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egyptian journal of basic and applied sciences ■■ (2016) ■■–■■

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1 bs_bs_query Full Length Article

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3 bs_bs_query Selective synthesis of acetone from isopropyl

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alcohol over active and stable CuO–NiO
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nanocomposites at relatively low-temperature
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Q1 Abd El-Aziz A. Said *, Mohamed M.M. Abd El-Wahab,
10 bs_bs_query Mohamed N. Goda
11 bs_bs_query Chemistry Department, Faculty of Science, Assiut University, 71516 Assiut, Egypt
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14 bs_bs_query A R T I C L E I N F O A B S T R A C T
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16 bs_bs_query Article history: CuO–NiO nanocomposite catalysts were synthesized by an oxalate precipitation route. The
17 bs_bs_query Received 5 May 2016 basicity of the catalysts was measured using adsorption–desorption of acetic acid. The cata-
18 bs_bs_query Received in revised form 17 August lytic conversion of isopropanol to acetone was carried out in a conventional fixed bed flow
19 bs_bs_query 2016 type reactor at 200 °C using N2 as a carrier gas. The results indicated that, the addition of
20 bs_bs_query Accepted 26 August 2016 NiO to CuO greatly enhanced the electrical conductivity via the creation of new charge car-
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Available online riers (Cu+–Ni3+). In addition, the results revealed that the catalyst containing 30 wt.% NiO
23 bs_bs_query calcined at 400 °C possesses the highest catalytic activity with 98% conversion and 100%
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bs_bs_query Keywords: selectivity to acetone. The remarkable catalytic performance of the synthesized catalysts
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bs_bs_query CuO–NiO is attributed to the decrease of the energy gap, the increase in the concentration of charge
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bs_bs_query Nanocomposites carries (Cu+–Ni3+), and to the creation of more weak and intermediate basic sites.
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bs_bs_query Electrical conductivity © 2016 Production and hosting by Elsevier B.V. on behalf of Mansoura University. This is
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bs_bs_query Isopropanol an open access article under the CC BY-NC-ND license (http://creativecommons.org/
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bs_bs_query Acetone licenses/by-nc-nd/4.0/).

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industrially via two routes, the first is the cumene hydroper-
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38 bs_bs_query 1. Introduction oxide oxidation and the second is the dehydrogenation of 55 bs_bs_query

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isopropyl alcohol (IPA). It is estimated that, at present, nearly 56 bs_bs_query

40 bs_bs_query Acetone is an important material in many laboratory and in- 85% of acetone world capacity is based on cumene hydroper- 57 bs_bs_query

41 bs_bs_query dustrial applications such as, a chemical intermediate in oxide route for the co-production of acetone and phenol. About 58 bs_bs_query

42 bs_bs_query pharmaceuticals and as a solvent for vinyl and acrylic resins, 0.62 tons of acetone is produced per ton of phenol obtained. 59 bs_bs_query

43 bs_bs_query lacquers, alkyd paints, inks, cosmetics and varnishes. It is also The production of acetone from only cumene would require 60 bs_bs_query

44 bs_bs_query used in the preparation of paper coatings, adhesives, and heat- a balancing of the market with the phenol product from this 61 bs_bs_query

45 bs_bs_query seals coatings and is also employed as starting material in the process. Therefore, there is a need of alternative routes 62 bs_bs_query

46 bs_bs_query synthesis of many compounds [1–3]. Acetone can be produced for acetone production other than the cumene process. 63 bs_bs_query

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49 bs_bs_query * Corresponding author.

50 bs_bs_query E-mail address: [email protected] (A.E.-A.A. Said)
51 bs_bs_query http://dx.doi.org/10.1016/j.ejbas.2016.08.004
52 bs_bs_query 2314-808X/© 2016 Production and hosting by Elsevier B.V. on behalf of Mansoura University. This is an open access article under the
53 bs_bs_query CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Please cite this article in press as: Abd El-Aziz A. Said, Mohamed M.M. Abd El-Wahab, Mohamed N. Goda, Selective synthesis of acetone from isopropyl alcohol over
active and stable CuO–NiO nanocomposites at relatively low-temperature, Egyptian Journal of Basic and Applied Sciences (2016), doi: 10.1016/j.ejbas.2016.08.004
 ARTICLE IN PRESS
2 egyptian journal of basic and applied sciences ■■ (2016) ■■–■■

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bs_bs_query Dehydrogenation of IPA over a metal, metal oxide or salt cata- 2.2. Preparation of pure and mixed oxide nanocomposites 124 bs_bs_query

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bs_bs_query lysts is the second route for the manufacture of acetone. The 125 bs_bs_query

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bs_bs_query preparation of nanostructured materials has received consid- Pure Nano CuO and NiO were prepared by precipitation method 126 bs_bs_query

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bs_bs_query erable attention owing to their unique properties and interesting as described previously [12,28–30]. The precipitates were dried 127 bs_bs_query

68
bs_bs_query potential applications [4–10]. Metal oxide nanomaterials are in- in the air overnight at room temperature to get the precur- 128 bs_bs_query

