Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity

APT 1612

No. of Pages 9, Model 5G

25 May 2017 Advanced Powder Technology xxx (2017) xxx–xxx 1

Contents lists available at ScienceDirect

Advanced Powder Technology journal homepage: www.elsevier.com/locate/apt

2

Original Research Paper

6 4 7

Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity

5 8 9 10 11 12 13 14 15 16 17 18 20 19 21 2 3 3 5 24 25 26 27 28 29 30 31 32 33 34

Ismat Bibi a,⇑, Nosheen Nazar a, Munawar Iqbal b,⇑, Shagufta Kamal c, Haq Nawaz d, Shazia Nouren e, Yursa Safa f, Kashif Jilani d, Misbah Sultan g, Sadia Ata g, Fariha Rehman h, Mazhar Abbas i a

Department of Chemistry, The Islamia University of Bahawalpur, Pakistan Department of Applied Chemistry & Biochemistry, GCU, Faisalabad, Pakistan Department of Chemistry, The University of Lahore, Lahore, Pakistan d Department of Biochemistry, University of Agriculture Faisalabad, Pakistan e Department of Chemistry, Women University of Azad Jammu and Kashmir, Bagh, Pakistan f Department of Chemistry, Lahore College for Women University Lahore, LCWU, Pakistan g Institute of Chemistry, University of the Punjab Lahore, Pakistan h Department of Environmental Sciences, Institute of Information Technology, Vehari, Pakistan i Institute of Molecular Biology and Biotechnology, The University of Lahore, Lahore, Pakistan b c

a r t i c l e

i n f o

Article history: Received 23 February 2017 Received in revised form 18 April 2017 Accepted 16 May 2017 Available online xxxx Keywords: Biosynthesis P. granatum Cobalt oxide nanoparticles Photo-catalytic activity

a b s t r a c t Cobalt-oxide nanoparticles (NPs) were fabricated using Punica granatum peel extract from cobalt nitrate hexahydrate at low temperature. The synthesized cobalt-oxide NPs were characterized using X-ray powder diffraction, scanning electron microscopy, energy-dispersive X-ray, Atomic force microscopy, Fourier transform infrared spectroscopy and UV-visible techniques. The cobalt-oxide NPs were in highly uniform shape and in the size range of 40–80 nm. Photo-catalytic activity (PCA) of the synthesized NPs was evaluated by degrading Remazol Brilliant Orange 3R (RBO 3R) dye and a degradation of 78.45% was achieved (150 mg/L) using 0.5 g cobalt-oxide NPs for 50 min irradiation time. In view of eco-benign, secure, costeffective nature, the biosynthesis has gained much for NPs synthesis and present investigation revealed that P. granatum could be used for the synthesis of cobalt-oxide NPs for photo-catalytic applications. Ó 2016 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan. All rights reserved.

36 37 38 39 40 41 42 43 44 45 46 47 48

49 50

1. Introduction

51

To date, researchers are focusing on the fabrication of NPs to tune the electronic, optical, catalytic and magnetic properties irrespective of bulk materials. The main aspects that are important in order to tune the properties are quantum effects and surface area [1]. Extensive research have been carried out to control the shape and size of NPs since size and shape have significant effect on physico-chemical properties [2,3]. Cobalt NPs have various applications due to their high resistance to corrosion as well as oxidation and have potential applications in everyday life [4]. Various physical and chemical methods have been used for the synthesis of cobalt NPs including; thermal decomposition, high temperature solution phase, reduction and hydrothermal micro emulsion etc [5–9]. However,

52 53 54 55 56 57 58 59 60 61 62 63

⇑ Corresponding authors.

biosynthesis of NPs is evolved into a significant offshoot of nanotechnology [10–20]. This technique is eco-friendly and cost effective versus conventional synthesis techniques, where high pressure, temperature, energy and chemical additive are used [1,21]. Therefore, there is a need to develop and utilize safe synthetic techniques, which must be environment friendly, nontoxic, efficient and low cost. In this contest, various researchers used biosynthesis technique for the fabrication of NPs [10,11,13,15,20,22–26]. Plant derived materials are used for the fabrication of NPs, which is eco-friendly and is credible alternatives to physical and chemical methods. The use of plant extract eliminates the laborious and complicated protocols of physicochemical methods. Plant extract contains bioactive compounds such as tannins, phenolic acids, saponin and flavonoids [27–29]. These bioactive compounds can quench singlet oxygen, donate hydrogen and are good chelation agents. Because of their redox activities plant mediated synthesis of nanoparticles is more compatible than the physico-chemical methods. Plant extracts

E-mail addresses: [email protected] (I. Bibi), [email protected], [email protected] (M. Iqbal). http://dx.doi.org/10.1016/j.apt.2017.05.008 0921-8831/Ó 2016 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan. All rights reserved.

Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008

64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79 80 81

APT 1612

No. of Pages 9, Model 5G

25 May 2017 2 82 83 84 85 86 87 88 89 90 91 92 93 94 95 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 111 112 113 114 115 116 117 118 119 120 121 122 123 124

I. Bibi et al. / Advanced Powder Technology xxx (2017) xxx–xxx

are non-toxic, easy to handle and can be processed using easy protocols [11,13,15,20,23–26,30–36]. P. granatum is a rich source of polyphenolic compounds, has extensive applications in various industrial process i.e., cosmetics, food and medicines etc. The major compounds (gallic acid, punicalagins A and B, Ellagic acid and gallotannins) in P. granatum could act as a reducing, stabilizing and capping agents [37]. The polyphenolic compounds could limit the particle growth and ruling out agglomeration of particles [38–40]. In recent years, the innovative cobalt catalytic properties attracted the attention of researchers due to non-precious cobalt source versus precious metals [41]. The cobalt exhibits a wide range of size-dependent structural, magnetic, electronic, and catalytic properties. Being a p-type antiferromagnetic semiconductor, it is a multi-functional material with various practical applications i.e., heterogeneous catalysis, energy storage, electro-chromic sensors, and anode materials in Li-ion rechargeable batteries [42–45]. The textile dyes are the one of major class of environmental pollutants [46] and most of the dyes are mutagenic and carcinogenic [47,48]. There are numerous conventional chemical and physical techniques such as chlorination, ozonation, adsorption, reverse osmosis, ultra-filtration, biodegradation and coagulation for the pollutants including textile dyes [49–64]. Nevertheless, the majority of these methods degrade dyes into harmless end product and secondary pollution issues are encountered. To date, the advance oxidation process is an efficient alternative for the treatment of toxic dyes and other organic compounds [3,65–69]. Radiation energy such as UV radiation is utilized in the process and treatment can be carried out under ambient conditions [50,70]. However, UV based processes are costly and solar light is viable alternative to UV radiation. In this regard, photo-catalyst active under light are needed, which is more promising then UV based processes. Nano scale cobalt particle have remarkable catalytic properties [71]. Particularly, owing to their large surface area, cobalt NPs displayed very high reactivity, which makes them appropriate for catalysis [72]. In view of importance of biosynthesis, nevertheless, the cobalt oxide NPs are synthesized using P. granatum extracts. Therefore, the principle objectives of current investigation were to synthesize the cobalt oxide NPs using P. granatum extracts. The synthesized cobalt oxide NPs was characterized using advance techniques and finally, PCA was evaluated by degrading RBO 3R dye under solar light irradiation.

