1 SYNTHESIS &APPLICATION OF ACTIVATED CARBON SUPPORTED ZERO

2 VALENT IRON FOR REMOVAL OF ACID RED-73: ADSORPTION AND KINETIC

3 STUDY

6 Abstract

7 The nanoscale zero valent iron was significantly used as an adsorbent for the removal of
8 organic contaminant. However, the problem of agglomeration and its easy oxidation in
9 ambient environment reduces its reactivity. Thus, the role of activated carbon (AC) was
10 investigated as a supporting material to stabilize the zero valent iron nanoparticles (nZVI) for
11 the degradation of azo dye acid red -73. The experiments were done under optimized
12 conditions (pH, dose, dye concentration and contact time) and highest removal efficiency was
13 achieved as 98%. The results were well fitted in the Langmuir and Freundlich isotherm
14 models at pH 4 with R2 value of 0.98. The kinetic study revealed that the adsorption study
15 follows the pseudo second order (R2=.99). The band shifting of dye from 509 nm to 256 nm
16 reveals that nano zero valent iron participated in the reduction of acid red-73, while
17 desorption study states that approximately 33% of dye was adsorbed on the activated carbon
18 and 67% was reduced through nZVI.. The synthesized composite could be an efficient
19 catalyst for the removal of acid red-73.

20 Keywords: Acid red -73, activated carbon, degradation, supporting material, nano zero
21 valent iron

22 1. Introduction

23 The unregulated release of dyes into the environment via industrial water remains a
24 significant source of water pollution. The Complexity and structural variations in dyes makes
25 them resistant to various treatment technologies. In textile processing 60-70% of dyes are
26 comprised of azo dyes (Robinson et al., 2001, Parshetti et al., 2010, Malakootian et al., 2013).
27 The presence of diazo bond (-N=N-) in their structure is responsible for the instability,
28 carcinogenicity, and toxicity of the azo dyes and often hinders the performance of
29 conventional treatment methods (ozonation, flocculation, adsorption) (Leite, et al., 2016,
30 Jong et al., 2016, Vacchi et al., 2016 ). Subsequently their by- products were found to be
31 toxic for both human and ecosystem (Leme et al, 2015., Gao et al., 2010). Nanotechnology
32 involves the synthesis and modulation of nanoparticles which is widely used in various
33 applications such as wastewater remediation, catalyst, and semiconductor (Zhao et al., 2016).
34 Zero valent iron is one of the most investigated nanoparticle employed for environmental
35 remediation due to its high reactivity, high absorptivity and strong reducing power (Eo =
36 0.44V). However, aggregation is the principle problem encountered while synthesizing iron
37 nanoparticles which is mainly because of the inter-particle forces like Van der wall, electric
38 dipolar and magnetic dipolar interactions. This can reduce its surface area and renders the
39 effectiveness of nZVI. The stability of nZVI can be increased by controlling their inter-
40 particle interactions (Zhao et al., 2016). The application of supporting materials like clays,
41 biochars, and activated carbon was often used to prevent the agglomeration and subsequently
42 increasing the reactivity of nZVI (He et al., 2005, Ponder et al., 2000, Wang et al., 2013,).
43 The aim of the current study was to investigate the application of activated carbon supported
44 nZVI for acid red-73 dye removal.

45 2. Materials & methods

46 Ferrous sulfate (FeSO4·7H2O), Sodium borohydride, (NaBH4), ethanol, and acetone were
47 procured from Merck chemicals, India. All the chemicals used in the experiments were of
48 analytical grade and the solutions were prepared using deionized water.

49 2.1 Preparation activated carbon

50 The eucalyptus saw wood was purchased from local market and then heated at 700º C for
51 one hour in muffle furnace. Activation was carried out with 0.6M sulphuric acid
52 (H2SO4).After the activation process was completed the sample were cooled down at room
53 temperatures (25ºC) and was washed with HCL followed by rinsing with deionized water to
54 eliminate the impurities. The resultant activated carbon was then vacuum dried at 100ºC for
55 24 hours and was preserved in desiccator for further use.

