G Model

JECE 479 1–9

Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Contents lists available at ScienceDirect

Journal of Environmental Chemical Engineering

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

1 Activated carbon xerogel–chitosan composite materials for

2 catalytic wet peroxide oxidation under intensified process
3 conditions
4 Q1 Maria T. Pinho a , Adrián M.T. Silva a , Nady A. Fathy b,1, Amina A. Attia b , Helder T. Gomes c,
5 Joaquim L. Faria a, *
6 a
LCM – Laboratory of Catalysis and Materials – Associate Laboratory LSRE/LCM, Faculdade de Engenharia, Universidade do Porto, Rua Dr. Roberto Frias, Porto
7 4200-465, Portugal
8 b
Surface Chemistry and Catalysis Laboratory, National Research Centre, Dokki, Cairo 12622, Egypt
9 c
LCM – Laboratory of Catalysis and Materials – Associate Laboratory LSRE/LCM, School of Technology and Management, Polytechnic Institute of Bragança,
10 Campus de Santa Apolónia, Bragança 5300-857, Portugal

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

Article history: Different activated carbon xerogels (ACX) and ACX–chitosan composite materials were tested for the
Received 7 August 2014 removal of the azo dye Orange II (OII) in aqueous solutions, either by pure adsorption or by catalytic
Accepted 30 October 2014 wet peroxide oxidation (CWPO). The ACX materials were produced by activation of an organic
resorcinol-formaldehyde xerogel (RFX), considering different activation procedures: chemical
Keywords: impregnation with H3PO4 at 773 K (ACX-P), chemical impregnation with monoethanolamine at
Activated carbon xerogel–chitosan 773 K (ACX–MEA) and alkali activation with KOH at 1073 K using a 1:1 mass ratio of KOH/RFX (ACX-K).
composites
The ACX–chitosan composites were produced by oxidation of ACX with oxalic acid followed by
Orange II
Catalytic wet peroxide oxidation
treatment with chitosan gel.
Hydrogen peroxide Either for adsorption and CWPO screening studies, the composites ACX-K–chitosan and ACX-P–
Intensified process conditions chitosan revealed the best performances among all the tested materials, namely OII removals between
69 and 73% were respectively obtained in CWPO after 150 min (pH 3.0, T = 323 K, material load of 0.2 g L 1,
OII concentration of 100 mg L 1 and hydrogen peroxide concentration of 1.18 g L 1). In process
intensification conditions, the CWPO process performance increased remarkably when using the
ACX-P–chitosan composite. Complete OII removal in 90 min and a TOC removal of 55% in 24 h was
achieved by CWPO, while less than 10% of OII was removed by pure adsorption (pH 3.5, T = 353 K, material
load of 2.5 g L 1, OII concentration of 4.5 g L 1 and, in CWPO, hydrogen peroxide concentration of
25 g L 1).
The superior performance of the ACX–chitosan composite at intensified process conditions was more
likely related with the high pollutant/catalyst ratio, which favors a more controllable H2O2
decomposition near the adsorbed pollutant species, thus avoiding parallel parasite reactions involving
hydroxyl radicals and leading to a consequent higher efficiency of its usage. These conditions are of major
interest in the treatment of highly polluted waste waters.
ã 2014 Published by Elsevier Ltd.

Abbreviations: ACX-K-Chitosan, carbon xerogel activated with potassium hydroxide and coated with chitosan; ACX-K, carbon xerogel activated with potassium hydroxide;
ACX–MEA–chitosan, carbon xerogel activated with monoethanol amine and coated with chitosan; ACX–MEA, carbon xerogel activated with monoethanol amine; ACX-P–
chitosan, carbon xerogel activated with phosphoric acid and coated with chitosan; ACX-P, carbon xerogel activated with phosphoric acid; ACX, activated carbon xerogels; AOP,
advanced oxidation process; C, catalyst; CWPO, catalytic wet peroxide oxidation; D, dilution ratio; EDX, energy dispersive X-ray spectroscopy; F, formaldehyde; H2O2,
hydrogen peroxide; HO, hydroxyl radical; HO2, hydroperoxyl radical; OII, orange II; R, resorcinol; RFX-Chitosan, resorcinol-formaldehyde xerogel coated with chitosan; RFX,
resorcinol-formaldehyde xerogel; SBET, specific surface area; SEM, scanning electron microscopy; TOC, total organic carbon; UV/vis spectrophotometry, ultraviolet–visible
spectrophotometry; VT, total pore volume; Wmean, average pore width.
* Corresponding author. Tel.: +351 225081645; fax: +351 225081449.
E-mail addresses: fathyna.77@hotmail.com (N.A. Fathy), jlfaria@fe.up.pt (J.L. Faria).
1
Tel.: +20 2 33371433; fax: +20 2 33370597.

http://dx.doi.org/10.1016/j.jece.2014.10.020
2213-3437/ ã 2014 Published by Elsevier Ltd.