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bs_bs_query teresting solids due to their surface acid–base properties and sors. Pure CuO and NiO were obtained by calcination of their 129 bs_bs_query

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bs_bs_query oxidation–reduction potentials and hence they constitute the precursors from 400 up to 700 °C in a muffle furnace under air 130 bs_bs_query

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bs_bs_query largest family of heterogeneous catalysts [11–16]. Several tran- atmosphere for 3 h. CuO–NiO mixed oxide systems were pre- 131 bs_bs_query

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bs_bs_query sition metal oxides exhibit the oxidation–reduction behavior pared by co-precipitation method as described previously. The 132 bs_bs_query

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bs_bs_query due to the ease with which they can be used as an oxidizing CuO–NiO nanocomposites with different ratios of NiO (1–50 133 bs_bs_query

74
bs_bs_query agent and then readily be generated [17–21]. In this context, wt.%) were obtained by annealing their precursors from 400 134 bs_bs_query

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bs_bs_query Turton et al. [22] mentioned that a single pass conversion of up to 700 °C in a muffle furnace under air atmosphere for 3 h. 135 bs_bs_query

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bs_bs_query 85–92% with respect to IPA with reactor conditions of 2 bars 136 bs_bs_query

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bs_bs_query and 350 °C is generally achieved. El-Shobaky et al. [23] have 2.3. Apparatus and techniques 137 bs_bs_query

78
bs_bs_query studied the catalytic conversion of IPA over CuO/MgO treated 138 bs_bs_query

79
bs_bs_query with K2O. They stated that the investigated system behaved as 2.3.1. Electrical conductivity 139 bs_bs_query

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bs_bs_query selective catalyst for dehydrogenation of isopropyl alcohol. In The electrical conductivity measurements were carried out with 140 bs_bs_query

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bs_bs_query addition, the surface properties, catalytic activities, and cata- the method described by Said et al. [31]. The powder sample 141 bs_bs_query

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bs_bs_query lytic selectivities toward IPA conversion of NiO/Al2O3 and CuO/ is compressed between two platinum discs whose ends are con- 142 bs_bs_query

83
bs_bs_query Al2O3 catalysts were investigated by Ashour [24]. The author nected to the electrometer. The whole sample is then placed 143 bs_bs_query

84
bs_bs_query concluded that the conversion of isopropanol at a reaction tem- inside an electric oven which opens along its generatrix. The 144 bs_bs_query

85
bs_bs_query perature of 260–350 °C proceeded to propene and to acetone oven is of a non-inductive type and has no temperature gra- 145 bs_bs_query

86
bs_bs_query with different selectivities. Moreover, the influence of precur- dient in its central part. A temperature controller is adjusted 146 bs_bs_query

87
bs_bs_query sor of MgO and preparation conditions on the catalytic within ±1 °C in the range of 100–300 °C. A Keithley Electrom- 147 bs_bs_query

88
bs_bs_query dehydrogenation of IPA over CuO/MgO catalysts has been eter model 610 C instrument is used for measuring the 148 bs_bs_query

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bs_bs_query studied by El-Molla et al. [25]. Furthermore, the physicochemi- resistivity. 149 bs_bs_query

90
bs_bs_query cal properties of individual and binary Ni and Ce oxide systems 150 bs_bs_query

2.3.2. Determination of basic sites 151

have been studied by Deraz and Al-Arifi [26]. They concluded
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91
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The basicity of pure CuO, pure NiO and CuO mixed with 30 wt.% 152
that at a reaction temperature of 250–450 °C, NiO and also CeO2
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92
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NiO catalysts calcined at 400 °C was investigated by the satu- 153

acted as dehydrogenation catalysts whereas their mixture con-
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ration of the basic sites with acetic acid according the following 154
taining 12 wt.% NiO acted as dehydrogenation and a
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94
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procedure: After measuring the conversion activity of IPA at 155

dehydration catalyst for isopropanol conversion. The maximum
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95
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steady state conditions over the investigated catalysts, at a re- 156

conversion obtained was 47% at a reaction temperature of 450 °C
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96
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action temperature of 200 °C, the catalyst was injected with 157
with selectivity to acetone of 62.2%. The surface and catalytic
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97
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different volumes of glacial acetic acid in the stream of reac- 158

properties of NiO/MgO system doped with Fe2O3 have been
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tants using N2 as a carrier gas and following up the activity 159

studied by Shaheen et al. [27] and they concluded that pure
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99
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variations. Moreover, the strength of the basic sites was studied 160
and variously doped solids behave as dehydrogenation and de-
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100
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by following up the change in the catalytic activity of IPA with 161

hydration catalysts leading to the formation of acetone and
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101
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the desorption of acetic acid from the presaturated samples 162

propene.
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102
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with time at 200 °C. 163

In our previous work [28], CuO–NiO mixed nanocomposites
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103
164
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104
bs_bs_query were synthesized by oxalate route and the catalysts were char- 2.3.3. Catalytic activity 165 bs_bs_query

105
bs_bs_query acterized by TG, DTA, XRD, TEM, nitrogen sorption and surface The activity of the catalysts toward dehydrogenation of iso- 166 bs_bs_query

