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Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

2 Efficient adsorption and photocatalytic degradation of Rhodamine B

3 dye over Bi2O3-bentonite nanocomposites: A kinetic study
4 Q1 Sandip P. Patil a, Bhaskar Bethi b, G.H. Sonawane c,*, V.S. Shrivastava a, Shirish Sonawane b
5 a
Nano-Chemistry Research Laboratory, G. T. Patil College, Nandurbar-425 412 (M.S.) India
6 b
Chemical Engineering Department, NIT, Warangal-506 004 (Telangana) India
7 c
Deptartment of Chemistry, Kisan Arts, Commerce and Science College, Parola-425 111 (M.S.) India

A R T I C L E I N F O A B S T R A C T

Article history: Bi2O3-bentonite nanocomposites successfully synthesized by intercalation method are used for
Received 20 April 2015 photocatalytic degradation of Rhodamine B (Rh B) under visible light irradiation. Bi2O3-bentonite shows
Received in revised form 16 October 2015 enhanced photocatalytic efficiency than pure Bi2O3 due to intercalation with bentonite. Removal of Rh B
Accepted 1 December 2015
is achieved upto 98.5% using 3 gL1 photocatalyst at pH 3. It is found that increase in light absorption and
Available online xxx
decrease in electron-hole recombination enhances photocatalytic efficiency. Photocatalytic degradation
of Rh B by Bi2O3-bentonite proceeds via advanced oxidative process. The plausible mechanism of
Keywords:
photocatalytic degradation Rh B reported by LC-MS shows generation of different degradation products
Bi2O3-bentonite
including benzoic acid and benzonium ion.
Rhodamine B
Visible light photodegradation ß 2015 Published by Elsevier B.V. on behalf of The Korean Society of Industrial and Engineering
Advanced oxidative process Chemistry.

8
9 Introduction for the excitation of electron from valence band to conduction band 30
require high energy UV radiations. Therefore lot of studies have 31
10 Ever increasing discharge of large excess of dyes by dye been devoted either to modify energy band gap of these 32
11 manufacturing and textile industries leads to severe environmen- semiconductor metal oxides or to find alternative to them in 33
12 tal problems [1–5]. Many of the dyes are hazardous to humans as order to utilise solar energy. These methods involves a) doping 34
13 well as aquatic life [6,7]. Rh B is one of them which is extensively with other elements, b) fabrication of hetero-junction structure by 35
14 used for dyeing and their discharge in water bodies impart adverse combining semiconductor with metals or other semiconductors to 36
15 effects on human and animal health [8,9]. Weathering of organic enhance solar light sensitivity [20]. 37
16 dyes in wastewater produces toxic metabolites [10]. Many There are several attempts has been made to use nanocompo- 38
17 researchers have tried various methods like oxidation, adsorption, sites as a photocatalyst for the dye degradation. Earlier studies 39
18 degradation and catalytic reduction for removal of various dyes indicate that clay supported semiconductor nanocomposites are 40
19 from wastewater [11–14]. Recent studies show that AOP is one of found to be promising method for wastewater treatment [21]. It 41
20 the effective techniques for the removal of dyes from wastewater has enhanced photocatalytic activity as it provides larger surface 42
21 [15–17]. AOPs are considered to be destructive and low or non- area, basal space and cation exchange capacity. Bentonite is 43
22 waste generating technologies for the treatment of polluted water abundant and inexpensive clay. It is effectively combined with 44
23 [18]. AOPs completely mineralize contaminants and their inter- different semiconductors to form composites due to its adsorption- 45
24 mediates. Thus post treatment is not required as secondary wastes desorption property. Meshram et al. [15] reported removal of 46
25 are not generated. phenol, Riaz et al. [22] reported removal of orange G and Hamane 47
26 Recently various researchers focus on degradation of toxic et al. [23] reported removal of Pb+2, using different bentonite based 48
27 organic compounds present in wastewater by photocatalysis using composites. 49
28 various semiconductor metal oxides [19]. Some of the semicon- Bi2O3 has lower band gap 2.58-2.85 eV [24] sensitive to visible 50
29 ductor metal oxides like TiO2 and ZnO have higher band gap thus light irradiation has also found to exhibit good photocatalytic 51
performances for removal of different dyes [25–29]. 52
The combination of Bi2O3 with bentonite clay is a promising 53
* Corresponding author. Tel.: +912597222441; fax: +912597223688. method to enhance the photocatalytic efficiency of Bi2O3. However, 54
E-mail address: drgunvantsonawane@gmail.com (G.H. Sonawane). Bi2O3-bentonite nanoclay composite is unique catalyst which 55