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020
 G Model
JECE 479 1–9

2 M.T. Pinho et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

11 Introduction chitosan composites (ACX–chitosan) were produced from an 76

organic xerogel (RFX) synthesized by polycondensation of 77

12 Azo dyes are intensively used in textile, paper, pharmaceutical resorcinol with formaldehyde. The obtained materials were tested 78
13 and food industries. Consequently, waste waters of these industrial for the removal of the azo dye Orange II (OII) by adsorption and by 79
14 sectors contain significant amounts of dyes. Many of them are CWPO. OII was chosen as a model pollutant due to its noxious 80
15 poorly biodegradable, or even non-biodegradable, and some of nature for the environment and because it is one important dye 81
16 their by-products are toxic, mutagenic and carcinogenic, causing typically found in waste waters of the textile industry. To the best 82
17 serious environmental, ecological and health problems. In this of our knowledge it is the first time that activated carbon xerogel– 83
18 context, these industries are still facing many challenges in the chitosan composite materials were tested as catalysts in CWPO 84
19 implementation of appropriate technologies for the treatment of and, in particular, under intensified process conditions. 85
20 their waste waters [1–3].
21 Several works have extensively studied the removal of dyes by Materials and methods 86
22 adsorption [4–6]. However, although complete removals are
23 attained by adsorption, this approach is only able to transfer the Chemicals 87
24 pollutants from one phase (liquid) to another (solid). In this
25 context, advanced oxidation processes (AOPs) appear as attractive Orange II (C16H11N2NaO4S, Mr = 350.32 g mol 1, color Index Acid 88
26 alternatives for the degradation of dyes and for the destruction of a Orange 7, molecular structure as shown in Fig. 1), hydrogen 89
27 wide range of other organic compounds [7]. These treatments, peroxide solution (H2O2, 30 % w/v, Mr = 34.01 g mol 1) and oxalic 90
28 typically operated near ambient temperature and atmospheric acid dehydrate (C2H2O4
2H2O, 99 wt.%, Mr = 126.07 g mol 1) were 91
29 pressure, involve in its mechanism the production of hydroxyl obtained from Fluka. Sulphuric acid (H2SO4, 95–98 wt.%, 92
30 radicals (HO), which act as oxidizing species in the mineralization Mr = 98.08 g mol 1), hydrochloric acid (HCl, 37 wt.%, Mr = 36.46 g 93
31 of the target pollutants [1,8–10]. AOPs may consider different mol 1) and a formaldehyde solution (HCHO, 36.5–38.0 wt.%, 94
32 reagents, such as ozone, hydrogen peroxide, oxygen or other Mr = 30.03 g mol 1), stabilized by 10–15 % methanol (CH3OH, 95
33 combinations [11] and are able to increase the biodegradability of 99 wt.%, Mr = 32.05 g mol 1) were purchased from Sigma–Aldrich. 96
34 the effluents [12,13]. When hydrogen peroxide is used as source of Sodium hydroxide (NaOH, 98 wt.%, Mr = 40.00 g mol 1), resorcinol 97
35 hydroxyl radicals for the degradation of organic matter, a suitable (C6H4(OH)2, 99 wt.%, Mr = 110.12 g mol 1), monoethanol amine 98
36 catalyst must be added to improve the efficiency of the reaction. (NH2CH2CH2OH, 99 wt.%, Mr = 61.08 g mol 1) were obtained from 99
37 This process is known as catalytic wet peroxide oxidation (CWPO) Panreac. Ortho phosphoric acid (H3PO4, 85 wt.%, Mr = 98.00 g 100
38 and current research focuses on the development of heteroge- mol 1) was supplied from Rasayan (Turkey). Potassium carbonate 101
39 neous catalysts, either metal supported catalysts or metal-free (K2CO3, 99 wt.%, Mr = 138.20 g mol 1) was obtained from POCH SA. 102
40 catalytic systems, such as activated carbon xerogels (ACX) [8,14]. Chitosan ((C6H11NO4)n, Mr = 6  105–8  105 g mol 1) was obtained 103
41 Activated carbon xerogel materials, prepared from organic from ACROS. Potassium hydroxide (KOH, 99 wt.%, Mr = 56.11 g 104
42 resorcinol-formaldehyde gels, emerged as alternatives to activated mol 1) was obtained from Modern laboratory. All solutions were 105
43 carbons in different processes, due to their capacity to tailor the prepared with distilled water. 106
44 pore texture and consequently to increase the catalytic perfor-
45 mance [15]. Depending on the synthesis conditions, it is possible to Preparation of activated carbon xerogel–chitosan composites 107
46 produce activated carbon xerogel materials with high porosity,
47 high surface area and large volume of mesopores [16]. These RFX precursor 108
48 materials can be associated with chitosan, producing activated RFX was initially synthesized by polycondensation of resorcinol 109
49 carbon xerogel–chitosan composites. Chitosan is an interesting (R) with formaldehyde (F), using distilled water as solvent and 110
50 functional material because this natural polymer has excellent potassium carbonate as catalyst (C), with an initial solution pH of 6. 111
51 properties such as biocompatibility, biodegradability, non-toxicity Resorcinol was first dissolved in distilled water under magnetic 112
52 and adsorption properties. Recently, much attention has been paid stirring and the formaldehyde was later added to the resultant 113
53 to chitosan as a potential polysaccharide resource. Chitosan, which solution. In all cases, the molar ratios of both resorcinol/ 114
54 is at least a 50% deacetylated chitin, is the only pseudonatural formaldehyde (R/F) and resorcinol/catalyst (R/C), and the dilution 115
55 cationic polymer and thus it finds many applications due to its ratio (D), were fixed at 0.5, 1000 and 5.7, respectively. This mixture 116
56 unique character [17,18]. Chitosan application as biosorbents is was stirred at 363 K for 60 min until the aquagel was formed. The 117
57 justified by its outstanding chelation behavior [19,20]. obtained aquagel was further transferred into a stoppered glass 118
58 The coating of porous carbons, such as activated carbon bottle to cool and then left at room temperature for 72 h to 119
59 xerogels, with biopolymer natural materials is a new trend for complete the curing and gelling process. After this period, the 120
60 the modification of the surface properties of carbon materials. aquagel was contacted with acetone to promote exchange with 121
61 With this modification, much lower quantities of porous carbon water in an open beaker for one day. The produced aquagel was 122
62 should be needed in adsorption and catalytic processes, allowing heated slowly in an air-oven to 363 K (heating rate of 283 K min 1) 123
63 the development of more cost-effective and environmentally
64 benign waste water treatment processes. The amine and hydroxyl
65 groups of chitosan are able to sorb metals through several
66 mechanisms including chemical interactions (such as chelation)
67 and electrostatic interactions (for example ion exchange or the
68 formation of ion pairs). The kind of interaction depends on the
69 metal type, its chemistry and the pH of the solution [21]. In recent
70 years, chitosan and its derivatives, such as cross linked chitosan,
71 chitosan beads and chitosan composites, have been studied as
72 adsorbents for the removal of dyes and heavy metal ions from
73 aqueous solutions [21–25].
74 In this work, aiming to extend the range of applications of
75 chitosan-based compounds, different activated carbon xerogel– Fig. 1. Molecular structure of Orange II.