106
bs_bs_query excess oxygen. propyl alcohol (IPA) in the gas phase was carried in a 167 bs_bs_query

107
bs_bs_query However, the highly catalytic conversion of IPA selectively conventional fixed bed flow type reactor. The gases after re- 168 bs_bs_query

108
bs_bs_query to acetone over nano CuO–NiO mixed oxide systems, to our action were chromatographically analyzed by an FID on a 169 bs_bs_query

109
bs_bs_query knowledge, has not yet been reported. Therefore, the chal- Unicam ProGc using 10% PEG 400 glass column (2 m). The re- 170 bs_bs_query

110
bs_bs_query lenge of this work was devoted to synthesize acetone from IPA action conditions were: 0.5 g catalyst weight, 1.6% IPA reactant 171 bs_bs_query

111
bs_bs_query over CuO–NiO nanocomposites as competitive catalysts with was fed into the reactor after nitrogen had been bubbled 172 bs_bs_query

112
bs_bs_query those previously reported. through thermostated IPA at a total flow rate of 110 mL min−1 173 bs_bs_query

113
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and the reaction temperature was 200 °C. The measurements 174 bs_bs_query

114
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of conversion, yield and selectivity (in %) were made after 1.5 h 175 bs_bs_query

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bs_bs_query 2. Experimental to achieve steady state conditions. 176 bs_bs_query

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bs_bs_query 177 bs_bs_query

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bs_bs_query 2.1. Materials 178 bs_bs_query

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3. Results and discussion 179 bs_bs_query

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bs_bs_query Acetone, ethanol and oxalic acid dihydrate were of analyti- 180 bs_bs_query

120
bs_bs_query cally pure reagent and were used without further purification. 3.1. Electrical conductivity measurements 181 bs_bs_query

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bs_bs_query Copper nitrate Cu(NO3)2.3H2O and nickel nitrate Ni(NO3)2.6H2O 182 bs_bs_query

122
bs_bs_query were supplied by WINLAB company for laboratory chemicals The electrical conductivity measurements of the pure CuO, pure 183 bs_bs_query

123
bs_bs_query (>99%). NiO and CuO–NiO mixed nanocomposite catalysts calcined at 184 bs_bs_query

Please cite this article in press as: Abd El-Aziz A. Said, Mohamed M.M. Abd El-Wahab, Mohamed N. Goda, Selective synthesis of acetone from isopropyl alcohol over
active and stable CuO–NiO nanocomposites at relatively low-temperature, Egyptian Journal of Basic and Applied Sciences (2016), doi: 10.1016/j.ejbas.2016.08.004
 ARTICLE IN PRESS
egyptian journal of basic and applied sciences ■■ (2016) ■■–■■ 3

2CuO + 2NiO → Cu2O + Ni2O3 (1) 212 bs_bs_query

213 bs_bs_query

or 214 bs_bs_query

215 bs_bs_query

Cu2 + + Ni2 + → Cu+ + Ni3+ (2) 216 bs_bs_query

217 bs_bs_query

On the other hand, the decrease in the electrical conduc- 218 bs_bs_query

tivity of the CuO–NiO mixed oxides upon increasing the wt.% 219 bs_bs_query

NiO above 30 may correspond to a possible decrease in the mo- 220 bs_bs_query

bility of charge carriers [37]. The observed decrease in the 221 bs_bs_query

electrical conductivity values of the pure and mixed oxide 222 bs_bs_query

nanocomposites upon increasing the calcination tempera- 223 bs_bs_query

ture from 400 to 700 °C may be attributed to the decrease in 224 bs_bs_query

the values of SBET [28,39,40]. 225 bs_bs_query

The effect of IPA vapor admission on the electrical con- 226 bs_bs_query

ductivity of the pure oxides and CuO–NiO mixed catalysts 227 bs_bs_query

calcined at different temperatures has been studied and the 228 bs_bs_query

results are shown in Fig. 1(b). The experimental conditions used 229 bs_bs_query

are similar to that used in catalytic activity runs. The results 230 bs_bs_query

indicated that a similar trend (as in Fig. 1(a)) was observed, but 231 bs_bs_query

with lower log σ values. This behavior entirely reflects that IPA 232 bs_bs_query

reactant decreases the charge carriers (Cu+ and Ni3+) created 233 bs_bs_query

in these catalysts via the electrons injected from IPA [40]. 234 bs_bs_query

On the other hand, it was established that the value of ac- 235 bs_bs_query

tivation energy provides a better information about the 236 bs_bs_query

conductivity changes. Therefore, log σ values were plotted as 237 bs_bs_query

a function of the reciprocal of absolute temperature and the 238 bs_bs_query

activation energies ΔEσ were calculated from the slope of the 239 bs_bs_query

straight lines of the following Arrhenius relationship [41]. 240 bs_bs_query

241 bs_bs_query

σ = σ *e− ΔEσ KT (3) 242 bs_bs_query

243 bs_bs_query

185 bs_bs_query Fig. 1 – Variation of log σ with the % mixing of NiO for CuO– where σ is the electrical conductivity, σ* is the pre-exponential 244 bs_bs_query