http://dx.doi.org/10.1016/j.jiec.2015.12.002
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: S.P. Patil, et al., J. Ind. Eng. Chem. (2015), http://dx.doi.org/10.1016/j.jiec.2015.12.002
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56 shows the activity in the visible light. Bentonite nanoclay has the BiONO3 [24,31,32], then 5wt% of modified nanoclay is added into it. 101
57 more cation exchange capacity for the adsorption. The novelty Resulting mixture is sonicated for 30 min to obtain uniform 102
58 involved in this work is the synthesis of heterogeneous visible light suspension. Then dil. NaOH is added to this solution with 103
59 activated photocatalyst and its performance in the dye degradation continuous stirring for 30 min. Then Bi2O3-bentonite nanocompo- 104
60 and its reusability for 3 times. Bi2O3-bentonite nanocomposite was sites are obtained by centrifugation and successive dispersions in 105
61 shown a good adsorption and photocatalytic property in visible alcohol. Finally nanocomposites are dried under vacuum and 106
62 light for the degradation of dye. It has indicates that, the scale-up for calcinated at 400 8C for 3-4 h. 107
63 the treatment of textile waste water in bulk volume is possible using
64 solar light and this photocatalyst. Present study involves incorpo- Characterization of nanocomposite 108
65 ration of Bi2O3 semiconductor with bentonite clay to obtained
66 Bi2O3-bentonite nanocomposite. The resulting nanocomposites The SEM images were taken using the Hitachi S-4800 (Japan) 109
67 were characterised by SEM, EDS and XRD. Then nanocomposites are FESEM. EDS analysis was performed by using Bruker X Flash 110
68 applied for photocatalytic and adsorptive removal of Rh B under 5030. The XRD pattern of the samples were measured on a Bruker 111
69 visible light irradiation. Effect of key operating parameters like D 8 Advance X-ray diffractometer (Germany) using monochro- 112
70 initial dye concentration, pH, contact time and catalyst dose for the matized Cu Ka (l = 0.15418 nm) radiation under 40 kV and 40 mA 113
71 degradation of Rh B were investigated systematically. Then and scanning over the range of 10o 2u 60o. 114
72 photodegradation intermediates were identified by LC-MS analysis
73 and degradation pathway of Rh B was proposed. Adsorption study 115

74 Experimental The adsorption of Rh B on Bi2O3-bentonite is studied in dark for 116

60 min. The mixtures are shaken to achieve equilibrium between 117
75 Materials and methods them. Then changes in Rh B concentration are determined by 118
Systronics-2203 UV-Visible double beam spectrophotometer at 119
76 All the chemicals used in the present study are of A.R. grade. lmax = 546 nm. The amount of Rh B adsorbed on Bi2O3-bentonite is 120
77 Natural bentonite was procured from Ganatra mines (Jaipur, calculated by eq.1. 121
78 India). Bismuth nitrate, Cetyl trimethyl ammonium bromide
ðC o C t ÞV
79 (CTAB), Rh B are procured from S.D.Fine Chemicals, India and qt ¼ (1)
W
80 are used as supplied without further purification.
where qt (mg g1) is the adsorption capacity at time t; Co (mg L1) 123
122
81 Preparation of Rh B solution is the initial Rh B dye concentration; Ct (mg L1) is the Rh B 124
concentration at time t; V (L) is the initial volume of dye solution 125
82 Stock solution (500mgL1) is prepared by distilled water. The and W (g) is the amount of nanocomposite. 126
83 experimental solutions are prepared by diluting stock solution with
84 distilled water. The molecular structure of Rh B is shown in Fig. 1. Photocatalytic experiment 127

