tubular furnace at about 450 ºC. The volatiled gas and decomposed organic materials were absorbed by a 10 wt% NaOH solution. The red water was dried at 90 ºC in an
4
ACCEPTED MANUSCRIPT
oven and then was burned in a furnace at about 450 ºC. The resulted porous carbon was washed with dilut HCl solution and then several times by distilled water. 2.4. Preparation of the C/Fe3O4 nanocomposite
RI PT
At first, the prepared porous carbon in the previous section (4.0 g) was mixed with 10.0 mL of FeCl3·6H2O solution (2.0 M) and 10.0 mL of FeCl2·6H2O solution (1.0 M). For the preparation of Fe3O4 nanoparticles by a co-precipitation method, the mole ratio of Fe(III)/Fe(II) was fixed at 2. Then,
SC
80.0 mL of 1.0 M NaOH solution was added dropwise to the mixture under a nitrogen atmosphere and continuous stirring to precipitate the Fe3O4 nanoparticles on porous carbon. The resulted C/Fe3O4
M AN U
nanocomposite was filtered and washed with hot distilled water for several times, and dried in an oven at 80 ºC for 1 h.
2.5. Preparation of the Ag NPs/C nanocomposite
To a dispersion containing 3.0 g porous carbon and 50.0 mL of the prepared extract, 15.0 mL of
TE D
AgNO3 solution (0.2 M) was added. This mixture was stirred at 70 °C for 10 min under continuous stirring. Finally, the synthesized Ag NPs in the presence of extract was immobilized on the surface of porous carbon as a support and prepared nanocomposite was filtered, washed with distilled water and
EP
then dried.
2.6. Preparation of the Ag/Fe3O4/C nanocomposite
AC C
3.0 g Fe3O4/C was dispersed in the solution of the prepared extract (50.0 mL) under stirring. Then, 15.0 mL of AgNO3 solution (0.2 M) was added to this mixture and stirred at 70 °C for 10 min under continuous stirring. Finally, the produced Ag/Fe3O4/C was filtered and washed with distilled water. 2.7. Reduction of the MO using porous carbon and its nanocomposites To a mixture containing 30 mL of MO (10 ppm or 3 × 10-5 M) and 30.0 mL aqueous NaBH4 solution (5.3 × 10-3 or 2.5 × 10-3 M), 3.0 mg (or 6.0 mg) of the porous carbon (or its nanocomposites)
5
ACCEPTED MANUSCRIPT
was added and stirred at room temperature. The reduction process of MO was monitored by recording the UV-Vis spectral analysis at certain intervals. 2.8. Reduction of the 4-NP by porous carbon and its nanocomposites
RI PT
To a dispersion containing 4-NP aqueous solution (2.5 × 10-3 M, 30 mL), 3.0 mg (or 6.0 mg) of the porous carbon (or its nanocomposites) was added. Finally, 30 mL of 44 × 10-3 M (or 88 × 10-3 M) NaBH4 was added and this mixture was then stirred at room temperature. 1.0 mL of 4-NP solution was
SC
diluted to 25.0 mL with distilled water for recording of the UV-Vis absorption peak at certain intervals.
M AN U
3. Results and discussion
The aim of this work was catalytic reduction of organic pollutants in the presence of biosynthesized Ag/C/Fe3O4 nanocomposite. For the preparation of porous carbon, the red water as a toxic waste product in toluene nitration process was used in the carbonization process. The co-precipitation method
TE D
was carried out for the synthesis of C/Fe3O4 nanocomposite. The C. gilliesii flower extract was used for reduction of silver ions to silver nanoparticles on the surface of nanocomposites. The prepared catalysts were characterized using FTIR, Raman, XRD, FESEM, EDS, elemental mapping, TEM, BET, and
EP
VSM.
3.1. Characterization of the C. gilliesii flower extract
AC C
The presence of phenolics constituents as antioxidant agents in the flower of C. gilliesii can be confirmed using FTIR and UV-Vis spectroscopic analyses. The observed peaks in the FTIR spectrum of C. gilliesii (Fig. 1) at 3426, 2925, 1650, 1458 and 1068-1238 cm-1 are concerned with hydroxyl groups, C–H, C=O, C=C aromatic rings and C–OH vibrations, respectively [54-56]. Fig. 2 shows a maximum peak at 270 nm in the UV-Vis spectrum of C. gilliesii flower extract which is assigned to π
6
ACCEPTED MANUSCRIPT
→ π* or n → π* transitions localized within the phenolics rings of organic compounds in aqueous
M AN U
SC
RI PT
extract [57].
AC C
EP
TE D
Fig. 1. FTIR spectrum of the C. gilliesii flower.
Fig. 2. UV-Vis spectrum of the C. gilliesii flower extract.
3.2. Characterization of the porous C and its nanocomposites FTIR spectra of carbon and its nanocomposites are given in Fig. 3. The absorption modes at about 1620 and 1250 cm−1 are related to the stretching vibrations of C=C and C–O bonds, respectively
7
ACCEPTED MANUSCRIPT
[58,59]. The broad absorption bands observed at 3426-3445 cm-1 correspond to the stretching vibration of O–H groups on the surface of carbon nanocomposites [33]. The new bands at 450-680 cm-1 in the FTIR spectra of Fe3O4 nanocomposites (Figs. 3c and 3d) are assigned to the Fe–O vibrations [60]. The
RI PT
functional groups in the FTIR spectra of carbon supports have not changed before and after loading of Ag NPs. Raman spectra of the Ag NPs/C and Ag/C/Fe3O4 are shown in Fig. 4. In the Raman spectrum of Ag NPs/C (Fig. 4a), the bands at 1561 cm−1 (i.e., G band) and 1366 cm-1 (also called D band) are
SC
related to the sp2-hybridized carbon bonds and defects involved in the sp2 lattice structure, respectively [61,62]. A broad 2D-signal was also observed at 2830 cm-1. The G and D bands in the Raman spectrum
AC C
EP
TE D
M AN U
of Ag/C/Fe3O4 (Fig. 4b) were observed at 1366 and 1556 cm−1, respectively.
Fig. 3. FTIR spectra of the porous C (a), Ag NPs/C (b), C/Fe3O4 (c) and Ag/C/Fe3O4 (d).
8
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 4. Raman spectra of Ag NPs/C (a) and Ag/C/Fe3O4 (b).
Fig. 5 shows XRD patterns of carbon support and its nanocomposites. Fig. 5a displays the XRD pattern of porous C with characteristic peaks at 2θ=20–30º and 40–50º which can be attributed to the (002) and (100) planes indicating graphite structures [63,64]. The new reflections were appeared at 2θ
TE D
= 38°, 44.2°, 64.4°and 77.3° in the XRD pattern of Ag/C (Fig. 5b). As it has been shown in previous works, these peaks can be attributed to the (111), (200), (220) and (311) reflections of face centered
EP
cubic (fcc) of the Ag NPs [53,54]. Figs. 5c and 5d show the XRD patterns of Fe3O4/C and Ag/Fe3O4/C nanocomposites, respectively. The peaks at about 2θ = 30.5°, 35.8°, 43.4°, 53.9°, 57.3°, 63.1 and 74.1°
AC C
were indexed for the (220), (311), (400), (422), (511), (440) and (533) planes of cubic spinel phase of Fe3O4 [65,66]. The diffraction peaks at 2θ = 38.3°, 44.5°, 64.6° and 77.6° were attributed to the fcc structure of Ag NPs on the Fe3O4/C support.
9
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 5. XRD diffractogram of the porous C (a), Ag NPs/C (b), C/Fe3O4 (c) and Ag/C/Fe3O4 (d).
The morphological characterizations of the Ag NPs/C and Ag/C/Fe3O4 nanocomposites were carried out by FESEM analysis. As seen in FESEM images (Figs. 6 and 7), spherical Ag NPs were produced
TE D
using the flower extract of C. gilliesii on the surface of nanocomposites. The average size of these nanoparticles on the surface of the Ag NPs/C and Ag/Fe3O4/C was at about 35 and 20 nm, respectively. The EDS spectra of the Ag NPs/C and Ag/C/Fe3O4 nanocomposites (Fig. 8) show the present of C, Ag,
EP
N, S, O or Fe in these nanocomposites. Also, distribution of Ag and Fe3O4 NPs in the Ag/C/Fe3O4 nanocomposite are shown in its elemental mapping images (Fig. 9). TEM images of the Ag/C/Fe3O4
AC C
nanocomposite (Fig. 10) show the size of spherical Fe3O4 NPs and Ag NPs were below 30 nm.
10
AC C
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 6. FESEM images of the Ag NPs/C nanocomposite.
11
AC C
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 7. FESEM images of the Ag/C/Fe3O4 nanocomposite.
12
AC C
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 8. EDS spectra of the Ag NPs/C (a) and Ag/C/Fe3O4 nanocomposites (b).
13
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
AC C
Fig. 9. Elemental mapping of the Ag/C/Fe3O4 nanocomposite.
14
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 10. TEM images of the Ag/C/Fe3O4 nanocomposite.
Fig. 11 shows the hysteresis loop of the Ag/Fe3O4/C nanocomposite in the magnetic field intensity
EP
(H) range of –8.5 to 8.5 kOe. The saturation magnetization (Ms) reaches about 17 emu/g at saturation point. This value is enough for convenient separation of the nanocomposite by an external magnetic
AC C
force in aqueous reactions.
15
SC
RI PT
ACCEPTED MANUSCRIPT
M AN U
Fig. 11. Magnetization curve of the Ag/Fe3O4/C nanocomposite.
According to the N2 adsorption–desorption isotherm and BJH pore size distribution plot (Fig. 12), the surface area, pore volume and mean pore diameter of the prepared porous C are 42.31 m2g-1, 0.31 cm3g-1 and 29.23 nm, respectively. After immobilization of the Ag NPs on the C support, the surface area and pore volume were decreased to 22.08 m2g-1 and 0.19 cm3g-1, respectively, while mean pore
TE D
diameter was increased to 34.34 nm. The surface area, pore volume and mean pore diameter of Ag/Fe3O4/C nanocomposite were 28.58 m2g-1, 0.18 cm3g-1 and 25.26 nm, respectively. The
AC C
these changes.
