APT 2022 No.

of Pages 7, Model 5G
28 July 2018

Advanced Powder Technology xxx (2018) xxx–xxx

1

Contents lists available at ScienceDirect

Advanced Powder Technology

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

2 Original Research Paper

6
4 Hydrothermal synthesis of NH2-UiO-66 and its application for
7
5 adsorptive removal of dye
8 Sneha N. Tambat a, Priyanka K. Sane a, Srinidhi Suresh a, O. Nilesh Varadan a, Aniruddha B. Pandit a,
9 Sharad M. Sontakke a,b,⇑
10 a
Department of Chemical Engineering, Institute of Chemical Technology, Mumbai 400019, India
11 b
Department of Chemical Engineering, Birla Institute of Technology and Science, Pilani, K K Birla Goa Campus, Goa 403726, India

13
12
14
a r t i c l e i n f o a b s t r a c t
1
2 6
9
17 Article history: In this research paper we report hydrothermal synthesis of NH2-UiO-66, a metal organic framework 30
18 Received 2 June 2018 (MOF) with zirconium as metal and amino terephthalic acid as a linker. The synthesized MOF was char- 31
19 Received in revised form 9 July 2018 acterized by XRD, FTIR, SEM and BET surface area. As a potential application in water treatment, an 32
20 Accepted 19 July 2018
adsorptive removal of safranin dye was studied using the synthesized material. The effect of initial con- 33
21 Available online xxxx
centration and pH of the dye solution was studied on the dye adsorption capacity of the material. An opti- 34
mum set of conditions resulting into maximum dye adsorption was found out. The maximum adsorption 35
22 Keywords:
capacity of the MOF was observed to be 390 mg/g at neutral pH of the solution and at room temperature. 36
23 NH2-UiO-66
24 Adsorption
The experimental data was fitted with Langmuir, Freundlich and Temkin adsorption isotherm models. 37
25 Safranin The kinetics of adsorption was studied using pseudo first order and pseudo second order model. The 38
26 Kinetics dye adsorption mechanism was also attempted. 39
27 Isotherm Ó 2018 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan. All rights 40
28 reserved. 41
42

43
44
45 1. Introduction lution [9,10]. Many of these chemical pollutants are identified as 64
mutagenic, carcinogenic and if consumed in excess quantity can 65
46 Metal organic frameworks (MOFs) are a class of advanced por- cause severe damage to human health [11]. In addition, the water 66
47 ous, crystalline materials synthesized from organic linkers and contaminated with these chemicals can be a potential threat to 67
48 transition metal ions (or clusters) [1]. These materials are receiving aquatic life [12]. Therefore, majority of the research in the field 68
49 increasing scientific attention for variety of applications owing to of water treatment is focused on removal of dye pollutants. Several 69
50 their ease of synthesis, high surface area, high porosity, high ther- conventional and advanced oxidation techniques are reported for 70
51 mal and mechanical stability, tunable structural and functional the removal of these pollutants [13–16]. Among the available tech- 71
52 properties, etc. [1,2]. niques, adsorption is an economical yet efficient method for the 72
53 The MOFs have been extensively investigated as an adsorbent removal of variety of synthetic dyes [6,17]. In this context, a con- 73
54 for the treatment of polluted water [3,4]. However, most of these siderable amount of literature is available on variety of adsorbents 74
55 materials are unstable in water and subject to degradation through including activated carbon, diatomaceous earth, resins, zeolites, 75
56 ligands displacement or hydrolysis [4]. Among the reported MOFs, carbon nanotubes, etc. In general, a good adsorbent should pos- 76
57 UiO-66 and NH2-UiO-66 (UiO = University of Oslo) exhibit high sesses high surface area, high porosity, ease of synthesis, less cost, 77
58 stability in water and have excellent adsorption properties [4,5] high thermal and mechanical properties, regeneration ability and 78
59 because of which these are receiving considerable attention for high adsorption capacity towards a wide range of pollutants within 79
60 adsorptive removal of water pollutants [4,6–8]. a short contact time [6,18]. Since UiO-66, NH2-UiO-66 and few 80
61 Residual synthetic dyes, in the effluent of textile, leather, paper, other MOFs satisfy most of the above requirements; these are con- 81
62 printing, cosmetics, petroleum, plastic, food, paint, rubber, and sidered to be potential alternative adsorbents for the treatment of 82
63 pharmaceutical industries are the major contributor to water pol- dye polluted water. 83
Chen and coworker studied the adsorptive removal of various 84
anionic and cationic dyes using UiO-66 and NH2-UiO-66 MOF [6]. 85
⇑ Corresponding author at: Department of Chemical Engineering, Institute of They observed superior adsorption of cationic dyes on to the 86
Chemical Technology, Mumbai 400019, India. NH2-UiO-66 compared to UiO-66. A microwave-assisted synthesis 87
E-mail address: sharads@goa.bits-pilani.ac.in (S.M. Sontakke).