186 bs_bs_query NiO nanocomposites calcined at 400–700 °C (a) without factor, ΔEσ is the activation energy by conduction, K is the 245 bs_bs_query

187 bs_bs_query isopropyl alcohol, and (b) with isopropyl alcohol. Boltzmann constant and T is the absolute temperature. 246 bs_bs_query

The graphical representations of the linear form of the 247 bs_bs_query

188
Arrhenius plot for each sample are given in Fig. 2(a–c). It can
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248 bs_bs_query

189 bs_bs_query 400–700 °C are carried out and graphically presented in Fig. 1(a). be seen from these figures that log σ varies linearly against 1/T 249 bs_bs_query

190 bs_bs_query The results show that the electrical conductivity of the pure for the pure and mixed oxide systems, indicating that one and 250 bs_bs_query

191 bs_bs_query NiO is higher than that of CuO whereas both conductivities the same conduction mechanism is established for all the in- 251 bs_bs_query

192 bs_bs_query are lower than that of the mixed oxide nanocomposites for all vestigated samples in the temperature range of 100–300 °C. 252 bs_bs_query

193 bs_bs_query calcination temperatures. In addition, the electrical conduc- Values of ΔEσ are obtained by least square fitting of the ob- 253 bs_bs_query

194 bs_bs_query tivity of the CuO–NiO mixed oxide systems increases with tained lines. 254 bs_bs_query

195 bs_bs_query
Q2 increasing the wt.% NiO reaching the maxima at 30%. Above The activation energy values of the electrical conduction 255 bs_bs_query

196 bs_bs_query this maxima, there is a continuous decrease in the conduc- of the catalysts under investigation (with and without IPA) are 256 bs_bs_query

197 bs_bs_query
Q3 tance values with further increase of NiO up to 50 wt.%. calculated and cited in Table 1. The results reveal that the values 257 bs_bs_query

198 bs_bs_query Moreover, upon increasing the calcination temperature from of ΔEσ of pure oxides in the absence of IPA possess the highest 258 bs_bs_query

199 bs_bs_query 400 up to 700 °C, log σ values decrease for the pure and mixed values. Upon mixing CuO with 30 wt.% NiO, the activation 259 bs_bs_query

200 bs_bs_query catalysts. 260 bs_bs_query

201 bs_bs_query However, it is well known that CuO is a p-type semicon- 261 bs_bs_query

202 bs_bs_query ductor [32] and its electrical conductivity is due to the presence Table 1 – Activation energy values (with and without 262 bs_bs_query

203 bs_bs_query of Cu+ ions in its non-stoichiometric structure. Also, NiO behaves IPA) for pure CuO, pure NiO and CuO mixed with 30 263 bs_bs_query

204 bs_bs_query also as a p-type semiconductor and its p-typeness exists from wt.% NiO nanocomposites calcined at 400 °C. 264 bs_bs_query

205 bs_bs_query a hopping mechanism [33] via an electron transfer between Catalyst ΔEσ (eV) 265 bs_bs_query

206 bs_bs_query Ni3+ and Ni2+. So, the observed increase in the electrical con- Without IPA With IPA 266 bs_bs_query

207 bs_bs_query ductivity of the CuO–NiO mixed oxide systems may be

Pure CuO 0.83 0.79 267
attributed to the increase in the concentration of charge car-
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208
CuO mixed with 30 wt.% NiO 0.12 0.03 268
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riers (Ni3+ and Cu+) [34,35]. The creation of these charge carriers
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209 bs_bs_query

Pure NiO 0.50 0.40 269 bs_bs_query

210 bs_bs_query due to a synergistic effect [17,36–38] can be explained accord-

IPA: Isopropyl alcohol. 270 bs_bs_query

211 bs_bs_query ing to the following proposed mechanistic synergism: 271 bs_bs_query

Please cite this article in press as: Abd El-Aziz A. Said, Mohamed M.M. Abd El-Wahab, Mohamed N. Goda, Selective synthesis of acetone from isopropyl alcohol over
active and stable CuO–NiO nanocomposites at relatively low-temperature, Egyptian Journal of Basic and Applied Sciences (2016), doi: 10.1016/j.ejbas.2016.08.004
 ARTICLE IN PRESS
4 egyptian journal of basic and applied sciences ■■ (2016) ■■–■■

272 bs_bs_query Fig. 2 – Variation of log σ versus 1/T for (a) pure CuO, (b) pure NiO, and (c) CuO mixed with 30 wt.% NiO, nanocomposites
273 bs_bs_query calcined at 400 °C.
274 bs_bs_query

275 bs_bs_query energy progressively decreases, reaching to (0.12 eV). This de- of the chemical bonds formed between the molecules and the 292 bs_bs_query

276 bs_bs_query crease in ΔEσ value of CuO mixed with 30 wt.% NiO catalyst catalyst surface. These factors control at the same time the ac- 293 bs_bs_query

277 bs_bs_query reflects again the pronounced increase in the creation of the tivity and selectivity of the catalyst as well as the mechanism 294 bs_bs_query