EP
immobilization of Ag NPs and entering of nanosized Fe3O4 into the cavities of porous carbon lead to
16
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
EP
Fig. 12. Nitrogen adsorption and desorption isotherms for the Ag NPs/C (a) Ag/Fe3O4/C (b); Barrett-Joyner-Halenda (BJH) pore size distribution plot of the Ag NPs/C (c) and Ag/Fe3O4/C (d).
AC C
3.3. Catalytic activity investigation of the carbon nanocomposites for the reduction of dyes The prepared carbon nanocomposites were used in the catalytic reduction of MO and 4-NP by NaBH4. As seen in Fig. 13, the reduction of MO and 4-NP in the presence of Ag/C/Fe3O4 nanocomposite were monitored by applying UV-Vis spectroscopic analysis at λmax of 493 and 400, respectively. As can be seen in this figure, the red and deep yellow colors of dye solutions became colorless at the end of the reduction process. Also, the reduction of MO (3 × 10-5 M) and 4-NP (2.5 ×
17
ACCEPTED MANUSCRIPT
10-5 M) using 6.0 mg of the Ag/C/Fe3O4 nanocomposite were completed within 3.5 and 7 min,
AC C
EP
TE D
M AN U
SC
RI PT
respectively.
18
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 13. UV-Vis spectra of catalytic reduction of MO (a) and 4-NP (b) at several intervals.
TE D
The reaction times of the reduction process for selected dyes in the presence of porous carbon and its nanocomposites are summarized in Tables 1 and 2. The shorter reduction times are resulted from
EP
applying higher amounts of catalysts and NaBH4. In the absence of NaBH4, no color changes were observed in 2 h for selected dyes. The as-produced Ag NPs nanocomposites are much more reactive
AC C
catalysts than the unmodified nanocomposites. It seems these metal nanoparticles facilitate electron transfer from BH4– to 4-NP. Fe3O4 NPs in the C/Fe3O4 and Ag/C/Fe3O4 nanocomposites facilitate the reduction process and separation of these catalysts from the reaction medium. From the results in Tables 1 and 2, it could be said that the efficiency of Ag/C/Fe3O4 nanocomposite in the reduction reactions of MO and 4-NP is comparable to the other synthesized carbon materials in this work and previously reported catalysts [67-69]. Table 1. Reaction time for the reduction of 10.0 ppm MO using NaBH4 in the presence of different catalysts.
19
ACCEPTED MANUSCRIPT
Catalyst (mg) C (3) Ag NPs/C (3) Fe3O4/C (3) Ag/Fe3O4/C (3) Ag/Fe3O4/C (3) Ag/Fe3O4/C (6) Ag/Fe3O4/C (3)
Time (min) 65 50 13.5 35 120a 4.5 3.5 6
RI PT
[NaBH4] (M) 5.3 × 10-3 5.3 × 10-3 5.3 × 10-3 5.3 × 10-3 5.3 × 10-3 5.3 × 10-3 2.5 × 10-3 a No reaction.
3.5. Catalyst recyclability
Time (min) 100 70 16.5 50 120a 12 9.5 7
M AN U
Catalyst (mg) C (3) Ag NPs/C (3) Fe3O4/C (3) Ag/Fe3O4/C (3) Ag/Fe3O4/C (3) Ag/Fe3O4/C (6) Ag/Fe3O4/C (6)
TE D
[NaBH4] (M) 44 × 10-3 44 × 10-3 44 × 10-3 44 × 10-3 44 × 10-3 44 × 10-3 88 × 10-3 a No reaction.
SC
Table 2. Reaction time for the reduction of 4-NP (2.5 × 10-3 M) using different amounts of catalysts and NaBH4.
When the reduction reaction of the MO dye was completed, the Ag/C/Fe3O4 catalyst was quickly
EP
removed from the reaction mixture by an external magnetic field and its recyclability was also investigated. After three catalytic runs, the completion times for the reduction process of the MO using
AC C
recovered catalyst does not change significantly which confirms the stability of nanocomposite and its appropriate recyclability. Fig. 14 shows the FESEM images and EDX spectrum of the recycled Ag/C/Fe3O4 catalyst. Also, the elemental mapping images of the recycled catalyst are seen in Fig. 15. The obtained results from these analyses show the morphology and the amount of the Ag NPs on the catalyst surface are approximately unchanged even after three catalytic runs.
20
ACCEPTED MANUSCRIPT
b
M AN U
SC
RI PT
a
AC C
EP
TE D
c
Fig. 14. FESEM images (a-c) and EDS spectrum (d) of recycled Ag/C/Fe3O4 nanocomposite.
21
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
AC C
4. Conclusions
EP
Fig. 15. Elemental mapping of recycled Ag/C/Fe3O4 nanocomposite.
The facile preparation of porous carbon and its Fe3O4 nanocomposite were performed by carbonization of red water and co-precipitation technique, respectively. Then, the flower extract of the C. gilliesii was used for reduction of Ag+ ions and stabilization of the preparead Ag NPs on the surface of the porous carbon and C/Fe3O4 nanocomposite. The as-prepared carbon nanocomposites were characterized by different methods and showed good activity in the reduction of the MO and 4-NP as
22
ACCEPTED MANUSCRIPT
toxic organic dyes. In this work, a toxic waste product in the industrial unit of 2,4,6-trinitrotluene (TNT) production was converted to a stable support.
RI PT
Acknowledgements
support of this work. References
SC
The authors acknowledge the University of Qom and Malek-Ashtar University of Technology for the
[1] J.T. Walsh, R.C. Shalk, C. Merritt, Application of liquid chromatography to pollution abatement studies of
M AN U
munitions wastes, Anal. Chem. 45 (1973) 1215–1220.
[2] Q. Zhao, Z. Ye, M. Zhang, Treatment of 2,4,6-trinitrotoluene (TNT) red water by vacuum distillation, Chemosphere 80 (2010) 947–950.
[3] S.J. Lee, I.H. Cho, H.K. Lee, K.D. Zoh, A study on the treatment of high explosives (TNT, RDX, HMX) using TiO2 photocatalyst, J. KSEE 24 (6) (2002) 1071–1080.
TE D
[4] K. Im, D. Nguyen, S. Kim, H.J. Kong, Y. Kim, C.S. Park, O.S. Kwon, H. Yoon, Graphene-embedded hydrogel nanofibers for detection and removal of aqueous-phase dyes, ACS Appl. Mater. Interfaces 9 (2017) 10768–10776. [5] K.R. Reddy, K.V. Karthik, S.B. Prasad, S.K. Soni, H.M. Jeong, A.V. Raghu, Enhanced photocatalytic activity of nanostructured titanium dioxide/polyaniline hybrid photocatalysts, Polyhedron. 120 (2016) 169–174.
EP
[6] K. Kasinathan, J. Kennedy, M. Elayaperumal, M. Henini, M. Malik, Photodegradation of organic pollutants RhB dye using UV simulated sunlight on ceria based TiO2 nanomaterials for antibacterial applications, Sci. Rep. 6
AC C
(2016) 38064.
[7] K. Kaviyarasu, C.M. Magdalane, K. Kanimozhi, J. Kennedy, B. Siddhardha, E.S. Reddy, N.K. Rotte, C.S. Sharma, F.T. Thema, D. Letsholathebe, G.T. Mola, M. Maaza, Elucidation of photocatalysis, photoluminescence and antibacterial studies of ZnO thin films by spin coating method, J. Photochem. Photobiol. B: Biol. 173 (2017) 466– 475. [8] K. Kaviyarasu, E. Manikandan, Z.Y. Nuru, M. Maaza, Investigation on the structural properties of CeO2 nanofibers via CTAB surfactant, Mater. Lett. 160 (2015) 61–63.
23
ACCEPTED MANUSCRIPT
[9] K. Kaviyarasu, E. Manikandan, M. Maaza, Synthesis of CdS flower-like hierarchical microspheres as electrode material for electrochemical performance, J. Alloys Compd. 648 (2015) 559–563. [10] C.M. Magdalane, K. Kaviyarasu, J.J. Vijaya, C. Jayakumar, M. Maaza, B. Jeyaraj, Photocatalytic degradation
RI PT
effect of malachite green and catalytic hydrogenation by UV–illuminated CeO2/CdO multilayered nanoplatelet arrays: Investigation of antifungal and antimicrobial activities, J. Photochem. Photobiol. B: Biol. 169 (2017) 110– 123.
[11] K. Kaviyarasu, A. Ayeshamariam, E. Manikandan, J. Kennedy, R. Ladchumananandasivam, U.U. Gomes, M.
SC
Jayachandran, M. Maaza, Solution processing of CuSe quantum dots: Photocatalytic activity under RhB for UV and visible-light solar irradiation, Mater. Sci. Eng. B. 210 (2016) 1–9.
M AN U
[12] C.M. Magdalane, K.K. aviyarasu, J.J. Vijaya, B. Siddhardha, B. Jeyaraj, Photocatalytic activity of binary metal oxide nanocomposites of CeO2/CdO nanospheres: Investigation of optical and antimicrobial activity, J. Photochem. Photobiol. B: Biol. 163 (2016) 77–86.
[13] K. Kaviyarasu, A. Mariappan, K. Neyvasagam, A. Ayeshamariam, P. Pandi, R. Rajeshwara Palanichamy, C. Gopinathan, G.T. Mola, M. Maaza, Photocatalytic performance and antimicrobial activities of HAp-TiO2 nanocomposite thin films by sol-gel method, Surf. Interfaces 6 (2017) 247–255.
TE D
[14] V. Mirkhani, S. Tangestaninejad, M. Moghadam, M.H. Habibi, A. Rostami-Vartooni, Photocatalytic degradation of azo dyes catalyzed by Ag doped TiO2 photocatalyst, J. Iran. Chem. Soc. 6 (2009) 578–587. [15] C.M. Magdalane, K. Kaviyarasu, J.J. Vijaya, B. Siddhardha, B. Jeyaraj, Facile synthesis of heterostructured
EP
cerium oxide/yttrium oxide nanocomposite in UV light induced photocatalytic degradation and catalytic reduction: Synergistic effect of antimicrobial studies, J. Photochem. Photobiol. B: Biol. 173 (2017) 23–34.
