- Email: [email protected]
Efficient degradation of organic dyes by heterogeneous cefdinir derived silver nanocatalyst
G Model
JIEC 2571 1–7 Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Journal of Industrial and Engineering Chemistry journal homepage: www.elsevier.com/locate/jiec 1 2 3 4 5 6
Efficient degradation of organic dyes by heterogeneous cefdinir derived silver nanocatalyst Q1 Muhammad a b
Safdar a,*, Yasmeen Junejo a,b, Aamna Balouch b
Department of Medical Biology and Genetics, University of Gaziantep, Gaziantep, Turkey National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080, Pakistan
A R T I C L E I N F O
A B S T R A C T
Article history: Received 12 March 2015 Received in revised form 8 May 2015 Accepted 25 June 2015 Available online xxx
Cefdinir derived silver nanocatalyst (Cef-Ag (0) NPs) was successfully synthesized in aqueous solution by efficient one-pot method and effectively employed for the ultrafast catalytic degradation of Rose Bengal and Eosin Gelblich dyes. The improvement was achieved in percent degradation of toxic dyes by varying and optimizing reaction time, and amount of catalyst reducing agent concentration. The catalytic study revealed that complete reduction 99.9% of dye was accomplished in short period of reaction time (60 s) by efficient cefdinir derived silver nanoparticles. The calculated K (rate constant) value for RB and EG catalytic degradation was achieved 7 10 2 and 10 10 2 s 1, respectively by plotting lnC vs time (s) and result show that reaction is following first order kinetics. ß 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.
Keywords: Heterogeneous silver nanocatalyst Cefdinir Green chemistry Catalytic reductive degradation Dyes
7 8
Introduction
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Nowadays, it is important to continue research toward synthesis of metal nanoparticles (MNPs) by using inexpensive and nontoxic chemicals [1,2], environmentally benign solvents, and clean and renewable/biodegradable materials [3,4]. These nanoparticles were utilized in most of chemical reactions of degradation of pollutant compounds [5–8]. Among the different noble metal nanoparticles, stabilized silver nanoparticles (AgNPs) have been widely employed as catalysts for a wide range of reactions [9,10]. Degradation of dyes effluent is a crucial and sensitive issue for industries [6]. Continuous exposure to these dyes has been exposed to exert influence on anaerobic biomass, irritation of the respiratory system, and gastro intestinal track. Hence, physical or chemical advanced treatment processes are essential and useful for the treatment of waste waters containing these dyes [11]. On the other hand, most of the dyes are useful for different industries purposes like pigmentation of textiles, cosmetics, paper, leather, ceramics, inks, and food processing products, which are derived from AZO dyes. About 15% of the dyes are discharged in the natural streams. This waste signals a great hazard and cause much harm to human and environmental health due to the toxicity of effluent of
* Corresponding author. Tel.: +90 507 5125460; fax: +90 2128663412. E-mail address: [email protected] (M. Safdar).
these dyes [12]. Many techniques are available for the removal of these dyes such as adsorption [13], nanofiltration [14], biological treatment [15] and so on. Dyes consist of one of the major groups of chemicals besides fertilizers, pharmaceuticals, and petrochemicals. During ancient times, people used dyes from natural resources like tesu flowers, so that they can make their clothes bright and colorful likewise, indigo, logwood, madder, etc. [6]. The dyeing and textile printing industry is a water-intensive industry requiring a large volume of freshwater at various steps of printing and therefore, the volume of wastewater produced is equally large. These effluents, with their high BOD (Biological Oxygen Demand), COD (Chemical Oxygen Demand), and poised solids, are very toxic in nature as they contain large quantities of dyes (azoic, indigo, and aniline), bleaching agents, acids/alkalis, and heavy metals in very high concentration [16]. Some textile dyes are relatively challenging to microbial degradation, besides that anaerobic microorganisms when degrading some dyes give birth to aromatic amines that might be dangerous and carcinogenic [17]. Therefore, in recent years, there have been many researches done on fungal depolarization of textile waste water. The use of fungi is a promising alternative to replace or add current treatments [18–20]. Textile industry is one of the most common and essential industrial sectors in the world that plays significant role in nation’s economy [21]. Because of drastic changes in customers’ demands, the textiles finishing
http://dx.doi.org/10.1016/j.jiec.2015.06.026 1226-086X/ß 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
G Model
JIEC 2571 1–7 2
M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79
industry is a challenge to use high quantity of dyes and auxiliaries that are necessary for modern textile processing [22]. Among all these dyes, Rose Bengal and Eosin Gelblich dyes are highly toxic [23], which contains heterocyclic aromatic compound due to its cationic in the nature [24], Rose Bengal and Eosin Gelblich functional groups pretense a hazard as pollutants to water resources [11]. The emergence applications of heterogeneous catalysts include metal and metal oxide nanoparticles for advanced techniques of waste water treatments so that it could produce successful result [25–28]. Therefore, it is the urge of time for the requirement of a technique which endorses very simple, costeffective, green, and prompt methods to use nano-based catalytic degradation/reduction of organic dyes pollutants. Previously, antibiotic-based silver nanoparticles were synthesized and used as catalyst for the degradation of some pharmaceutical drugs [29]. Herein, we report a very simple one-pot method for the synthesis of silver nanocatalysts by green method using cefdinir antibiotic and their effective application as heterogeneous, recoverable, and reusable catalyst for remarkably faster and complete degradation of Rose Bengal and Eosin Gelblich dyes in the presence of LiAlH4. The entire research work is based on excellent economy of the process in terms of using cheaper chemicals, facile, and simpler synthesis of catalyst, with shorter time for product formation (quicker procedure) and easy recovery and recycle of this catalyst.
The FTIR (Fourier transform infrared) spectra of AgNPs and cefdinir were performed by model (Perkin Elmer BX FTIR) after incorporating the dried sample in solid state KBr disk. FTIR spectra in the range 4000–400 cm 1 were recorded, so that it would be easy to investigate the nature of the chemical bonds formed. X-ray powder diffraction (XRD) analysis was conducted on a Rigaku Smart Lab Diffractometer operated at 40 kV and 35 mA by using Cu Ka radiation. High-resolution transmission electron microscopy (HRTEM) analysis was studied by using a JEOL JEM 2100 microscope. A drop of diluted sample in alcohol was dripped on a TEM grid.
110 111 112 113 114 115 116 117 118 119 120
Sample preparation for XRD and FTIR and TEM
121
In each case, the yellow colloidal solution of Cef-AgNPs was poured into petri dish and heated on temperature controlled electric water bath set at 100 8C until solvent evaporation. The dried product was washed several times with both deionized water and ethanol in order to remove any unreacted cefdinir. The product was carefully dried in an oven at 100 8C at least for 60 min. The black particles adsorbed on the glass of petri dish were removed with a clean glass slide. The resulting sample was collected in a small sample ampoule before each analysis.
122 123 124 125 126 127 128 129 130
Procedure for catalytic degradation of dyes
131
80
Experimental
81
Cleaning of glassware
82 83 84 85 86 87
All glassware were soaked in 1 M HNO3 solution overnight followed by washing with detergent containing solution, tap water, and ultrapure water. The glassware were finally washed several times with deionized water and put in an oven at 100 8C for 1 h. The dried glass wares were properly cooled in room temperature before use.