85 Synthesis of Bi2O3-bentonite nanocomposite The photocatalytic performance of Bi2O3-bentonite nanocom- 128

posite is studied through photocatalytic degradation of Rh B under 129
86 The bentonite was ground, sieved and washed with deionised visible light irradiation. The photocatalytic degradation of Rh B is 130
87 water for several times. Differential sedimentation technique was carried out in photocatalytic reactor, having 500 W halogen lamp. 131
88 used to remove silica and iron oxides. Then mixture was stirred for Cooling water jacket is used to maintain temperature inside the 132
89 1 h and kept undisturbed for overnight. After filtration, the solid reactor. Different nanocomposite doses are added to the 50 mL dye 133
90 mass was exposed to slow evaporation to obtain dry purified solution and then placed in a photocatalytic reactor. After certain 134
91 bentonite. Intercalation of bentonite was carried out as reported by time intervals, adequate amount of sample is withdrawn and 135
92 Sonawane et al. [30] by using CTAB. 3.64 g CTAB (on the basis of CEC centrifuged to remove the nanocomposite. Then changes in dye 136
93 of bentonite) was dissolved in 75 mL distilled water having concentration are determined by Systronics-2203 UV-Visible 137
94 3.9  103 gmol HCl. This mixture was stirred under sonication double beam spectrophotometer. The percentage removal of Rh 138
95 at 80 8C for 30 min to get clear solution. 3.25 g purified bentonite B is calculated by eq. (2). 139
96 (CEC 72meq/100 g) was added to above solution and sonicated for
 
97 another 1.5 h. Then solid obtained by filtration was dispersed in hot C o C t
Removal percentage ¼ 100 (2)
98 water for several times to obtain chloride free, modified nanoclay. Co
99 2 g Bi(NO3)3.5H2O is dissolved in 20 mL nitric acid (1.5 M) to
100 avoid hydrolyzation of Bi3+ ions by preventing precipitation of 140
141
Results and discussion 142

H 3C CH 3
SEM and EDS analysis 143
-
+ Cl
H 3C N O N CH 3 Elemental analysis of material surface layer is obtained by 144
electron dispersive X-ray spectroscopy (EDS). Fig. 2a shows that 145
Bi2O3-bentonite contains C K(3.46%), O K(55.87%),Bi K(20.7%), Na 146
K(2.72%), Si K(11.08%), Al K (3.3%), Ca K(2.03%) and Mg K(0.83%). 147
Absence of Bi peaks in EDS of bentonite while presence of peaks of 148
COOH Bi and O in EDS of Bi2O3-bentonite micrograph proves existence of 149
Bi2O3 in the nanocomposite. 150
Fig. 2b shows absence of crystalline particles on bentonite clay. 151
The Bi2O3 material has nanorod shape [24]. From Fig. 2c it was 152
Fig. 1. The structure of Rh B. clearly observed that, Bi2O3 nanorods are well dispersed over 153

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Fig. 2. The EDS spectra of (a) Bi2O3-bentonite; The SEM images of (b) bentonite and (c) Bi2O3-bentonite.

154 bentonite clay which reflects good combination between them and shown in Fig. 3. XRD patterns of bentonite clay contain major 160
155 also proves existence of Bi2O3-bentonite nanocomposite. peaks at 2u of 19.64o, 24.56o, 25.76o and 34.1o. The diffraction 161
pattern of Bi2O3 shows major peaks at 2u of 21.28o, 28.64o, 162
156 XRD analysis 33.47o and 34.41o. The XRD analysis indicates that, all the 163
diffraction peaks of Bi2O3-bentonite are similar to those of 164
157 X-ray powder diffraction (XRD) is a useful tool to Bi2O3. The broadening of peaks probably occurs due to bridging 165
158 characterise the phase structure of the materials. The X-ray of Bi2O3 to the neighbouring silicate units between the layers of 166
159 diffraction pattern of Bi2O3, bentonite and Bi2O3-bentonite are bentonite clay. 167

Fig. 3. XRD patterns of the bentonite, Bi2O3 and Bi2O3-bentonite.

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(a) 14
25
12

20 10

t/qt
qt (mg g-1)

15
6

10 4

2
5
0
0 20 40 60 80 100
0
0 20 40 60 80 100 Time (min)
Time (min) Fig. 5. Second order kinetics plots for the removal of Rh B at different initial dye
(b) concentrations; Bi2O3-bentonite dose 3 gL1, pH 3.
90
80
zero indicates heterogeneity. The greater 1/n values (Table 1) 196
70 indicates adsorption of Rh B on Bi2O3-bentonite is co-operative. 197
60 Langmuir assumes that monolayer homogeneous adsorption 198
qt (mg g-1)

50 occurs only at finite number of identical and equivalent sites 199

40 without interaction between adsorbed molecules. Langmuir 200
30 isotherm is described by dimensionless factor RL. The RL values 201
indicate nature of adsorption. RL > 1 indicates unfavourable 202
20
adsorption; RL = 1 indicates linear adsorption; 0< RL < 1 indicates 203
10 favourable adsorption and RL = 0 indicates irreversible adsorption. 204
0 The present study with RL values between 0 and 1 indicates 205
0 20 40 60 80 100 favourable adsorption process (Table 1). 206
Time (min) Freundlich isotherm has higher r2 values, 1/n and KF values 207
while Langmuir isotherm has lower r2 values. Thus, Freundlich 208
Fig. 4. a. Effect of contact time on adsorption of Rh B with catalyst dose 1 gL1; pH
adsorption isotherm is the most appropriate isotherm for 209
3 and dye concentration 20 mgL1. b. Amount of dye adsorbed qt (mg g1) with time
for different initial dye concentration; pH 3, Bi2O3-bentonite dose 1gL1. adsorption of Rh B on Bi2O3-bentonite. 210