278 bs_bs_query charge carriers (Cu+ and Ni3+). On the other hand, the activa- of the catalytic reaction. 295 bs_bs_query

279 bs_bs_query tion energy values measured in the presence of IPA indicated 296 bs_bs_query

280 bs_bs_query that the ΔEσ variation with NiO loading exhibits similar be- 3.2. Basicity of catalysts 297 bs_bs_query

281 bs_bs_query havior, but with lower values than that measured in the absence 298 bs_bs_query

282 bs_bs_query of IPA. The reason for such behavior is due to the injected Saturation of the active basic sites by acetic acid over pure 299 bs_bs_query

283 bs_bs_query electrons by IPA into the catalyst surface during the dehydro- oxides and CuO mixed with 30 wt.% NiO catalysts calcined at 300 bs_bs_query

284 bs_bs_query genation process [35]. These electrons are trapped in or on the 400 °C during the IPA conversion was studied and the results 301 bs_bs_query

285 bs_bs_query catalyst surface, causing a downward bending of the conduc- obtained are represented in Fig. 3(a–c). Curve (a) shows the in- 302 bs_bs_query

286 bs_bs_query tion band toward the Fermi level and consequently decrease fluence of acetic acid additions on the catalytic dehydrogenation 303 bs_bs_query

287 bs_bs_query the activation energy ΔEσ. Therefore, the decrease of ΔEσ should of IPA over NiO catalyst. It appears that the saturation of the 304 bs_bs_query

288 bs_bs_query facilitate the electron exchange between the conduction and basic sites on NiO by acetic acid was obtained after injection 305 bs_bs_query

289 bs_bs_query valence bands [42]. Moreover, its width is an important factor of 1.8 μL. In addition, the IPA conversion decreases from 44% 306 bs_bs_query

290 bs_bs_query in controlling the redox mechanism, the number of chemisorbed to 1% with increasing the volume of acetic acid up to 3 μL. Curve 307 bs_bs_query

291 bs_bs_query molecules in the course of a catalytic reaction and the nature (b) shows the influence of acetic acid injection on the IPA 308 bs_bs_query

Please cite this article in press as: Abd El-Aziz A. Said, Mohamed M.M. Abd El-Wahab, Mohamed N. Goda, Selective synthesis of acetone from isopropyl alcohol over
active and stable CuO–NiO nanocomposites at relatively low-temperature, Egyptian Journal of Basic and Applied Sciences (2016), doi: 10.1016/j.ejbas.2016.08.004
 ARTICLE IN PRESS
egyptian journal of basic and applied sciences ■■ (2016) ■■–■■ 5

309 bs_bs_query Fig. 3 – Effect of acetic acid injections on the catalytic

310 bs_bs_query conversion of IPA to acetone over (a) pure NiO, (b) pure CuO Fig. 4 – Activity variation of IPA with reaction time over 347 bs_bs_query

311 bs_bs_query and (c) CuO mixed with 30 wt.% NiO nanocomposites presaturated catalysts with acetic acid, (a) pure NiO, (b) pure 348 bs_bs_query

312 bs_bs_query calcined at 400 °C. CuO and (c) CuO mixed with 30 wt.% NiO nanocomposites 349 bs_bs_query

calcined at 400 °C. 350 bs_bs_query

313 bs_bs_query

351 bs_bs_query

314 bs_bs_query activity over pure CuO. It illustrates that the IPA conversion de- acid and the strong basic sites. According to the results ob- 352 bs_bs_query

315 bs_bs_query creases from 54% to 1% with increasing the volume of acetic tained from the desorption of acetic acid from the surfaces of 353 bs_bs_query

316 bs_bs_query acid reaching its steady state after addition of 4 μL. On the other both pure oxides, it is interesting to mention here that the 354 bs_bs_query

317 bs_bs_query hand curve (c) represents the effect of poisoning the active basic amount of acetic acid retained is approximately equal. This may 355 bs_bs_query

318 bs_bs_query sites CuO mixed with 30 wt.% NiO. It shows that upon addi- support that the distribution of the basic sites over both oxide 356 bs_bs_query

319 bs_bs_query tion of acetic acid by 3.5 μL, the conversion activity decreases catalysts surfaces almost the same. In addition, the major 357 bs_bs_query

320 bs_bs_query from 98% to 19%. These results revealed that the acetic acid strength of these sites is strong and uncomfortable for con- 358 bs_bs_query

321 bs_bs_query approximately saturated the available active basic sites re- version of IPA to acetone. 359 bs_bs_query

322 bs_bs_query sponsible for dehydrogenation of IPA over pure oxides whereas Curve 4(c) represents the effect of time on the desorption 360 bs_bs_query

323 bs_bs_query 19% is still working in case of the mixed oxide (30 wt.% NiO). of acetic acid from CuO mixed with 30 wt.% NiO catalyst. It 361 bs_bs_query

324 bs_bs_query In addition, the distribution of the basic sites on the mixed oxide shows that desorption of acetic acid occurs rapidly and hence 362 bs_bs_query

325 bs_bs_query is quite improved. the conversion of the IPA and the yield of acetone increase 363 bs_bs_query