88
Chemicals and reagents
The catalytic activity of cefdinir derived silver nanoparticles was experienced by reduction of RB and EG dyes with an excessive quantity of LiAlH4 only with the quantity of Cef-AgNPs. Under optimized conditions, 10 mg/l dyes (100 ml) along 0.1 M LiAlH4 (100 ml) were taken in a 3.0 ml capacity quartz cuvette and then, the volume of the mixture was adjusted 3.0 ml with distilled water and after that the catalytic degradation of dyes was monitored by recording UV–vis spectra. For application studies, NPs were placed on a piece of glass cover slip by drop casting method followed by solvent evaporation on hot plate at the temperature of 100 8C. The weight of glass cover slip was measured before and after NPs deposition to check out the weight of NPs deposited by difference.
132 133 134 135 136 137 138 139 140 141 142 143
89 90 91 92 93 94
Analytical grade 99% AgNO3, 99% NaOH, 98% LiAlH4 and 99%Cefdinir, 97% Rose Bengal (RB), and 97% Eosin Gelblich (EG) were purchased from Sigma–Aldrich and Merck respectively, and utilized without further purification. All solutions that is acidic, basic, and salt solutions were prepared in ultrapure water (conductivity below than 0.05 mS/cm).
Results and discussion
144
UV–vis spectroscopy
145
95
Preparation of standard stock solutions
96 97 98 99
To prepare the standard solutions of compound such as 0.01 M cefdinir, AgNO3, NaOH Rose Bengal and Eosin Gelblich, and 0.1 M LiAlH4, the exact masses of each reagent was taken in 100 ml of volumetric flask and dissolved in ultrapure water.
100
Synthetic procedure for cefdinir capped-Ag NPs
101 102 103 104 105
Highly efficient cefdinir capped-Ag NPs were successfully synthesized by following protocol. In typical procedure 0.4 ml of AgNO3 solution was taken in 20 ml test tube and 0.3 ml cefdinir and 0.2 ml NaOH was added. Solution was shaken properly and final volume was made up to 10 ml with ultrapure water.
UV–vis spectrometry was performed to follow and confirm the formation of cefdinir stabilized silver nanoparticles (Cef-Ag (0) NP). The reduction of Ag+ ions into Ag nanoparticles was monitored by recording the absorption spectrum of the reaction mixture with time in the range of 300–900 nm. It is observed in UV–vis spectrum of the Cef-Ag (0) NPs that the colloidal silver exhibits a strong absorption between 400 and 415 nm, which corresponds to the surface Plasmon resonance (SPR) of AgNPs [9,30] suggesting the formation of NPs as shown in Fig. 1. The appearance of absorption band in the range of 350–450 nm is due to surface plasmon vibrations of conducting electrons [9,31]. CefAgNPs were synthesized with very slow kinetics and showed excellent stability until several months and no significant change is observed in the intensity of the SPR band. The sharp intense band evident the formation of monodispersed and spherical nanoparticles and the absence of any absorption peak in the range of 450– 900 nm indicate the no apparent aggregation of nanoparticles [32].
146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162
106
Instrumentations
HRTEM analysis
163
107 108 109
The resulting Cef-AgNPs solution was analyzed by ultraviolet– visible (UV–vis) spectrometer model Shimadzu UV–vis 2600 in the range of 300–800 nm.
Fig. 2 shows the typical HRTEM image of the AgNPs prepared using chemical reduction approach. TEM analysis on the sample indicated crystalline spherical Cef-AgNPs with 6.80 2.1 nm
164 165 166
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
3.0
1.05
Time study of Cefdinir derived silver nanoparticles
1.00
408 nm
a
0.95
2.5
0.90
6 month 3 month 1 month 1 week 12 hour 6 hour 3 hour 2 hour 1 hour
2.0 1.5 1.0
% Transmittance (a.u)
Absorbance (a.u.)
3
Cefdinir Standard
0.85 0.80 0.75 0.70
b
0.65 0.60
Cef-Ag (0) NPs
0.55 0.50
0.5
0.45 0.0 300
0.40 400
500
600
700
800
900
Wavelength (nm) Fig. 1. The UV–vis spectra recorded for time study of Cef-Ag (0) NPs samples showing stable absorption band at 408 nm after 1 h to 6 months successively.
167 168 169 170 171 172 173 174 175
particle size of Cef-AgNPs. The formation crystalline spherical AgNPs is assumed as the effective combinative effect of antibiotic cefdinir and NaOH reducing agent used during the growth process. These smaller monodispersed nanospheres may act as a nanoreactor and offer enhanced efficiency as a catalytic for reduction/degradation of toxic chemicals [33]. The smaller size may facilitate enhanced mobility of charge carriers to different reaction positions and a more effective reaction process. Thus, enhanced catalytic properties are expected from these nanostructures.
176
FT-IR spectroscopy
177 178 179 180 181 182 183 184 185 186 187 188 189 190
For further confirmation of formation of AgNPs the FTIR spectroscopy was used to clarify the surface interaction of cefdinir to the AgNPs and the results are presented in Fig. 3a, b. FTIR spectrum of cefdinir standard show two broad and strong signals at 3290 and 1390 cm 1 assigned to amine groups [34], primary and secondary amines shows stretching vibrations at 16, 781, 625, and 1520 cm 1, in this region aromatic carbon ring is also present [35]. Additionally, the C–O group stretching vibrations at 1350 cm 1 [36] while other related peaks 1180 and 1020 cm 1 showed the C–N and N–H stretching [34,35]. Furthermore, it describes the bending vibrations between 748–536 cm 1 that corresponds to aromatic sulphur [37] (Fig. 3a). Moreover, in the FTIR spectrum of silver nanoparticles, the broad band at 3290 and 3060 cm 1 are completely disappeared
0.35 4000
3500
3000
2500 2000 1500 -1 Wavenumber (cm )
1000
500
Fig. 2. FTIR Spectra of Cefdinir (a) and silver nanoparticles (b).
which could be attributed to the bonding of amine with silver ion. Also the slight shift in peak of amine group from 1520 to 1595 cm 1 further confirm the bond formation as shown in Fig. 3b. XRD analysis of silver nanoparticles Powder pattern of Cef-AgNPs were obtained by using solid product as the result of drying of Cef-AgNPs (Fig. 4). Nearly 2 mg of dark black solid sample were analyzed, Cef-AgNPs with face centered cubic (fcc) structure also matched with literature [38,39]. A number of Bragg reflections with two theta values of 37.6, 43.8, 64.03, and 76.048 correspond to the (111), (200), (220), and (311) sets of lattice planes were observed, which was indexed as the band to face centered cubic structures of silver. The XRD pattern thus verified that the Cef-AgNPs synthesized by the green method are crystalline in nature [40]. The XRD pattern thus clearly showed that the AgNPs synthesized by the green method are crystalline in nature. Scherrer equation (also referred to as the Debye–Scherrer equation) has been applied to estimate the size of Cef-Ag crystallites. It was estimated at around 13.8 nm.
191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209
Catalytic degradation of dyes using Cef-AgNPs
210
The catalytic degradation experiment was carried out directly in quartz cuvets, 100 ml (10 mg/l) aliquot of azo dyes (Rose Bengal) was taken and 0.1 M LiAlH4 (100 ml) was added and finally the volume of the mixture was adjusted to 3.0 ml with ultrapure
211 212 213 214
Fig. 3. HRTEM images and particle size distribution diagram of Cefdinir derived Ag (0) NPs.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
4
exp. fit
Intensity (a.u.)