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020
 G Model
JECE 479 1–9

M.T. Pinho et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 3

124 and held at that temperature for 12 h. After heating again to 383 K (SBET, m2 g 1) was calculated applying the BET equation to the 175
125 for 120 min, the organic RF xerogel (RFX) was obtained. adsorption data (for p/p0 between 0.06 and 0.30) and the total pore 176

volume (VT) determined from the volume of N2 (as liquid) 177

126 Activated carbon xerogels calculated at p/p0 = 0.975. The average pore width (Wmean, Å) 178
127 Starting from the RFX material, the following catalysts were was calculated from (2VT/SBET)  104. 179
128 prepared: (a) ACX-P, by impregnation of RFX with 50% (v/v)
129 phosphoric acid (H3PO4), followed by pyrolysis at 773 K for 2 h Adsorption and CWPO experiments 180
130 (considering a heating rate of 10 K min 1) under its own
131 atmosphere; (b) ACX–MEA, by impregnation of RFX with 30 mL The adsorption and CWPO experiments were performed in a 181
132 of monoethanol amine (MEA) solution (at room temperature), glass reactor (500 mL), stirred and heated by a heating/stirring 182
133 followed by pyrolysis at 773 K for 2 h (considering a heating rate of plate (VWR, VMS-C7) and equipped with a condenser and a 183
134 10 K min 1); (c) ACX-K, by alkali activation of RFX with KOH, thermocouple (VWR, VT-5). Under screening conditions used in 184
135 considering a mass ratio KOH/RFX of 1:1, followed by pyrolysis at previous works [27], 250 mL of OII solution with a concentration of 185
136 1073 K for 1 h (considering a heating rate of 10 K min 1). The cooled 100 mg L 1 was introduced in the reactor and heated by immersion 186
137 materials were washed with distilled water to neutral filtrate and in a water bath, being the temperature monitored/controlled by 187
138 finally dried overnight in an air oven at 383 K. the thermocouple. After stabilization of the temperature, the 188

solution pH was adjusted to 3.0, using a H2SO4 solution with a 189

139 Activated carbon xerogel–chitosan composites concentration of 1.0 mol L 1. The experiments were performed 190
140 The final activated carbon xerogel–chitosan composites were during 150 min at T = 323 K with an adsorbent/catalyst load = 0.2 191
141 prepared using the same dip-coating route described earlier by g L 1. In the adsorption experiments, time started to count 192
142 Boddu et al. [26]. Briefly, 50 g of chitosan was slowly added to 1 L of (t0 = 0 min) immediately after addition of the material, just after 193
143 10% (v/v) oxalic acid with constant stirring. The mixture was pH adjustment. In the CWPO runs, H2O2 was injected into the 194
144 heated to 323 K to facilitate mixing and then allowed to cool down system at the same time that the catalyst was added, being this 195
145 to room temperature. A whitish viscous gel of chitosan–oxalic acid moment considered the beginning of reaction (t0 = 0 min). The 196
146 mixture was thus obtained. In a separate procedure, the organic volume of H2O2 (6 wt.%) was calculated in order to obtain a 197
147 RFX and its activated carbon xerogels were added to 10% (v/v) concentration of 1.18 g L 1 (corresponding to approximately three 198
148 oxalic acid solution, stirred for 2 h, then filtered and dried times the stoichiometric amount needed to completely mineralize 199
149 overnight at 363 K. These samples were then added to the chitosan OII). A blank test, without any catalyst, was also carried out to study 200
150 gel previously prepared with oxalic acid. The mixture was stirred the ability of H2O2 to degrade the pollutant. 201
151 for about 36 h and filtered. The process was repeated for a second In process intensification studies, the experimental procedure 202
152 time to enhance the coating on the once-coated xerogels. The solid was the same as previously described, but the experiments were 203
153 pasty material was treated with 1 N NaOH, filtered and washed conducted under different conditions. In this case, 50 mL of azo dye 204
154 with distilled water until the filtrate was neutral. Twice-coated solution with a concentration of 4.5 g L 1 was introduced in the 205
155 xerogel was then allowed to dry overnight under vacuum at 333 K. glass reactor (250 mL) and the experiments were run during 24 h at 206

T = 353 K, adsorbent/catalyst load = 2.5 g L 1, pH 3.5 (adjusted with 207

156 Characterization techniques an HCl solution with a concentration of 1.0 mol L 1) and, in the 208

CWPO runs, a concentration of H2O2 of 25 g L 1. 209

157 The prepared carbon samples were subjected to the determi-
158 nation of slurry pH (pHslurry) by contacting 0.15 g of sample with Analytical methods 210
159 50 mL of distilled water. The suspension was well stirred for 5 min
160 and left overnight in stoppered bottles. Finally the pH of the In both processes (adsorption and CWPO), periodic withdrawal 211
161 supernatant liquid was measured (pHslurry) using a pH meter of small samples was considered during the experimental runs, 212
162 (HANNA pH 20). being the samples further analyzed by UV/Vis spectrophotometry 213
163 Scanning electron microscopy (SEM) images were obtained to (Jasco V560) at a wavelength of 486 nm (the maximum absorbance 214
164 determine the morphology and the elemental chemical composi- of OII [27]) to follow the removal of OII present in the solution. 215
165 tion of the samples using a scanning electron microscope Total organic carbon (TOC) was measured using a Shimadzu 216
166 combined with energy dispersive X-ray (EDX) spectroscopy (JEOL TOC-5000A apparatus. 217
167 JXA-840A Electron Probe Microanalyzer, INCAx-sight, Oxford).
168 The porous characteristics of the developed materials were Results and discussion 218
169 determined by the analysis of N2 adsorption isotherms at 77 K,
170 obtained using an automatic volumetric apparatus (Quantachrome Catalyst characterization 219
171 NOVA Automated Gas Sorption system version 1.12). The samples
172 were primarily degassed overnight at 573 K under a vacuum of Table 1 shows the elemental chemical analysis of the 220
173 10 5 Torr to constant pressure for 2 h before carrying the synthesized activated carbon xerogel–chitosan composites, as 221
174 adsorption measurements. The specific surface area well as of the ACX-K sample, which was used for comparison 222

Table 1
Elemental chemical analysis and pHslurry of the synthesized activated carbon xerogel–chitosan composites and of the ACX-K sample used for comparison purposes.

Sample pHslurry %C %H %N %O %P Cata Hata Oata H/C O/C

RFX–chitosan 7.0 75.7 0.8 n.d. 23.5 n.d. 6.3 0.8 1.5 0.13 0.23
ACX-K 8.6 75.0 2.3 n.d. 22.7 n.d. 6.2 2.3 1.4 0.37 0.23
ACX-K–chitosan 5.5 72.5 1.0 n.d. 26.5 n.d. 6.0 1.0 1.7 0.16 0.27
ACX-P–chitosan 8.4 90.3 2.0 n.d. 5.6 2.1 7.5 2.0 0.4 0.26 0.05
ACX–MEA–chitosan 10.1 81.7 3.3 8.2 6.8 n.d. 6.8 3.3 0.4 0.48 0.06

n.d.: not detected.

a
Refers to atomic content of either component.

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020
 G Model
JECE 479 1–9

4 M.T. Pinho et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Fig. 2. SEM images of different materials prepared before (column left) and after (column right) chitosan coating: RFX (a), ACX-P (b), ACX-K (c) and ACX–MEA (d).