https://doi.org/10.1016/j.apt.2018.07.010
0921-8831/Ó 2018 Published by Elsevier B.V. on behalf of The Society of Powder Technology Japan. All rights reserved.

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88 of UiO-66 and its application for the adsorptive removal of acid 2.2. Synthesis of NH2-UiO-66 149
89 chrome blue K is reported by Li and coworkers [8]. He and cowor-
90 ker reported adsorptive removal of Rhodamine B on UiO-66 [19]. In a typical synthesis of NH2-UiO-66, 2.17 g of 2-amino tereph- 150
91 They observed increase in the adsorption capacity with tempera- thalic acid and 3.8 g of Zirconium chloride was added to 36 mL of 151
92 ture and the maximum dye adsorption capacity was observed to DMF. The mixture was stirred for 30 min. It was then transferred to 152
93 be about 75 mg/g at 323 K. They also studied the regeneration of a stainless steel teflon-lined autoclave and maintained at 120 °C for 153
94 the spent adsorbent and demonstrated reuse of the material for 24 h. The solid thus obtained was washed first with DMF and then 154
95 six cycles of sorption/desorption. In an another study, an adsorp- repeatedly with methanol. Finally, the as-obtained solids was dried 155
96 tive behavior of UiO-66 for the removal of acid orange 7 (AO7) at room temperature and further in an oven kept at 150 °C for 4 h. 156
97 dye was investigated and a maximum adsorption capacity of about
98 358 mg/g was observed at 318 K [20]. Recently, Embaby et al. stud- 2.3. Characterization of the synthesized material 157
99 ied adsorption of a series of anionic (Alizarin Red S, Eosin, Fuchsin
100 Acid and Methyl Orange) and cationic (Neutral Red, Fuchsin Basic, The synthesized material, NH2-UiO-66, was characterized by 158
101 Methylene Blue and Safranine T) dyes onto the UiO-66 and XRD, FTIR, SEM, Zeta potential analysis and BET surface area. A 159
102 reported a record maximum adsorption capacity of 400 mg/g for powder X-ray diffraction pattern was recorded on a Bruker D8 160
103 adsorption of Alizarin Red S dye [21]. In literature, most of the Advance X-ray diffractometer (Bruker, USA), with Cu Ka radiation 161
104 studies are performed with UiO-66 however, application of NH2- in a range of 10–90° at a scanning speed of 0.2 s/0.02°. The crystal- 162
105 UiO-66 for the adsorptive removal of dyes is least investigated. lite size was calculated using Scherrer’s calculator. An FTIR spec- 163
106 The synthesis of MOFs is mainly reported by hydrothermal and trum was recorded on a Spectrum TwoTM spectrometer (Perkin 164
107 microwave methods [6,8,19]. The hydrothermal method, under Elmer, USA) in the range of 4000 cm-1 to 500 cm-1. The surface 165
108 elevated temperature and pressure conditions, ensures complete morphology of the as-synthesized material was studied by a scan- 166
109 solubilization of the organic molecules used as linker. These exper- ning electron micrograph taken on a JEOL JSM-6380 SEM instru- 167
110 imental conditions also help to overcome the activation energy ment (JEOL, Japan). Zeta potential analysis of the synthesized 168
111 required for intermediate metastable phases of synthesis and materials was performed using a Zetasizer instrument (Malvern 169
112 therefore, the synthesized material becomes highly crystalline Instruments, UK). The BET surface area was measured by nitrogen 170
113 [22,23]. The hydrothermally synthesized of UiO-66 family MOFs adsorption-desorption isotherm using a PMI BET sorptometer 171
114 has been well reported in the literature. However, its application (BET-201AEL-2OSEL, USA). 172
115 for dye adsorption is least investigated. For example, Shen and
116 coworkers reported application of hydrothermally synthesis of 2.4. Batch adsorption experiments 173
117 NH2-UiO-66 for photocatalytic applications [24]. Luu and cowork-