111
200
20
30
40 50 2 Theta (deg.)
311
220
60
70
80
Fig. 4. XRD powder pattern of Cefdinir derived Ag (0) NPs.
215 216 217 218 219 220 221 222 223 224
water. Afterward, 0.5 mg Cef-AgNPs was introduced in the Rose Bengal dye solution to catalyze the reaction. The catalytic degradation was observed by changing the color of the solution, and observation was continued until the color completely vanished. Fig. 5 represents a typical evolution of the UV–vis spectra of Rose Bengal dye. It can be observed that no important changes occurred in the reduction of RB (100 ml, 10 mg/l) even after 24 h in the presence of LiAlH4 only (Fig. 5a). But after the addition of Cef-AgNPs (0.1–0.5 mg), the absorbance intensity has showed a decreasing trend which indicates that the catalytic
degradation of RB (100 ml, 10 mg/l) has been achieved through the inclusion of Ag nanoparticles which is shown in Fig. 5b. Also we observed the complete catalytic degradation of RB (100 ml, 10 mg/ l) at 545 nm [41,42] just within 60 s in the presence of our newly synthesized Cef-AgNPs (0.5 mg) (Fig. 5c). Similarly the catalytic degradation of Eosin Gelblich dye was done by following same protocol and monitored the reaction till color of the solution vanished and it indicated the complete degradation of the EG dye solution. EG is a heterocyclic aromatic dye, the freshly prepared aqueous EG solution having concentration of 100 ml, 10 mg/l with a relative absorbance of band at 515 nm [43,44]. More than 24 h were required for reduction of EG without Ag nanocatalyst (Fig. 6a). But after the addition of Cef-AgNPs (0.1–0.6 mg), the absorbance intensity has showed a decreasing trend which indicates that the catalytic degradation of EG (100 ml, 10 mg/l) has been achieved through the inclusion of Ag nanoparticles which is shown in Fig. 6b. This indicates that the complete catalytic degradation of EG Q2 (100 ml, 10 mg/l) to a colorless within 80 s in the presence of our newly synthesized Cef-AgNPs (0.6 mg) (Fig. 6c). Khataee et al. [45] studied the degradation of basic red 46 by combining photoelectron-Fenton and heterogeneous photocatalytic process. The authors observed 99.2% mineralization of 15 mg/l dye in 6 h. Similarly, Daneshvar et al. [46] systematically investigated the degradation of acid red 14 using ZnO photocatalyst. Moreover, Vignesh et al. [47] observed 85% degradation of rose Bengal in 150 min with Ag-doped SnO2 nanoparticles modified with curcumin.
(b) (a)
(d) (c)
Fig. 5. Degradation of Rose Bengal dye; (a) Degradation in the presence of LiAlH4 only, (b) at fixed concentration of Rose Bengal dye (10 mg/l) degradation with varying amounts 0.1–0.5 mg Cef-Ag (0) NPs and 0.1 M LiAlH4 (c) at fixed concentration of Rose Bengal dye (10 mg/l) degradation at fixed amount of Cef-Ag (0) NPs (0.5 mg) and 0.1 M LiAlH4 (d) Linear regression for pseudo first order kinetics for the reductive degradation of Rose Bengal dye.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
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
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
5
(b) (a)
(d)
(c)
Fig. 6. Degradation of Eosin Gelblich dye; (a) Degradation in the presence of 0.1 M LiAlH4 only, (b) at fixed concentration of Eosin Gelblich dye (10 mg/L) degradation with varying amounts 0.1–0.6 mg Cef-Ag (0) NPs and 0.1 M LiAlH4, (c) at fixed concentration of Eosin Gelblich dye (10 mg/l) degradation at fixed amount of Cef-Ag (0) NPs (0.6 mg) and 0.1 M LiAlH4, (d) Linear regression for pseudo first order kinetics for the reductive degradation of Eosin Gelblich dye.
253 254 255 256 257 258
The kinetics of reaction was also investigated and compared with literature. It is evident from the calculated rate constants for the catalytic degradation of RB and EG with the Cef-AgNPs in the presence of LiAlH4 are 7 10 and 10 10 2 s 1 respectively which is much higher than reported in literatures [47,48] (Fig. 5d and Fig. 6d).
259
Recycling of Cef-Ag NPs
260 261 262
After the catalytic degradation was complete, Cef-AgNPs were separated and the process was repeated to investigate the recyclability of the catalysts.
a
100 100%
99.5%
b
100 100%
99%
98.6%
98.2%
60
40
99.4%
98.9%
98.4%
97.9%
97.4%
4
5
6
80
97.7%
Efficiency%
80
Efficiency%
In typical method, glass supported Cef-AgNPs (0.6 mg) were removed from reaction vial and sequentially washed in ultrapure water and dried before reusing. The washed particles were reused six times for catalytic reduction of targeted dyes. The reducing potential of recovered and reused Cef-AgNPs for RB and EG dyes was calculated, which is shown in Fig. 7. It is apparent that potential of Cef-AgNPs for bleaching of color which showed slight decrease in activity of Cef-AgNPs, which confirms that recovered Cef-AgNPs are highly active even with some possible loss during each repeated washing. The slow deactivation of catalysts Cef-AgNPs also verify that poisoning of catalysts is insignificant. This work promises a
60
40
20
20
0
0 1
2
3 No. of Cycles
4
5
6
1
2
3 No. of Cycles
Fig. 7. The efficiency of Cef-Ag (0) NPs for the degradation of (a) Rose Bengal dye, (b) Eosin Gelblich dye.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
263 264 265 266 267 268 269 270 271 272 273 274
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
6
Scheme 1. The catalytic and recovery mechanism of Cef-Ag (0) NPs for the degradation of (a) Rose Bengal dye, (b) Eosin Gelblich dye.
275 276 277 278 279 280 281 282 283 284 285
sound environmental safety for several water-based systems against dye pollution. Compared with other metal nanoparticles which are generally oxidized on the surface in alkali condition leading to activity loss [49], the Ag nanocatalyst developed in this work was stable and exhibited excellent catalytic ability. Current report assures a sound environmental safety for several water-based systems against dyes and other aromatic pollutions. The catalytic and recovery mechanism of Cef-Ag (0) NPs is presented in Scheme 1 for the catalytic reductive degradation of RB (a) and EG (b) dyes.
286
Conclusion
287 288 289 290 291 292 293 294 295 296 297 298 299 300
Highly efficient catalytic degradation of toxic RB AND EG DYES has been demonstrated using Cef-Ag nanocatalyst grown by chemical reduction method. In the typical process, the system may effectively degrade the dyes with a removal yield as high as 99.9% for only within 60 s of the reaction time. The small size with highly surface area, spherical structure Cef-Ag is considered a key factor for the high performance of the nanocatalyst for the heterogeneous process. Current report suggested simple, cost effectiveness and safety of the present nanoparticle fabrication route supersedes numerous procedures to manufacture wel-dispersed and highly stable CEFAGNPS with spherical shapes. Moreover CEF-AG nanocatalyst could be further used in analogous reactions and also in other experiments of environmental and industrial importance.
Acknowledgements
301
Authors would like to thank to TUBITAK for Research Fellowship program for foreign citizens (BIDEB 2216) & HECPAKISTAN and Gaziantep University who support the research work.