326 bs_bs_query In an attempt to shed light on the strength of the basic sites rapidly with time. Also, the sample nearly restores its activ- 364 bs_bs_query

327 bs_bs_query over the catalyst presaturated with acetic acid, the activity varia- ity ~95% after about 10 minutes. The remained value of ~3% 365 bs_bs_query

328 bs_bs_query tion of IPA at the reaction temperature of 200 °C was measured may be attributed to the adsorption of acetic acid on strong 366 bs_bs_query

329 bs_bs_query with time and the results are presented in Fig. 4(a–c). Curve basic sites on the catalyst surface. 367 bs_bs_query

330 bs_bs_query (a) shows that desorption of acetic acid from the surface of pure The comparison between the desorption studies of acetic 368 bs_bs_query

331 bs_bs_query NiO has been almost rapid where the conversion of the IPA and acid over the catalysts under investigation reveals that CuO 369 bs_bs_query

332 bs_bs_query the yield of acetone attained a steady state after 12 min. The mixed with 30 wt.% NiO catalyst restored almost its original 370 bs_bs_query

333 bs_bs_query value of % conversion and yield of acetone at the steady state activity rapidly compared with CuO and NiO catalysts. This con- 371 bs_bs_query

334 bs_bs_query was 13% only. This means that about 30% of acetic acid was firms that the creation of weak and intermediate basic sites 372 bs_bs_query

335 bs_bs_query retained on the catalyst surface as indicated in Fig. 3(a) for the on the surface of the catalyst containing 30 wt.% NiO en- 373 bs_bs_query

336 bs_bs_query unsaturated NiO. This behavior reflects that the strength hances the reaction of IPA to acetone and consequently the 374 bs_bs_query

337 bs_bs_query of ≈ 71% of the available basic sites on NiO is strong. addition of NiO into CuO promotes its basicity to be comfort- 375 bs_bs_query

338 bs_bs_query Curve 4(b) shows that the desorption of acetic acid from CuO able for dehydrogenation of IPA [43–45]. 376 bs_bs_query

339 bs_bs_query catalyst occurs slowly where the steady state value of conver- 377 bs_bs_query

340 bs_bs_query sion was obtained after 25 min. Furthermore, the conversion 3.3. Catalytic activity 378 bs_bs_query

341 bs_bs_query at the steady state reaches 20% compared to 54% for the un- 379 bs_bs_query

342 bs_bs_query saturated catalyst. These results reflect that the basicity of CuO The dehydrogenation of IPA over CuO–NiO nanocomposite 380 bs_bs_query

343 bs_bs_query catalyst is reduced by 34%. This behavior suggests that the re- systems calcined at 400, 500, 600 and 700 °C was carried out 381 bs_bs_query

344 bs_bs_query tained acetic acid (34%) on the surface of pure CuO may be due and the results are presented in Fig. 5(a). It shows that IPA con- 382 bs_bs_query

345 bs_bs_query to the presence of ≈ 63% strong basic sites which need higher verts to acetone (major) and propene (minor) over pure 383 bs_bs_query

346 bs_bs_query temperature to overcome the binding energy between the acetic CuO and CuO mixed with 1 and 3 wt.% NiO whereas upon 384 bs_bs_query

Please cite this article in press as: Abd El-Aziz A. Said, Mohamed M.M. Abd El-Wahab, Mohamed N. Goda, Selective synthesis of acetone from isopropyl alcohol over
active and stable CuO–NiO nanocomposites at relatively low-temperature, Egyptian Journal of Basic and Applied Sciences (2016), doi: 10.1016/j.ejbas.2016.08.004
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6 egyptian journal of basic and applied sciences ■■ (2016) ■■–■■

385 bs_bs_query Fig. 5 – (a) Variation of IPA conversion with the % mixing of NiO for CuO–NiO nanocomposite catalysts calcined at
386 bs_bs_query 400–700 °C, (b) effect of reaction temperature, and (c) effect of reaction time on the catalytic dehydrogenation of IPA over CuO
387 bs_bs_query mixed with 30 wt.% NiO nanocomposites calcined at 400 °C.
388 bs_bs_query

389 bs_bs_query increasing the wt.% NiO up to 50%, IPA conversion proceeds containing 30 wt.% NiO. Above this maximum, further addi- 405
bs_bs_query

390 bs_bs_query to acetone only with selectivity 100%. From these results, one tions of NiO lead to a decrease of both conversion and yield 406
bs_bs_query

391 bs_bs_query can observe that pure CuO possesses catalytic activity toward of acetone. The observed remarkable catalytic activity of the 407
bs_bs_query

392 bs_bs_query IPA conversion to acetone higher than that of pure NiO [46]. mixed oxide catalysts may be not only due to the presence of 408
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393 bs_bs_query Such results may be correlated with the higher values of the the one component sites [47,48] Cu2+–Cu+, Ni3+–Ni2+, but also due 409
bs_bs_query

394 bs_bs_query surface area and the amount of surface excess oxygen as dis- to the creation of new active ion pairs sites (Cu+–Ni3+). Such 410
bs_bs_query