AC C
[16] C.M. Magdalane, K. Kaviyarasu, J.J. Vijaya, B. Siddhardha, B. Jeyaraj, J. Kennedy, M. Maaza, Evaluation on the heterostructured CeO2/Y2O3 binary metal oxide nanocomposites for UV/Vis light induced photocatalytic degradation of Rhodamine - B dye for textile engineering application, J. Alloys Compd. 727 (2017) 1324–1337. [17] X. Fuku, N. Matinise, M. Masikini, K. Kasinathan, M. Maaza, An electrochemically active green synthesized polycrystalline NiO/MgO catalyst: Use in photo-catalytic applications, Mater. Res. Bull. 97 (2018) 457–465. [18] S.K. Jesudoss, J.J. Vijaya, P.I. Rajan, K. Kaviyarasu, M. Sivachidambaram, L. John Kennedy, H. A. Al-Lohedan, R. Jothiramalingam, M.A. Munusamy, High performance multifunctional green Co3O4 spinel nanoparticles:
24
ACCEPTED MANUSCRIPT
photodegradation of textile dye effluents, catalytic hydrogenation of nitro-aromatics and antibacterial potential, Photochem. Photobiol. Sci. 16 (2017) 766–778. [19] P.I. Rajan, J.J. Vijaya, S.K. Jesudoss, K. Kaviyarasu, L.J. Kennedy, R. Jothiramalingam, H.A. Al-Lohedan, M-A.
RI PT
Vaali-Mohammed, Green-fuel-mediated synthesis of self-assembled NiO nano-sticks for dual applications photocatalytic activity on Rose Bengal dye and antimicrobial action on bacterial strains, Mater. Res. Express. 4 (2017) 085030.
[20] M. Sivachidambaram, J.J. Vijaya, K. Kaviyarasu, L.J. Kennedy, H.A. Al-Lohedan, R.J. Ramalingam, A novel
SC
synthesis protocol for Co3O4 nanocatalysts and their catalytic applications, RSC Adv.7 (2017) 38861–38870. [21] K. Kaviyarasu, P.P. Murmu, J. Kennedy, F.T. Thema, D. Letsholathebe, L. Kotsedi, M. Maaza, Structural, optical
(2017) 147–152.
M AN U
and magnetic investigation of Gd implanted CeO2 nanocrystals, Nucl. Instrum. Methods Phys. Res. Sect. B. 409
[22] J.H. Oliver, K.P. Kotu, M.C. Jin, Wet oxidation of TNT red water and bacterial toxicity of treated waste, Water Res. 28 (2) (1994) 283–290.
[23] Q. Zhao, Y. Gao, Z. Ye, Reduction of COD in TNT red water through adsorption on macroporous polystyrene resin RS 50B, Vacuum 95 (2013) 71–75.
TE D
[24] K.B.Tan, M.T. Vakili, B.A. Horri, P.E. Poh, A.Z. Abdullah, B. Salamatini, Adsorpsion of dyes by nanomaterial: Recent developments and adsorption mechanisms, Separation and Purification Technology 150 (2015) 229–242. [25] J.-H. Jo, T. Ernest, K.-J. Kim, Treatment of TNT red water by layer melt crystallization, J. Hazard. Mater. 280
EP
(2014) 185–190.
[26] Z.Y. Wang, Z.F. Ye, C.Y. Wang, J.H. Mou, H.C. Jiao, Z. Shen, TNT red water treatment with vacuum distillation
AC C
coupling in immobilized microorganism process, China Environ. Sci. 28 (2008) 883–887. [27] M. Nasrollahzadeh, M. Atarod, S.M. Sajadi, Green synthesis of the Cu/Fe3O4 nanoparticles using Morinda morindoides leaf aqueous extract: A highly efficient magnetically separable catalyst for the reduction of organic
dyes in aqueous medium at room temperature, Appl. Surf. Sci. 364 (2016) 636–644. [28] A. Rostami-Vartooni, M. Alizadeh, M. Bagherzadeh, Green synthesis, characterization and catalytic activity of natural bentonite supported copper nanoparticles for the solvent-free synthesis of 1-substituted 1H-1,2,3,4tetrazoles and reduction of 4-nitrophenol, Beilstein J. Nanotechnol. 6 (2015) 2300–2309.
25
ACCEPTED MANUSCRIPT
[29] M. Olivares-Marin, C. Fernandez-Gonzalez, A. Macias-Garcia, V. Gomez-Serrano, Preparation of activated carbons from cherry stones by activation with potassium hydroxide, Appl. Surf. Sci. 252 (2006) 5980–5983. [30] R.B. Rios, F. Wilton, M. Silva, A. Eurico, B. Torres, D.C.S. Azevedo, L. Celio, J. Cavalcante, Adsorption of
RI PT
methane in activated carbons obtained from coconut shells using H3PO4 chemical activation, Adsorption. 15 (2009) 271–277.
[31] P. Pragya, S. Sripal and Y. Maheshkumar, Preparation and study of properties of activated carbon produced from agricultural and industrial waste shells, Research Journal of Chemical Sciences, 3 (2013) 12–15.
SC
[32] S.K. Papageorgiou, E.P. Favvas, A.A. Sapalidis, G.E. Romanos, F.K. Katsaros, Facile synthesis of carbon supported copper nanoparticles from alginate precursor with controlled metal content and catalytic NO reduction
M AN U
properties, J. Hazard. Mater. 189 (2011) 384–90.
[33] M. Nasrollahzadeh, B. Jaleh, P. Fakhri, A. Zahraei, E, Ghadery, Synthesis and catalytic activity of carbon supported copper nanoparticles for the synthesis of aryl nitriles and 1,2,3-triazoles, RSC Adv. 5 (2015) 2785–2793. [34] B. Kumru, M. Antonietti, B.V.K.J. Schmidt, Enhanced dispersibility of graphitic carbon nitride particles in aqueous and organic media via a one-pot grafting approach, Langmuir 33 (2017) 9897–9906. [35] D.R. Son, A.V. Raghu, K.R. Reddy, H.M Jeong, Compatibility of thermally reduced graphene with polyesters, J.
TE D
Macromol. Sci. Part B: Phys. 55 (2016) 1099–1110.
[36] K.R. Reddy, B.C. Sin, K.S. Ryu, J. Noh, Y. Lee, In situ self-organization of carbon black–polyaniline composites from nanospheres to nanorods: Synthesis, morphology, structure and electrical conductivity, Synthetic Metals. 159
EP
(2009) 1934–1939.
[37] M. Hassan, E. Haque, K.R. Reddy, A. I. Minett, J. Chenc, V.G. Gomes, Edge-enriched graphene quantum dots for
AC C
enhanced photo-luminescence and supercapacitance, Nanoscale. 6 (2014) 11988–11994. [38] Y.R. Lee, S.C. Kim, H. Lee, H.M. Jeong, A.V. Raghu, K.R. Reddy, B.K. Kim, Graphite oxides as effective fire retardants of epoxy resin, Macromol. Res. 19 (2011) 66–71. [39] M. Cakici, R.K. Reddy, F. Alonso-Marroquin, Advanced electrochemical energy storage supercapacitors based on the flexible carbon fiber fabric-coated with uniform coral-like MnO2 structured electrodes, Chemical Eng. J. 309 (2017) 151–158. [40] M.U. Khan, K.R. Reddy, T. Snguanwongchai, E. Haque, V.G. Gomes, Polymer brush synthesis on surface modified carbon nanotubes via in situ emulsion polymerization, Colloid and Polymer Sci. 294 (2016) 1599–1610.
26
ACCEPTED MANUSCRIPT
[41] R. Wu, J.-H. Liu, L. Zhao, X. Zhang, J. Xie, B. Yu, X. Ma, S.-T. Yang, H. Wang, Y. Liu, Hydrothermal preparation of magnetic Fe3O4@C nanoparticles for dye adsorption, Journal of Environmental Chemical Engineering 2 (2014) 907–913.
RI PT
[42] P.T.L. Huong, L.T. Huy, H. Lan, L.H. Thang, T.T. An, N.V. Quy, P.A. Tuan, J. Alonso, M.-H. Phan, A.-T. Le, Magnetic iron oxide-carbon nanocomposites: Impacts of carbon coating on the As(V) adsorption and inductive heating responses, Journal of Alloys and Compounds 739 (2018) 139–148.
[43] K. Cheng, Y.M. Zhou, Z.Y. Sun, H.B. Hu, H. Zhong, X.K. Kong, Q.W. Chen, Synthesis of carbon-coated, porous
SC
and water-dispersive Fe3O4 nanocapsules and their excellent performance for heavy metal removal applications, Dalton Trans. 41 (2012) 5854–5861.
M AN U
[44] F. Chai, K. Li , C. Song, X. Guo, Synthesis of magnetic porous Fe3O4/C/Cu2O composite as an excellent photoFenton catalyst under neutral condition, J. Colloid Interf. Sci. 475 (2016) 119–125. [45] B.R. Cuenya, Synthesis and catalytic properties of metal nanoparticles: Size, shape, support, composition, and oxidation state effects, Thin Solid Films 518 (2010) 3127–3150.
[46] K. Shameli, M.B. Ahmad, M. Zargar, W.M.Z.W. Yunus, N.A. Ibrahim, Fabrication of silver nanoparticles doped in the zeolite framework andantibacterial activity, Int. J. Nanomedicine 6 (2011) 331–341.
TE D
[47] Y. Ioni, E. Buslaeva, S. Gubin, Synthesis of graphene with noble metals nanoparticles on its surface, Materials Today: Proceedings 3S ( 2016 ) S209 –S213.
[48] M. Nasrollahzadeh, M. Maham, A. Rostami-Vartooni, M. Bagherzadeh, S.M. Sajadi, Barberry fruit extract
EP
assisted in situ green synthesis of Cu nanoparticles supported on a reduced graphene oxide–Fe3O4 nanocomposite as a magnetically separable and reusable catalyst for the O-arylation of phenols with aryl halides under ligand-free
AC C
conditions, RSC Adv. 5 (2015) 64769–64780. [49] K.R. Reddy, B.C. Sin, C.H. Yoo, W. Park, K.S. Ryu, J.S. Lee, D. Sohn, Y. Lee, A new one-step synthesis method for coating multi-walled carbon nanotubes with cuprous oxide nanoparticles, Scripta Materialia. 58 (2008) 1010– 1013.