223 purposes between ACX and ACX–chitosan materials to assess the O = 23.5%, which corresponds to atomic H/C and O/C ratios of 226
224 role of chitosan in the composites. The elemental analysis of 0.13 and 0.23, respectively. According to the different activation 227
225 RFX-Chitosan shows a mass composition of C = 75.7%, H = 0.8% and procedures, the composition of C, H and O varies for each sample. 228

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020
 G Model
JECE 479 1–9

M.T. Pinho et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 5

229 The composition of C has the highest value for ACX-P–chitosan reveal a large decrease in all cases, meaning that the modification 283
230 (90.3%) and the lowest for ACX-K–chitosan (72.5%). The composi- with chitosan has a considerable effect on the porous structure. In 284
231 tion of H has the highest value for the ACX–MEA–chitosan (3.3%) addition to the changes in the textural properties of the materials, 285
232 and the lowest for the RFX–chitosan (0.8%), while that of O shows the presence of chitosan creates new adsorptive sites on the carbon 286
233 the highest value for the ACX-K–chitosan (26.5%) and the lowest surface, such as amino and hydroxyl groups, making these 287
234 for ACX-P–chitosan (5.6%). The acid-base character (pHslurry) of the materials suitable candidates for adsorption processes. 288
235 samples is also given in Table 1. While the ACX-K–chitosan
236 composite exhibit the most acidic character, with a slurry pH value Screening experiments 289
237 of 5.5, the composites RFX–chitosan, ACX-P–chitosan and
238 ACX–MEA–chitosan present increasingly higher basic surfaces, Adsorption 290
239 with pHslurry values of 7.0, 8.4 and 10.1, respectively. It is Adsorption experiments were performed to assess the capacity 291
240 noteworthy the change of the pHslurry values occurring upon the of the different synthesized activated carbon xerogel–chitosan 292
241 preparation of the activated carbon xerogel–chitosan composites, composites to adsorb the azo dye and to understand the possible 293
242 which are affected by the process of coating with chitosan. participation of adsorption in the OII degradation mechanism 294
243 Chitosan is a weak base (pHpzc 6.3) that is insoluble in water and involved in the CWPO experiments. The adsorption removal curves 295
244 organic solvents. However, it is soluble in dilute aqueous acidic obtained with the ACX–chitosan materials and with the ACX-K and 296
245 solutions (pH < 6.3), which can convert the glucosamine units into RFX–chitosan samples, under the screening conditions referred in Q2 297
246 a soluble form (R-NH3+ and free —OH groups). For example, the “Adsorption and CWPO experiments”, are presented in Fig. 3. 298
247 pHslurry of ACX-P changed from acidic (pHslurry = 3.8) before coating The composite materials ACX-P–chitosan and ACX-K-Chitosan 299
248 to basic (pHslurry = 8.4) after coating, while the pHslurry of ACX-K were found to adsorb OII with a superior performance than the 300
249 changed from 8.4 (before coating) to 5.5 (after coating), which is other materials, followed, in decreasing order, by ACX-K > ACX- 301
250 slightly acidic and comparable to the pHpzc of chitosan alone MEA-Chitosan > RFX-Chitosan. The higher adsorption perform- 302
251 (6.3). These variations in the pHslurry of the materials may be ances of ACX-P–chitosan and ACX-K–chitosan relatively to the 303
252 attributed to unreacted and/or unattached amine (—NH2 of lone other materials may be explained by the very high specific surface 304
253 pair electrons) and hydroxyl groups on the surface of the coated areas of these materials (Table 2) [28], except for ACX-K. The 305
254 activated carbon xerogels. Accordingly, from the initial organic superior adsorption performance of ACX-K–chitosan relatively to 306
255 carbon xerogel (RFX), it is possible to create composite materials the parent ACX-K material (which shows higher specific surface 307
256 with different acid-base surface characteristics using different area than ACX-K–chitosan), puts in evidence the role of chitosan in 308
257 activating agents. the composites. This deacetylated derivative of chitin is well 309
258 Fig. 2 shows the surface of the activated carbon xerogel known for its high adsorption capacities, due to the presence of 310
259 materials before (left SEM images) and after (right SEM images) the hydroxyl (—OH) and amino (—NH2) groups, and due to the 311
260 addition of chitosan. The surface of the RFX material after chitosan flexibility of its chains. Chitosan is sensible to the acidic pH, since 312
261 coating became slightly flat and homogeneously covered by under these conditions the amino group (—NH2) can be easily 313
262 chitosan (Fig. 2a). On the other hand, the surfaces of ACX-P, protonated to form amine (—NH3), increasing its adsorption 314
263 ACX-K and ACX–MEA before coating with chitosan are coarse with capacity due to electrostatic attraction between the negatively 315
264 crispy appearance of holes, while after coating the surfaces lose its charged dye molecule and positively charged amine group. Orange 316
265 rough structure and become smoother, containing some cavities or II in solution presents a pKa1 of 11.4 (for the deprotonation of the 317
266 some blocking holes, as shown in Fig. 2b–d. It is thus concluded naphthalene OH) and a pKa2 of 1 (deprotonation of the SO3H group) 318
267 that chitosan covers the entire external surface through a thin [29,30]. Thus, at pH 3, OII is found in solution in the anionic form 319
268 layer. [31], which is favorable for adsorption onto materials containing 320
269 The textural properties of the materials before and after positively charged amine groups from chitosan. This also explains 321
270 chitosan coating are summarized in Table 2. The total surface areas the higher removal performance obtained with the 322
271 of the activated carbon xerogel materials before chitosan coating
272 are high and varied from 212 m2 g 1 (for ACX–MEA) to 1700 m2 g 1
273 (for ACX-K). After the coating process with chitosan, the surface
274 area of ACX-K decreased to 1455 m2 g 1 (ACX-K–chitosan) and
275 increased to 1275 and 257 m2 g 1 for ACX-P–chitosan and
276 ACX–MEA–chitosan, respectively. These variations in the surface
277 areas of the different materials fall in the range of 10–20%, being
278 low to conclude about different mechanisms involved in the
279 process of chitosan coating with notorious influence on the final
280 textural properties of the coated materials. On the other hand, the
281 analysis of the variations in the total pore volume of the activated
282 carbon xerogels after chitosan coating (in the range of 35–75%),

Table 2
Textural properties of the synthesized activated carbon xerogels–chitosan
composites, before and after chitosan addition.