395 bs_bs_query cussed earlier [28]. On the other hand, it is well known that active sites which existed via the synergism [17,36–38] are ex- 411
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396 bs_bs_query NiO precedes the dehydrogenation reaction for hydrocarbons hibiting weak and intermediate strength as discussed above 412
bs_bs_query

397 bs_bs_query and alcohols, thus the formation of acetone as a major product in the basicity section. The improvement in their strength is 413
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398 bs_bs_query is quite expected. Hence, the observed increase in the selec- playing a major role for the dehydrogenation of IPA. In this 414
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399 bs_bs_query tivity toward acetone formation due to the increase of NiO ratio context, El-Molla et al. [25] have reported that the presence of 415
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400 bs_bs_query suggests an increase in the number of active sites respon- medium-strength basic sites on the surface of catalyst cata- 416
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401 bs_bs_query sible for dehydrogenation of IPA. So, the addition of NiO lyzes the rate determining step of the energetically easier Hα 417
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402 bs_bs_query (1–30 wt.%) into CuO as presented in Fig. 5(a) leads to a con- abstraction from adsorbed 2-propoxide forming carbanion in- 418
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403 bs_bs_query tinuous increase in the conversion of IPA and selectivity toward termediate that finally leads to acetone. In addition, it was 419
bs_bs_query

404 bs_bs_query acetone reaching a maximum yield of (98%) over the catalyst reported that Cu2+, Cu+ and Cu0 are the active and selective sites 420
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Please cite this article in press as: Abd El-Aziz A. Said, Mohamed M.M. Abd El-Wahab, Mohamed N. Goda, Selective synthesis of acetone from isopropyl alcohol over
active and stable CuO–NiO nanocomposites at relatively low-temperature, Egyptian Journal of Basic and Applied Sciences (2016), doi: 10.1016/j.ejbas.2016.08.004
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egyptian journal of basic and applied sciences ■■ (2016) ■■–■■ 7

421 bs_bs_query responsible for IPA dehydrogenation into acetone over CuO/MgO 3.3.2. Effect of catalyst weight 481 bs_bs_query

422 bs_bs_query catalysts [25,49]. They concluded that, at a reaction tempera- The effect of the weight of catalyst containing 30 wt.% NiO on 482 bs_bs_query

423 bs_bs_query ture of 175–275 °C, the different investigated solids behave the percentages conversion, yield and selectivity of IPA dehy- 483 bs_bs_query

424 bs_bs_query mainly as a dehydrogenation catalyst yielding acetone beside drogenation was studied at 200 °C and the results are shown 484 bs_bs_query

425 bs_bs_query MIBK (mesityl isobutyl keton) formation via aldol condensa- in Fig. S1, Supplementary material. It shows that the % con- 485 bs_bs_query

426 bs_bs_query tion mechanism. At lower temperature, 175 °C, the reaction is version of IPA increases with increasing the catalyst weigh from 486 bs_bs_query

427 bs_bs_query completely selective to MIBK, and on increasing the reaction (0.1–0.8) reaching its steady state value of 98% with selectiv- 487 bs_bs_query

428 bs_bs_query temperature up to and above 200 °C, selectivity to acetone starts ity of 100% toward acetone at a catalyst weight of 0.5 g. These Q5 488 bs_bs_query

429 bs_bs_query to begin reaching to its high value (maximum 92%) at a reac- data reflect that as the catalyst weight increases, the number 489 bs_bs_query

430 bs_bs_query tion temperature of 275 °C. Moreover, the catalytic performance of active basic sites responsible for the dehydrogenation process 490 bs_bs_query

431 bs_bs_query of CuO/MgO treated with K2O catalysts toward IPA conver- is normally expected to increase. On further increase in the 491 bs_bs_query

432 bs_bs_query sion, at a reaction temperature of 150–400 °C, was reported [23]. catalyst weight up to 0.8 g a little amount of propene not ex- 492 bs_bs_query

433 bs_bs_query They stated that the system behaved as selective catalyst for ceeding 2% is observed. 493 bs_bs_query

434 bs_bs_query dehydrogenation of isopropyl alcohol to acetone (major) with 494 bs_bs_query

435 bs_bs_query selectivity >80% besides propene as a minor product. 3.3.3. Catalyst stability 495 bs_bs_query

436 bs_bs_query Therefore, from the comparison between our CuO–NiO To evaluate the stability of the catalyst containing 30 wt.% NiO, 496 bs_bs_query

437 bs_bs_query mixed oxide nanocomposite systems with that previously re- the dehydrogenation of IPA to acetone was investigated and 497 bs_bs_query

438 bs_bs_query ported systems [22–27], we can conclude that our system has the results are presented in Fig. 5(c). It shows that the maximum 498 bs_bs_query

439 bs_bs_query two advantages: (1) the reaction temperature for complete IPA conversion of IPA (98%) with selectivity 100% to acetone was 499 bs_bs_query

440 bs_bs_query conversion to acetone, 200 °C, is relatively low compared with obtained after 60 min from the introduction of reactant fol- 500 bs_bs_query

441 bs_bs_query the previous reported systems, and (2) the selectivity to acetone lowed by a steady state till 60 h, which means that the catalyst 501 bs_bs_query