[50] K.R. Reddy, K.P. Lee, A.I. Gopalan, M.S. Kim, A.M. Showkat, Y.C. Nho, Synthesis of metal (Fe or Pd)/alloy (Fe–Pd)‐nanoparticles‐embedded multiwall carbon nanotube/sulfonated polyaniline composites by γ irradiation, J. Polymer Sci. Part A: Polymer Chem. 44 (2006) 3355–3364.
27
ACCEPTED MANUSCRIPT
[51] K.R. Reddy, K. Nakata, T. Ochiai, T. Murakami, D.A. Tryk, A. Fujishima, Facile Fabrication and Photocatalytic Application of Ag Nanoparticles-TiO2 Nanofiber Composites, Nanosci. and Nanotech. 11 (2011) 3692–3695. [52] K. Kaviyarasu, X. Fuku, G.T. Mola, E. Manikandan, J. Kennedy, M. Maaza, Photoluminescence of well-aligned
RI PT
ZnO doped CeO2 nanoplatelets by a solvothermal route, Mater. Lett. 183 (2016) 351–354. [53] A. Rostami-Vartooni, M. Nasrollahzadeh, M. Alizadeh, Green synthesis of seashell supported silver nanoparticles using Bunium persicum seeds extract: Application of the particles for catalytic reduction of organic dyes, J. Colloid Interf. Sci. 470 (2016) 268–275.
SC
[54] A. Rostami-Vartooni, M. Nasrollahzadeh, M. Alizadeh, Green synthesis of perlite supported silver nanoparticles using Hamamelis virginiana leaf extract and investigation of its catalytic activity for the reduction of 4-nitrophenol
M AN U
and Congo red, Journal of Alloys and Compounds 680 (2016) 309–314.
[55] M. Bordbara, N. Negahdara, M. Nasrollahzadeh, Melissa Officinalis L. leaf extract assisted green synthesis of CuO/ZnO nanocomposite for the reduction of 4-nitrophenol and Rhodamine B, Separation and Purification Technology 191 (2018) 295–300.
[56] J. M. DiTomaso, E. A. Healy, Weeds of California and Other Western States, Vol. 1, University of California, Agriculture and Natural Resources, UCANR Publications, 2 (2007).
TE D
[57] B. Khodadadi, M. Bordbar, M. Nasrollahzadeh, Green synthesis of Pd nanoparticles at Apricot kernel shell substrate using Salvia hydrangea extract: Catalytic activity for reduction of organic dyes, J. Colloid Interf. Sci. 490 (2017) 1–10.
EP
[58] E.Y. Choi, T.H. Han, J.E. Hong, J. Kim, S.H. Lee, H.W. Kim, S.O. Kim, Noncovalent functionalization of graphene with end-functional polymers, J. Mater. Chem. 20 (2010) 1907–1912.
AC C
[59] C. Song, S.-J. Park, S. Kim, Effect of modification by polydopamine and polymeric carbon nitride on methanol oxidation ability of Pt catalysts-supported on reduced graphene oxide, Journal of The Electrochemical Society 163 (7) (2016) F668–F676.
[60] E. Karaoglu, A. Baykal, M. Senel, H. Sozeri, M.S. Toprak, Synthesis and characterization of Piperidine-4carboxylic acid functionalized Fe3O4 nanoparticles as a magnetic catalyst for Knoevenagel reaction, Materials Research Bulletin 47 (2012) 2480–2486. [61] Y.-h. Wana, X.-q. Shi, H. Xia, J. Xie, Synthesis and characterization of carbon-coated Fe3O4 nanoflakes as anode material for lithium-ion batteries, Materials Research Bulletin 48 (2013) 4791–4796.
28
ACCEPTED MANUSCRIPT
[62] C.H.A. Wong, A. Ambrosi, M. Pumera, Thermally reduced graphenes exhibiting a close relationship to amorphous Carbon, Nanoscale 4 (2012) 4972–4977. [63] W.N.R.W. Isahak, M.W.M. Hisham, M.A. Yarmo, Highly porous carbon materials from biomass by chemical and
RI PT
carbonization method: A Comparison Study, Journal of Chemistry, 2013 (2013) 1–6. [64] H. Gu, D. Cao, J. Wang, X. Lu, Z. Li, C. Niu, H. Wang, Micro-CaCO3 conformal template synthesis of hierarchical porous carbon bricks: As a host for SnO2 nanoparticles with superior lithium storage performance, Materials Today Energy 4 (2017) 75–80.
agent, International Nano Letters 3 (2013) 23–28.
SC
[65] F. Ahangaran1, A. Hassanzadeh, S. Nouri, Surface modification of Fe3O4@SiO2 microsphere by silane coupling
M AN U
[66] Y.-F. Zhang, L.-G. Qiu, Y.-P. Yuan, Y.-J. Zhu, X. Jiang, J.-D. Xiao, Magnetic Fe3O4@C/Cu and Fe3O4@CuO core–shell compositesconstructed from MOF-based materials and their photocatalytic properties under visible light, Appl. Catal. B: Environ. 144 (2014) 863–869.
[67] D. Shah, H. Kaur, Resin-trapped gold nanoparticles: An efficient catalyst for reduction of nitro compounds and Suzuki-Miyaura coupling, J. Mol. Catal. A Chem. 381 (2014) 70–76.
[68] R.J. Kalbasi, A.A. Nourbakhsh, F. Babaknezhad, Synthesis and characterization of Ni nanoparticles-
955–960.
TE D
polyvinylamine/SBA-15 catalyst for simple reduction of aromatic nitro compounds, Catal. Commun. 12 (2011)
[69] M. Atarod, M. Nasrollahzadeh, S.M. Sajadi, Euphorbia heterophylla leaf extract mediated green synthesis of
EP
Ag/TiO2 nanocomposite and investigation of its excellent catalytic activity for reduction of variety of dyes in
AC C
water, J. Colloid Interf. Sci. 462 (2016) 272–279.
29
ACCEPTED MANUSCRIPT
Highlights: Preparation of porous carbon via carbonization of red water as a carbon source. Conversion of a toxic waste product to a stable support.
RI PT
Synthesis of C/Fe3O4 nanocomposite by co-precipitation reaction. Immobolization of Ag NPs on the surface of carbon nanocomposites using Caesalpinia gilliesii flower extract.
AC C
EP
TE D
M AN U
SC
Reduction of methyl orange and 4-nitrophenol at room temperature.
S0254-0584(18)30691-6
DOI:
10.1016/j.matchemphys.2018.08.026
Reference:
MAC 20869
To appear in:
Materials Chemistry and Physics
Received Date: 4 February 2018 Revised Date:
15 June 2018
Accepted Date: 10 August 2018
Please cite this article as: A. Rostami-Vartooni, A. Moradi-Saadatmand, M. Mahdavi, Catalytic reduction of organic pollutants using biosynthesized of Ag/C/Fe3O4 nanocomposite by red water and Caesalpinia gilliesii flower extract, Materials Chemistry and Physics (2018), doi: 10.1016/ j.matchemphys.2018.08.026. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
AC C
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
ACCEPTED MANUSCRIPT
Catalytic reduction of organic pollutants using biosynthesized of Ag/C/Fe3O4 nanocomposite by red water and Caesalpinia gilliesii flower extract Akbar Rostami-Vartooni,*,a Abolfazl Moradi-Saadatmanda and Mohammad Mahdavib
b
Department of Chemistry, Faculty of Science, University of Qom, Qom 3716146611, Iran
RI PT
a
Department of Chemistry, Malek-ashtar University of Technology, Shahin-shahr P.O. Box 83145/115, Islamic Republic of Iran
Abstract
SC
In this study, a facile synthesis of porous carbon and its Fe3O4 nanocomposite were synthesized via carbonization of red water and co-precipitation reaction, respectively. Then, an aqueous extract of
M AN U
Caesalpinia gilliesii flower was used for reduction of the Ag+ ions to Ag nanoparticles (Ag NPs) and their stabilization on the surface of carbon supports. The formation of the Ag NPs occurs at room temperature within a few minutes. The synthesized porous carbon and its nanocomposites were characterized by FTIR, Raman, XRD, FESEM, EDS, elemental mapping, TEM, BET, and VSM
TE D
techniques. According to the FESEM and TEM images, the average size of the Ag NPs on the surface of porous carbon and C/Fe3O4 was below 35 nm. The magnetically recoverable Ag/Fe3O4/C nanocomposite demonstrated favorable catalytic activity on the reduction of methyl orange (MO) and
AC C
in its activity.
EP
4-nitrophenol (4-NP). In addition, the catalyst can be reused at least 3 times without considerable loss
Keywords: Green synthesis; Ag/Fe3O4/C nanocomposite; Red water; C. gilliesii; Catalytic Reduction
*
Corresponding authors: A. Rostami-Vartooni (E-mail: [email protected] and [email protected]).
1
ACCEPTED MANUSCRIPT
1. Introduction In one of the steps of toluene nitration process, the aqueous Na2SO3 solution was used to remove
RI PT
unwanted products and less stable isomers. The sellite waste solution in this purification process is known as red water which is a toxic waste product. The real composition of pollutants in red water is unknown. This wastewater contains aromatic compounds such as 1,3,5-trinitrobenzene, mono, di and 2-methyl-3,5-dinitrophenol,
5-methyl-2-nitrophenol,
3-methyl-2-nitro-phenol,
SC
trinitrotoluene,
unidentified S-containing compounds, etc [1-3]. The removal of these pollutants and other
M AN U
environmental contaminants such as toxic and carcinogenic dyes from wastewaters is one of the problems of human society [4-10]. In this field, advanced oxidation process (AOPs) [11-21], wet oxidation [22], catalytic adsorption [23,24], ice crystallization [25], vacuum distillation [26] and reduction process with heterogeneous catalysts and NaBH4 [27,28] can be used as efficient methods for the removal of such pollutants.