Photocatalytic study 211

168 Adsorption of Rh B on bentonite, Bi2O3 and Bi2O3-bentonite Photocatalytic activity of bentonite, Bi2O3 and Bi2O3-bentonite 212
is studied for the removal of Rh B. The dye solutions along with 213
169 Effect of contact time catalyst are placed in dark to carry out adsorption for 60 min, then 214
170 The effect of contact time on adsorption of Rh B by bentonite, photocatalytic degradation preceded by considering t = 0 under 215
171 Bi2O3 and Bi2O3-bentonite is shown in Fig. 4a. This shows that visible light irradiation. Fig. 7 shows that A/Ao decreases rapidly 216
172 adsorption of Rh B is higher over Bi2O3-bentonite as compare to when degradation was carried out with Bi2O3-bentonite than 217
173 bentonite and Bi2O3. Fig. 4b shows that initially amount of Rh B bentonite and Bi2O3 alone. Where Ao is the initial absorbance and A 218
174 adsorbed increases with increase in initial dye concentration and is absorbance at time t. The percentage removal of Rh B by 219
175 contact time. The rate of adsorption is faster for first 20 min then it bentonite, Bi2O3 and Bi2O3-bentonite after 60 min adsorption are 220
176 becomes slower to attain equilibrium. The faster adsorption in first 57.2%, 8.7% and 72.3% respectively. These values indicate that 221
177 20 min is due to availability of more number of sites for adsorption. Bi2O3-bentonite has higher adsorption efficiency as compare to 222
178 Later on repulsion between solute and bulk phase causes bentonite and Bi2O3. 223
179 difficulties to occupy remaining sites. After visible light irradiation for 80 min, removal of Rh B 224
by bentonite achieved upto 62%, by Bi2O3 upto 58.4% and by 225
180 Adsorption kinetics
181 Mechanism of adsorption is given by adsorption kinetics. The
182 adsorption kinetics of Rh B was studied with pseudo-second-order 2.5
183 model. The pseudo-second-order model is given as [33],where K2 is
184 pseudo-second-order rate constant (g mg1 min1), h is initial rate
2
185 (mg g1 min1). The linear plot of t/qt vs t with correlation
186 coefficient r2  0.998 shows good agreement with experimental qe
187 values (Fig. 5). This indicates that adsorption belongs to pseudo- 1.5
log q

188 second-order kinetics.

1
189 Adsorption isotherm
0.5
190 Freundlich isotherm describes non-ideal, reversible and multi-
191 layer adsorption with heterogeneous system. Linear nature of plot 0
192 of log qe vs log Ce (Fig. 6) shows the applicability of Freundlich 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8
193 adsorption isotherm. The slope (1/n) value of plot indicates nature log Ce
194 adsorption. The slope (1/n) less than one indicates chemisorption;
195 more than one indicates co-operative adsorption while closer to Fig. 6. Freundlich plot for adsorption of Rh B by Bi2O3-bentonite.

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Table 1
Freundlich and Langmuir isotherm constants for adsorption of Rh B on Bi2O3-bentonite for different dye concentration and photocatalyst dose of 0.4 to 2.8 gL1 at pH 3,
contact time 60 min.

Dye concentration mgL1 Freundlich coefficient Langmuir coefficient

KF (Lg1) n 1/n r2 a (mgg1) b (gL1) RL r2

20 12.62 0.4968 2.013 0.944 31.25 0.7273 0.0643 0.892

40 9.70 0.5917 1.690 0.915 47.62 0.4375 0.0540 0.999
60 11.07 0.6689 1.495 0.933 111.11 0.1956 0.0785 0.979
80 1.13 0.3425 2.920 0.983 166.67 0.0822 0.0132 0.964