302 303 304 305
References
306
[1] Q. Sun, X. Cai, J. Li, M. Zheng, Z. Chen, C. Ping, A. Colloids Surf, Physicochem. Eng. Asp. 444 (2014) 226. [2] Y. Junejo, E. Karaog˘lu, A. Baykal, Sirajuddin, J. Inorg. Organomet. Polym. Mater. 23 (2013) 970. [3] G. Aksomaityte, M. Poliakoff, E. Lester, Chem. Eng. Sci. 85 (2013) 2. [4] Y. Junejo, A. Baykal, Turk. J. Chem. 38 (2014) 765. [5] S.E. Kim, J.H. Park, B. Lee, J.C. Lee, Y.K. Kwon, Radiat. Phys. Chem. 81 (2012) 978. [6] A. Balamurugan, K.C. Ho, S.M. Chen, Synth. Met. 159 (2009) 2544. [7] Z.A. Tagar, N. Sirajuddin, M.H. Memon, Y. Agheem, S.S. Junejo, N.H. Hassan, M.I. Kalwar, Khattak, Sens Actuators B 157 (2011) 430. [8] Y. Junejo, A. Sirajuddin, M. Baykal, A. Safdar, Balouch, Appl. Surf. Sci. 290 (2014) 499. [9] N. Salam, B. Banerjee, A.S. Roy, P. Mondal, S. Roy, A. Bhaumik, S.M. Islam, Appl. Catal., A 477 (2014) 184. [10] M. Sasidharan, C. Senthil, V. Kumari, A. Bhaumik, Chem. Commun. 51 (2015) 733. [11] P. Kouvaris, A. Delimitis, V. Zaspalis, D. Papadopoulos, S.A. Tsipas, N. Michailidis, Mater Lett. 76 (2012) 18. [12] U.B. Jagtap, V.A. Bapat, Ind Crop. Prod. 46 (2013) 132. [13] H. Bar, D.K. Bhui, G.P. Sahoo, P. Sarkar, S. Pyne, A. Misra, Colloids Surf A. Physicochem. Eng. Asp. 348 (2009) 212. [14] S. Saha, J.M. Wang, A. Pal, Sep. Purif. Technol. 89 (2012) 147. [15] A. Nanda, M. Saravanan, Nanomed. Nanotech. Biol. Med. 5 (2009) 452. [16] K.H. Cho, J.E. Park, T. Osaka, S.G. Park, Electrochim. Acta 51 (2005) 956. [17] I. Sondi, B.S. Sondi, J. Colloid Interface Sci. 275 (2004) 177. [18] A.R. Shahverdi, A. Fakhimi, H.R. Shahverdi, S. Minaian, Nanomed. Nanotech. Biol. Med. 3 (2007) 168.
307 308 309 310 311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329 330 331
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351
[19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33]
T. Maneerung, S. Tokura, R. Rujiravanit, Carbohydr. Polym. 72 (2008) 43. N. Pradhan, A. Pal, T. Pal, Langmuir 17 (2001) 1800. C. Burda, X. Chen, R. Narayanan, M.A. El- Sayed, Chem. Rev. 105 (2005) 1025. A. Siani, K.R. Wigel, O.S. Alexeev, M.D. Amiridis, J. Catal. 257 (2008) 5. Y. Junejo, A. Baykal, Sirajuddin, J. Inorg. Organomet. Polym. 24 (2013) 401. M.A. Brown, S.C. De Vito, Crit Rev Env. Sci. Technol. 23 (1993) 249. I. Safarik, L. Ptackova, M. Safarikova, Eur. Cell. Mater. 3 (2002) 52. J. Lin, R. Zong, M. Zhou, Y. Zhu, Appl. Catal., B: Environ. 89 (2009) 425. A.O. Ibhadon, G.M. Greenway, Y. Yue, Catal. Commun. 9 (2008) 153. H. Lachheb, E. Puzenat, A. Houas, M. Ksibi, E. Elaloui, C. Guillard, J.M. Herrmann, Appl. Catal., B: Environ. 39 (2002) 75. Y. Junejo, A. Gu¨ner, A. Baykal, Appl. Surf. Sci. 317 (2014) 914. J. Xiong, X. Wu, Q. Xue, Colloids Surf., A: Physicochem., Eng. Aspects 423 (2013) 89. C. So¨nnichsen, T. Franzl, T. Wilk, G. von Plessen, J. Feldmann, New J. Phys. 4 (2002), 93.1. M. Potara, E. Jakab, A. Damert, O. Popescu, V. Canpean, S. Astilean, Nanotechnology 22 (2011) 135101. M. Stevanovic´, I. Savanovic´, V. Uskokovic´, S.D. Sˇkapin, I. Bracˇko, U. Jovanovic´, D. Uskokovic´, Colloid Polym. Sci. 290 (2012) 221.
7
[34] J.H. Lee, Y.A. Kim, K. Kim, Y.D. Huh, J.W. Hyun, H.S. Kim, S.J. Noh, C.S. Hwang, Bull. Korean Chem. Soc. 28 (2007) 1091. [35] M.L. Singla, A. Negi, V. Mahajan, K.C. Singh, D.V.S. Jain, Appl. Catal., A 323 (2007) 51. [36] B.B. Koleva, Vib. Spectrosc. 44 (2007) 30. [37] S. Bloxham, O. Eicher-Lorka, R. Jakube˙nas, G. Niaura, Chemija 13 (2002) 185. [38] H. Peng, A. Yang, J. Xiong, Carbohydr. Polym. 91 (2013) 348. [39] D. Philip, C. Unni, S.A. Aromal, V.K. Vidhu, Spectrochim Acta Part A 78 (2011) 899. [40] T. Wejrzanowski, R. Pielaszek, A. Opalinska, H. Matysiak, W. Łojkowski, K.J. Kurzydowski, Appl. Surf. Sci. 31 (2006) 253. [41] S. Ameen, H. Seo, M.S. Akhtar, H.S. Shin, Chem. Eng. J. 210 (2012) 220. [42] A.K. Dutta, S.K. Maji, B. Adhikary, Mater. Res. Bull. 49 (2014) 28. [43] F. Zhang, J. Zhaoa, T. Shen, H. Hidakab, E. Pelizzettic, N. Serponed, Appl. Catal., B 15 (1998) 147. [44] V.K. Vidhu, Micron 56 (2014) 54. [45] A.R. Khataee, M. Zarei, J. Ordikhani-Seyedlar, J. Mol. Catal. A: Chem. 338 (2011) 84. [46] N. Daneshvar, D. Salari, A.R. Khataee, J. Photochem. Photobiol., A 162 (2004) 317. [47] K. Vignesh, R. Hariharan, Solid State Sci. 21 (2013) 91. [48] N. Gupta, H. Premananda Singh, R. Kumar Sharma, J. Mol. Catal. A: Chem. 335 (2011) 248. [49] M. Gra´tzel, A.J. Frank, J. Phys. Chem. 86 (1982) 2964.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
352 353 354 355 356 357 358 359 360 361 362 363 364 365 366 367 368 369 370 371
JIEC 2571 1–7 Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
Contents lists available at ScienceDirect
Journal of Industrial and Engineering Chemistry journal homepage: www.elsevier.com/locate/jiec 1 2 3 4 5 6
Efficient degradation of organic dyes by heterogeneous cefdinir derived silver nanocatalyst Q1 Muhammad a b
Safdar a,*, Yasmeen Junejo a,b, Aamna Balouch b
Department of Medical Biology and Genetics, University of Gaziantep, Gaziantep, Turkey National Center of Excellence in Analytical Chemistry, University of Sindh, Jamshoro 76080, Pakistan
A R T I C L E I N F O
A B S T R A C T
Article history: Received 12 March 2015 Received in revised form 8 May 2015 Accepted 25 June 2015 Available online xxx
Cefdinir derived silver nanocatalyst (Cef-Ag (0) NPs) was successfully synthesized in aqueous solution by efficient one-pot method and effectively employed for the ultrafast catalytic degradation of Rose Bengal and Eosin Gelblich dyes. The improvement was achieved in percent degradation of toxic dyes by varying and optimizing reaction time, and amount of catalyst reducing agent concentration. The catalytic study revealed that complete reduction 99.9% of dye was accomplished in short period of reaction time (60 s) by efficient cefdinir derived silver nanoparticles. The calculated K (rate constant) value for RB and EG catalytic degradation was achieved 7 10 2 and 10 10 2 s 1, respectively by plotting lnC vs time (s) and result show that reaction is following first order kinetics. ß 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.