TE D
In recent years, carbon materials have obtained from carbonization or pyrolysis of agricultural waste products followed by chemical activation using dehydrating agents (i.e. KOH, H3PO4, H2SO4, ZnCl2) or physical activation in the presence of air, steam or carbon dioxide as oxidizing gases at
EP
temperatures below 700 °C [29-31]. Carbon structures have been used in various applications such as
AC C
catalyst supports and adsorbents for gases or metal species due to singular structure, appropriate electronic conductivity and improved accessibility of compounds to their active sites [32-40]. The Fe3O4/C composites have been employed as absorbents for organic dyes and heavy metal ions removal applications [41-43]. An important property of these materials is easy separation from a reaction mixture using an external magnetic force. Li et al. [44] prepared porous Fe3O4/C and Fe3O4/C/Cu2O composites by calcining iron tartrate precursor and precipitation-reduction methods,
2
ACCEPTED MANUSCRIPT
respectively. These composites exhibited photo-Fenton catalytic performance for removal of dye (methylene blue) under visible light irradiation. Distributing of metal nanoparticles (MNPs) over the surface of magnetic materials and other
RI PT
inorganic supports such as metal oxides [45], zeolites [46], carbon structures [47-52], seashell [53] and perlite [54] lead to lower agglomeration, more reactivity, stability and simple separation of catalyst. Nowadays, plants and their extractives as nontoxic reducing and stabilizing agents are important in
SC
the synthesis of the MNPs [53-55]. This ecofriendly biosynthesis approach is simple and it does not require chemical materials, time-consuming and harsh working conditions. The water soluble phenolic
M AN U
compounds, terpenoids, and alkaloids in the plants extract not only are responsible for the reduction of metal ions into metals, but also act as capping agents in the synthesis of nanoparticles with a welldefined size and morphology.
Caesalpinia gilliesii (bird of paradise) as a shrub in the legume family has health benefits for curing
TE D
cough, sores, and fever, but the seeds and the green seed pods of this plant are toxic which causes vomiting and other abdominal symptoms [56].
Here we report the preparation of porous carbon via carbonization of red water as a low cost and
EP
easy process. Also, the biosynthesized of Ag/C/Fe3O4 nanocomposite was synthesized using C. gilliesii extract. The catalytic efficiency of the Ag/C/Fe3O4 nanocomposite was evaluated through reduction of
AC C
methyl orange (MO), and 4-nitrophenol (4-NP).
2. Experimental
2.1. Chemical substances and instruments All chemical substances were obtained from Merck KGaA, Darmstadt, Germany. The red water soloution was obtanied from an industrial unit of 2,4,6-trinitrotluene (TNT) production. The flowers of C. gilliesii were collected from Vartoon village (Isfahan, Iran). UV-Vis spectral analysis was carried 3
ACCEPTED MANUSCRIPT
out on a double‐beam spectrophotometer (Hitachi, U‐2900). Fourier transform infrared (FTIR) spectra were recorded on Nicolet 370 FT/IR spectrometer (Thermo Nicolet, USA) in the range of wavenumbers 3900-400 cm-1. Raman spectra were obtained using a Takram P50C0R10 spectrometer
RI PT
with a 532 nm Nd: YAG laser. X-ray powder diffraction (XRD) measurements were performed using an XRD PHILIPS powder diffractometer type PW1730 goniometer employing Cu Ka radiation (λ = 1.5418 Å) in the 2θ range from 10 to 90˚. Field emission scanning electron microscope (FESEM) and
SC
elemental mapping images were obtained on Cam scan MV2300 equipped with an energy dispersive X-ray spectroscopy (EDX). TEM images of nanocomposite were obtained on Philips-EM-208S
M AN U
transmission electron microscope operating at 100 kV. Vibrating sample magnetometer (VSM) measurement was performed by using a SQUID magnetometer at room temperature (Quantum Design MPMS XL). The Brunauer-Emmett-Teller (BET) surface area and pore volume of the nanocomposites were measured by a Bell Japan BELSORP mini II apparatus.
TE D
2.2. Preparation of the C. gilliesii flower extract
10.0 g of dried flowers of C. gilliesii were added to 100.0 mL of distilled water and then heated at 70 °C for 20 min. Finally, the aqueous extract was filtered by applying a Whatman No.1 filter paper to
EP
obtain a clear solution of extract.
2.3. Preparation of the porous carbon
AC C
The porous carbon was synthesized from red water as a cheap carbon source. The red water from explosive industries is a byproudt of 2,4,6-Trinitrotoluene (TNT) purification process. The red water has 5.3 w.t% organic materials such as 2,4-dinitrotoluene-3-sulfonate, 2,4-dinitrotoluene-5-sulfonate and other derivatives. About 2000 ml of red water was dried at 90 ºC in an oven under good ventilation of a hood, and then was burned in a tubular furnace at about 450 ºC. The volatiled gas and decomposed organic materials were absorbed by a 10 wt% NaOH solution. The red water was dried at 90 ºC in an
4
ACCEPTED MANUSCRIPT
oven and then was burned in a furnace at about 450 ºC. The resulted porous carbon was washed with dilut HCl solution and then several times by distilled water. 2.4. Preparation of the C/Fe3O4 nanocomposite
RI PT
At first, the prepared porous carbon in the previous section (4.0 g) was mixed with 10.0 mL of FeCl3·6H2O solution (2.0 M) and 10.0 mL of FeCl2·6H2O solution (1.0 M). For the preparation of Fe3O4 nanoparticles by a co-precipitation method, the mole ratio of Fe(III)/Fe(II) was fixed at 2. Then,
SC
80.0 mL of 1.0 M NaOH solution was added dropwise to the mixture under a nitrogen atmosphere and continuous stirring to precipitate the Fe3O4 nanoparticles on porous carbon. The resulted C/Fe3O4
M AN U
nanocomposite was filtered and washed with hot distilled water for several times, and dried in an oven at 80 ºC for 1 h.
2.5. Preparation of the Ag NPs/C nanocomposite
To a dispersion containing 3.0 g porous carbon and 50.0 mL of the prepared extract, 15.0 mL of
TE D
AgNO3 solution (0.2 M) was added. This mixture was stirred at 70 °C for 10 min under continuous stirring. Finally, the synthesized Ag NPs in the presence of extract was immobilized on the surface of porous carbon as a support and prepared nanocomposite was filtered, washed with distilled water and
EP
then dried.
2.6. Preparation of the Ag/Fe3O4/C nanocomposite
AC C
3.0 g Fe3O4/C was dispersed in the solution of the prepared extract (50.0 mL) under stirring. Then, 15.0 mL of AgNO3 solution (0.2 M) was added to this mixture and stirred at 70 °C for 10 min under continuous stirring. Finally, the produced Ag/Fe3O4/C was filtered and washed with distilled water. 2.7. Reduction of the MO using porous carbon and its nanocomposites To a mixture containing 30 mL of MO (10 ppm or 3 × 10-5 M) and 30.0 mL aqueous NaBH4 solution (5.3 × 10-3 or 2.5 × 10-3 M), 3.0 mg (or 6.0 mg) of the porous carbon (or its nanocomposites)
5
ACCEPTED MANUSCRIPT
was added and stirred at room temperature. The reduction process of MO was monitored by recording the UV-Vis spectral analysis at certain intervals. 2.8. Reduction of the 4-NP by porous carbon and its nanocomposites
RI PT
To a dispersion containing 4-NP aqueous solution (2.5 × 10-3 M, 30 mL), 3.0 mg (or 6.0 mg) of the porous carbon (or its nanocomposites) was added. Finally, 30 mL of 44 × 10-3 M (or 88 × 10-3 M) NaBH4 was added and this mixture was then stirred at room temperature. 1.0 mL of 4-NP solution was
SC
diluted to 25.0 mL with distilled water for recording of the UV-Vis absorption peak at certain intervals.
M AN U
3. Results and discussion
The aim of this work was catalytic reduction of organic pollutants in the presence of biosynthesized Ag/C/Fe3O4 nanocomposite. For the preparation of porous carbon, the red water as a toxic waste product in toluene nitration process was used in the carbonization process. The co-precipitation method
TE D
was carried out for the synthesis of C/Fe3O4 nanocomposite. The C. gilliesii flower extract was used for reduction of silver ions to silver nanoparticles on the surface of nanocomposites. The prepared catalysts were characterized using FTIR, Raman, XRD, FESEM, EDS, elemental mapping, TEM, BET, and
EP
VSM.
3.1. Characterization of the C. gilliesii flower extract
AC C
The presence of phenolics constituents as antioxidant agents in the flower of C. gilliesii can be confirmed using FTIR and UV-Vis spectroscopic analyses. The observed peaks in the FTIR spectrum of C. gilliesii (Fig. 1) at 3426, 2925, 1650, 1458 and 1068-1238 cm-1 are concerned with hydroxyl groups, C–H, C=O, C=C aromatic rings and C–OH vibrations, respectively [54-56]. Fig. 2 shows a maximum peak at 270 nm in the UV-Vis spectrum of C. gilliesii flower extract which is assigned to π
6
ACCEPTED MANUSCRIPT
→ π* or n → π* transitions localized within the phenolics rings of organic compounds in aqueous
M AN U
SC
RI PT
extract [57].
AC C
EP
TE D
Fig. 1. FTIR spectrum of the C. gilliesii flower.
Fig. 2. UV-Vis spectrum of the C. gilliesii flower extract.
3.2. Characterization of the porous C and its nanocomposites FTIR spectra of carbon and its nanocomposites are given in Fig. 3. The absorption modes at about 1620 and 1250 cm−1 are related to the stretching vibrations of C=C and C–O bonds, respectively
7
ACCEPTED MANUSCRIPT
[58,59]. The broad absorption bands observed at 3426-3445 cm-1 correspond to the stretching vibration of O–H groups on the surface of carbon nanocomposites [33]. The new bands at 450-680 cm-1 in the FTIR spectra of Fe3O4 nanocomposites (Figs. 3c and 3d) are assigned to the Fe–O vibrations [60]. The
RI PT
functional groups in the FTIR spectra of carbon supports have not changed before and after loading of Ag NPs. Raman spectra of the Ag NPs/C and Ag/C/Fe3O4 are shown in Fig. 4. In the Raman spectrum of Ag NPs/C (Fig. 4a), the bands at 1561 cm−1 (i.e., G band) and 1366 cm-1 (also called D band) are
SC
related to the sp2-hybridized carbon bonds and defects involved in the sp2 lattice structure, respectively [61,62]. A broad 2D-signal was also observed at 2830 cm-1. The G and D bands in the Raman spectrum
AC C
EP
TE D
M AN U
of Ag/C/Fe3O4 (Fig. 4b) were observed at 1366 and 1556 cm−1, respectively.
Fig. 3. FTIR spectra of the porous C (a), Ag NPs/C (b), C/Fe3O4 (c) and Ag/C/Fe3O4 (d).
8
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 4. Raman spectra of Ag NPs/C (a) and Ag/C/Fe3O4 (b).