118 ers studied the application of NH2-UiO-66 for adsorption of CO2 Batch adsorption studies were performed using the synthesized 174
119 and CH4 [25]. The only study available in the literature on applica- material for the removal of Safranin dye from aqueous solution. 175
120 tion of hydrothermally synthesized NH2-UiO-66 for dye adsorption Initially, a stock solution (1000 mL) of 1000 ppm of Safranin dye 176
121 is reported by Chen and coworker [6]. In the above work, they in DI water was prepared. A required concentration of the solution 177
122 reported adsorptive removal of three cationic dyes (Methylene was prepared by diluting the stock solution. The observed error in 178
123 Blue, Rhodamine B and Neutral Red) and two anionic dyes (Methyl the initial dye concentration of the solution was ±2 ppm. To this 179
124 Orange and Acid Chrome Blue K) using UiO-66 and NH2-UiO-66. solution, a pre-weighed amount of adsorbent was added and the 180
125 They observed preferential adsorption for cationic dye onto the suspension was stirred on a magnetic stirrer at room temperature 181
126 MOFs. However, in the above work, the experiments were carried conditions. For analysis, samples were withdrawn for the solution 182
127 out at 20 ppm and the equilibrium dye adsorption capacity is at a regular interval of time. The samples were centrifuged in a 183
128 reported as 96 mg/g for adsorption of methylene blue dye. The OptimaTM MAX-XP centrifuge, (Beckman Coulter, USA) in order to 184
129 authors (Chen and coworkers) have not studied the effect of initial remove the adsorbent material and absorbance of the supernatant 185
130 dye concentration or pH and there was no attempt of optimizing solution was noted using a UV–Vis spectrophotometer (Carry 50 186
131 the experimental conditions. UV–Vis, USA). The concentration of the unknown solution was then 187
132 In the present study, we report hydrothermal synthesis of NH2- determined with the help of a pre-plotted calibration curve 188
133 UiO-66 and its application for the removal of cationic Safranin dye. between the concentration of known solutions and their corre- 189
134 The effect of initial concentration and pH of the dye solution was sponding absorbance values. The experiments were continued 190
135 studied on the dye adsorption capacity of the material. The exper- until a constant concentration of the dye was observed at least in 191
136 imental data was fitted with Langmuir, Freundlich and Temkin 5 successive readings. This constant concentration was attributed 192
137 adsorption isotherm models. The dye adsorption mechanism was to equilibrium concentration. 193
138 also attempted. The amount of dye adsorbed on the adsorbent at different time, 194
t, is represented by qt and calculated by: 195
196
V
qt ¼ ðC0  Ct Þ  ð1Þ 198
139 2. Experimental W
where Co is the initial concentration (in mg/L) of dye, Ct is the con- 199
140 2.1. Chemicals and materials centration (in mg/L) of dye at time, t, V is the volume (in L) of the 200
solution and W is the amount (in g) of adsorbent. 201
141 All the chemicals used in the experiments were of analyt- Further, the amount of adsorption at equilibrium, qe (mg/g), 202
142 ical grade and were used without any further purification. was calculated by: 203
204
143 The chemicals used were Zirconium chloride (S.D. Fine Chem-
V
144 icals Limited, Mumbai), 2-amino terephthalic acid (Sigma qe ¼ ðC0  Ce Þ  ð2Þ 206
145 Aldrich), N,N-dimethyl formamide (DMF) (S.D. Fine Chemicals W
146 Limited, Mumbai) and methanol (S.D. Fine Chemicals Limited, where Ce is the equilibrium concentration (in mg/L) of dye. All other 207
147 Mumbai). deionized (DI) water was used to prepare all the quantities on right side of the above equation have same meaning 208
148 solutions. as that in Eq. (1). 209