125

2. Material and methods

126

2.1. Chemical and reagents

127

Cobalt nitrate hexahydrate (Co(NO3)2
6H2O), (99%), RBO 3R (Table 1) were purchased from Sigma Aldrich chemical supplier company. For the preparation of solution, ultrapure water with a

128 129

Table 1 Physico-chemical properties of Remazol Brilliant Orange 3R dye (RBO 3R). Purity

70%

Synonym Empirical formula Molecular weight Colour index number EC number Chemical structure

Remazol Brilliant Orange 3R C20H17N3Na2O11S3 617.54 17757 235-431-5

resistivity of 18.2 MX cm from Milli-Q system (Millipore) was used throughout this study.

130

2.2. Preparation of green reducing and stabilizing agent

132

The P. granatum peels were collected from the local market, Bahawalpur, Pakistan. Peels were sliced into pieces and washed with ultrapure water to remove impurities. P. granatum peels (20 g) and 150 mL waster was homogenized in an electrical grinder. Then mixture was heating at 75 °C along with continuous stirring, cooled down and filtered. The filtrate (brown color) was collected and used for the synthesis of cobalt oxide NPs.

133

2.3. Synthesis of Cobalt-Oxide nanoparticles

140

For the fabrication of cobalt oxide NPs, freshly prepared peels extract (90 mL) was added to 1 M solution of cobalt nitrate hexahydrate, heated at  70 °C till precipitates appeared and then, the temperature reduced to 60 °C and kept the solution at 60 °C for 90 min. The mixture was kept overnight at room temperature and then centrifuged at 14,000 rpm for 10 min. The precipitates were washed thrice with ultrapure water and absolute ethanol to remove un-reacted particles and impurities. The obtained precipitates were dried in an oven at 60 °C for 8–9 h [73], grinded and subjected characterization.

141

2.4. Characterization

151

The purity of the synthesized cobalt oxide NPs was confirmed by XRD analysis (Bruker, German), using Cu Ka radiation in the range of 2h = 20–80° at a scanning rate of 5° min1. The element analysis was performed by Energy Dispersive X-Ray Spectroscopy (EDX) (JEOL, Japan). The structural morphology was examined by scanning electron microscopy (SEM) (Hitachi SX-650, Tokyo, Japan). To confirm the functional bio-molecules associated with the cobalt oxide NPs, FTIR analysis was carried out (Nexus 470, FTIR) in the range of 500–4000 cm1 with resolution setting of 4 cm1. The UV–Vis absorption spectra was recorded on UV–Vis spectrophotometer (Perkin Elmer, USA). Moreover, the confirmation of the particle size and morphology of fabricated cobalt oxide NPs was carried out by atomic force microscopy (AFM).

152

2.5. Photo-catalytic activity procedure

165

The PCA of as-synthesised cobalt oxide NPs was evaluated by degrading RBO 3R. For PCA study, 0.5 mg of cobalt oxide NPs was mixed with 100 mL dye solution (150 mg/L). The suspension was kept in the dark for 30 min in order to ensure the adsorption–desorption equilibrium and then, irradiated to solar light generated by solar simulator (150 W Xe lamp having cutoff filter (k  420 nm). After stipulated time intervals (10, 20, 30, 50 min), the samples were drawn, filtered by Millipore filter and analyzed for dye residual concentration by UV-vis spectrophotometer (Perkin Elmer, USA) at 495 nm along with scanning from 190–900 nm. To evaluate the pure photolysis effect, blank experiment was also performed under similar conditions. Triplicate degradation experiments were run under ambient conditions (25 °C). The dye percentage degradation was estimated by employing the relation shown in Eq. (1).

166



134 135 136 137 138 139

142 143 144 145 146 147 148 149 150

153 154 155 156 157 158 159 160 161 162 163 164

167 168 169 170 171 172 173 174 175 176 177 178 179 180

181



ðC i  C f Þ Decolorization ð%Þ ¼
100 Ci

131

ð1Þ

where Ci is the initial concentration of RBO 3R dye and Cf is the concentration of dye after photocatalytic degradation. Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008

183 184 185

APT 1612

No. of Pages 9, Model 5G

25 May 2017 3

I. Bibi et al. / Advanced Powder Technology xxx (2017) xxx–xxx 186

3. Results and discussion

187

3.1. Characterization

188

General scheme for biosynthesis of cobalt oxide NPs synthesis is shown in Fig. 1. The reaction progress between components in P. granatum extract and metal ions was examined by UV–visible spectra. UV-vis absorption spectrum of synthesized cobalt oxide NPs shows absorption band at about 508 nm (Fig. 2). This absorption band can be attributed to the plasma resonance absorption of the cobalt oxide NPs. Origin of light absorption by metal nanoparticles is the consistent oscillation of the electrons in conduction band induced by the interaction of electro-magnetic field [74]. The distinguishing feature of the CoONPs is to exhibit a surface plasmon absorption band in the regions of 350–550 nm [75]. The strong surface plasmon might be owing to the formation of nonoxidized cobalt nanoparticles. The peel extracts of P. granatum acts as a reducing-cum-surface capping agent that can be credited to the fabrication of nanoscale cobalt oxide [76]. Cobalt oxide NPs were formed from the reduction of cobalt(II) nitrate hexahydrate

190 191 192 193 194 195 196 197 198 199 200 201 202 203

Fig. 1. (A) General mechanism for the biosynthesis of cobalt oxide nanoparticles using Punica granatum peel extract.