56 2.2. Preparation nZVI-AC

57 The prepared activated carbon was used as a supporting material for nZVI. The synthesis
58 process includes the following steps: firstly 1:1 ratio of nZVI and AC was dissolved in a
59 mixture of ethanol and water (3:7) in 100 ml. Then 50 ml NaBH4 (0.5M) was added dropwise
60 to the nZVI-AC mixture with constant stirring. After the reaction was completed 57the nZVI-
61 AC was vacuum filtered followed by three times washing through ethanol to 58removal the
62 excess NaBH4. The obtained composite were then dried in vacuum oven 59overnight and was
63 used for further analysis.
64 2.3 Batch Experiment

65 The adsorption and kinetic study was performed to investigate AR-73 adsorption by nZVI-
66 AC. All experiments were carried out in conical flasks having capacity of 250 ml with
67 varying operational parameters like adsorbent dose (1-4 g/L), contact time (0-120 min), pH
68 (2-10) and dye concentration (100-400 mg/L). The pH was adjusted with 1N HCl and 1 N
69 NaOH solution. As the reaction started the samples were kept in incubator shaker with a
70 constant speed of 120 rpm at room temperature. The dye solution was taken within 15 min of
71 interval and then centrifuged at 3000 rpm for 30 min. The supernatant of the dye was 68then
72 measured at 509 nm using UV-Visible spectrophotometer.

73 2.4 Point of zero charge determination

74 The point of zero charge of the synthesized nZVI-AC was estimated through zeta potential. A
75 significant amount of nZVI-AC was added in 100 ml of deionized water and pH values were
76 adjusted from 2-12. Then the solution was agitated for 24 hour in incubator shaker at speed of
77 120 RPM at room temperature (25º C). The pH at which the curve crossed the line of equality
78 was taken as the point of zero charge of AC-nZVI.

79

80 2.5 UV–Vis spectral analysis & Desorption study

81 The UV-Vis spectral analysis was carried out to investigate the transformation products
82 formed during dye degradation. The experiment was conducted on the basis of above
83 optimized parameters in which a 100 ml aqueous solution of AR-73 with a concentration of
84 200 mg/L was taken. The pH was set at 4 with a dose of 0.4 g/L of nZVI-AC. The reaction
85 mixture was then kept for shaking at 120 RPM and the aliquots was taken at an interval of
86 every 15 min. Desorption study was conducted to extract the AR-73 by–82products adsorbed
87 to the AC-nZVI through reduction process. The experimented dye 83solution was centrifuged
88 at 3000 rpm for 15 min and then the pellet obtained was dissolved in 15 ml acetone.
89 Furthermore, the solution was again centrifuged and the supernatant was taken for further
90 analysis.

91

92 3. Results and Discussion

 93 3.1 Characterization of AC-nZVI nanocomposite.

94 The composition and morphology of the catalyst was measured by SEM and EDX. The SEM
95 images of the AC and the AC-nZVI (Figure 1) shows that the nZVI particles produced in this
96 study were spherical in shapes which were dispersed on the pores of activated carbon. The
97 EDX spectrum shows that the AC-nZVI composite was composed of carbon (44 %) and Iron
98 (29 %).The surface functional groups present in nZVI/AC shows intensities at 3422 cm-1,
99 1394 cm-1, 1663 cm-1 and 1100 cm-1 which were the corresponding stretching of O-H, C=C,
100 H-O-H, and FeOOH bond respectively (Dada et al., 2017).

(a) (b)

101
(c)
102

103 Figure 1 The SEM image of (a) activated carbon, (b) nZVI-AC and (c) FTIR of the
104 synthesized nZVI-AC

105 3.2 Effect of pH

106 The pH of dye solution is a significant parameter in adsorption process. The number of active
107 sites, charge and functional groups of the synthesized composite can be affected by varying
108 pH. The adsorption study of AR-73 revealed that the highest removal efficiency was in acidic
109 medium at pH 4. This can be attributed to the fact that at low pH the electrostatic interaction
110 between positively charged surfaced of nZVI-AC and negatively charged molecules of AR-
111 73 (Freyria, et al., 2017) is increased due to their attraction while at higher pH this interaction
112 get reduced because of repulsion between the adsorbent surface and dye molecules. Thus the
113 removal efficiency was kept on decreasing from low to high pH (2-10) from 97% to 60 %.
114

115 3.5 Point of zero charge determination (PZC)

116 Point of zero charge plays very important role in adsorption process as it refers to pH at
117 which the electrical charge density on a surface is zero. The pH value above the PZC reveals
118 that the nZVI-AC has negatively charged surface and attract cations, while pH value below
119 PZC attributed to the positively charged surface of the synthesized composite which
120 subsequently repels cations. Therefore, this parameter determines the potential of nZVI-AC
121 to adsorb AR-73. In present study, point of zero charge of nZVI-AC was at found pH 6.73.

122

123 Figure 2 Point of zero charge determination through zeta potential

124 3.3Effect of adsorbent dose

125 The adsorption study was carried out with varying doses of the nZVI-AC from (1-4 g/L).
126 Figure 3 shows that as the adsorbent dose increases the removal efficiency increases from
127 77% to 98% (Zhang et al., 2012).