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210 The procedure for kinetic experiments was similar to the equi- 100
211 librium studies. Samples were collected at specific time interval
212 and the unknown concentration of dye was measured with the
213 help of calibration curve. 98

3452

% transmission
96 3348 2988
214 3. Results and discussion
Asymmetric and C-H streching
symmetric
215 3.1. Characterization of synthesized NH2-UiO-66 N-H vibration
94
1564
216 Fig. 1 shows a XRD pattern of the synthesized material. The Asymmetric
217 recorded pattern shows crystalline nature of the material and is 92 O=C-OH stretch 1378
218 in good agreement with the earlier reports [22,23]. The crystallite Symmetric
219 size calculated using Scherrer’s calculator was found to be 15 ± 2 O=C-OH stretch
220 nm. The FTIR spectrum of the synthesized MOF is shown in 90
221 Fig. 2. From the figure, the presence of major peaks can be observed 4000 3500 3000 2500 2000 1500 1000 500
-1
222 at a wavelength of 3452 cm-1, 3348 cm-1, 2988 cm-1, 1564 cm-1 wavenumber, cm
223 and 1378 cm-1. The absorption bands at 3452 cm-1 and 3348 cm-1
Fig. 2. FTIR spectrum of the synthesized NH2-UiO-66.
224 are attributed to the asymmetric and symmetric vibration of N-H
225 group [26]. The presence of distinct peak at 2988 cm-1 can be
226 attributed to the C-H stretching of the physisorbed DMF molecules
227 [18,21,27]. Whereas, the two distinct peaks at 1564 cm-1 and 1378
228 cm-1 can be attributed to the asymmetric and symmetric stretch-
229 ing of carboxyl functional groups, respectively [18,26]. An SEM
230 image depicting the surface morphology of the synthesized mate-
231 rial is shown in Fig. 3. From the image, an agglomeration of the uni-
232 formed shaped particles with a size in the range of 14–16 nm can
233 be observed. The zeta potential of NH2-UiO-66 is shown in Fig. 4
234 and the value of point of zero charge (pzc) was observed at a pH
235 of 3.5. Above the zpc, the material was electropositive whereas
236 below the zpc, it was electronegative. The BET surface area, pore
237 size and pore volume of the synthesized material was found to
238 be 246.80 m2/g, 0.019 cc/g and 31.06 Å, respectively.

239 3.2. Effect of initial concentration of dye on adsorption

Fig. 3. SEM image of the synthesized NH2-UiO-66.

240 Initially, the effect of initial dye concentration (55 mg/L, 80 mg/
241 L and 135 mg/L) on the adsorption capacity of the synthesized MOF
242 was investigated. The amount of adsorbent in each batch
10
243 experimental run was kept constant to 0.1 g/L and the experiments
244 were carried out at a natural pH of the solution. Each experiment
5
245 run was continued till a constant concentration of the dye was
246 observed (which was attributed to the equilibrium concentration,
247 Ce). The amount of dye adsorbed on the adsorbent at different time, 0
248 t, is calculated by Eq. (1). Fig. 5 shows a plot of qt versus time for
-5 2 4 6 8 10 12
3.5
Pottential (mV)

pH
-10
4000 (111)
-15

3000 -20
Intensity (a.u.)