2.0

1.5

Absorbance

189

in the presence of P. granatum peel extract, which act as a reducing, stabilizing and capping agent [77]. One-step in-situ green synthesis consists of the nucleation and growth processes through reduction of cobalt ions into neutral cobalt atoms and the particles are nucleated and finally stabilized with the bioactive compound in extracts [78]. The phenolic compounds have hydroxyl and carboxylic groups, which have high affinity to combine with metals, on conjugation with ortho-phenolic hydroxyl group and ester oxygen atom on ellagic acid. On chelate formation, the hydrogen is removed from ortho position of phenolic hydroxyl group and resultantly, a semi-quinone type structure is produced. H+ radical is generated owing to the electron losing property of ellagic acid. As a results of this process, Co(II) is reduced to Co atom and due to capping effect the particle produced were in nano-size [79,80]. The XRD of fabricated cobalt oxide NPs is shown in Fig. 3. XRD pattern are well indexed at 2 theta values of 20.05 (1 1 1), 31.19 (2 2 0), 36.56 (3 1 1), 44.29 (4 0 0) corresponding to the face centred cubic crystalline phase of cobalt oxide (JCPDS card 073–1701) an also in line with. Co structure reported previously [81]. The lattice constants (Å) was recorded to be 7.925 Å of cobalt oxide NPs. The

508 nm

1.0

0.5

0.0

-0.5 300

400

500

600

700

800

900

1000

Wavelength (nm) Fig. 2. UV–Visible spectrum of cobalt-oxide nanoparticles fabricated using Punica granatum peel extract.

Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008

204 205 206 207 208 209 210 211 212 213 214 215 216 217 218 219 220 221 222 223

APT 1612

No. of Pages 9, Model 5G

25 May 2017 I. Bibi et al. / Advanced Powder Technology xxx (2017) xxx–xxx

Intensity (a.u)

4

111 311 400

220

15

20

25

30

35

40

45

2θ (degree) Fig. 3. XRD spectrum of cobalt oxide nanoparticles fabricated using Punica granatum peel extract.

Fig. 4. Scanning Electron Microscopy image of cobalt oxide nanoparticles fabricated using Punica granatum peel extract.

average size calculated using Debye Scherrer’s equation (D = 0.9 k/ß Cos h) was in the range of 43.78–73.10 nm. In Scherrer’s equation 0.92 is a constant, k is the wavelength of the Xrays and ß is the full width at half maximum (FWHM) of the diffraction peaks and h is the diffraction angle. The surface morphology of cobalt oxide NPs was investigated by SE) and response is shown in Fig. 4, it is obvious from the SEM image that the synthesized particles were in the range of nanoscale. Particles were spherical in shape, agglomerated with average size of less than 80 nm, which is also supported by XRD data. Agglomerations in the particles depend upon the nature of the extract and the compounds present in the extract [82] because biomolecule cap and stabilize the individual particle. Reactivity and attraction of the functional groups results in the formation of larger size particles. These particles have coatings of the different biological compounds which have surface hydroxyl groups. Due to intermolecular hydrogen bonding among these agents, the particles appear to be agglomerated [83]. EDX analysis of cobalt oxide NPs was carried out by using internal standard at energy from 0 to 10 keV. EDX spectra (Fig. 5) showed strong signal of cobalt in prepared samples. It is confirmed that the cobalt oxide NPs were in pure form since no additional peaks were observed. FTIR analysis was performed to sort out the potential functional groups of the bio-molecules in the P. granatum peel extract involved in the formation of cobalt oxide NPs. As it is clear from Fig. 6, a wide broad peak around 3225 cm1 is characteristic peak of hydroxyl group of polyphenolic compounds. Bands present at 1569 cm1, 1313 cm1 and 1049 cm1 are the representative peaks of aromatic rings, in plane bending of OH and C-O stretching of alcohols and carboxylic acids, which are responsible for the formation of cobalt oxide NPs [84]. The confirmation of the particle size and morphology of cobalt oxide NPs was also confirmed by AFM analysis and response is shown in Fig. 7. Particle size distribution of cobalt oxide NPs was recorded in the range of 40–80 nm. Grooves are not homogenous as depicted by three dimensional image, which is mainly due to agglomeration caused due to coating of biomolecules on nanoparticles surface. The plant extracts are the rich source of biological compounds, which acted as reducing agents as well as stabilizing agents for the fabricated of metal nanoparticles [10,22,85] and in

Fig. 5. Energy dispersive X-ray spectrum of cobalt oxide nanoparticles fabricated using Punica granatum peel extract.

Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008

224 225 226 227 228 229 230 231 232 233 234 235 236 237 238 239 240 241 242 243 244 245 246 247 248 249 250 251 252 253 254 255 256 257 258 259 260 261 262

APT 1612

No. of Pages 9, Model 5G

25 May 2017 I. Bibi et al. / Advanced Powder Technology xxx (2017) xxx–xxx

5

Fig. 6. FTIR spectrum of cobalt oxide nanoparticles fabricated using Punica granatum peel extract.

Fig. 7. Atomic force microscopy o of cobalt oxide nanoparticles fabricated using Punica granatum peel extract (A) Particle size distribution curve (B) Three dimensional image.

263 264

present investigation cobalt oxide NPs were successfully fabricated using P. granatum peel extract.

265

3.2. Photo-catalytic activity

266

Photo-catalytic degradation of RBO 3R was studied using assynthesized cobalt oxide NPs under solar light irradiation. The dye color faded considerably in first 20 min irradiation and after 50 min of reaction, the decolorization reached up to 78.45% for 150 mg/L dye initial concentration using 0.5 mg cobalt oxide NPs. The visual color of treated dye and UV-vis spectrum is shown in Fig. 8, whereas dye degradation mechanism is depicted in Fig. 9. The dye band reduced as the reaction time increased and new peak

267 268 269 270 271 272 273

was appeared, which indicates that dye degraded completely through photocatalytic treatment [3,66,68]. The photo-catalytic degradation of target dye is associated with the breakdown of the chromophoric group and the transformation of dye into low molecular weight by-products. The dye degradation is mainly due to the generation of electron and hole (e & h+) on catalyst surface under irradiation [3,66] (Fig. 9, Eqs. 25). Water molecule combine with hole and converted into OH radical. On the other hand, the O2 scavange the e and converted into OH through HOO and H2O2 intermediate. The OH is strong oxidizing species, which degrade the organic molecule (dye) non-selectively into H2O, CO2 and inorganic ions [3,66,68]. The RBO 3R dye degradation (78.45%) for the 50 min radiation exposure indicates that the

Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008

274 275 276 277 278 279 280 281 282 283 284 285 286

APT 1612

No. of Pages 9, Model 5G

25 May 2017 6

I. Bibi et al. / Advanced Powder Technology xxx (2017) xxx–xxx

Fig. 8. UV absorption spectra of dye before and after treatment using cobalt oxide nanoparticle as a catalyst under solar light irradiation and (A-B) Visual observation of dye before and after treatment.

