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Spectrochimica Acta Part A 92 (2012) 105112

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Spectrochimica Acta Part A: Molecular and


Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Dielectric characterization and catalytic activity studies of nickel chloride doped


carboxymethyl cellulose lms
Zeinhom M. El-Bahy a,1 , Khaled H. Mahmoud b,,2
a
Chemistry Department, Faculty of Science, Taif University, Taif, Saudi Arabia
b
Physics Department, Faculty of Science, Taif University, Taif, Saudi Arabia

a r t i c l e i n f o a b s t r a c t

Article history: Cast technique was used to prepare lms of sodium carboxymethyl cellulose (CMC) doped with different
Received 2 December 2011 ratios of NiCl2 6H2 O in the range of 040 Ni2+ wt.%. Thermal analysis (DTA) in the range of 25600 C and
Received in revised form 1 February 2012 dielectric properties in the temperature range of 30150 C and frequency range of 0.1100 kHz were
Accepted 10 February 2012
measured for the prepared samples. DTA analysis showed new exothermic peaks which were attributed
to structural phase transitions. Different molecular motions are separated via dielectric relaxation spec-
Keywords:
troscopy. In the high temperature range (higher than 100 C), the -relaxation, which is associated with
CMC
the hopping motion of ions through polymer material, was detected. The detailed analysis of the results
Dielectric relaxation
4-Nitrophenol
showed that the dielectric dispersion consists of both dipolar and interfacial polarization. Measurements
Hydrogenation of ac conductivity as a function of frequency at different temperatures indicated that the correlated barrier
hopping model (CBH) is the most suitable mechanism for the ac conduction behavior.
The catalytic activity of CMC doped with Ni2+ was tested in the reduction of the hazardous pollutant
4-nitrophenol to the functional 4-aminophenol with an excess amount of NaBH4 . Ni-free CMC did not
exhibit any catalytic activity for the studied reaction. However, Ni2+ -doped CMC showed a signicant
catalytic activity that is proportional to the ratio of Ni2+ included in CMC. The activation energy (Ea ) was
estimated in the temperature range of 2540 C. The estimated value of Ea decreased with increasing the
ratio of Ni2+ . Finally, the optimum catalyst mass was found to be 0.6 g/l.
2012 Elsevier B.V. All rights reserved.

1. Introduction distinguish between the primary relaxation (-relaxation), which


is related to the glass transition, and several secondary relax-
Polymer inorganic composite materials have been extensively ations, which are related either to the local main chain dynamic
studied to generate new materials having the functions of inorganic (-relaxation) or to different side-group motions (-relaxation).
materials and polymers. They are expected to be used as a toner for Recently, it was found that there is an additional dielectric relax-
xerography or laser printers, dry paints, drug delivery and medi- ation process called (-relaxation) in the higher temperature range
cal diagnostic tests. Also, they have been successfully employed in of 80180 C for amorphous solid systems, polysaccharides and
areas such as removal of harmful trace metal ions, because of their other polymers, which obviously could not be assigned to any
highly selective adsorptivity for heavy metal ions [1]. One of the molecular dipolar group orientation [35]. This process is associ-
methods to characterize materials is based on the analysis of their ated with the hopping motion of ions in the disordered structure of
dielectric spectra. Dielectric analysis provides information about the polymeric material and it is strongly related to the dc conduc-
the motion of entities having an electric charge or an electric dipole tivity of the polymeric system.
moment, i.e., dipole reorientation, rotation of the main and seg- In recent years Ni2+ doped optical materials received much
mental chains and conductivity mechanisms [2]. It is quite common attention [610]. They can be used as active media for broadband
in the dielectric spectroscopy of natural and synthetic polymers to optical ampliers and tunable near-infrared laser systems. CMC is
an important industrial polymer with a wide range of applications
in occulation, drag reduction, detergents, textiles, paper, foods,
drugs, and oil well drilling operation. It has a number of sodium
Corresponding author. Tel.: +966 530175838. carboxymethyl groups (CH2 COONa), introduced into the cellulose
E-mail address: cairouni1@yahoo.com (K.H. Mahmoud). molecule, which promote water solubility.
1
Permanent address: Chemistry Department, Faculty of Science, Al-Azhar Uni-
versity, Nasr city, Cairo, Egypt.
Wastewaters containing phenolic compounds present a serious
2
Permanent address: Physics Department, Faculty of Science, Cairo University, environmental problem. Aromatic pollutants, in particular phenols
Giza, Egypt. and phenolic derivatives such as p-nitrophenol are widely used