Keywords: Heterogeneous silver nanocatalyst Cefdinir Green chemistry Catalytic reductive degradation Dyes
7 8
Introduction
9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28
Nowadays, it is important to continue research toward synthesis of metal nanoparticles (MNPs) by using inexpensive and nontoxic chemicals [1,2], environmentally benign solvents, and clean and renewable/biodegradable materials [3,4]. These nanoparticles were utilized in most of chemical reactions of degradation of pollutant compounds [5–8]. Among the different noble metal nanoparticles, stabilized silver nanoparticles (AgNPs) have been widely employed as catalysts for a wide range of reactions [9,10]. Degradation of dyes effluent is a crucial and sensitive issue for industries [6]. Continuous exposure to these dyes has been exposed to exert influence on anaerobic biomass, irritation of the respiratory system, and gastro intestinal track. Hence, physical or chemical advanced treatment processes are essential and useful for the treatment of waste waters containing these dyes [11]. On the other hand, most of the dyes are useful for different industries purposes like pigmentation of textiles, cosmetics, paper, leather, ceramics, inks, and food processing products, which are derived from AZO dyes. About 15% of the dyes are discharged in the natural streams. This waste signals a great hazard and cause much harm to human and environmental health due to the toxicity of effluent of
* Corresponding author. Tel.: +90 507 5125460; fax: +90 2128663412. E-mail address: [email protected] (M. Safdar).
these dyes [12]. Many techniques are available for the removal of these dyes such as adsorption [13], nanofiltration [14], biological treatment [15] and so on. Dyes consist of one of the major groups of chemicals besides fertilizers, pharmaceuticals, and petrochemicals. During ancient times, people used dyes from natural resources like tesu flowers, so that they can make their clothes bright and colorful likewise, indigo, logwood, madder, etc. [6]. The dyeing and textile printing industry is a water-intensive industry requiring a large volume of freshwater at various steps of printing and therefore, the volume of wastewater produced is equally large. These effluents, with their high BOD (Biological Oxygen Demand), COD (Chemical Oxygen Demand), and poised solids, are very toxic in nature as they contain large quantities of dyes (azoic, indigo, and aniline), bleaching agents, acids/alkalis, and heavy metals in very high concentration [16]. Some textile dyes are relatively challenging to microbial degradation, besides that anaerobic microorganisms when degrading some dyes give birth to aromatic amines that might be dangerous and carcinogenic [17]. Therefore, in recent years, there have been many researches done on fungal depolarization of textile waste water. The use of fungi is a promising alternative to replace or add current treatments [18–20]. Textile industry is one of the most common and essential industrial sectors in the world that plays significant role in nation’s economy [21]. Because of drastic changes in customers’ demands, the textiles finishing
http://dx.doi.org/10.1016/j.jiec.2015.06.026 1226-086X/ß 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering Chemistry.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
G Model
JIEC 2571 1–7 2
M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
55 56 57 58 59 60 61 62 63 64 65 66 67 68 69 70 71 72 73 74 75 76 77 78 79
industry is a challenge to use high quantity of dyes and auxiliaries that are necessary for modern textile processing [22]. Among all these dyes, Rose Bengal and Eosin Gelblich dyes are highly toxic [23], which contains heterocyclic aromatic compound due to its cationic in the nature [24], Rose Bengal and Eosin Gelblich functional groups pretense a hazard as pollutants to water resources [11]. The emergence applications of heterogeneous catalysts include metal and metal oxide nanoparticles for advanced techniques of waste water treatments so that it could produce successful result [25–28]. Therefore, it is the urge of time for the requirement of a technique which endorses very simple, costeffective, green, and prompt methods to use nano-based catalytic degradation/reduction of organic dyes pollutants. Previously, antibiotic-based silver nanoparticles were synthesized and used as catalyst for the degradation of some pharmaceutical drugs [29]. Herein, we report a very simple one-pot method for the synthesis of silver nanocatalysts by green method using cefdinir antibiotic and their effective application as heterogeneous, recoverable, and reusable catalyst for remarkably faster and complete degradation of Rose Bengal and Eosin Gelblich dyes in the presence of LiAlH4. The entire research work is based on excellent economy of the process in terms of using cheaper chemicals, facile, and simpler synthesis of catalyst, with shorter time for product formation (quicker procedure) and easy recovery and recycle of this catalyst.
The FTIR (Fourier transform infrared) spectra of AgNPs and cefdinir were performed by model (Perkin Elmer BX FTIR) after incorporating the dried sample in solid state KBr disk. FTIR spectra in the range 4000–400 cm 1 were recorded, so that it would be easy to investigate the nature of the chemical bonds formed. X-ray powder diffraction (XRD) analysis was conducted on a Rigaku Smart Lab Diffractometer operated at 40 kV and 35 mA by using Cu Ka radiation. High-resolution transmission electron microscopy (HRTEM) analysis was studied by using a JEOL JEM 2100 microscope. A drop of diluted sample in alcohol was dripped on a TEM grid.
110 111 112 113 114 115 116 117 118 119 120
Sample preparation for XRD and FTIR and TEM
121
In each case, the yellow colloidal solution of Cef-AgNPs was poured into petri dish and heated on temperature controlled electric water bath set at 100 8C until solvent evaporation. The dried product was washed several times with both deionized water and ethanol in order to remove any unreacted cefdinir. The product was carefully dried in an oven at 100 8C at least for 60 min. The black particles adsorbed on the glass of petri dish were removed with a clean glass slide. The resulting sample was collected in a small sample ampoule before each analysis.
122 123 124 125 126 127 128 129 130
Procedure for catalytic degradation of dyes
131
80
Experimental
81
Cleaning of glassware
82 83 84 85 86 87
All glassware were soaked in 1 M HNO3 solution overnight followed by washing with detergent containing solution, tap water, and ultrapure water. The glassware were finally washed several times with deionized water and put in an oven at 100 8C for 1 h. The dried glass wares were properly cooled in room temperature before use.