226 Bi2O3-bentonite upto 95.8% respectively. In the removal of Rh B by was investigated. To study its reusability, the powdered nano- 245
227 Bi2O3 and Bi2O3-bentonite, photocatalytic degradation is the composite was allowed to settle by gravity after completion of 246
228 dominant process than adsorption. each photocatalytic experiment. The recovered nanocomposite 247
229 To investigate the optimum amount of photocatalyst required was reused for 3 times under same experimental conditions. Fig. 8 248
230 for the removal of Rh B, amount of photocatalyst was varied. The shows removal Rh B by Bi2O3-bentonite after 1st run achieved upto 249
231 percentage removal of Rh B by Bi2O3-bentonite at different 98.5% after 80 min. After 4th run it decreases down to 91.7%. The 250
232 photocatalyst doses 0.4 to 2.8 gL1 for 20 mgL1 dye concentration catalytic activity was found to decrease slightly after 4th run. This 251
233 was studied under same experimental conditions. It was observed decrease may be attributed to loss of reused catalyst during 252
234 that, as Bi2O3-bentonite dose increases from 0.4 to 2.8gL1, the sampling each time and irreversible changes of the surface of the 253
235 percentage removal also increases from 90.9 to 97.6% under visible photocatalyst by dye molecules [37]. Fig. 8 shows that Bi2O3- 254
236 light irradiation. bentonite has excellent stability and does not suffer from photo- 255
237 It was concluded from Table 2 that, Rh B removal by Bi2O3- corrosion during photodegradation. This reflects significant 256
238 bentonite was an efficient method by comparison of various efficiency and practical applicability of Bi2O3-bentonite nanocom- 257
239 removal efficiencies, operational times and initial dye concentra- posite. 258
240 tions with similar studies in the literature.
241 To confirm the stability and efficiency of high performance of Effect of pH on Rh B degradation 259
242 Bi2O3-bentonite nanocomposite as well as cost effectiveness of the
243 process, the reusability of Bi2O3-bentonite nanocomposite in the Photocatalytic degradation of dyes is significantly affected by 260
244 photocatalytic degradation of Rh B under visible light irradiation pH of the dye solution [38,39]. The effect of pH is studied from pH 261
1 to 9 at 20mgL1 initial dye concentration for 1gL1 photocatalyst 262
dose. It is observed that percent removal at pH 1 is 87.9%, then it 263
1.0 increases upto 95.8% for pH 3 then it decreases down to 57.8% for 264
pH 9. Several other authors also reported, the optimum pH for the 265
removal of Rh B has been found to be about 3 [40]. 266
0.8
Degradation mechanism and identification of metabolites 267

0.6 Bi2O3-bentonite Degradation of Rh B can be explained on the basis of AOPs 268

Bentonite promoted by heterogeneous photocatalysis. This process involves 269
A/Ao

Bi2O3 generation of e and h+ which again generates O2 and OH 270
0.4 radicals respectively. These radicals are highly reactive and act as 271
degrading agents. Moreover, photo-generated hydrogen atom 272
from water is responsible for reductive degradation. 273
0.2 Since Rh B is cationic dye and poor e donor, the initial step 274
during its photodegradation is adsorption of dye on clay surface 275
then e--hole pair get generated by absorption of light by Bi2O3 276
0.0 nanorods intercalated between bentonite clay structure. e and h+ 277
0 20 40 60 80
Time (min) 120

Fig. 7. Photocatalytic degradation of Rh B (20mgL1) with Bentonite, Bi2O3 and 100

Bi2O3-bentonite.
Percent removal

80
1st run
60
Table 2 2nd run
Rh B removal efficiencies (%) of various methods.
40 3rd run
Nanomaterial Removal Operation Sources
efficiency (%) time (min) 4th run
20
BiVO4/reduced graphene oxide 98.5 600 [4]
BiOBr/montmorillonite 98.9 120 [8] 0
BiOBr-Graphene oxide 95 45 [34] 1st run 2nd run 3rd run 4th run
BiOBr-Graphene 87.4 135 [35]
Cycles
Vis-Fe0-H2O2-citrate-O2 62 120 [36]
Bi2O3-bentonite 98.5 80 This study
Fig. 8. Reusability performance of Bi2O3-bentonite nanocomposite.