Fig. 9. Suggested degradation pathway of RR 16 dye using cobalt oxide as phtocatalyst (where CB is the conduction band, VB is the valence band).

305 287 288 289 290 291 292 293 294 295

296 298

cobalt oxide NPs are highly efficient for the degradation of dye under solar light irradiation. Previous reported also indicated that NPs synthesized through green techniques are highly active photocatalyst [10,11,13,15,20,22–26]. Since textile dyes are the one of major class of environmental pollutants [46,52,63,64,86–90] and conventional methods [69,91–116] are inefficient for the remediation of pollutant and cobalt oxide NPs proves to be highly active for the degradation of RBO 3R dye and could possibly be used for dyes treatment in textile wastewater. þ

Catalyst surface ðIrradiationÞ ! e þ h

ð2Þ

299 301

h þ H2 O !  OH þ Hþ

ð3Þ

302 304

e þ O2 ! O 2

ð4Þ

þ



OH þ dye ! Oxidative products ! CO2 þ H2 O þ NHþ4 þ NO3 þ SO2 4

ð5Þ

307

4. Conclusions

308

Cobalt oxide NPs were fabricated using P. granatum peel extract from cobalt nitrate hexahydrate at low temperature and characterized by advanced techniques. The synthesized cobalt oxide size was in the range of 40–80 nm. The PCA was evaluated by degrading RBO 3R dye under solar light irradiation. In response photoactivity of cobalt oxide NPs under solar light irradiation, 78.45% degradation of RBO 3R was achieved within 50 min of irradiation. It can be concluded that the P. granatum peel extract has considerable amount of bioactive compounds and able to reduced and stabilize

309

Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008

310 311 312 313 314 315 316 317

APT 1612

No. of Pages 9, Model 5G

25 May 2017 I. Bibi et al. / Advanced Powder Technology xxx (2017) xxx–xxx

322

the cobalt oxide NPs. The method is simple and cost effective, which could be used for the synthesis of cobalt oxide NPs in nano-size range. This technique could also be extended for the synthesis of other metal NPs since this method is eco-benign and cost effective.

323

References

318 319 320 321

324 325 326 327 328 329 330 331 332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351 352 353 354 355 356 357 358 359 360 361 362 363 364 365 366 367 368 369 370 371 372 373 374 375 376 377 378 379 380 381 382 383 384 385 386 387 388 389 390 391 392 393 394 395 396 397

[1] J. Xiong, Y. Wang, Q. Xue, X. Wu, Synthesis of highly stable dispersions of nanosized copper particles using L-ascorbic acid, Green Chem. 13 (2011) 900– 904. [2] I. Lisiecki, F. Billoudet, M. Pileni, Syntheses of copper nanoparticles in gelified microemulsion and in reverse micelles, J. Mol. Liq. 72 (1997) 251–261. [3] A. Ashar, M. Iqbal, I.A. Bhatti, M.Z. Ahmad, K. Qureshi, J. Nisar, I.H. Bukhari, Synthesis, characterization and photocatalytic activity of ZnO flower and pseudo-sphere: Nonylphenol ethoxylate degradation under UV and solar irradiation, J. Alloy. Comp. 678 (2016) 126–136. [4] M. Chen, J. Liu, S. Sun, One-step synthesis of FePt nanoparticles with tunable size, J. Am. Chem. Soc. 126 (2004) 8394–8395. [5] N. Matoussevitch, A. Gorschinski, W. Habicht, J. Bolle, E. Dinjus, H. Bönnemann, S. Behrens, Surface modification of metallic Co nanoparticles, J. Magnet. Magnet. Mater. 311 (2007) 92–96. [6] W. Liu, W. Zhong, X. Wu, N. Tang, Y. Du, Hydrothermal microemulsion synthesis of cobalt nanorods and self-assembly into square-shaped nanostructures, J. Cryst. Growth. 284 (2005) 446–452. [7] Y. Su, X. OuYang, J. Tang, Spectra study and size control of cobalt nanoparticles passivated with oleic acid and triphenylphosphine, Appl. Surf. Sci. 256 (2010) 2353–2356. [8] X. Liang, L. Zhao, Room-temperature synthesis of air-stable cobalt nanoparticles and their highly efficient adsorption ability for Congo red, RSC Adv. 2 (2012) 5485–5487. [9] V.R. Remya, V.K. Abitha, P.S. Rajput, A.V. Rane, A. Dutta, Silver nanoparticles green synthesis: A mini review, Chem. Int. 3 (2017) 165–171. [10] H. Joy Prabu, I. Johnson, Plant-mediated biosynthesis and characterization of silver nanoparticles by leaf extracts of Tragia involucrata, Cymbopogon citronella, Solanum verbascifolium and Tylophora ovata, Karbala Int. J. Mod. Sci. 1 (2015) 237–246. [11] B. Ahmmad, K. Leonard, M. Shariful Islam, J. Kurawaki, M. Muruganandham, T. Ohkubo, Y. Kuroda, Green synthesis of mesoporous hematite (a-Fe2O3) nanoparticles and their photocatalytic activity, Adv. Powder Technol. 24 (2013) 160–167. [12] J. Chandradass, D.S. Bae, K.H. Kim, A simple method to prepare indium oxide nanoparticles: Structural, microstructural and magnetic properties, Adv. Powder Technol. 22 (2011) 370–374. [13] K. Elumalai, S. Velmurugan, S. Ravi, V. Kathiravan, G. Adaikala, Raj, Bioapproach: Plant mediated synthesis of ZnO nanoparticles and their catalytic reduction of methylene blue and antimicrobial activity, Adv. Powder Technol. 26 (2015) 1639–1651. [14] S.J. Hoseini, M. Darroudi, R. Kazemi Oskuee, L. Gholami, A. Khorsand Zak, Honey-based synthesis of ZnO nanopowders and their cytotoxicity effects, Adv. Powder Technol. 26 (2015) 991–996. [15] S.K. Kannan, M. Sundrarajan, Green synthesis of ruthenium oxide nanoparticles: Characterization and its antibacterial activity, Adv. Powder Technol. 26 (2015) 1505–1511. [16] J.K. Patra, Y. Kwon, K.-H. Baek, Green biosynthesis of gold nanoparticles by onion peel extract: Synthesis, characterization and biological activities, Adv. Powder Technol. (2016), http://dx.doi.org/10.1016/j.apt.2016.08.005. [17] A. Phukan, R.P. Bhattacharjee, D.K. Dutta, Stabilization of SnO2 nanoparticles into the nanopores of modified Montmorillonite and their antibacterial activity, Adv. Powder Technol. (2016), http://dx.doi.org/10.1016/j. apt.2016.09.005. [18] C. Ragupathi, L. John, Kennedy, J. Judith Vijaya, A new approach: Synthesis, characterization and optical studies of nano-zinc aluminate, Adv. Powder Technol. 25 (2014) 267–273. [19] A.B. Samui, D.S. Patil, C.D. Prasad, N.M. Gokhale, Synthesis of nanocrystalline 8YSZ powder for sintering SOFC material using green solvents and dendrimer route, Adv. Powder Technol. (2016), http://dx.doi.org/10.1016/j. apt.2016.06.010. [20] M. Sundrarajan, S. Ambika, K. Bharathi, Plant-extract mediated synthesis of ZnO nanoparticles using Pongamia pinnata and their activity against pathogenic bacteria, Adv. Powder Technol. 26 (2015) 1294–1299. [21] P. Raveendran, J. Fu, S.L. Wallen, Completely ‘‘green” synthesis and stabilization of metal nanoparticles, J. Am. Chem. Soc. 125 (2003) 13940– 13941. [22] R.S. Patil, M.R. Kokate, S.S. Kolekar, Bioinspired synthesis of highly stabilized silver nanoparticles using Ocimum tenuiflorum leaf extract and their antibacterial activity, Spectrochim. Acta A Mol. Biomol. Spectrosc. 91 (2012) 234–238. [23] M. Fazlzadeh, K. Rahmani, A. Zarei, H. Abdoallahzadeh, F. Nasiri, R. Khosravi, A novel green synthesis of zero valent iron nanoparticles (NZVI) using three plant extracts and their efficient application for removal of Cr(VI) from aqueous solutions, Adv. Powder Technol. 28 (2017) 122–130.