-25
2000
(002) -30

Fig. 4. Zeta potential measurement of the synthesized NH2-UiO-66.

1000
(224)
(022) (115) (046)
(004) different initial concentrations of the dye solution. It was observed 249
0 that for any initial concentration of the dye solution, the parameter 250
10 20 30 40 50 60 70 qt increases rapidly in the initial 90 min of contact time. Between 251

2 theta (degree) 90 and 480 min, qt increases almost linearly with time and beyond 252
480 min, it remains constant till prolonged contact time. With the 253
Fig. 1. XRD pattern of the synthesized NH2-UiO-66. help of above experimental adsorption data, the value of qe for 254

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500 500

400 400

300 300

q t (mg/g)
q t (mg/g)

200 200
pH 4
pH 7
100 135 ppm 100
pH 9
80 ppm
55 ppm
0 0
0 2 4 6 8 18 20 22 24 0 2 4 6 8 18 20 22 24
Time (h) Time (h)

Fig. 5. Effect of initial concentration of dye on adsorption capacity of the Fig. 6. Effect of pH of dye on adsorption capacity of the synthesized NH2-UiO-66.
synthesized NH2-UiO-66.

255 different initial concentration of the dye solution viz. 55 mg/L, 80 increased significantly due to the similar surface charges on the 295
256 mg/ L and 135 mg/ L was estimated as 177 mg/g, 248 mg/g and material as observed from the zeta potential. 296
257 390 mg/g, respectively. In a study reported on the removal of Safranin basic dye onto 297
258 In literature, the adsorption of Safranin dye is studied using the corncob activated carbon (with a zpc of 2.5), a maximum 298
259 different adsorbents. Table SI 1 (see supporting information) pre- adsorption capacity is reported with a solution pH in the range 299
260 sent list of materials reported for the adsorptive removal of safra- of 5–9 [11]. In another study by Chen and co-worker, the zeta 300
261 nin dye. From the table it can be seen that activated carbon and potential of NH2-UiO-66 was observed to be more electronegative 301
262 clay are mostly reported materials with an adsorption capacity as (4.91 mV) than UiO-66 (3.65 mV) and thus the former material 302
263 high as 1428.57 mg/g. In one of the recent publication by Ade- showed better affinity towards cationic dyes [6]. The above study 303
264 bowale et al. [28], the values of adsorption capacities of different also concluded that the side group –NH2 captures proton and yield 304
265 adsorbents for the removal of the Safranin dye are compared. In –NH3+ thus, leading to efficient dye adsorbent onto the NH2-UiO- 305
266 comparison to the literature, adsorption capacity of synthesized 66 surface [6]. Thus, it can be concluded that the electronegative 306
267 NH2-UiO-66 observed in the present study (390 mg/g) is second surface charges helps in efficient dye adsorption and the presence 307
268 best, among the reported adsorbents. of –NH2 group further help in proton exchange of the adsorbed 308
269 Supplementary data associated with this article can be found, in cationic dye molecules which enhances the overall process 309
271
270 the online version, at https://doi.org/10.1016/j.apt.2018.07.010. efficiency. 310
In the present work, the observed value of maximum adsorp- 311
tion capacity at neutral pH is in agreement with the literature. 312
The study, therefore, suggests that the treatment can be employed 313
272 3.3. Effect of pH without addition of any other chemicals (in order to change the 314
pH). 315
273 Solution pH plays an important role in the adsorption process. At optimum conditions (initial dye concentration of 135 mg/L 316
274 The pH of the as-prepared Safranin dye solution with an initial con- and as-prepared pH), the adsorption performance of NH2-UiO-66 317
275 centration of 55–135 mg/L was found to be 7.08 ± 0.02. was also compared with pristine UiO-66 and the results are shown 318
276 Fig. 6 show the effect of pH on the adsorption capacity synthe- in Fig. 7. The dye adsorption onto NH2-UiO-66 was observed to be 319
277 sized MOF for the removal of Safranin dye. The experimental superior compared to UiO-66. As described earlier, the higher 320
278 adsorption data showed very similar patterns to that observed adsorption onto NH2-UiO-66 is attributed to the favorable electro- 321
279 with changing the initial concentration of the dye solution. A rapid static interactions between the adsorbents and cationic dyes. The 322
280 increase in qt in the beginning till 90 min was followed by a linear observations are also in agreement with the earlier report [6]. 323
281 increase between 90 and 480 min and thereafter remained con-
282 stant till prolong time. 3.4. Adsorption isotherms 324
283 From the data, the values of qe for the solution with pH of 4, 7
284 and 9 was observed to be 332 mg/g, 384 mg/g and 390 mg/g. Thus, In the present study, the experimental batch adsorption data 325
285 a maximum adsorption at neutral pH was observed. From the zeta was examined to fit with Langmuir, Freundlich, or Temkin adsorp- 326
286 potential measurements of NH2-UiO-66 (Fig. 4), a zpc (point of zero tion isotherm models. The applicability of the isotherm models to 327
287 charge) was observed at a pH of 3.5. Therefore, at any pH value the experimental batch adsorption data was decided based on the 328
288 above 3.5, the MOF was negatively charged whereas, at any pH correlation coefficient (R2) of the linear fit. 329
289 value below 3.5, the MOF was positively charged. Since Safranin The Langmuir isotherm assumes monolayer adsorption onto a 330
290 is a cationic dye, increasing the pH of the solution from 4 to 7 surface containing a finite number of adsorption sites and is 331
291 favoured the electrostatic interaction between dye molecules and expressed as: 332
292 the adsorbent and thereby resulted into increased adsorption 333
capacity of the material. Whereas, when the solution pH was fur- Ce 1 Ce
293 ¼ þ ð3Þ
294 ther increased from 7 to 9, the adsorption capacity did not qe qm K L qm 335