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100 degradation pathway of Rh B is shown in Fig. 11a. Fig. 11a 292

90 indicates the N-deethylation, ring opening of Rh B to form different 293
80 degradation products including benzoic acid and benzonium ion 294
Percentage Removal

70 which are relatively non-toxic compare to Rh B. The plausible 295

mechanism for catalytic oxidation of Rh B on Bi2O3-bentonite 296
60
nanocomposite photocatalyst is shown below. 297
50
40 ½DyeðRh BÞ þ H2 O
30 adsorption
þ Bi2 O3 bentonite ! Rh BBi2 O3 bentonite (4)
20 299
298
10
hv þ
0 Bi2 O3 bentonite þ H2 O!e þ h (5)
Aqueous soluon 0.1 M i-PrOH 301
300

Fig. 9. Photocatlytic degradation of Rh B with addition of 0.1 M i-PrOH. þ H2 O

h ! OH (6)
303
302
278 again generate degrading agents, O2 and OH radicals. These are
O2
279 responsible for degradation of Rh B. Isopropanol is commonly used e !O2  (7)
280 as diagnostic tool for OH mediated mechanisms [41–45]. The 305
304
281 present study involves isopropanol as a scavenger. As direct yields
282 oxidation of smaller alcohols by photogenerated holes is negligible, Rh Bþ OH þ O2  ! CO2 þ H2 O þ Benzolc acid
283 it is neglected. The results in Fig. 9 show that photodegradation of þ Benzonium ion (8)
284 Rh B decreases down to 66.3% with the addition of 0.1 M i-PrOH as
285 compare to reaction in aqueous medium. The inhibition of Mechanistic pathway of photodegradation of Rh B dye using 306
308
307
286 photodegradation of Rh B suggests that OH are predominantly Bi2O3–bentonite nanocomposite is shown in Fig. 11b. Initially clay 309
287 active species in the photocatalytic degradation of Rh B. is intercalated with higher d spacing. Catalyst Bi2O3 is attached 310
288 In order to understand the degradation pathway and inter- onto surface of the clay platelets. With the irradiation of the visible 311
289 mediates that are formed during photocatalytic degradation of Rh light, there is generation of electron and hole which are attacking 312
290 B, LC-MS analysis was carried out. The mass spectra of Rh B before onto the Rh B dye molecule. Though the complete mineralization is 313
291 and after degradation are shown in Fig. 10. The probable not possible but the formation of the side products benzoic acid 314

Fig. 10. Mass spectra of Rh B solution (a) before and (b) after photodegradation.

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(a)
+
O H 2N
H 3C Rh B CH 3
m/z 104 HO NH2
+
H 3C N O N CH 3
m/z 114
H 2N NH
COOH
COOH

m/z 196 m/z 122

m/z 443
H 2N O

CH 3

+
H 3C NH O N CH 3
CH 3

H 2N O NH
m/z 274 COOH

COOH
m/z 415

m/z 362

(b)

Fig. 11. a The possible reaction intermediates after photocatalytic degradation under visible light irradiation. b Mechanistic pathway of photodegradation of Rh B dye using
Bi2O3–Bentonite nanocomposite.

315 and benzonium ion takes place which are less toxic than the Rh B dimensionless factor RL values show the favourable adsorption 331
316 dye. process. The scavenging study by addition i-PrOH shows that, OH 332
are the active species responsible for the photodegradation Rh B. 333
317 Conclusion LC-MS analysis shows the non generation of secondary waste after 334
degradation of Rh B by Bi2O3-bentonite. Furthermore, catalyst 335
318 Bi2O3-bentonite nanocomposites have been successfully syn- reusability study reveals that reusable Bi2O3-bentonite nanocom- 336
319 thesized by sonochemical method and its photocatalytic perfor- posite has high stability, high mineralization efficiency. Thus 337
320 mances under visible light are investigated. The results indicate Bi2O3-bentonite nanocomposite could be potential material for 338
321 that the Bi2O3-bentonite nanocomposite exhibits enhanced wastewater treatment. 339
322 photocatalytic efficiency in Rh B removal than Bi2O3 and bentonite
323 clay. Increase in photocatalytic efficiency is due to increased Acknowledgements 340
324 adsorption and decrease in recombination of photo e--hole pair in
325 the Bi2O3 with bentonite. The semiconductor based photocatalyst, The authors have gratefully acknowledged to Central 341
326 the Bi2O3 incorporated with bentonite clay can be a promising Instrumentation Centre, University Institute of Chemical Tech- 342
327 photocatalyst used effectively for the removal of dyes from nology, NMU, Jalgaon for SEM and XRD analysis. Authors are also 343
328 wastewater. Dye removal is favoured at pH 3. Adsorption kinetics thankful to Principal, Kisan College, Parola and Principal, G. T. 344
329 is found to follow pseudo-second-order kinetics. Whereas Patil College, Nandurbar for providing necessary laboratory 345
330 adsorption isotherm found to follow Freundlich isotherm. The facilities. 346

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