88
Chemicals and reagents
The catalytic activity of cefdinir derived silver nanoparticles was experienced by reduction of RB and EG dyes with an excessive quantity of LiAlH4 only with the quantity of Cef-AgNPs. Under optimized conditions, 10 mg/l dyes (100 ml) along 0.1 M LiAlH4 (100 ml) were taken in a 3.0 ml capacity quartz cuvette and then, the volume of the mixture was adjusted 3.0 ml with distilled water and after that the catalytic degradation of dyes was monitored by recording UV–vis spectra. For application studies, NPs were placed on a piece of glass cover slip by drop casting method followed by solvent evaporation on hot plate at the temperature of 100 8C. The weight of glass cover slip was measured before and after NPs deposition to check out the weight of NPs deposited by difference.
132 133 134 135 136 137 138 139 140 141 142 143
89 90 91 92 93 94
Analytical grade 99% AgNO3, 99% NaOH, 98% LiAlH4 and 99%Cefdinir, 97% Rose Bengal (RB), and 97% Eosin Gelblich (EG) were purchased from Sigma–Aldrich and Merck respectively, and utilized without further purification. All solutions that is acidic, basic, and salt solutions were prepared in ultrapure water (conductivity below than 0.05 mS/cm).
Results and discussion
144
UV–vis spectroscopy
145
95
Preparation of standard stock solutions
96 97 98 99
To prepare the standard solutions of compound such as 0.01 M cefdinir, AgNO3, NaOH Rose Bengal and Eosin Gelblich, and 0.1 M LiAlH4, the exact masses of each reagent was taken in 100 ml of volumetric flask and dissolved in ultrapure water.
100
Synthetic procedure for cefdinir capped-Ag NPs
101 102 103 104 105
Highly efficient cefdinir capped-Ag NPs were successfully synthesized by following protocol. In typical procedure 0.4 ml of AgNO3 solution was taken in 20 ml test tube and 0.3 ml cefdinir and 0.2 ml NaOH was added. Solution was shaken properly and final volume was made up to 10 ml with ultrapure water.
UV–vis spectrometry was performed to follow and confirm the formation of cefdinir stabilized silver nanoparticles (Cef-Ag (0) NP). The reduction of Ag+ ions into Ag nanoparticles was monitored by recording the absorption spectrum of the reaction mixture with time in the range of 300–900 nm. It is observed in UV–vis spectrum of the Cef-Ag (0) NPs that the colloidal silver exhibits a strong absorption between 400 and 415 nm, which corresponds to the surface Plasmon resonance (SPR) of AgNPs [9,30] suggesting the formation of NPs as shown in Fig. 1. The appearance of absorption band in the range of 350–450 nm is due to surface plasmon vibrations of conducting electrons [9,31]. CefAgNPs were synthesized with very slow kinetics and showed excellent stability until several months and no significant change is observed in the intensity of the SPR band. The sharp intense band evident the formation of monodispersed and spherical nanoparticles and the absence of any absorption peak in the range of 450– 900 nm indicate the no apparent aggregation of nanoparticles [32].
146 147 148 149 150 151 152 153 154 155 156 157 158 159 160 161 162
106
Instrumentations
HRTEM analysis
163
107 108 109
The resulting Cef-AgNPs solution was analyzed by ultraviolet– visible (UV–vis) spectrometer model Shimadzu UV–vis 2600 in the range of 300–800 nm.
Fig. 2 shows the typical HRTEM image of the AgNPs prepared using chemical reduction approach. TEM analysis on the sample indicated crystalline spherical Cef-AgNPs with 6.80 2.1 nm
164 165 166
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
3.0
1.05
Time study of Cefdinir derived silver nanoparticles
1.00
408 nm
a
0.95
2.5
0.90
6 month 3 month 1 month 1 week 12 hour 6 hour 3 hour 2 hour 1 hour
2.0 1.5 1.0
% Transmittance (a.u)
Absorbance (a.u.)
3
Cefdinir Standard
0.85 0.80 0.75 0.70
b
0.65 0.60
Cef-Ag (0) NPs
0.55 0.50
0.5
0.45 0.0 300
0.40 400
500
600
700
800
900
Wavelength (nm) Fig. 1. The UV–vis spectra recorded for time study of Cef-Ag (0) NPs samples showing stable absorption band at 408 nm after 1 h to 6 months successively.
167 168 169 170 171 172 173 174 175
particle size of Cef-AgNPs. The formation crystalline spherical AgNPs is assumed as the effective combinative effect of antibiotic cefdinir and NaOH reducing agent used during the growth process. These smaller monodispersed nanospheres may act as a nanoreactor and offer enhanced efficiency as a catalytic for reduction/degradation of toxic chemicals [33]. The smaller size may facilitate enhanced mobility of charge carriers to different reaction positions and a more effective reaction process. Thus, enhanced catalytic properties are expected from these nanostructures.
176
FT-IR spectroscopy
177 178 179 180 181 182 183 184 185 186 187 188 189 190
For further confirmation of formation of AgNPs the FTIR spectroscopy was used to clarify the surface interaction of cefdinir to the AgNPs and the results are presented in Fig. 3a, b. FTIR spectrum of cefdinir standard show two broad and strong signals at 3290 and 1390 cm 1 assigned to amine groups [34], primary and secondary amines shows stretching vibrations at 16, 781, 625, and 1520 cm 1, in this region aromatic carbon ring is also present [35]. Additionally, the C–O group stretching vibrations at 1350 cm 1 [36] while other related peaks 1180 and 1020 cm 1 showed the C–N and N–H stretching [34,35]. Furthermore, it describes the bending vibrations between 748–536 cm 1 that corresponds to aromatic sulphur [37] (Fig. 3a). Moreover, in the FTIR spectrum of silver nanoparticles, the broad band at 3290 and 3060 cm 1 are completely disappeared
0.35 4000
3500
3000
2500 2000 1500 -1 Wavenumber (cm )
1000
500
Fig. 2. FTIR Spectra of Cefdinir (a) and silver nanoparticles (b).
which could be attributed to the bonding of amine with silver ion. Also the slight shift in peak of amine group from 1520 to 1595 cm 1 further confirm the bond formation as shown in Fig. 3b. XRD analysis of silver nanoparticles Powder pattern of Cef-AgNPs were obtained by using solid product as the result of drying of Cef-AgNPs (Fig. 4). Nearly 2 mg of dark black solid sample were analyzed, Cef-AgNPs with face centered cubic (fcc) structure also matched with literature [38,39]. A number of Bragg reflections with two theta values of 37.6, 43.8, 64.03, and 76.048 correspond to the (111), (200), (220), and (311) sets of lattice planes were observed, which was indexed as the band to face centered cubic structures of silver. The XRD pattern thus verified that the Cef-AgNPs synthesized by the green method are crystalline in nature [40]. The XRD pattern thus clearly showed that the AgNPs synthesized by the green method are crystalline in nature. Scherrer equation (also referred to as the Debye–Scherrer equation) has been applied to estimate the size of Cef-Ag crystallites. It was estimated at around 13.8 nm.
191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209
Catalytic degradation of dyes using Cef-AgNPs
210
The catalytic degradation experiment was carried out directly in quartz cuvets, 100 ml (10 mg/l) aliquot of azo dyes (Rose Bengal) was taken and 0.1 M LiAlH4 (100 ml) was added and finally the volume of the mixture was adjusted to 3.0 ml with ultrapure
211 212 213 214
Fig. 3. HRTEM images and particle size distribution diagram of Cefdinir derived Ag (0) NPs.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
4
exp. fit
Intensity (a.u.)