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the heat of adsorption of all the molecules in the layer decreases 374

400 linearly with coverage. A linearized form of Temkin isotherm is 375

given by following equation: 376

  377
RT RT
300 qe ¼ ln AT þ ln C e ð6Þ
KT KT 379
qt (mg/g)

where qe and Ce has the same meaning as in Eq. (3), AT is the 380
200 equilibrium binding constant, KT is the constant related to the vari- 381
ation of adsorption energy, R the universal gas constant, T is the 382
absolute temperature in K. The isotherm constants, AT and KT can 383
be calculated from a plot of qe versus ln Ce. The values of isotherm 384
100
constants AT and KT (calculated using Fig. SI 3, see supporting infor- 385
NH2-UiO-66
mation) were found to be 0.060 and 11.61, respectively. In addi- 386
UiO-66 tion, the R2 value of the fit (Fig. SI 3, see supporting information) 387
0 was observed as 0.96 indicating a good fit. 388
389
0 2 4 6 8 18 20 22 24 Table 1 summarizes the equilibrium constants of different iso- 390
Time (h) therms along with the value of correlation coefficient of a lin- 391
earized model fit. From this, it can be concluded that the 392
Fig. 7. Adsorption performance comparison between NH2-UiO-66 and pristine experimental batch adsorption data follow Freundlich isotherm. 393
UiO-66.