Sample SBET (m2 g 1

) VT (cm3 g 1
) Wmean (Å)
RFX–chitosan 154 0.04 5.77
ACX-K 1700 1.67 19.6
ACX-P 1146 0.94 16.5
ACX–MEA 212 0.22 21.1 Fig. 3. Concentration decay curves obtained in the adsorption of Orange II (OII)
ACX-K–chitosan 1455 0.70 9.63 under screening conditions ([OII] = 100 mg L 1, adsorbent load = 0.2 g L 1, T = 323 K
ACX-P–chitosan 1275 0.60 9.36 and pH 3.0) with the synthesized activated carbon xerogel–chitosan composites
ACX–MEA–chitosan 257 0.06 5.04 (RFX–chitosan, ACX–MEA–chitosan, ACX-K–chitosan and ACX-P–chitosan) and
with the ACX-K sample used for comparison purposes.

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020
 G Model
JECE 479 1–9

6 M.T. Pinho et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

Catalytic wet peroxide oxidation 335

The removals of OII by CWPO, obtained under the screening 336

conditions referred in “Adsorption and CWPO experiments”, are Q3 337

registered in Fig. 4. The analysis of the results reveal that the 338

composite materials ACX-P–chitosan and ACX-K–chitosan are also 339

able to remove OII by CWPO with a superior performance than the 340

other materials, followed by ACX-K > ACX-MEA-Chitosan > RFX– 341

chitosan. The highest removal of OII was found with ACX-P– 342

chitosan (73% after 150 min) and the lowest with RFX–chitosan 343

(22% after 150 min). 344

Analyzing the results obtained in more detail, it is concluded 345

that the activated carbon xerogel–chitosan composites show 346

similar removals in the adsorption and catalytic experiments 347

(Fig. 5) and, thus, it is difficult to discriminate the difference 348

between the possible catalytic activity of these materials and the 349

respective pure adsorption of OII under these experimental 350

conditions. 351

Fig. 6 shows the TOC and OII removals after 150 min of reaction. 352

As found for OII reduction, the ACX-P–chitosan composite was also 353
Fig. 4. Concentration decay curves obtained in the CWPO of Orange II (OII), under
that presenting the highest TOC removal (53%) relatively to the 354
screening conditions ([OII] = 100 mg L 1, catalyst load = 0.2 g L 1, [H2O2] = 1.18 g L 1,
T = 323 K and pH 3.0) with the synthesized activated carbon xerogel–chitosan other materials, which show the following decreasing TOC 355
composites (RFX–chitosan, ACX–MEA–chitosan, ACX-K–chitosan and removals: ACX-K (43%) > ACX-K–chitosan (40%) > ACX–MEA–chi- 356
ACX-P–chitosan) and with the ACX-K sample used for comparison purposes. 357
tosan (25%) > RFX–chitosan (3%). It is also observed that TOC
abatement is always lower than OII removal, being ascribed to the 358

existence of by-products formed as a result of the mineralization of 359

OII. In these cases, the decrease of color is significant, thus 360

323 ACX-P–chitosan, despite its lower surface area, when compared to
suggesting that the radicals attacked preferentially the chromic 361
324 the removal obtained with ACX-K–chitosan. Since the pHslurry of
species, forming new products. The incomplete TOC abatement 362
325 ACX-P–chitosan is higher than the pHslurry of ACX-K-Chitosan, the
may also be explained by the competition process between H2O2 363
326 attractive electrostatic interactions between dye and the surface of
and the organic molecules to the surface active sites as well as by 364
327 the carbon material is higher in the case of ACX-P–chitosan, this
partial decomposition of H2O2 via formation of non-radicalar 365
328 effect being superior than the lower value of its surface area, when
species [3,7,32–34]. 366
329 compared with ACX-K–chitosan. In summary, the high adsorption
330 capacity of ACX-P–chitosan and ACX-K–chitosan composites may
331 be explained by the combined effect of high specific surface area 367
Process intensification
332 and high electrostatic properties promoted by the presence of
333 chitosan in its structure. The higher removal performance of ACX-P 368
Catalysts ACX-P–chitosan and ACX-K–chitosan were further
334 –chitosan is mainly explained by surface chemistry interactions. 369
tested under intensified process conditions, which may be more

Fig. 5. Comparison of adsorption and CWPO after 150 min, under screening
conditions ([OII] = 100 mg L 1, catalyst load = 0.2 g L 1, T = 323 K, pH 3.0 and, in the
CWPO runs, [H2O2] = 1.18 g L 1) with the synthesized activated carbon xerogel–
chitosan composites (RFX–chitosan, ACX–MEA–chitosan, ACX-K–chitosan and ACX-
P–chitosan) and with the ACX-K sample used for comparison purposes.
Fig. 6. Removals of OII and TOC in the CWPO experiments after 150 min, under
screening conditions ([OII] = 100 mg L 1, catalyst load = 0.2 g L 1, [H2O2] = 1.18 g L 1,
T = 323 K and pH 3.0) with the synthesized activated carbon xerogel–chitosan
composites (RFX–chitosan, ACX–MEA–chitosan, ACX-K–chitosan and ACX-P–
chitosan) and with the ACX-K sample used for comparison purposes.