128 3.4 Effect of dye concentration

129 The dye adsorption mechanism is significantly depends upon the initial concentration of dye.
130 The experiments were carried out at a fixed adsorbent dose (4 g/L) and at different initial dye
131 concentrations of (100, 200, 300, 400, 500 mg/L) for different time intervals (15-120
132 minutes). Adsorption efficiency was clear from the trend of adsorption (Fig.3). The result
133 shows that the percentage of removal of dye decreases from 83% to 15.5% as the
134 concentration of dye increases from 100 mg/l to 400 mg/l. This could be due to the saturation
135 of the active sites of the nZVI-AC.

(a)
(b)

(c)
136
137 Figure 3 (a) Effect of dye concentration, adsorbent dose (b) and (c) pH on AR-73 removal
138 (C0= 100 mg/L, time=120 min, dose= 4g/L)

139

140 3.6 Adsorption Kinetics and Isotherms

141 The study of adsorption kinetics is a significant step to understand the mass transfer between
142 the adsorbate with respect to time. The pseudo-first order, pseudo-second order and intra-
143 particle diffusion models were applied to the experimental data with initial dye concentration
144 of 200 mg/L as shown in Figure 4. The results states that the equilibrium was reached one
145 hour and R2 value were 0.84 and 0.99 for pseudo first order and pseudo second order
146 respectively. The higher R2 values for pseudo second order could be due to chemisorption.
147 The intra-particle diffusion implies that the diffusion occurs between the dye molecules and
148 pores of adsorbent (Table 1) (Dogan et al., 2004). The R2 value of this model was 0.87 in
149 this study. The adsorption isotherm models Langmuir and Freundlich were also applied to
150 define the adsorption mechanism of monolayer adsorption onto homogeneous and
151 heterogeneous surface respectively (Zhu et al., 2009). Figure 5 shows the isotherm models
152 (Table 1) and the results were found to fit well with both isotherm models (R2 = 0.98).

153

154
 (a)
(b)

155
(c)

(d)
(e)

156
157 Figure.4. Absorption kinetics (a) pseudo-first order, (b) pseudo-second order, (c) Inter-
158 particle diffusion model, (d) Langmuir and (e) Freundlich isotherm models.

159

160
161 Table 1

162 Kinetics and isotherm models for AR-73 adsorption onto nZVI/AC

163 Models/Equations Parameters R2

164

165 Langmuir Qm (mg/g) =136 0.98

1 1 1
166 1𝑞𝑒 = 𝑄𝑜 + 𝑄𝑜𝐾𝐿𝐶𝑒 KL=0.21

167 Freundlich n=1.79 0.98

168 𝑄𝑒 = 𝐾𝑓 𝐶𝑒1/𝑛 Kf = 1.425

169 Pseudo first order Qe (mg/g) = 49.29 0.84

170 Qe (mg/g) = 8.13

171 Pseudo second order Qe (mg/g) = 49.29 0.99

172 Qe (mg/g) = 49.33

173 Intra-particle diffusion model KIPD (mg/g. min1/2) = 0.17 0.87

174

175 3.7 UV-Spectral analysis and desorption study

176 The UV-Vis spectrum of AR-73 was shown in figure 5. As the reaction started (0 min)
177 characteristic peak of dye molecule appeared in the visible region at 509 nm while presence
178 of benzene ring and naphthalene shows absorption bands at 246 nm and 345 nm respectively.
179 After 15 min the bands shifting of benzene ring and naphthalene started and the chromophore
180 was completely destroyed. The absorption peak at 256 nm corresponds to the transformation
181 product of AR-73 which was in good agreement to the previously reported work (Kumar et
182 al., 2017). This band shifting indicates that nZVI plays a significant role in degradation and
183 formation of by-products of the dye.
184

185 Figure 5 UV-Vis spectral analysis of AR-73 after reduction

186

187 4. Conclusion

188 Nano scale nZVI-AC n was synthesized for the removal of azo dye namely acid red-73. The
189 compositional data from SEM and EDS confirms that presence of nZVI and was dispersed in
190 the pores of activated carbon. Batch experimental study reveals that nZVI-AC is an effective
191 adsorbent for the reduction of AR-73. The highest removal rate was obtained at pH 4 with
192 98% removal efficiency. The adsorption kinetics follows pseudo-second order adsorption
193 capacity of 136.23 mg/g and seems to fit in both isotherm models. The desorption study and
194 UV-spectral analysis suggests the formation of transformation products which could be
195 attributed to the degradation of the dye through reduction by nZVI.

196

197

198

199

200
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