Fig. 5 shows XRD patterns of carbon support and its nanocomposites. Fig. 5a displays the XRD pattern of porous C with characteristic peaks at 2θ=20–30º and 40–50º which can be attributed to the (002) and (100) planes indicating graphite structures [63,64]. The new reflections were appeared at 2θ
TE D
= 38°, 44.2°, 64.4°and 77.3° in the XRD pattern of Ag/C (Fig. 5b). As it has been shown in previous works, these peaks can be attributed to the (111), (200), (220) and (311) reflections of face centered
EP
cubic (fcc) of the Ag NPs [53,54]. Figs. 5c and 5d show the XRD patterns of Fe3O4/C and Ag/Fe3O4/C nanocomposites, respectively. The peaks at about 2θ = 30.5°, 35.8°, 43.4°, 53.9°, 57.3°, 63.1 and 74.1°
AC C
were indexed for the (220), (311), (400), (422), (511), (440) and (533) planes of cubic spinel phase of Fe3O4 [65,66]. The diffraction peaks at 2θ = 38.3°, 44.5°, 64.6° and 77.6° were attributed to the fcc structure of Ag NPs on the Fe3O4/C support.
9
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 5. XRD diffractogram of the porous C (a), Ag NPs/C (b), C/Fe3O4 (c) and Ag/C/Fe3O4 (d).
The morphological characterizations of the Ag NPs/C and Ag/C/Fe3O4 nanocomposites were carried out by FESEM analysis. As seen in FESEM images (Figs. 6 and 7), spherical Ag NPs were produced
TE D
using the flower extract of C. gilliesii on the surface of nanocomposites. The average size of these nanoparticles on the surface of the Ag NPs/C and Ag/Fe3O4/C was at about 35 and 20 nm, respectively. The EDS spectra of the Ag NPs/C and Ag/C/Fe3O4 nanocomposites (Fig. 8) show the present of C, Ag,
EP
N, S, O or Fe in these nanocomposites. Also, distribution of Ag and Fe3O4 NPs in the Ag/C/Fe3O4 nanocomposite are shown in its elemental mapping images (Fig. 9). TEM images of the Ag/C/Fe3O4
AC C
nanocomposite (Fig. 10) show the size of spherical Fe3O4 NPs and Ag NPs were below 30 nm.
10
AC C
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 6. FESEM images of the Ag NPs/C nanocomposite.
11
AC C
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 7. FESEM images of the Ag/C/Fe3O4 nanocomposite.
12
AC C
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 8. EDS spectra of the Ag NPs/C (a) and Ag/C/Fe3O4 nanocomposites (b).
13
EP
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
AC C
Fig. 9. Elemental mapping of the Ag/C/Fe3O4 nanocomposite.
14
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 10. TEM images of the Ag/C/Fe3O4 nanocomposite.
Fig. 11 shows the hysteresis loop of the Ag/Fe3O4/C nanocomposite in the magnetic field intensity
EP
(H) range of –8.5 to 8.5 kOe. The saturation magnetization (Ms) reaches about 17 emu/g at saturation point. This value is enough for convenient separation of the nanocomposite by an external magnetic
AC C
force in aqueous reactions.
15
SC
RI PT
ACCEPTED MANUSCRIPT
M AN U
Fig. 11. Magnetization curve of the Ag/Fe3O4/C nanocomposite.
According to the N2 adsorption–desorption isotherm and BJH pore size distribution plot (Fig. 12), the surface area, pore volume and mean pore diameter of the prepared porous C are 42.31 m2g-1, 0.31 cm3g-1 and 29.23 nm, respectively. After immobilization of the Ag NPs on the C support, the surface area and pore volume were decreased to 22.08 m2g-1 and 0.19 cm3g-1, respectively, while mean pore
TE D
diameter was increased to 34.34 nm. The surface area, pore volume and mean pore diameter of Ag/Fe3O4/C nanocomposite were 28.58 m2g-1, 0.18 cm3g-1 and 25.26 nm, respectively. The
AC C
these changes.
EP
immobilization of Ag NPs and entering of nanosized Fe3O4 into the cavities of porous carbon lead to
16
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
EP
Fig. 12. Nitrogen adsorption and desorption isotherms for the Ag NPs/C (a) Ag/Fe3O4/C (b); Barrett-Joyner-Halenda (BJH) pore size distribution plot of the Ag NPs/C (c) and Ag/Fe3O4/C (d).
AC C
3.3. Catalytic activity investigation of the carbon nanocomposites for the reduction of dyes The prepared carbon nanocomposites were used in the catalytic reduction of MO and 4-NP by NaBH4. As seen in Fig. 13, the reduction of MO and 4-NP in the presence of Ag/C/Fe3O4 nanocomposite were monitored by applying UV-Vis spectroscopic analysis at λmax of 493 and 400, respectively. As can be seen in this figure, the red and deep yellow colors of dye solutions became colorless at the end of the reduction process. Also, the reduction of MO (3 × 10-5 M) and 4-NP (2.5 ×
17
ACCEPTED MANUSCRIPT
10-5 M) using 6.0 mg of the Ag/C/Fe3O4 nanocomposite were completed within 3.5 and 7 min,
AC C
EP
TE D
M AN U
SC
RI PT
respectively.
18
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
Fig. 13. UV-Vis spectra of catalytic reduction of MO (a) and 4-NP (b) at several intervals.
TE D
The reaction times of the reduction process for selected dyes in the presence of porous carbon and its nanocomposites are summarized in Tables 1 and 2. The shorter reduction times are resulted from
EP
applying higher amounts of catalysts and NaBH4. In the absence of NaBH4, no color changes were observed in 2 h for selected dyes. The as-produced Ag NPs nanocomposites are much more reactive
AC C
catalysts than the unmodified nanocomposites. It seems these metal nanoparticles facilitate electron transfer from BH4– to 4-NP. Fe3O4 NPs in the C/Fe3O4 and Ag/C/Fe3O4 nanocomposites facilitate the reduction process and separation of these catalysts from the reaction medium. From the results in Tables 1 and 2, it could be said that the efficiency of Ag/C/Fe3O4 nanocomposite in the reduction reactions of MO and 4-NP is comparable to the other synthesized carbon materials in this work and previously reported catalysts [67-69]. Table 1. Reaction time for the reduction of 10.0 ppm MO using NaBH4 in the presence of different catalysts.
19
ACCEPTED MANUSCRIPT
Catalyst (mg) C (3) Ag NPs/C (3) Fe3O4/C (3) Ag/Fe3O4/C (3) Ag/Fe3O4/C (3) Ag/Fe3O4/C (6) Ag/Fe3O4/C (3)
Time (min) 65 50 13.5 35 120a 4.5 3.5 6
RI PT
[NaBH4] (M) 5.3 × 10-3 5.3 × 10-3 5.3 × 10-3 5.3 × 10-3 5.3 × 10-3 5.3 × 10-3 2.5 × 10-3 a No reaction.
3.5. Catalyst recyclability
Time (min) 100 70 16.5 50 120a 12 9.5 7
M AN U
Catalyst (mg) C (3) Ag NPs/C (3) Fe3O4/C (3) Ag/Fe3O4/C (3) Ag/Fe3O4/C (3) Ag/Fe3O4/C (6) Ag/Fe3O4/C (6)
TE D
[NaBH4] (M) 44 × 10-3 44 × 10-3 44 × 10-3 44 × 10-3 44 × 10-3 44 × 10-3 88 × 10-3 a No reaction.
SC
Table 2. Reaction time for the reduction of 4-NP (2.5 × 10-3 M) using different amounts of catalysts and NaBH4.
When the reduction reaction of the MO dye was completed, the Ag/C/Fe3O4 catalyst was quickly
EP
removed from the reaction mixture by an external magnetic field and its recyclability was also investigated. After three catalytic runs, the completion times for the reduction process of the MO using
AC C
recovered catalyst does not change significantly which confirms the stability of nanocomposite and its appropriate recyclability. Fig. 14 shows the FESEM images and EDX spectrum of the recycled Ag/C/Fe3O4 catalyst. Also, the elemental mapping images of the recycled catalyst are seen in Fig. 15. The obtained results from these analyses show the morphology and the amount of the Ag NPs on the catalyst surface are approximately unchanged even after three catalytic runs.
20
ACCEPTED MANUSCRIPT
b
M AN U
SC
RI PT
a
AC C
EP
TE D
c
Fig. 14. FESEM images (a-c) and EDS spectrum (d) of recycled Ag/C/Fe3O4 nanocomposite.
21
TE D
M AN U
SC
RI PT
ACCEPTED MANUSCRIPT
AC C
4. Conclusions
EP
Fig. 15. Elemental mapping of recycled Ag/C/Fe3O4 nanocomposite.
The facile preparation of porous carbon and its Fe3O4 nanocomposite were performed by carbonization of red water and co-precipitation technique, respectively. Then, the flower extract of the C. gilliesii was used for reduction of Ag+ ions and stabilization of the preparead Ag NPs on the surface of the porous carbon and C/Fe3O4 nanocomposite. The as-prepared carbon nanocomposites were characterized by different methods and showed good activity in the reduction of the MO and 4-NP as
22
ACCEPTED MANUSCRIPT
toxic organic dyes. In this work, a toxic waste product in the industrial unit of 2,4,6-trinitrotluene (TNT) production was converted to a stable support.
RI PT
Acknowledgements
support of this work. References
SC
The authors acknowledge the University of Qom and Malek-Ashtar University of Technology for the
[1] J.T. Walsh, R.C. Shalk, C. Merritt, Application of liquid chromatography to pollution abatement studies of
M AN U
munitions wastes, Anal. Chem. 45 (1973) 1215–1220.
[2] Q. Zhao, Z. Ye, M. Zhang, Treatment of 2,4,6-trinitrotoluene (TNT) red water by vacuum distillation, Chemosphere 80 (2010) 947–950.
[3] S.J. Lee, I.H. Cho, H.K. Lee, K.D. Zoh, A study on the treatment of high explosives (TNT, RDX, HMX) using TiO2 photocatalyst, J. KSEE 24 (6) (2002) 1071–1080.