336 where Ce is the equilibrium concentration of the dye (mg/L), qe is

3.5. Adsorption kinetics 394
337 the amount of adsorption at equilibrium (mg/g), qm is the theoret-
338 ical maximum adsorption capacity (mg/g) and KL is the Langmuir
The experimental batch adsorption data was fitted to pseudo 395
339 constant (L/mg) related to rate of adsorption. The values of qm
first-order and pseudo second-order kinetic model represented 396
340 and KL can be found out from a graph of Ce/qe versus Ce. To confirm
by Eqs. (7) and (8), respectively. 397
341 the favorability of the adsorption, the separation factor (RL) was cal-
398
342 culated as:
ln ðqe  qt Þ ¼ ln qe  k1 t ð7Þ 400
343
1
RL ¼ ð4Þ 401
345 1 þ C0K L t 1 t
¼ þ ð8Þ
346 where C0 is the initial dye concentration (mg/L). The value of RL qt k2 q2e qe 403
347 between 0 and 1 indicates favourable isotherm. For the present In above Eqs. (7) and (8), qe and qt are the amounts of dye 404
348 work, the values of qm and KL were found to be 1428.57 and adsorbed on the adsorbent (mg/g) at equilibrium and time t, 405
349 0.0038, respectively. However, the R2 (correlation coefficient) respectively. k1 (1/h) and k2 (g/mgh) are the rate constants of 406
350 value of the graph of Ce/qe versus Ce (Fig. SI 1, see supporting infor- the pseudo first-order and pseudo second-order adsorption kinetic 407
351 mation) was 0.83. Further the value of separation factor (RL) for ini- model, respectively. The parameters qe and k1, in the pseudo first- 408
352 tial dye concentration of 55 mg/L, 80 mg/ L and 135 mg/ L, order model was estimated from a graph of ln (qe  qt) versus t 409
353 calculated using Eq. (4), was found to be 0.826, 0.765 and 0.659, (Fig. 8a) as 185.47 mg/g and 0.469 h-1, respectively. Moreover, 410
354
355 respectively which indicates a favourable adsorption. the correlation coefficient (R2) for the linear fit in Fig. 8a was 411
356 Freundlich adsorption isotherm is used to describe the adsorp- 0.93. The parameters qe and k2 in the pseudo second-order model 412
357 tion characteristics for more than one monolayer coverage of the estimated from a graph of t/qt versus t (Fig. 8b) were found to be 413
358 surface. A logarithmic form of Freundlich adsorption isotherm is 384.61 mg/g and 0.014 g/mgh, respectively. The correlation coeffi- 414
359 shown in Eq. (6): cient (R2) for the linear fit in this case was observed as 0.99. Fur- 415
360 thermore, the value of qe estimated by pseudo second-order 416
1
362 lnqe ¼ lnK F þ lnC e ð5Þ kinetic model shows a better match with qe obtained experimen- 417
n tally, compared to pseudo first-order kinetic model. Thus, on the 418
363 where qe and Ce has the same meaning as in Eq. (3). KF and n are basis of above observations, it can be concluded that the experi- 419
364 the Freundlich constants indicating favourability of the adsorption mental batch adsorption data followed pseudo second-order 420
365 process and adsorption capacity of the adsorbent, respectively and kinetics. 421
366 can be found out by plotting a graph of ln qe versus ln Ce. The val- Chen et al. reported a similar observation for adsorptive 422
367 ues of KF and n for the current data (calculated using Fig. SI 2, see removal of methylene blue and methyl orange using NH2-UiO-66 423
368 supporting information) were found to be 2.235 and 0.436, respec- [6]. In comparison to this, the rate constant as well as maximum 424
369 tively. In addition, the R2 value of the fit (Fig. SI 2, see supporting adsorption capacity are observed to be much superior in the pre- 425
371
370 information) was observed as 0.99 indicating a good fit. sent work. Apart from this single study reported by Chen and 426
372 The Temkin isotherm describes the effect of indirect adsorbate/ coworkers, there are no reports in the literature on the kinetics 427
373 adsorbate interactions on the adsorption isotherm. It assumes that of dye adsorption onto NH2-UiO-66. 428

Table 1
Equilibrium constants of different isotherms for Safranin dye adsorption onto the synthesized MOF (pH of the dye solution = natural, 7.08 ± 2; temperature: room temperature).