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020
 G Model
JECE 479 1–9

M.T. Pinho et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 7

370 attractive for industrial applications (for example to treat waste hydroxide ions (OH ), the former exhibiting high oxidizing 416
371 waters with high pollutant concentrations). Under intensified potential and serving as effective species for the degradation of 417
372 process conditions the experiments were performed during 24 h at several organic pollutants in liquid phase. It should be noted that 418
373 T = 353 K and pH 3.5, the OII concentration was increased to this pHslurry is associated to the acidic/basic character of the carbon 419
374 4.5 g L 1, the material load increased to 2.5 g L 1 and the materials that is developed according to the treatment and 420
375 concentration of H2O2 increased to 25 g L 1. In these experiments temperature at which these materials were activated, resulting 421
376 the temperature and pH used were slightly higher than in in different types of surface oxygenated groups, such as carboxylic, 422
377 screening experiments with the aim to increase the CWPO process lactonic, phenolic and carbonyl groups. These surface oxygenated 423
378 efficiency. groups influence the acid-base character of the materials. When 424
379 Fig. 7 shows the results obtained with ACX-P–chitosan and low treatment temperatures are considered, the materials develop 425
380 ACX-K–chitosan under the intensified process conditions in acidic surface functional groups, more specifically carboxylic acid 426
381 adsorption (a) and CWPO (b) experiments. In the adsorption tests groups (—COOH), which are hydrophilic in character, but the 427
382 the saturation of the catalysts is obtained after 1 h, a behavior catalysts often present basic surfaces when treated at high 428
383 largely different from that observed in the experiments performed temperatures. The surface of basic materials, when in solution 429
384 under the screening conditions, where the catalysts did not with a pH < pHslurry, gets positively charged, thus attracting the 430
385 reached saturation during the 150 min of the experiments (Fig. 3). negative portion of dyes [35–37]. This phenomena explains the 431
386 This is more likely related with the higher pollutant/adsorbent higher catalytic activity of the catalyst ACX-P–chitosan 432
387 ratio used in intensification conditions than with the slight (pHslurry = 8.4, Table 1), possibly due to a stronger interaction 433
388 increase in temperature and pH. Regarding the CWPO experiments between the catalyst surface and the dye, and to the electron- 434
389 under intensified process conditions (Fig. 7), a steep decrease of donating characteristics of the surface groups present in the 435
390 the OII concentration is observed at the beginning of reaction for material, which promote a more effective decomposition of H2O2 436
391 the catalyst ACX-P–chitosan. The removal of the azo dye is towards hydroxyl radicals. Thus, it seems that the pollutant 437
392 complete in about only 1.5 h (i.e., 90 min). Regarding the catalyst molecules, as shown by the adsorption results, largely occupy the 438
393 ACX-K-Chitosan, more time (24 h) is necessary to achieve the surface and that there are enough active sites near the adsorbed 439
394 complete removal of OII. Comparing these results with the results pollutant responsible for H2O2 decomposition towards hydroxyl 440
395 obtained under the screening conditions, it can be concluded that radicals. 441
396 the efficiency of the materials largely increases under intensifica- The TOC and OII removals after 24 h are shown in Fig. 8 for the 442
397 tion process conditions. intensified process conditions. It is observed that the catalyst ACX- 443
398 The texture of the catalysts, more specifically the surface area P–chitosan also presents higher TOC abatement (55%) than ACX-K– 444
399 and the pore volume, influences the bulk diffusion of the H2O2 chitosan (43%). This is in line with the removal of OII observed with 445
400 molecules. The development of pores, caused by heat-treatment at both catalysts (Fig. 7b). Even so, the complete mineralization of the 446
401 high temperatures and by low concentrations of activating agents dye was not achieved with any catalyst, the decomposition of OII 447
402 facilitates the diffusion of H2O2 to the catalyst active sites. resulting in different by-products and in the partial mineralization 448
403 According to Khalil et al. [35], the materials with higher surface of the dye. TOC abatement is also influenced by the amount of 449
404 area possess catalytic active sites widely distributed in such a hydroxyl radicals, which in turn depends on the hydrogen peroxide 450
405 manner that H2O2 decomposition is enhanced, whereas in concentration. Higher concentration of hydrogen peroxide may 451
406 materials with higher number of catalytic active sites per unit of cause scavenging reactions (parallel parasite reactions), which 452
407 surface area an inhibiting action may prevail. annihilate hydroxyl radicals, forming other radicals (such as HO2) 453
408 It is also well known that the surface chemistry affects the rate with an oxidizing potential lower than that of HO [2,7], and 454
409 and extent of H2O2 decomposition. The decomposition changes inactive total decomposition products (O2 and H2O). 455
410 when carried out with materials with different pHslurry and tends Comparing the results obtained in this work with others 456
411 to increase for materials with pHslurry above 8. Under the previously reported in the literature [14,27] it is possible to 457
412 conditions used in this work (pH 3.5), the functional groups conclude about the superior characteristics of activated carbon 458
413 present electron-donating characteristics, interacting with hydro- xerogel–chitosan composite materials for catalytic wet peroxide 459
414 gen peroxide molecules and promoting its decomposition through oxidation, especially when carried out under intensified process 460
415 the formation of hydroxyl radicals (HO) and reduction to conditions. 461

Fig. 7. Concentration decay curves obtained in the adsorption (a) and CWPO (b) of Orange II (OII), under intensified process conditions ([OII] = 4.5 g L 1, catalyst load = 2.5 g L 1,
[H2O2] = 25 g L 1, T = 353 K and pH 3.5).