111
200
20
30
40 50 2 Theta (deg.)
311
220
60
70
80
Fig. 4. XRD powder pattern of Cefdinir derived Ag (0) NPs.
215 216 217 218 219 220 221 222 223 224
water. Afterward, 0.5 mg Cef-AgNPs was introduced in the Rose Bengal dye solution to catalyze the reaction. The catalytic degradation was observed by changing the color of the solution, and observation was continued until the color completely vanished. Fig. 5 represents a typical evolution of the UV–vis spectra of Rose Bengal dye. It can be observed that no important changes occurred in the reduction of RB (100 ml, 10 mg/l) even after 24 h in the presence of LiAlH4 only (Fig. 5a). But after the addition of Cef-AgNPs (0.1–0.5 mg), the absorbance intensity has showed a decreasing trend which indicates that the catalytic
degradation of RB (100 ml, 10 mg/l) has been achieved through the inclusion of Ag nanoparticles which is shown in Fig. 5b. Also we observed the complete catalytic degradation of RB (100 ml, 10 mg/ l) at 545 nm [41,42] just within 60 s in the presence of our newly synthesized Cef-AgNPs (0.5 mg) (Fig. 5c). Similarly the catalytic degradation of Eosin Gelblich dye was done by following same protocol and monitored the reaction till color of the solution vanished and it indicated the complete degradation of the EG dye solution. EG is a heterocyclic aromatic dye, the freshly prepared aqueous EG solution having concentration of 100 ml, 10 mg/l with a relative absorbance of band at 515 nm [43,44]. More than 24 h were required for reduction of EG without Ag nanocatalyst (Fig. 6a). But after the addition of Cef-AgNPs (0.1–0.6 mg), the absorbance intensity has showed a decreasing trend which indicates that the catalytic degradation of EG (100 ml, 10 mg/l) has been achieved through the inclusion of Ag nanoparticles which is shown in Fig. 6b. This indicates that the complete catalytic degradation of EG Q2 (100 ml, 10 mg/l) to a colorless within 80 s in the presence of our newly synthesized Cef-AgNPs (0.6 mg) (Fig. 6c). Khataee et al. [45] studied the degradation of basic red 46 by combining photoelectron-Fenton and heterogeneous photocatalytic process. The authors observed 99.2% mineralization of 15 mg/l dye in 6 h. Similarly, Daneshvar et al. [46] systematically investigated the degradation of acid red 14 using ZnO photocatalyst. Moreover, Vignesh et al. [47] observed 85% degradation of rose Bengal in 150 min with Ag-doped SnO2 nanoparticles modified with curcumin.
(b) (a)
(d) (c)
Fig. 5. Degradation of Rose Bengal dye; (a) Degradation in the presence of LiAlH4 only, (b) at fixed concentration of Rose Bengal dye (10 mg/l) degradation with varying amounts 0.1–0.5 mg Cef-Ag (0) NPs and 0.1 M LiAlH4 (c) at fixed concentration of Rose Bengal dye (10 mg/l) degradation at fixed amount of Cef-Ag (0) NPs (0.5 mg) and 0.1 M LiAlH4 (d) Linear regression for pseudo first order kinetics for the reductive degradation of Rose Bengal dye.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
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
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
5
(b) (a)
(d)
(c)
Fig. 6. Degradation of Eosin Gelblich dye; (a) Degradation in the presence of 0.1 M LiAlH4 only, (b) at fixed concentration of Eosin Gelblich dye (10 mg/L) degradation with varying amounts 0.1–0.6 mg Cef-Ag (0) NPs and 0.1 M LiAlH4, (c) at fixed concentration of Eosin Gelblich dye (10 mg/l) degradation at fixed amount of Cef-Ag (0) NPs (0.6 mg) and 0.1 M LiAlH4, (d) Linear regression for pseudo first order kinetics for the reductive degradation of Eosin Gelblich dye.
253 254 255 256 257 258
The kinetics of reaction was also investigated and compared with literature. It is evident from the calculated rate constants for the catalytic degradation of RB and EG with the Cef-AgNPs in the presence of LiAlH4 are 7 10 and 10 10 2 s 1 respectively which is much higher than reported in literatures [47,48] (Fig. 5d and Fig. 6d).
259
Recycling of Cef-Ag NPs
260 261 262
After the catalytic degradation was complete, Cef-AgNPs were separated and the process was repeated to investigate the recyclability of the catalysts.
a
100 100%
99.5%
b
100 100%
99%
98.6%
98.2%
60
40
99.4%
98.9%
98.4%
97.9%
97.4%
4
5
6
80
97.7%
Efficiency%
80
Efficiency%
In typical method, glass supported Cef-AgNPs (0.6 mg) were removed from reaction vial and sequentially washed in ultrapure water and dried before reusing. The washed particles were reused six times for catalytic reduction of targeted dyes. The reducing potential of recovered and reused Cef-AgNPs for RB and EG dyes was calculated, which is shown in Fig. 7. It is apparent that potential of Cef-AgNPs for bleaching of color which showed slight decrease in activity of Cef-AgNPs, which confirms that recovered Cef-AgNPs are highly active even with some possible loss during each repeated washing. The slow deactivation of catalysts Cef-AgNPs also verify that poisoning of catalysts is insignificant. This work promises a
60
40
20
20
0
0 1
2
3 No. of Cycles
4
5
6
1
2
3 No. of Cycles
Fig. 7. The efficiency of Cef-Ag (0) NPs for the degradation of (a) Rose Bengal dye, (b) Eosin Gelblich dye.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
263 264 265 266 267 268 269 270 271 272 273 274
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
6
Scheme 1. The catalytic and recovery mechanism of Cef-Ag (0) NPs for the degradation of (a) Rose Bengal dye, (b) Eosin Gelblich dye.
275 276 277 278 279 280 281 282 283 284 285
sound environmental safety for several water-based systems against dye pollution. Compared with other metal nanoparticles which are generally oxidized on the surface in alkali condition leading to activity loss [49], the Ag nanocatalyst developed in this work was stable and exhibited excellent catalytic ability. Current report assures a sound environmental safety for several water-based systems against dyes and other aromatic pollutions. The catalytic and recovery mechanism of Cef-Ag (0) NPs is presented in Scheme 1 for the catalytic reductive degradation of RB (a) and EG (b) dyes.
286
Conclusion
287 288 289 290 291 292 293 294 295 296 297 298 299 300
Highly efficient catalytic degradation of toxic RB AND EG DYES has been demonstrated using Cef-Ag nanocatalyst grown by chemical reduction method. In the typical process, the system may effectively degrade the dyes with a removal yield as high as 99.9% for only within 60 s of the reaction time. The small size with highly surface area, spherical structure Cef-Ag is considered a key factor for the high performance of the nanocatalyst for the heterogeneous process. Current report suggested simple, cost effectiveness and safety of the present nanoparticle fabrication route supersedes numerous procedures to manufacture wel-dispersed and highly stable CEFAGNPS with spherical shapes. Moreover CEF-AG nanocatalyst could be further used in analogous reactions and also in other experiments of environmental and industrial importance.
Acknowledgements
301
Authors would like to thank to TUBITAK for Research Fellowship program for foreign citizens (BIDEB 2216) & HECPAKISTAN and Gaziantep University who support the research work.