TE D
[4] K. Im, D. Nguyen, S. Kim, H.J. Kong, Y. Kim, C.S. Park, O.S. Kwon, H. Yoon, Graphene-embedded hydrogel nanofibers for detection and removal of aqueous-phase dyes, ACS Appl. Mater. Interfaces 9 (2017) 10768–10776. [5] K.R. Reddy, K.V. Karthik, S.B. Prasad, S.K. Soni, H.M. Jeong, A.V. Raghu, Enhanced photocatalytic activity of nanostructured titanium dioxide/polyaniline hybrid photocatalysts, Polyhedron. 120 (2016) 169–174.
EP
[6] K. Kasinathan, J. Kennedy, M. Elayaperumal, M. Henini, M. Malik, Photodegradation of organic pollutants RhB dye using UV simulated sunlight on ceria based TiO2 nanomaterials for antibacterial applications, Sci. Rep. 6
AC C
(2016) 38064.
[7] K. Kaviyarasu, C.M. Magdalane, K. Kanimozhi, J. Kennedy, B. Siddhardha, E.S. Reddy, N.K. Rotte, C.S. Sharma, F.T. Thema, D. Letsholathebe, G.T. Mola, M. Maaza, Elucidation of photocatalysis, photoluminescence and antibacterial studies of ZnO thin films by spin coating method, J. Photochem. Photobiol. B: Biol. 173 (2017) 466– 475. [8] K. Kaviyarasu, E. Manikandan, Z.Y. Nuru, M. Maaza, Investigation on the structural properties of CeO2 nanofibers via CTAB surfactant, Mater. Lett. 160 (2015) 61–63.
23
ACCEPTED MANUSCRIPT
[9] K. Kaviyarasu, E. Manikandan, M. Maaza, Synthesis of CdS flower-like hierarchical microspheres as electrode material for electrochemical performance, J. Alloys Compd. 648 (2015) 559–563. [10] C.M. Magdalane, K. Kaviyarasu, J.J. Vijaya, C. Jayakumar, M. Maaza, B. Jeyaraj, Photocatalytic degradation
RI PT
effect of malachite green and catalytic hydrogenation by UV–illuminated CeO2/CdO multilayered nanoplatelet arrays: Investigation of antifungal and antimicrobial activities, J. Photochem. Photobiol. B: Biol. 169 (2017) 110– 123.
[11] K. Kaviyarasu, A. Ayeshamariam, E. Manikandan, J. Kennedy, R. Ladchumananandasivam, U.U. Gomes, M.
SC
Jayachandran, M. Maaza, Solution processing of CuSe quantum dots: Photocatalytic activity under RhB for UV and visible-light solar irradiation, Mater. Sci. Eng. B. 210 (2016) 1–9.
M AN U
[12] C.M. Magdalane, K.K. aviyarasu, J.J. Vijaya, B. Siddhardha, B. Jeyaraj, Photocatalytic activity of binary metal oxide nanocomposites of CeO2/CdO nanospheres: Investigation of optical and antimicrobial activity, J. Photochem. Photobiol. B: Biol. 163 (2016) 77–86.
[13] K. Kaviyarasu, A. Mariappan, K. Neyvasagam, A. Ayeshamariam, P. Pandi, R. Rajeshwara Palanichamy, C. Gopinathan, G.T. Mola, M. Maaza, Photocatalytic performance and antimicrobial activities of HAp-TiO2 nanocomposite thin films by sol-gel method, Surf. Interfaces 6 (2017) 247–255.
TE D
[14] V. Mirkhani, S. Tangestaninejad, M. Moghadam, M.H. Habibi, A. Rostami-Vartooni, Photocatalytic degradation of azo dyes catalyzed by Ag doped TiO2 photocatalyst, J. Iran. Chem. Soc. 6 (2009) 578–587. [15] C.M. Magdalane, K. Kaviyarasu, J.J. Vijaya, B. Siddhardha, B. Jeyaraj, Facile synthesis of heterostructured
EP
cerium oxide/yttrium oxide nanocomposite in UV light induced photocatalytic degradation and catalytic reduction: Synergistic effect of antimicrobial studies, J. Photochem. Photobiol. B: Biol. 173 (2017) 23–34.
AC C
[16] C.M. Magdalane, K. Kaviyarasu, J.J. Vijaya, B. Siddhardha, B. Jeyaraj, J. Kennedy, M. Maaza, Evaluation on the heterostructured CeO2/Y2O3 binary metal oxide nanocomposites for UV/Vis light induced photocatalytic degradation of Rhodamine - B dye for textile engineering application, J. Alloys Compd. 727 (2017) 1324–1337. [17] X. Fuku, N. Matinise, M. Masikini, K. Kasinathan, M. Maaza, An electrochemically active green synthesized polycrystalline NiO/MgO catalyst: Use in photo-catalytic applications, Mater. Res. Bull. 97 (2018) 457–465. [18] S.K. Jesudoss, J.J. Vijaya, P.I. Rajan, K. Kaviyarasu, M. Sivachidambaram, L. John Kennedy, H. A. Al-Lohedan, R. Jothiramalingam, M.A. Munusamy, High performance multifunctional green Co3O4 spinel nanoparticles:
24
ACCEPTED MANUSCRIPT
photodegradation of textile dye effluents, catalytic hydrogenation of nitro-aromatics and antibacterial potential, Photochem. Photobiol. Sci. 16 (2017) 766–778. [19] P.I. Rajan, J.J. Vijaya, S.K. Jesudoss, K. Kaviyarasu, L.J. Kennedy, R. Jothiramalingam, H.A. Al-Lohedan, M-A.
RI PT
Vaali-Mohammed, Green-fuel-mediated synthesis of self-assembled NiO nano-sticks for dual applications photocatalytic activity on Rose Bengal dye and antimicrobial action on bacterial strains, Mater. Res. Express. 4 (2017) 085030.
[20] M. Sivachidambaram, J.J. Vijaya, K. Kaviyarasu, L.J. Kennedy, H.A. Al-Lohedan, R.J. Ramalingam, A novel
SC
synthesis protocol for Co3O4 nanocatalysts and their catalytic applications, RSC Adv.7 (2017) 38861–38870. [21] K. Kaviyarasu, P.P. Murmu, J. Kennedy, F.T. Thema, D. Letsholathebe, L. Kotsedi, M. Maaza, Structural, optical
(2017) 147–152.
M AN U
and magnetic investigation of Gd implanted CeO2 nanocrystals, Nucl. Instrum. Methods Phys. Res. Sect. B. 409
[22] J.H. Oliver, K.P. Kotu, M.C. Jin, Wet oxidation of TNT red water and bacterial toxicity of treated waste, Water Res. 28 (2) (1994) 283–290.
[23] Q. Zhao, Y. Gao, Z. Ye, Reduction of COD in TNT red water through adsorption on macroporous polystyrene resin RS 50B, Vacuum 95 (2013) 71–75.
TE D
[24] K.B.Tan, M.T. Vakili, B.A. Horri, P.E. Poh, A.Z. Abdullah, B. Salamatini, Adsorpsion of dyes by nanomaterial: Recent developments and adsorption mechanisms, Separation and Purification Technology 150 (2015) 229–242. [25] J.-H. Jo, T. Ernest, K.-J. Kim, Treatment of TNT red water by layer melt crystallization, J. Hazard. Mater. 280
EP
(2014) 185–190.
[26] Z.Y. Wang, Z.F. Ye, C.Y. Wang, J.H. Mou, H.C. Jiao, Z. Shen, TNT red water treatment with vacuum distillation
AC C
coupling in immobilized microorganism process, China Environ. Sci. 28 (2008) 883–887. [27] M. Nasrollahzadeh, M. Atarod, S.M. Sajadi, Green synthesis of the Cu/Fe3O4 nanoparticles using Morinda morindoides leaf aqueous extract: A highly efficient magnetically separable catalyst for the reduction of organic
dyes in aqueous medium at room temperature, Appl. Surf. Sci. 364 (2016) 636–644. [28] A. Rostami-Vartooni, M. Alizadeh, M. Bagherzadeh, Green synthesis, characterization and catalytic activity of natural bentonite supported copper nanoparticles for the solvent-free synthesis of 1-substituted 1H-1,2,3,4tetrazoles and reduction of 4-nitrophenol, Beilstein J. Nanotechnol. 6 (2015) 2300–2309.
25
ACCEPTED MANUSCRIPT
[29] M. Olivares-Marin, C. Fernandez-Gonzalez, A. Macias-Garcia, V. Gomez-Serrano, Preparation of activated carbons from cherry stones by activation with potassium hydroxide, Appl. Surf. Sci. 252 (2006) 5980–5983. [30] R.B. Rios, F. Wilton, M. Silva, A. Eurico, B. Torres, D.C.S. Azevedo, L. Celio, J. Cavalcante, Adsorption of
RI PT
methane in activated carbons obtained from coconut shells using H3PO4 chemical activation, Adsorption. 15 (2009) 271–277.
[31] P. Pragya, S. Sripal and Y. Maheshkumar, Preparation and study of properties of activated carbon produced from agricultural and industrial waste shells, Research Journal of Chemical Sciences, 3 (2013) 12–15.
SC
[32] S.K. Papageorgiou, E.P. Favvas, A.A. Sapalidis, G.E. Romanos, F.K. Katsaros, Facile synthesis of carbon supported copper nanoparticles from alginate precursor with controlled metal content and catalytic NO reduction
M AN U
properties, J. Hazard. Mater. 189 (2011) 384–90.
[33] M. Nasrollahzadeh, B. Jaleh, P. Fakhri, A. Zahraei, E, Ghadery, Synthesis and catalytic activity of carbon supported copper nanoparticles for the synthesis of aryl nitriles and 1,2,3-triazoles, RSC Adv. 5 (2015) 2785–2793. [34] B. Kumru, M. Antonietti, B.V.K.J. Schmidt, Enhanced dispersibility of graphitic carbon nitride particles in aqueous and organic media via a one-pot grafting approach, Langmuir 33 (2017) 9897–9906. [35] D.R. Son, A.V. Raghu, K.R. Reddy, H.M Jeong, Compatibility of thermally reduced graphene with polyesters, J.
TE D
Macromol. Sci. Part B: Phys. 55 (2016) 1099–1110.
[36] K.R. Reddy, B.C. Sin, K.S. Ryu, J. Noh, Y. Lee, In situ self-organization of carbon black–polyaniline composites from nanospheres to nanorods: Synthesis, morphology, structure and electrical conductivity, Synthetic Metals. 159
EP
(2009) 1934–1939.