7

[24] J.K. Patra, Y. Kwon, K.-H. Baek, Green biosynthesis of gold nanoparticles by onion peel extract: Synthesis, characterization and biological activities, Adv. Powder Technol. 27 (2016) 2204–2213. [25] A. Phukan, R.P. Bhattacharjee, D.K. Dutta, Stabilization of SnO2 nanoparticles into the nanopores of modified Montmorillonite and their antibacterial activity, Adv. Powder Technol. 28 (2017) 139–145. [26] B. Siripireddy, B.K. Mandal, Facile green synthesis of zinc oxide nanoparticles by Eucalyptus globulus and their photocatalytic and antioxidant activity, Adv. Powder Technol. 28 (2017) 785–797. [27] M. Asif, Pharmacologically potentials of different substituted coumarin derivatives, Chem. Int. 1 (2015) 1–11. [28] M. Asif, Chemistry and antioxidant activity of plants containing some phenolic compounds, Chem. Int. 1 (2015) 35–52. [29] M. Asif, Antiviral and antiparasitic activities of various substituted triazole derivatives: A mini, Chem. Int. 1 (2015) 71–80. [30] G. Singaravelu, J. Arockiamary, V.G. Kumar, K. Govindaraju, A novel extracellular synthesis of monodisperse gold nanoparticles using marine alga, Sargassum wightii Greville, Colloid. Surf. B. 57 (2007) 97–101. [31] M.W. Ashraf, M. Bilal, M. Iqbal, Antiglycation activity of vegetables aqueous and methanolic extracts, Curr. Sci. Perspect. 1 (2015) 12–15. [32] J.K. Mensah, D. Golomeke, Antioxidant and antimicrobial activities of the extracts of the Calyx of Hibiscus Sabdariffa Linn, Curr. Sci. Perspect. 1 (2015) 69–76. [33] K. Benouis, Phytochemicals and bioactive compounds of pulses and their impact on health, Chem. Int. 3 (2017) 224–229. [34] A.H. Cahyana, N. Kam, Ellyn, Study on the stability of antioxidant and anti-aglucosidase activities using soaking treatment of Okra (Abelmoschus esculentus L.) mucilage extracts, Chem. Int. 3 (2017) 203–212. [35] Y.M. Hailu, M. Atlabachew, B.S. Chandravanshi, M. Redi-Abshiro, Composition of essential oil and antioxidant activity of Khat (Catha edulis Forsk), Ethiopia, Chem. Int. 3 (2017) 25–31. [36] S. Isah, A.A. Oshodi, V.N. Atasie, Physicochemical properties of cross linked acha (digitaria exilis) starch with citric acid, Chem. Int. 3 (2017) 150–157. [37] M. Yoshimura, Y. Watanabe, K. Kasai, J. Yamakoshi, T. Koga, Inhibitory effect of an ellagic acid-rich pomegranate extract on tyrosinase activity and ultraviolet-induced pigmentation, Biosci. Biotechnol. Biochem. 69 (2005) 2368–2373. [38] A.K. Mittal, Y. Chisti, U.C. Banerjee, Synthesis of metallic nanoparticles using plant extracts, Biotechnol. Adv. 31 (2013) 346–356. [39] V. Makarov, A. Love, O. Sinitsyna, S. Makarova, I. Yaminsky, M. Taliansky, N. Kalinina, ‘‘Green” nanotechnologies: synthesis of metal nanoparticles using plants, Acta Nat. 6 (2014) 35–44. [40] M. Lerma-García, M. Ávila, E.F. Simó-Alfonso, Á. Ríos, M. Zougagh, Synthesis of gold nanoparticles using phenolic acids and its application in catalysis, J. Mater. Environ. Sci. 5 (2014) 1919–1926. [41] Y. Yu, A. Mendoza-Garcia, B. Ning, S. Sun, Cobalt-substituted magnetite nanoparticles and their assembly into ferrimagnetic nanoparticle arrays, Adv. Mater. 25 (2013) 3090–3094. [42] P. Jodłowski, R. Je˛drzejczyk, A. Rogulska, A. Wach, P. Kus´trowski, M. Sitarz, T. Łojewski, A. Kołodziej, J. Łojewska, Spectroscopic characterization of Co3 O4 catalyst doped with CeO2 and PdO for methane catalytic combustion, Spectrochim. Acta Mol. Biomol. Spectrosc. 131 (2014) 696–701. [43] G. Wang, X. Shen, J. Horvat, B. Wang, H. Liu, D. Wexler, J. Yao, Hydrothermal synthesis and optical, magnetic, and supercapacitance properties of nanoporous cobalt oxide nanorods, J. Phys. Chem. C. 113 (2009) 4357–4361. [44] P.Y. Keng, B.Y. Kim, I.-B. Shim, R. Sahoo, P.E. Veneman, N.R. Armstrong, H. Yoo, J.E. Pemberton, M.M. Bull, J.J. Griebel, Colloidal polymerization of polymercoated ferromagnetic nanoparticles into cobalt oxide nanowires, ACS Nano. 3 (2009) 3143–3157. [45] J.S. Chen, T. Zhu, Q.H. Hu, J. Gao, F. Su, S.Z. Qiao, X.W. Lou, Shape-controlled synthesis of cobalt-based nanocubes, nanodiscs, and nanoflowers and their comparative lithium-storage properties, ACS Appl. Mater. Interfaces 2 (2010) 3628–3635. [46] M. Hepel, J. Luo, Photoelectrochemical mineralization of textile diazo dye pollutants using nanocrystalline WO3 electrodes, Electrochim. Acta. 47 (2001) 729–740. [47] S. Joseph, B. Mathew, Microwave-assisted green synthesis of silver nanoparticles and the study on catalytic activity in the degradation of dyes, J. Mol. Liq. 204 (2015) 184–191. [48] M. Iqbal, Vicia faba bioassay for environmental toxicity monitoring: a review, Chemosphere 144 (2016) 785–802. [49] H. Lachheb, E. Puzenat, A. Houas, M. Ksibi, E. Elaloui, C. Guillard, J.-M. Herrmann, Photocatalytic degradation of various types of dyes (Alizarin S, Crocein Orange G, Methyl Red, Congo Red, Methylene Blue) in water by UVirradiated titania, Appl. Catal. B Environ. 39 (2002) 75–90. [50] V. Subramanian, R.K. Roeder, E.E. Wolf, Synthesis and UV-visible-light photoactivity of noble-metal-SrTiO3 composites, Ind. Eng. Chem. Res. 45 (2006) 2187–2193. [51] A. Babarinde, K. Ogundipe, K.T. Sangosanya, B.D. Akintola, A.-O. Elizabeth, Hassan, Comparative study on the biosorption of Pb(II), Cd(II) and Zn(II) using Lemon grass (Cymbopogon citratus): kinetics, isotherms and thermodynamics, Chem. Int. 2 (2016) 89–102. [52] A. Babarinde, G.O. Onyiaocha, Equilibrium sorption of divalent metal ions onto groundnut (Arachis hypogaea) shell: kinetics, isotherm and thermodynamics, Chem. Int. 2 (2016) 37–46.

Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008

398 399 400 401 402 403 404 405 406 407 408 409 410 411 412 413 414 415 416 417 418 419 420 421 422 423 424 425 426 427 428 429 430 431 432 433 434 435 436 437 438 439 440 441 442 443 444 445 446 447 448 449 450 451 452 453 454 455 456 457 458 459 460 461 462 463 464 465 466 467 468 469 470 471 472 473 474 475 476 477 478 479 480 481 482 483

APT 1612

No. of Pages 9, Model 5G

25 May 2017 8 484 485 486 487 488 489 490 491 492 493 494 495 496 497 498 499 500 501 502 503 504 505 506 507 508 509 510 511 512 513 514 515 516 517 518 519 520 521 522 523 524 525 526 527 528 529 530 531 532 533 534 535 536 537 538 539 540 541 542 543 544 545 546 547 548 549 550 551 552 553 554 555 556 557 558 559 560 561 562 563 564 565 566 567 568

I. Bibi et al. / Advanced Powder Technology xxx (2017) xxx–xxx

[53] N.K. Benabdallah, D. Harrache, A. Mir, M. de la Guardia, F.-Z. Benhachem, Bioaccumulation of trace metals by red alga Corallina elongata in the coast of Beni Saf, west coast, Algeria. Chem. Int. 3 (2017) 220–231. [54] M. Iqbal, R.A. Khera, Adsorption of copper and lead in single and binary metal system onto Fumaria indica biomass, Chem. Int. 1 (2015) 157b–163b. [55] S. Jafarinejad, Control and treatment of sulfur compounds specially sulfur oxides (SOx) emissions from the petroleum industry: a review, Chem. Int. 2 (2016) 242–253. [56] S. Jafarinejad, Recent developments in the application of sequencing batch reactor (SBR) technology for the petroleum industry wastewater treatment, Chem. Int. 3 (3) (2017). [57] M.A. Jamal, M. Muneer, M. Iqbal, Photo-degradation of monoazo dye blue 13 using advanced oxidation process, Chem. Int. 1 (2015) 12–16. [58] A.O. Majolagbe, A.A. Adeyi, O. Osibanjo, Vulnerability assessment of groundwater pollution in the vicinity of an active dumpsite (Olusosun), Lagos, Nigeria, Chem. Int. 2 (2016) 232–241. [59] A.O. Majolagbe, A.A. Adeyi, O. Osibanjo, A.O. Adams, O.O. Ojuri, Pollution vulnerability and health risk assessment of groundwater around an engineering Landfill in Lagos, Nigeria, Chem. Int. 3 (2017) 58–68. [60] K.D. Ogundipe, A. Babarinde, Comparative study on batch equilibrium biosorption of Cd(II), Pb(II) and Zn(II) using plantain (Musa paradisiaca) flower: kinetics, isotherm, and thermodynamics, Chem. Int. 3 (2017) 135– 149. [61] U.C. Peter, U. Chinedu, Model prediction for constant area, variable pressure drop in orifice plate characteristics in flow system, Chem. Int. 2 (2016) 80–88. [62] K. Qureshi, M. Ahmad, I. Bhatti, M. Iqbal, A. Khan, Cytotoxicity reduction of wastewater treated by advanced oxidation process, Chem. Int. 1 (2015) 53– 59. [63] A. Shindy, Problems and solutions in colors, dyes and pigments chemistry: A Review, Chem. Int. 3 (2017) 97–105. [64] H. Shindy, Basics in colors, dyes and pigments chemistry: A review, Chem. Int. 2 (2016) 29–36. [65] M. Iqbal, M. Abbas, M. Arshad, T. Hussain, A.U. Khan, N. Masood, M.A. Tahir, S. M. Hussain, T.H. Bokhari, R.A. Khera, Gamma radiation treatment for reducing cytotoxicity and mutagenicity in industrial wastewater, Pol. J. Environ. Stud. 24 (2015) 2745–2750. [66] M. Iqbal, I.A. Bhatti, Gamma radiation/H2O2 treatment of a nonylphenol ethoxylates: degradation, cytotoxicity, and mutagenicity evaluation, J. Hazard. Mater. 299 (2015) 351–360. [67] M. Iqbal, J. Nisar, Cytotoxicity and mutagenicity evaluation of gamma radiation and hydrogen peroxide treated textile effluents using bioassays, J. Environ. Chem. Eng. 3 (2015) 1912–1917. [68] M. Iqbal, J. Nisar, M. Adil, M. Abbas, M. Riaz, M.A. Tahir, M. Younus, M. Shahid, Mutagenicity and cytotoxicity evaluation of photo-catalytically treated petroleum refinery wastewater using an array of bioassays, Chemosphere 168 (2017) 590–598. [69] J. Nisar, M. Sayed, F.U. Khan, H.M. Khan, M. Iqbal, R.A. Khan, M. Anas, Gamma – irradiation induced degradation of diclofenac in aqueous solution: Kinetics, role of reactive species and influence of natural water parameters, J. Environ. Chem. Eng. 4 (2016) 2573–2584. [70] D. Liao, B. Liao, Shape, size and photocatalytic activity control of TiO2 nanoparticles with surfactants, J. Photochem. Photobiol. A Chem. 187 (2007) 363–369. [71] T. Hyeon, S.S. Lee, J. Park, Y. Chung, H.B. Na, Synthesis of highly crystalline and monodisperse maghemite nanocrystallites without a size-selection process, J. Am. Chem. Soc. 123 (2001) 12798–12801. [72] S. Gubin, G.Y. Yurkov, N. Kataeva, Microgranules and nanoparticles on their surfaces, Inorgan. Mater. 41 (2005) 1017–1032. [73] B. Sone, E. Manikandan, A. Gurib-Fakim, M. Maaza, S2O3 nanoparticles green synthesis via Callistemon viminalis’ extract, J. Alloy. Comp. 650 (2015) 357– 362. [74] U. Kreibig, M. Vollmer, Optical properties of metal clusters, Springer, New York, 1995. [75] P.K. Jain, K.S. Lee, I.H. El-Sayed, M.A. El-Sayed, Calculated absorption and scattering properties of gold nanoparticles of different size, shape, and composition: applications in biological imaging and biomedicine, J. Phys. Chem. B. 110 (2006) 7238–7248. [76] G. Nazeruddin, S. Prasad, Y. Shaikh, J. Ansari, K. Sonawane, A. Nayak, M. Deshmukh, P. Patil, B. Rathor, N. Prasad, In-vitro bio-fabrication of multiapplicative silver nanoparticles using Nicotiana tabacum leaf extract, Res. J. Life Sci. Bioinformat. Pharmaceut, Chem. Sci. 2 (2016) 6–33. [77] A.R. Vilchis-Nestor, V. Sánchez-Mendieta, M.A. Camacho-López, R.M. GómezEspinosa, M.A. Camacho-López, J.A. Arenas-Alatorre, Solventless synthesis and optical properties of Au and Ag nanoparticles using Camellia sinensis extract, Mater. Lett. 62 (2008) 3103–3105. [78] I. Lisiecki, M. Pileni, Synthesis of well-defined and low size distribution cobalt nanocrystals: the limited influence of reverse micelles, Langmuir 19 (2003) 9486–9489. [79] N. Ahmad, S. Sharma, R. Rai, Rapid green synthesis of silver and gold nanoparticles using peels of Punica granatum, Adv. Mater. Lett. 3 (2012) 376– 380. [80] G.A. Kahrilas, L.M. Wally, S.J. Fredrick, M. Hiskey, A.L. Prieto, J.E. Owens, Microwave-assisted green synthesis of silver nanoparticles using orange peel extract, ACS Sustain. Chem. Eng. 2 (2013) 367–376.