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020
 G Model
JECE 479 1–9

8 M.T. Pinho et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx

[5] E. Alver, A.Ü. Metin, Anionic dye removal from aqueous solutions using
modified zeolite: adsorption kinetics and isotherm studies, Chem. Eng. J. 500
200-202 (2012) 59–67, doi:http://dx.doi.org/10.1016/j.cej.2012.06.038. 501
[6] M. Danish, R. Hashim, M.N. Mohamad Ibrahim, O. Sulaiman, Response surface
methodology approach for methyl orange dye removal using optimized acacia 502
Mangium wood activated carbon, Wood Sci. Technol. 48 (5) (2014) 1085–1105, 503
doi:http://dx.doi.org/10.1007/s00226-014-0659-7. 504
[7] J.H. Ramirez, C.A. Costa, L.M. Madeira, Experimental design to optimize the
degradation of the synthetic dye Orange II using Fenton’s reagent, Catal. Today 505
107-108 (2005) 68–76, doi:http://dx.doi.org/10.1016/j.cattod.2005.07.060. 506
[8] S. Azabou, W. Najjar, M. Bouaziz, A. Ghorbel, S. Sayadi, A compact process for
the treatment of olive mill wastewater by combining wet hydrogen peroxide 507
catalytic oxidation and biological techniques, J. Hazard. Mater. 183 (1–3) 508
(2010) 62–69, doi:http://dx.doi.org/10.1016/j.jhazmat.2010.06.104. 20678864. 509
[9] R.C. Martins, A.M. Silva, S. Castro-Silva, P. Garção-Nunes, R.M. Quinta-Ferreira,
Advanced oxidation processes for treatment of effluents from a detergent 510
industry, Environ. Technol. 32 (9–10) (2011) 1031–1041, doi:http://dx.doi.org/ 511
10.1080/09593330.2010.523439. 21882556. 512
[10] J.A. Zazo, J. Bedia, C.M. Fierro, G. Pliego, J.A. Casas, J.J. Rodriguez, Highly stable
Fe on activated carbon catalysts for CWPO upon FeCl3 activation of lignin from 513
black liquors, Catal. Today 187 (1) (2012) 115–121, doi:http://dx.doi.org/ 514
10.1016/j.cattod.2011.10.003. 515
[11] L.F. Liotta, M. Gruttadauria, G. Di Carlo, G. Perrini, V. Librando, Heterogeneous
catalytic degradation of phenolic substrates: catalysts activity, J. Hazard. 516
Mater. 162 (2–3) (2009) 588–606, doi:http://dx.doi.org/10.1016/j.jhaz- 517
Fig. 8. Removals of OII and TOC in the CWPO experiments after 24 h, under mat.2008.05.115. 18586389. 518
intensified process conditions ([OII] = 4.5 g L 1, catalyst load = 2.5 g L 1, [H2O2] = 25 [12] A. Rubalcaba, M.E. Suárez-Ojeda, J. Carrera, J. Font, F. Stüber, C. Bengoa, A.
g L 1, T = 353 K and pH 3.5). Fortuny, A. Fabregat, Biodegradability enhancement of phenolic compounds 519
by hydrogen peroxide promoted catalytic wet air oxidation, Catal. Today 124 520
(3–4) (2007) 191–197, doi:http://dx.doi.org/10.1016/j.cattod.2007.03.037.
462 Conclusions [13] P.S. Dudala, S. Dhakhwa, A. Garg, Biodegradability enhancement of synthetic
pulping liquor (generated from sugarcane baggase digestion) by non-catalytic 521
wet oxidation process, J. Environ. Chem. Eng. 2 (2) (2014) 1182–1185, doi: 522
463 Activated carbon xerogels (ACX) and ACX–chitosan composite http://dx.doi.org/10.1016/j.jece.2014.05.001. 523
464 materials were prepared by different routes of synthesis, and [14] H.T. Gomes, S.M. Miranda, M.J. Sampaio, A.M.T. Silva, J.L. Faria, Activated
465 524
tested for the removal of an anionic azo dye (Orange II) by carbons treated with sulphuric acid: catalysts for catalytic wet peroxide
oxidation, Catal. Today 151 (1–2) (2010) 153–158, doi:http://dx.doi.org/ 525
466 adsorption and by CWPO. ACX-P–chitosan and ACX-K–chitosan,
10.1016/j.cattod.2010.01.017. 526
467 obtained by activation of an organic resorcinol-formaldehyde [15] M.S. Contreras, C.A. Páez, L. Zubizarreta, A. Léonard, S. Blacher, C.G. Olivera-
468 527
xerogel (RFX) with H3PO4 and KOH, respectively, followed by Fuentes, A. Arenillas, J. Pirard, N. Job, A comparison of physical activation of
469 carbon xerogels with carbon dioxide with chemical activation using 528
oxidation of the resulting ACX with oxalic acid and by treatment 529
470 hydroxides, Carbon 48 (11) (2010) 3157–3168, doi:http://dx.doi.org/10.1016/j.
with chitosan gel, have shown the highest adsorption and CWPO carbon.2010.04.054. 530
471 performances, removing OII between 69 and 73% and TOC between [16] T. Yamamoto, T. Sugimoto, T. Suzuki, S.R. Mukai, H. Tamon, Preparation and
472 characterization of carbon cryogel microspheres, Carbon 40 (8) (2002) 531
40 and 53% after 150 min in screening experiments. 532
473 1345–1351, doi:http://dx.doi.org/10.1016/S0008-6223(01)00294-9.
ACX-P–chitosan was found to be the most efficient catalyst under [17] M.N.V. Ravi Kumar, A review of chitin and chitosan applications, React. Funct.
474 process intensification conditions, a complete removal of the azo 533
Polym. 46 (1) (2000) 1–27, doi:http://dx.doi.org/10.1016/S1381-5148(00)
475 00038-9. 534
dye being obtained in 90 min. This performance was ascribed to its
476 [18] M. Rinaudo, Chitin and chitosan: properties and applications, Prog. Polym. Sci.
chemical and textural properties, such as its basic surface nature, 31 (7) (2006) 603–632, doi:http://dx.doi.org/10.1016/j.progpo- 535
477 high specific surface area and percentage of micropores, meso- 536
lymsci.2006.06.001.
478 pores and macropores, as well as to the presence of chitosan. It is [19] G. Crini, P. Badot, Application of chitosan, a natural aminopolysaccharide, for
dye removal from aqueous solutions by adsorption processes using batch 537
479 thus concluded that activated carbon xerogel–chitosan composites studies: a review of recent literature, Prog. Polym. Sci. 33 (4) (2008) 399–447, 538
480 may be promising catalysts for CWPO under intensified process 539
doi:http://dx.doi.org/10.1016/j.progpolymsci.2007.11.001.
481 conditions. [20] S. Chatterjee, S. Chatterjee, B.P. Chatterjee, A.K. Guha, Adsorptive removal of
Congo red, a carcinogenic textile dye by chitosan hydrobeads: binding 540
mechanism, equilibrium and kinetics, Colloids Surf. A Physicochem. Eng. 541
482 Acknowledgments 542
Aspects 299 (1–3) (2007) 146–152, doi:http://dx.doi.org/10.1016/j.col-
surfa.2006.11.036. 543
483 Work supported by projects PTDC/AAC-AMB/110088/2009, [21] M.S. Dzul Erosa, T.I. Saucedo Medina, R. Navarro Mendoza, M. Avila Rodriguez,
E. Guibal, Cadmium sorption on chitosan sorbents: kinetic and equilibrium 544
484 PEst-C/EQB/LA0020/2013 and NORTE-07-0124-FEDER-0000015, 545
studies, Hydrometallurgy 61 (3) (2001) 157–167, doi:http://dx.doi.org/
485 Q4 co-financed by FEDER through COMPETE, QREN and ON2, and 10.1016/S0304-386X(01)00166-9. 546
486 by FCT – Fundação para a Ciência e a Tecnologia. [22] V.K. Konaganti, R. Kota, S. Patil, G. Madras, Adsorption of anionic dyes on
chitosan grafted poly(alkyl methacrylate)s, Chem. Eng. J. 158 (3) (2010) 547
393–401, doi:http://dx.doi.org/10.1016/j.cej.2010.01.003. 548
487 References [23] G. Huang, C. Yang, K. Zhang, J. Shi, Adsorptive removal of copper ions from
aqueous solution using cross-linked magnetic chitosan beads, Chin. J. Chem. 549
Eng. 17 (6) (2009) 960–966, doi:http://dx.doi.org/10.1016/S1004-9541(08) 550
[1] A. Özcan, M.A. Oturan, N. Oturan, Y. Şahin, Removal of acid orange 7 from water 551
488 by electrochemically generated Fenton’s reagent, J. Hazard. Mater. 163 (2–3) 60303-1.
489 (2009) 1213–1220, doi:http://dx.doi.org/10.1016/j.jhazmat.2008.07.088. [24] S. Hydari, H. Sharififard, M. Nabavinia, M.r Parvizi, A comparative investigation
490 on removal performances of commercial activated carbon, chitosan biosorbent 552
18804327. 553
[2] F. Duarte, F.J. Maldonado-Hódar, L.M. Madeira, New insight about Orange II and chitosan/activated carbon composite for cadmium, Chem. Eng. J. 193–194
491 (2012) 276–282, doi:http://dx.doi.org/10.1016/j.cej.2012.04.057. 554
elimination by characterization of spent activated carbon/Fe Fenton-like
492 catalysts, Appl. Catal. B. Environ. 129 (2013) 264–272, doi:http://dx.doi.org/ [25] M. Auta, B.H. Hameed, Coalesced chitosan activated carbon composite for
493 batch and fixed-bed adsorption of cationic and anionic dyes, Colloids Surf. B. 555
10.1016/j.apcatb.2012.09.037. 556
[3] J.M. Peralta-Hernández, Y. Meas-Vong, F.J. Rodríguez, T.W. Chapman, M.I. Biointerfaces 105 (2013) 199–206, doi:http://dx.doi.org/10.1016/j.col-
494 surfb.2012.12.021. 23376092. 557
Maldonado, L.A. Godínez, Comparison of hydrogen peroxide-based processes
495 for treating dye-containing wastewater: decolorization and destruction of [26] V.M. Boddu, K. Abburi, J.L. Talbott, E.D. Smith, Removal of hexavalent chro-
496 mium from wastewater using a new composite chitosan biosorbent, Environ. 558
Orange II azo dye in dilute solution, Dyes Pigm. 76 (3) (2008) 656–662, doi: 559
497 http://dx.doi.org/10.1016/j.dyepig.2007.01.001. Sci. Technol. 37 (19) (2003) 4449–4456, doi:http://dx.doi.org/10.1021/
es021013a. 14572099. 560
[4] C. He, X. Hu, Anionic dye adsorption on chemically modified ordered meso-
498 porous carbons, Ind. Eng. Chem. Res. 50 (24) (2011) 14070–14083, doi:http:// [27] R.S. Ribeiro, N.A. Fathy, A.A. Attia, A.M.T. Silva, J.L. Faria, H.T. Gomes, Activated
499 carbon xerogels for the removal of the anionic azo dyes Orange II and chro- 561
dx.doi.org/10.1021/ie201469p.