Langmuir isotherm Freundlich isotherm Temkin isotherm

qm KL R2 n KF R2 AT KT R2
1428.57 0.0038 0.830 0.436 2.235 0.994 0.060 11.61 0.967

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0.020
6 (a) (b)

0.015
5
ln (qe-qt)

4 0.010

t/qt
3
0.005

2
0.000

1
0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8
t (h) t (h)

Fig. 8. A graph of (a) ln (qe-qt) versus t to test the pseudo first-order model and (b) t/qt versus t to test the pseudo second-order kinetic model fit to the experimental batch
adsorption data.

429 3.6. Mechanism of adsorption conducted. In this, the spent MOF material was recovered by filtra- 443
tion, washed with deionised water and dried at 120 °C. The mate- 444
430 Fig. 9 compares the FTIR spectra of fresh NH2-UiO-66 with the rial was then regenerated by washing with 0.01 N sodium 445
431 spent (after adsorption) material. In the FTIR spectra of spent hydroxide and dried. The regenerated MOF was reused in the next 446
432 material, two distinct peaks at 1564 cm-1 and 1378 cm-1 were adsorption cycle. Fig. 10 shows the regeneration efficiency of NH2- 447
433 observed similar to the fresh material. However, the other three UiO-66 after a few cycles of regeneration. It was observed even 448
434 distinct peaks at 3452 cm-1, 3348 cm-1 and 2988 cm-1 which were after 3 adsorption cycles, the regeneration efficiency was signifi- 449
435 present in case of fresh material, were replaced by a broad peak at cant (above 90%). The result confirms that the NH2-UiO-66 MOF 450
436 3428 cm-1 and the same is attributed to the hydrogen bonded N-H can be regenerated and reused multiple times. 451
437 stretch [29]. The broad peak at 3428 cm-1 clearly indicates the
438 hydrogen bonding between the dye molecule and the MOF [6].
3.8. Comparison with literature 452
439 3.7. Regeneration study
Table SI 2 (see supporting information) present list of MOFs 453
440 The techno-economic efficacy of MOFs is directly related to its reported for the removal of dye effluents. From the table, it can 454
441 reuse for multiple adsorption cycles. Therefore, in order to check be noted that Amino-MIL-101(Al) is reported to possess a maxi- 455
442 the stability of the MOF, regeneration and reuse studies were mum dye adsorption capacity of 1409 mg/g at a solution tempera- 456
ture of 50 °C. However, the material is reported as a very poor 457
100 sorbent upon reuse [30]. Further, materials such as MIL 100(Fe) 458
(b) Spent material (after adsorption) have shown to possess an adsorption capacity of 485 mg/g at a 459
80 solution temperature of 50 °C [31]. However, near room tempera- 460

60
100
40
Regeneration efficiency (%)

1564 80
% transmission

20 1378
Hydrogen
3428 Asymmetric
Symmetric
bonded N-H stretch O=C-OH stretch
O=C-OH stretch
1000
60
98

3452 3348 40
96
Asymmetric
2988
C-H streching
94 and symmetric
N-H vibration 1564 20
Asymmetric Symmetric
92 (a) 1378 O=C-OH
O=C-OH stretch
Fresh material (before adsorption) stretch 0
90 0 1 2 3
4000 3000 2000 1000
-1
Adsorption cycle (no.)
wavenumber (cm )
Fig. 10. Regeneration and reusability study of adsorptive removal of safranin dye
Fig. 9. FTIR spectrum of (a) fresh and (b) spent NH2-UiO-66. using NH2-UiO-66.

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 APT 2022 No. of Pages 7, Model 5G
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Please cite this article in press as: S.N. Tambat et al., Hydrothermal synthesis of NH2-UiO-66 and its application for adsorptive removal of dye, Advanced
Powder Technology (2018), https://doi.org/10.1016/j.apt.2018.07.010