[81] M. Salavati-Niasari, A. Khansari, F. Davar, Synthesis and characterization of cobalt oxide nanoparticles by thermal treatment process, Inorgan. Chim. Acta 362 (2009) 4937–4942. [82] G. Nazeruddin, N. Prasad, S. Prasad, K. Garadkar, A.K. Nayak, In-vitro biofabrication of silver nanoparticle using Adhathoda vasica leaf extract and its anti-microbial activity, Phys. E Low-Dimen. Syst. Nanostruct. 61 (2014) 56– 61. [83] N.A. Dhas, C.P. Raj, A. Gedanken, Synthesis, characterization, and properties of metallic copper nanoparticles, Chem. Mater. 10 (1998) 1446–1452. [84] U.A. Fischer, R. Carle, D.R. Kammerer, Identification and quantification of phenolic compounds from pomegranate (Punica granatum L.) peel, mesocarp, aril and differently produced juices by HPLC-DAD–ESI/MS n, Food Chem. 127 (2011) 807–821. [85] A. Dzimitrowicz, P. Jamróz, G.C. diCenzo, I. Sergiel, T. Kozlecki, P. Pohl, Preparation and characterization of gold nanoparticles prepared with aqueous extracts of Lamiaceae plants and the effect of follow-up treatment with atmospheric pressure glow microdischarge, Arab. J. Chem. (2016), http://dx.doi.org/10.1016/j.arabjc.2016.04.004. [86] S. Adeel, M. Usman, W. Haider, M. Saeed, M. Muneer, M. Ali, Dyeing of gamma irradiated cotton using Direct Yellow 12 and Direct Yellow 27: improvement in colour strength and fastness properties, Cellulose 22 (2015) 2095–2105. [87] M. Ajmal, S. Adeel, M. Azeem, M. Zuber, N. Akhtar, N. Iqbal, Modulation of pomegranate peel colourant characteristics for textile dyeing using high energy radiations, Indu. Crop. Product. 58 (2014) 188–193. [88] F. Bouatay, N. Meksi, S. Adeel, F. Salah, F. Mhenni, Dyeing behavior of the cellulosic and jute fibers with cationic dyes: Process development and optimization using statistical analysis, J. Nat. Fiber. 13 (2016) 423–436. [89] T. Gulzar S. Adeel I. Hanif F. Rehman R. Hanif M. Zuber N. Akhtar Eco-friendly dyeing of gamma ray induced cotton using natural quercetin extracted from acacia bark (A. nilotica) J. Nat. Fiber. 12 2015 494 504. [90] M. Muneer, S. Adeel, S. Ayub, M. Zuber, F. Ur-Rehman, M. Kanjal, M. Iqbal, M. Kamran, Dyeing behaviour of microwave assisted surface modified polyester fabric using disperse orange 25: improvement in colour strength and fastness properties, Oxid. Comm. 39 (2016) 1430–1439. [91] S.K. Sharma, D. Agarwal, Synthesis of cetylpyridiniumtribromide (CetPyTB) reagent by noble synthetic route and bromination of organic compounds using CetPyTB, Chem. Int. 1 (2015) 164–173. [92] C. Ukpaka, Development of model for bioremediation of crude oil using moringa extract, Chem. Int. 2 (2016) 19–28. [93] C. Ukpaka, Predictive model on the effect of restrictor on transfer function parameters on pneumatic control system, Chem. Int. 2 (2016) 128–135. [94] C. Ukpaka, Empirical model approach for the evaluation of pH and conductivity on pollutant diffusion in soil environment, Chem. Int. 2 (2016) 267–278. [95] C. Ukpaka, B.T.X. Degradation, The concept of microbial integration, Chem Int 3 (2016) 8–18. [96] C. Ukpaka, T. Izonowei, Model prediction on the reliability of fixed bed reactor for ammonia production, Chem. Int. 3 (2017) 46–57. [97] C. Ukpaka, C. Ukpaka, Characteristics of groundwater in Port-Harcourt local Government area, Chem. Int. 2 (2016) 136–144. [98] C.P. Ukpaka, F.U. Igwe, Modeling of the velocity profile of a bioreactor: the concept of biochemical process, Chem. Int. 3 (2017) 258–267. [99] F. Hussain, S.Z. Shah, W. Zhou, M. Iqbal, Microalgae screening under CO2 stress: Growth and micro-nutrients removal efficiency, J. Photochem. Photobiol. B. Biol. 170 (2017) 91–98. [100] M. Iqbal, N. Iqbal, I.A. Bhatti, N. Ahmad, M. Zahid, Response surface methodology application in optimization of cadmium adsorption by shoe waste: A good option of waste mitigation by waste, Ecol. Eng. 88 (2016) 265– 275. [101] M. Mushtaq, H.N. Bhatti, M. Iqbal, S. Noreen, Eriobotrya japonica seed biocomposite efficiency for copper adsorption: Isotherms, kinetics, thermodynamic and desorption studies, J. Environ. Manage. 176 (2016) 21–33. [102] R. Nadeem, Q. Manzoor, M. Iqbal, J. Nisar, Biosorption of Pb (II) onto immobilized and native Mangifera indica waste biomass, J. Ind. Eng. Chem. 35 (2016) 185–194. [103] H. Naeem, H.N. Bhatti, S. Sadaf, M. Iqbal, Uranium remediation using modified Vigna radiata waste biomass, Appl. Radiat. Isotop. 123 (2017) 94– 101. [104] S. Nouren, H.N. Bhatti, M. Iqbal, I. Bibi, S. Kamal, S. Sadaf, M. Sultan, A. Kausar, Y. Safa, By-product identification and phytotoxicity of biodegraded Direct Yellow 4 dye, Chemosphere 169 (2017) 474–484. [105] A. Rashid, H.N. Bhatti, M. Iqbal, S. Noreen, Fungal biomass composite with bentonite efficiency for nickel and zinc adsorption: a mechanistic study, Ecological engineering 91 (2016) 459–471. [106] S. Shoukat, H.N. Bhatti, M. Iqbal, S. Noreen, Mango stone biocomposite preparation and application for crystal violet adsorption: A mechanistic study, Micropor. Mesopor. Mater. 239 (2017) 180–189. [107] M.A. Tahir, H.N. Bhatti, M. Iqbal, Solar Red and Brittle Blue direct dyes adsorption onto Eucalyptus angophoroides bark: Equilibrium, kinetics and thermodynamic studies, J. Environ. Chem. Eng. 4 (2016) 2431–2439. [108] N. Tahir, H.N. Bhatti, M. Iqbal, S. Noreen, Biopolymers composites with peanut hull waste biomass and application for Crystal Violet adsorption, Int. J. Biol. Macromol. 94 (2016) 210–220. [109] M. Saeed, S. Adeel, M. Ilyas, M.A. Shahzad, M. Usman, E.-U. Haq, M. Hamayun, Oxidative degradation of Methyl Orange catalyzed by lab prepared nickel

Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008

569 570 571 572 573 574 575 576 577 578 579 580 581 582 583 584 585 586 587 588 589 590 591 592 593 594 595 596 597 598 599 600 601 602 603 604 605 606 607 608 609 610 611 612 613 614 615 616 617 618 619 620 621 622 623 624 625 626 627 628 629 630 631 632 633 634 635 636 637 638 639 640 641 642 643 644 645 646 647 648 649 650 651 652 653

APT 1612

No. of Pages 9, Model 5G

25 May 2017 I. Bibi et al. / Advanced Powder Technology xxx (2017) xxx–xxx 654 655 656 657 658 659 660 661 662 663 664

hydroxide in aqueous medium, Desalin. Water Treat. 57 (2016) 12804– 12813. [110] M. Saeed, A. Haq, M. Muneer, S. Adeel, M. Hamayun, M. Ismail, M. Younas, Degradation of Direct Black 38 dye catalyzed by Lab Prepared Nickel Hydroxide in Aquous medium, Global Nest J. 18 (2016) 309–320. [111] A. Sasmaz, I.M. Dogan, M. Sasmaz, Removal of Cr, Ni and Co in the water of chromium mining areas by using Lemna gibba L. and Lemna minor L, Water Environ. J. 30 (2016) 235–242. [112] M. Sasmaz, B. Akgül, A. Sasmaz, Distribution and accumulation of selenium in wild plants growing naturally in the Gumuskoy (Kutahya) Mining Area, Turkey, Bull. Environ. Contam. Toxicol. 94 (2015) 598–603.

9

[113] M. Sasmaz, B. Akgul, D. Yıldırım, A. Sasmaz, Bioaccumulation of thallium by the wild plants grown in soils of mining area, Int. J. Phytoremediat. 18 (2016) 1164–1170. [114] M. Sasmaz, B. Akgül, D. Yıldırım, A. Sasmaz, Mercury uptake and phytotoxicity in terrestrial plants grown naturally in the Gumuskoy (Kutahya) mining area, Turkey, Int. J. Phytoremediat. 18 (2016) 69–76. [115] M. Sasmaz, E. Obek, A. Sasmaz, Bioaccumulation of Uranium and Thorium by Lemna minor and Lemna gibba in Pb-Zn-Ag Tailing Water, Bull. Environ. Contam. Toxicol. 97 (2016) 832–837. [116] M. Sasmaz, E.I.A. Topal, E. Obek, A. Sasmaz, The potential of Lemna gibba L. and Lemna minor L. to remove Cu, Pb, Zn, and As in gallery water in a mining area in Keban, Turkey, J. Environ. Manage. 163 (2015) 246–253.

665 666 667 668 669 670 671 672 673 674 675 676 677

Please cite this article in press as: I. Bibi et al., Green and eco-friendly synthesis of cobalt-oxide nanoparticle: Characterization and photo-catalytic activity, Advanced Powder Technology (2017), http://dx.doi.org/10.1016/j.apt.2017.05.008