[37] M. Hassan, E. Haque, K.R. Reddy, A. I. Minett, J. Chenc, V.G. Gomes, Edge-enriched graphene quantum dots for
AC C
enhanced photo-luminescence and supercapacitance, Nanoscale. 6 (2014) 11988–11994. [38] Y.R. Lee, S.C. Kim, H. Lee, H.M. Jeong, A.V. Raghu, K.R. Reddy, B.K. Kim, Graphite oxides as effective fire retardants of epoxy resin, Macromol. Res. 19 (2011) 66–71. [39] M. Cakici, R.K. Reddy, F. Alonso-Marroquin, Advanced electrochemical energy storage supercapacitors based on the flexible carbon fiber fabric-coated with uniform coral-like MnO2 structured electrodes, Chemical Eng. J. 309 (2017) 151–158. [40] M.U. Khan, K.R. Reddy, T. Snguanwongchai, E. Haque, V.G. Gomes, Polymer brush synthesis on surface modified carbon nanotubes via in situ emulsion polymerization, Colloid and Polymer Sci. 294 (2016) 1599–1610.
26
ACCEPTED MANUSCRIPT
[41] R. Wu, J.-H. Liu, L. Zhao, X. Zhang, J. Xie, B. Yu, X. Ma, S.-T. Yang, H. Wang, Y. Liu, Hydrothermal preparation of magnetic Fe3O4@C nanoparticles for dye adsorption, Journal of Environmental Chemical Engineering 2 (2014) 907–913.
RI PT
[42] P.T.L. Huong, L.T. Huy, H. Lan, L.H. Thang, T.T. An, N.V. Quy, P.A. Tuan, J. Alonso, M.-H. Phan, A.-T. Le, Magnetic iron oxide-carbon nanocomposites: Impacts of carbon coating on the As(V) adsorption and inductive heating responses, Journal of Alloys and Compounds 739 (2018) 139–148.
[43] K. Cheng, Y.M. Zhou, Z.Y. Sun, H.B. Hu, H. Zhong, X.K. Kong, Q.W. Chen, Synthesis of carbon-coated, porous
SC
and water-dispersive Fe3O4 nanocapsules and their excellent performance for heavy metal removal applications, Dalton Trans. 41 (2012) 5854–5861.
M AN U
[44] F. Chai, K. Li , C. Song, X. Guo, Synthesis of magnetic porous Fe3O4/C/Cu2O composite as an excellent photoFenton catalyst under neutral condition, J. Colloid Interf. Sci. 475 (2016) 119–125. [45] B.R. Cuenya, Synthesis and catalytic properties of metal nanoparticles: Size, shape, support, composition, and oxidation state effects, Thin Solid Films 518 (2010) 3127–3150.
[46] K. Shameli, M.B. Ahmad, M. Zargar, W.M.Z.W. Yunus, N.A. Ibrahim, Fabrication of silver nanoparticles doped in the zeolite framework andantibacterial activity, Int. J. Nanomedicine 6 (2011) 331–341.
TE D
[47] Y. Ioni, E. Buslaeva, S. Gubin, Synthesis of graphene with noble metals nanoparticles on its surface, Materials Today: Proceedings 3S ( 2016 ) S209 –S213.
[48] M. Nasrollahzadeh, M. Maham, A. Rostami-Vartooni, M. Bagherzadeh, S.M. Sajadi, Barberry fruit extract
EP
assisted in situ green synthesis of Cu nanoparticles supported on a reduced graphene oxide–Fe3O4 nanocomposite as a magnetically separable and reusable catalyst for the O-arylation of phenols with aryl halides under ligand-free
AC C
conditions, RSC Adv. 5 (2015) 64769–64780. [49] K.R. Reddy, B.C. Sin, C.H. Yoo, W. Park, K.S. Ryu, J.S. Lee, D. Sohn, Y. Lee, A new one-step synthesis method for coating multi-walled carbon nanotubes with cuprous oxide nanoparticles, Scripta Materialia. 58 (2008) 1010– 1013.
[50] K.R. Reddy, K.P. Lee, A.I. Gopalan, M.S. Kim, A.M. Showkat, Y.C. Nho, Synthesis of metal (Fe or Pd)/alloy (Fe–Pd)‐nanoparticles‐embedded multiwall carbon nanotube/sulfonated polyaniline composites by γ irradiation, J. Polymer Sci. Part A: Polymer Chem. 44 (2006) 3355–3364.
27
ACCEPTED MANUSCRIPT
[51] K.R. Reddy, K. Nakata, T. Ochiai, T. Murakami, D.A. Tryk, A. Fujishima, Facile Fabrication and Photocatalytic Application of Ag Nanoparticles-TiO2 Nanofiber Composites, Nanosci. and Nanotech. 11 (2011) 3692–3695. [52] K. Kaviyarasu, X. Fuku, G.T. Mola, E. Manikandan, J. Kennedy, M. Maaza, Photoluminescence of well-aligned
RI PT
ZnO doped CeO2 nanoplatelets by a solvothermal route, Mater. Lett. 183 (2016) 351–354. [53] A. Rostami-Vartooni, M. Nasrollahzadeh, M. Alizadeh, Green synthesis of seashell supported silver nanoparticles using Bunium persicum seeds extract: Application of the particles for catalytic reduction of organic dyes, J. Colloid Interf. Sci. 470 (2016) 268–275.
SC
[54] A. Rostami-Vartooni, M. Nasrollahzadeh, M. Alizadeh, Green synthesis of perlite supported silver nanoparticles using Hamamelis virginiana leaf extract and investigation of its catalytic activity for the reduction of 4-nitrophenol
M AN U
and Congo red, Journal of Alloys and Compounds 680 (2016) 309–314.
[55] M. Bordbara, N. Negahdara, M. Nasrollahzadeh, Melissa Officinalis L. leaf extract assisted green synthesis of CuO/ZnO nanocomposite for the reduction of 4-nitrophenol and Rhodamine B, Separation and Purification Technology 191 (2018) 295–300.
[56] J. M. DiTomaso, E. A. Healy, Weeds of California and Other Western States, Vol. 1, University of California, Agriculture and Natural Resources, UCANR Publications, 2 (2007).
TE D
[57] B. Khodadadi, M. Bordbar, M. Nasrollahzadeh, Green synthesis of Pd nanoparticles at Apricot kernel shell substrate using Salvia hydrangea extract: Catalytic activity for reduction of organic dyes, J. Colloid Interf. Sci. 490 (2017) 1–10.
EP
[58] E.Y. Choi, T.H. Han, J.E. Hong, J. Kim, S.H. Lee, H.W. Kim, S.O. Kim, Noncovalent functionalization of graphene with end-functional polymers, J. Mater. Chem. 20 (2010) 1907–1912.
AC C
[59] C. Song, S.-J. Park, S. Kim, Effect of modification by polydopamine and polymeric carbon nitride on methanol oxidation ability of Pt catalysts-supported on reduced graphene oxide, Journal of The Electrochemical Society 163 (7) (2016) F668–F676.
[60] E. Karaoglu, A. Baykal, M. Senel, H. Sozeri, M.S. Toprak, Synthesis and characterization of Piperidine-4carboxylic acid functionalized Fe3O4 nanoparticles as a magnetic catalyst for Knoevenagel reaction, Materials Research Bulletin 47 (2012) 2480–2486. [61] Y.-h. Wana, X.-q. Shi, H. Xia, J. Xie, Synthesis and characterization of carbon-coated Fe3O4 nanoflakes as anode material for lithium-ion batteries, Materials Research Bulletin 48 (2013) 4791–4796.
28
ACCEPTED MANUSCRIPT
[62] C.H.A. Wong, A. Ambrosi, M. Pumera, Thermally reduced graphenes exhibiting a close relationship to amorphous Carbon, Nanoscale 4 (2012) 4972–4977. [63] W.N.R.W. Isahak, M.W.M. Hisham, M.A. Yarmo, Highly porous carbon materials from biomass by chemical and
RI PT
carbonization method: A Comparison Study, Journal of Chemistry, 2013 (2013) 1–6. [64] H. Gu, D. Cao, J. Wang, X. Lu, Z. Li, C. Niu, H. Wang, Micro-CaCO3 conformal template synthesis of hierarchical porous carbon bricks: As a host for SnO2 nanoparticles with superior lithium storage performance, Materials Today Energy 4 (2017) 75–80.
agent, International Nano Letters 3 (2013) 23–28.
SC
[65] F. Ahangaran1, A. Hassanzadeh, S. Nouri, Surface modification of Fe3O4@SiO2 microsphere by silane coupling
M AN U
[66] Y.-F. Zhang, L.-G. Qiu, Y.-P. Yuan, Y.-J. Zhu, X. Jiang, J.-D. Xiao, Magnetic Fe3O4@C/Cu and Fe3O4@CuO core–shell compositesconstructed from MOF-based materials and their photocatalytic properties under visible light, Appl. Catal. B: Environ. 144 (2014) 863–869.
[67] D. Shah, H. Kaur, Resin-trapped gold nanoparticles: An efficient catalyst for reduction of nitro compounds and Suzuki-Miyaura coupling, J. Mol. Catal. A Chem. 381 (2014) 70–76.
[68] R.J. Kalbasi, A.A. Nourbakhsh, F. Babaknezhad, Synthesis and characterization of Ni nanoparticles-
955–960.
TE D
polyvinylamine/SBA-15 catalyst for simple reduction of aromatic nitro compounds, Catal. Commun. 12 (2011)
[69] M. Atarod, M. Nasrollahzadeh, S.M. Sajadi, Euphorbia heterophylla leaf extract mediated green synthesis of
EP
Ag/TiO2 nanocomposite and investigation of its excellent catalytic activity for reduction of variety of dyes in
AC C
water, J. Colloid Interf. Sci. 462 (2016) 272–279.
29
ACCEPTED MANUSCRIPT
Highlights: Preparation of porous carbon via carbonization of red water as a carbon source. Conversion of a toxic waste product to a stable support.
RI PT
Synthesis of C/Fe3O4 nanocomposite by co-precipitation reaction. Immobolization of Ag NPs on the surface of carbon nanocomposites using Caesalpinia gilliesii flower extract.
AC C
EP
TE D
M AN U
SC
Reduction of methyl orange and 4-nitrophenol at room temperature.