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020
 G Model
JECE 479 1–9

M.T. Pinho et al. / Journal of Environmental Chemical Engineering xxx (2014) xxx–xxx 9

562 motrope 2R by adsorption and catalytic wet peroxide oxidation, Chem. Eng. J. Catal. B. Environ. 121–122 (2012) 123–134, doi:http://dx.doi.org/10.1016/j. 575
563 195–196 (2012) 112–121, doi:http://dx.doi.org/10.1016/j.cej.2012.04.065. apcatb.2012.04.002. 576
[28] E. Raymundo-Piñero, P. Azaïs, T. Cacciaguerra, D. Cazorla-Amorós, A. Linares- [33] C. di Luca, F. Ivorra, P. Massa, R. Fenoglio, Alumina supported Fenton-like
564 Solano, F. Béguin, KOH and NaOH activation mechanisms of multiwalled systems for the catalytic wet peroxide oxidation of phenol solutions, Ind. Eng. 577
565 carbon nanotubes with different structural organisation, Carbon 43 (4) (2005) Chem. Res. 51 (26) (2012) 8979–8984, doi:http://dx.doi.org/10.1021/ 578
566 786–795, doi:http://dx.doi.org/10.1016/j.carbon.2004.11.005. ie300416n. 579
[29] J. Bandara, J.A. Mielczarski, J. Kiwi, Molecular mechanism of surface recog- [34] L. Hou, Q. Zhang, F. Jérôme, D. Duprez, H. Zhang, S. Royer, Shape-controlled
567 nition. azo dyes degradation on Fe, Ti, and Al oxides through metal sulfonate nanostructured magnetite-type materials as highly efficient Fenton catalysts, 580
568 complexes, Langmuir 15 (22) (1999) 7670–7679, doi:http://dx.doi.org/ Appl. Catal. B. Environ. 144 (2014) 739–749, doi:http://dx.doi.org/10.1016/j. 581
569 10.1021/la9900270. apcatb.2013.07.072. 582
[30] M. Greluk, Z. Hubicki, Efficient removal of Acid Orange 7 dye from water using [35] L.B. Khalil, B.S. Girgis, T.A.M. Tawfik, Decomposition of H2O2 on activated
570 the strongly basic anion exchange resin Amberlite IRA-958, Desalination 278 carbon obtained from olive stones, J. Chem. Technol. Biotechnol. 76 (2001) 583
(1–3) (2011) 219–226, doi:http://dx.doi.org/10.1016/j.desal.2011.05.024. 1132–1140. 584
[31] L. Abramian, H. El-Rassy, Adsorption kinetics and thermodynamics of azo-dye [36] Y. Al-Degs, M.A.M. Khraisheh, S.J. Allen, M.N. Ahmad, Effect of carbon surface
571 Orange II onto highly porous titania aerogel, Chem. Eng. J. 150 (2–3) (2009) chemistry on the removal of reactive dyes from textile effluent, Water Res. 34 585
572 403–410, doi:http://dx.doi.org/10.1016/j.cej.2009.01.019. (3) (2000) 927–935, doi:http://dx.doi.org/10.1016/S0043-1354(99)00200-6. 586
[32] X. Zhong, J. Barbier, D. Duprez, H. Zhang, S. Royer, Modulating the copper oxide [37] F. Rodríguez-reinoso, The role of carbon materials in heterogeneous catalysis,
573 morphology and accessibility by using micro-/mesoporous SBA-15 structures Carbon 36 (3) (1998) 159–175, doi:http://dx.doi.org/10.1016/S0008-6223(97) 587
574 as host support: effect on the activity for the CWPO of phenol reaction, Appl. 00173-5. 588

Please cite this article in press as: M.T. Pinho, et al., Activated carbon xerogel–chitosan composite materials for catalytic wet peroxide oxidation
under intensified process conditions, J. Environ. Chem. Eng. (2014), http://dx.doi.org/10.1016/j.jece.2014.10.020