442 bs_bs_query as the desired product, reached 100%. These two advantages under test has a good stability toward production of acetone. 502 bs_bs_query

443 bs_bs_query make our system, which was prepared by a facile route 503 bs_bs_query

444 bs_bs_query (nanocomposite), a competitive one than those reported

504 bs_bs_query

445 bs_bs_query
Q4 previously.
446 bs_bs_query In fact a good contribution of our system for proceeding IPA
4. Conclusions 505 bs_bs_query

447 bs_bs_query to acetone may be supported with the results of electrical con- 506 bs_bs_query

448 bs_bs_query ductivity as illustrated from the behaviors of both Fig. 5(a) and The main conclusions derived from the results obtained can 507 bs_bs_query

449 bs_bs_query Fig. 1(a and b) with the wt.% NiO. So, the decrease in ΔEσ as be summarized as follows: 508 bs_bs_query

450 bs_bs_query shown in Table 1 should enhance the electron exchange 509 bs_bs_query

451 bs_bs_query between IPA and the catalyst surface during the reaction and • Pure and mixed solids of CuO and NiO nanocomposites have 510 bs_bs_query

452 bs_bs_query consequently increases the conversion and selectivity toward been synthesized by direct, facile co-precipitation method 511 bs_bs_query

453 bs_bs_query acetone formation. Moreover, the decrease in the catalytic ac- (oxalic acid rout). 512 bs_bs_query

454 bs_bs_query tivity of the mixed oxides above 30 wt.% may be due to the • The addition of NiO to CuO resulted in increasing the elec- 513 bs_bs_query

455 bs_bs_query decrease in their conductivity and the mobility of charge car- trical conductivity, whereas the activation energy of 514 bs_bs_query

456 bs_bs_query riers [37]. On increasing the calcination temperature above conduction decreases. 515 bs_bs_query

457 bs_bs_query 400 °C, the results of catalytic activity of the pure and mixed • Incorporation of NiO with CuO creates more weak and in- 516 bs_bs_query

458 bs_bs_query oxides exhibit similar behavior as that observed for the cata- termediate basic sites which play the main role for the 517 bs_bs_query

459 bs_bs_query lysts calcined at 400 °C but with lower values. These results selective dehydrogenation of IPA into acetone. 518 bs_bs_query

460 bs_bs_query can be discussed in terms of the possible change in the con- • The catalyst containing 30 wt.% NiO calcined at 400 °C pos- 519 bs_bs_query

461 bs_bs_query centration of cation pairs acting as active sites for the catalyzed sesses the highest catalytic activity with 98% conversion and 520 bs_bs_query

462 bs_bs_query reaction [50] and a possible decrease in the SBET of the cata- 100% selectivity to acetone at the reaction temperature of 521 bs_bs_query

463 bs_bs_query lysts [28,39,51]. 200 °C, and it exhibits good stability with duration time up 522 bs_bs_query

464 bs_bs_query To achieve the best conditions that will give the maximum to 60 h. 523 bs_bs_query

465 bs_bs_query yield of acetone over the catalyst containing 30 wt.% NiO cal- • The remarkable activity and selectivity of the catalysts under 524 bs_bs_query

466 bs_bs_query cined at 400 °C, the factors affecting the catalytic conversion investigation are correlated well with both electrical con- 525 bs_bs_query

467 bs_bs_query of IPA into acetone were studied in the following. ductivity and basicity. 526 bs_bs_query

468 bs_bs_query
527 bs_bs_query

469 bs_bs_query 3.3.1. Effect of catalytic reaction temperature 528 bs_bs_query

470 bs_bs_query The effect of reaction temperature on the catalytic conver- Appendix: Supplementary material 529 bs_bs_query

471 bs_bs_query sion of IPA in the range 100–300 °C was studied. The percentages 530 bs_bs_query

472 bs_bs_query of conversion, yield and selectivity are represented in Fig. 5(b).
Supplementary data to this article can be found online at 531 bs_bs_query

473 bs_bs_query It shows that the IPA conversion and acetone yield increase
doi:10.1016/j.ejbas.2016.08.004. 532 bs_bs_query

474 bs_bs_query monotonically with increasing the reaction temperature reach-

475 bs_bs_query ing the value of 98% at the reaction temperature of 200 °C. Above 533 bs_bs_query

476 bs_bs_query 200 °C, propene started to appear and it increases with in- REFERENCES 534 bs_bs_query

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Please cite this article in press as: Abd El-Aziz A. Said, Mohamed M.M. Abd El-Wahab, Mohamed N. Goda, Selective synthesis of acetone from isopropyl alcohol over
active and stable CuO–NiO nanocomposites at relatively low-temperature, Egyptian Journal of Basic and Applied Sciences (2016), doi: 10.1016/j.ejbas.2016.08.004
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8 egyptian journal of basic and applied sciences ■■ (2016) ■■–■■

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active and stable CuO–NiO nanocomposites at relatively low-temperature, Egyptian Journal of Basic and Applied Sciences (2016), doi: 10.1016/j.ejbas.2016.08.004