302 303 304 305
References
306
[1] Q. Sun, X. Cai, J. Li, M. Zheng, Z. Chen, C. Ping, A. Colloids Surf, Physicochem. Eng. Asp. 444 (2014) 226. [2] Y. Junejo, E. Karaog˘lu, A. Baykal, Sirajuddin, J. Inorg. Organomet. Polym. Mater. 23 (2013) 970. [3] G. Aksomaityte, M. Poliakoff, E. Lester, Chem. Eng. Sci. 85 (2013) 2. [4] Y. Junejo, A. Baykal, Turk. J. Chem. 38 (2014) 765. [5] S.E. Kim, J.H. Park, B. Lee, J.C. Lee, Y.K. Kwon, Radiat. Phys. Chem. 81 (2012) 978. [6] A. Balamurugan, K.C. Ho, S.M. Chen, Synth. Met. 159 (2009) 2544. [7] Z.A. Tagar, N. Sirajuddin, M.H. Memon, Y. Agheem, S.S. Junejo, N.H. Hassan, M.I. Kalwar, Khattak, Sens Actuators B 157 (2011) 430. [8] Y. Junejo, A. Sirajuddin, M. Baykal, A. Safdar, Balouch, Appl. Surf. Sci. 290 (2014) 499. [9] N. Salam, B. Banerjee, A.S. Roy, P. Mondal, S. Roy, A. Bhaumik, S.M. Islam, Appl. Catal., A 477 (2014) 184. [10] M. Sasidharan, C. Senthil, V. Kumari, A. Bhaumik, Chem. Commun. 51 (2015) 733. [11] P. Kouvaris, A. Delimitis, V. Zaspalis, D. Papadopoulos, S.A. Tsipas, N. Michailidis, Mater Lett. 76 (2012) 18. [12] U.B. Jagtap, V.A. Bapat, Ind Crop. Prod. 46 (2013) 132. [13] H. Bar, D.K. Bhui, G.P. Sahoo, P. Sarkar, S. Pyne, A. Misra, Colloids Surf A. Physicochem. Eng. Asp. 348 (2009) 212. [14] S. Saha, J.M. Wang, A. Pal, Sep. Purif. Technol. 89 (2012) 147. [15] A. Nanda, M. Saravanan, Nanomed. Nanotech. Biol. Med. 5 (2009) 452. [16] K.H. Cho, J.E. Park, T. Osaka, S.G. Park, Electrochim. Acta 51 (2005) 956. [17] I. Sondi, B.S. Sondi, J. Colloid Interface Sci. 275 (2004) 177. [18] A.R. Shahverdi, A. Fakhimi, H.R. Shahverdi, S. Minaian, Nanomed. Nanotech. Biol. Med. 3 (2007) 168.
307 308 309 310 311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329 330 331
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
G Model
JIEC 2571 1–7 M. Safdar et al. / Journal of Industrial and Engineering Chemistry xxx (2015) xxx–xxx
332 333 334 335 336 337 338 339 340 341 342 343 344 345 346 347 348 349 350 351
[19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] [31] [32] [33]
T. Maneerung, S. Tokura, R. Rujiravanit, Carbohydr. Polym. 72 (2008) 43. N. Pradhan, A. Pal, T. Pal, Langmuir 17 (2001) 1800. C. Burda, X. Chen, R. Narayanan, M.A. El- Sayed, Chem. Rev. 105 (2005) 1025. A. Siani, K.R. Wigel, O.S. Alexeev, M.D. Amiridis, J. Catal. 257 (2008) 5. Y. Junejo, A. Baykal, Sirajuddin, J. Inorg. Organomet. Polym. 24 (2013) 401. M.A. Brown, S.C. De Vito, Crit Rev Env. Sci. Technol. 23 (1993) 249. I. Safarik, L. Ptackova, M. Safarikova, Eur. Cell. Mater. 3 (2002) 52. J. Lin, R. Zong, M. Zhou, Y. Zhu, Appl. Catal., B: Environ. 89 (2009) 425. A.O. Ibhadon, G.M. Greenway, Y. Yue, Catal. Commun. 9 (2008) 153. H. Lachheb, E. Puzenat, A. Houas, M. Ksibi, E. Elaloui, C. Guillard, J.M. Herrmann, Appl. Catal., B: Environ. 39 (2002) 75. Y. Junejo, A. Gu¨ner, A. Baykal, Appl. Surf. Sci. 317 (2014) 914. J. Xiong, X. Wu, Q. Xue, Colloids Surf., A: Physicochem., Eng. Aspects 423 (2013) 89. C. So¨nnichsen, T. Franzl, T. Wilk, G. von Plessen, J. Feldmann, New J. Phys. 4 (2002), 93.1. M. Potara, E. Jakab, A. Damert, O. Popescu, V. Canpean, S. Astilean, Nanotechnology 22 (2011) 135101. M. Stevanovic´, I. Savanovic´, V. Uskokovic´, S.D. Sˇkapin, I. Bracˇko, U. Jovanovic´, D. Uskokovic´, Colloid Polym. Sci. 290 (2012) 221.
7
[34] J.H. Lee, Y.A. Kim, K. Kim, Y.D. Huh, J.W. Hyun, H.S. Kim, S.J. Noh, C.S. Hwang, Bull. Korean Chem. Soc. 28 (2007) 1091. [35] M.L. Singla, A. Negi, V. Mahajan, K.C. Singh, D.V.S. Jain, Appl. Catal., A 323 (2007) 51. [36] B.B. Koleva, Vib. Spectrosc. 44 (2007) 30. [37] S. Bloxham, O. Eicher-Lorka, R. Jakube˙nas, G. Niaura, Chemija 13 (2002) 185. [38] H. Peng, A. Yang, J. Xiong, Carbohydr. Polym. 91 (2013) 348. [39] D. Philip, C. Unni, S.A. Aromal, V.K. Vidhu, Spectrochim Acta Part A 78 (2011) 899. [40] T. Wejrzanowski, R. Pielaszek, A. Opalinska, H. Matysiak, W. Łojkowski, K.J. Kurzydowski, Appl. Surf. Sci. 31 (2006) 253. [41] S. Ameen, H. Seo, M.S. Akhtar, H.S. Shin, Chem. Eng. J. 210 (2012) 220. [42] A.K. Dutta, S.K. Maji, B. Adhikary, Mater. Res. Bull. 49 (2014) 28. [43] F. Zhang, J. Zhaoa, T. Shen, H. Hidakab, E. Pelizzettic, N. Serponed, Appl. Catal., B 15 (1998) 147. [44] V.K. Vidhu, Micron 56 (2014) 54. [45] A.R. Khataee, M. Zarei, J. Ordikhani-Seyedlar, J. Mol. Catal. A: Chem. 338 (2011) 84. [46] N. Daneshvar, D. Salari, A.R. Khataee, J. Photochem. Photobiol., A 162 (2004) 317. [47] K. Vignesh, R. Hariharan, Solid State Sci. 21 (2013) 91. [48] N. Gupta, H. Premananda Singh, R. Kumar Sharma, J. Mol. Catal. A: Chem. 335 (2011) 248. [49] M. Gra´tzel, A.J. Frank, J. Phys. Chem. 86 (1982) 2964.
Please cite this article in press as: M. Safdar, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.06.026
352 353 354 355 356 357 358 359 360 361 362 363 364 365 366 367 368 369 370 371