1386-1425/$ see front matter 2012 Elsevier B.V. All rights reserved.
doi:10.1016/j.saa.2012.02.043
106 Z.M. El-Bahy, K.H. Mahmoud / Spectrochimica Acta Part A 92 (2012) 105112

as intermediates in the production of dyes, plastics and pharma-


ceuticals. Moreover, these compounds are considered hazardous
pollutants because of their potential to harm humans. However,
they have been on the EPAs priority pollutants list since 1976 [11].
Among various phenolic compounds, 4-nitrophenil is one of the
frequently occurring by-products, which is toxic to the environ-

DTA (a.u)
ment. On the other hand, 4-aminophenol is of great commercial CMC
importance as an intermediate for the preparation of analgesic and
5Ni-CMC
antipyretic drugs [1215]. In view of the hazardous effect of 4-
aminophenol and the growing demand for p-aminophenol, direct 10Ni-CMC
catalytic hydrogenation of the former to the later becomes impor- 20Ni-CMC
tant, because this could be an efcient and greener route [16,17].
40Ni-CMC
NaBH4 has the potential to be a useful hydrogen storage compound.
It reacts slowly with water to liberate 4 mol of hydrogen/mol of the
compound at room temperature (NaBH4 + 2H2 O NaBO2 + 4H2 ). 100 200 300 400 500 600
Reduction of 4-nitrophenol (4-NP) with NaBH4 in the aqueous
Temperature, C
medium is a kinetically inert reaction, and generally the reac-
tion occurs in the presence of metal containing catalysts. In the Fig. 1. DTA thermograms for Ni-CMC composites.
present study, the reduction reaction has been carried out cat-
alytically using Ni2+ ions incorporated in the eco-friendly CMC
contact with the specimen. The dielectric constant was calculated
polymer.
using the relation  = Ks /K0 , where Ks is the capacitance of the
Therefore, in this work, we have attempted the preparation of
sample which is measured directly from RLC meter and K0 is that
Ni2+ -CMC composite systems with different Ni2+ ratios. The differ-
of free space, the dielectric loss also given by  =  tan , where
ent relaxation processes is revealed via the dielectric spectroscopic
tan is the dielectric loss tangent (also this parameter measured
analysis. The inuence of Ni2+ , on dielectric properties and asso-
directly from RLC meter). Finally the ac electrical conductivity  ac ,
ciated relaxation phenomena is examined. Moreover, the catalytic
was obtained using the relation ac = 0  . The accuracy of both
reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) over
 and tan was about 3%.
Ni2+ -CMC catalysts were investigated and the effect of various
parameters such as the incorporated amount of Ni2+ in CMC, the
reaction temperature and the catalyst mass on the catalytic activ- 2.3. The catalytic activity
ity was studied. At the same time, the catalytic activity of Ni2+ -free
CMC was compared to that of Ni2+ -containing CMC catalysts. The evaluation of the catalytic activity of the prepared xNi-CMC
samples was carried out in a cylindrical beaker using the reduction
of 4-NP by NaBH4 as a model reaction. A magnetic stirrer was used
2. Experimental continuously to guarantee the good mixing of the solution. In a typ-
ical test, to 140 ml (7.18 104 M) aqueous solution of 4-NP taken
2.1. Preparation of solid samples in the beaker, freshly prepared aqueous solution of NaBH4 (0.1 g
in 10 ml distilled water) was introduced. The concentration of the
CMC (Mw 250,000) was supplied by BDH Chemical Ltd. Poole NaHB4 was chosen to exceed the concentration of the 4-NP by far.
England. NiCl2 6H2 O was supplied by BDH Chemicals Company; Thus, in agreement with previous literature [1821], the kinetics
Japan. The solution method was used to obtain lm samples. of the reduction can be treated as pseudo rst-order, [ln(C0 /C) = kt]
Weighed amounts of CMC were dissolved in a mixture of distilled where, C0 and C are the extinction of 4-NP maxima at 400 nm at
water and ethanol with the ratio of 4:1 using a magnetic stirrer at the beginning of the reaction (t = 0) and after time t, respectively.
50 C on water bath for 4 h. The appropriate weighed amounts of To the mixture, unless otherwise stated, 30 mg of Ni2+ -containing
NiCl2 6H2 O were dissolved in distilled water at room temperature CMC was added at zero reaction time (t0 ) with continuous stirring
to give 5, 10, 20 and 40 wt.% of Ni2+ -CMC. Solutions of Ni2+ and CMC at room temperature. The process of the reduction was monitored
were mixed using magnetic stirrer at 6080 C. Pure NaCMC and by measuring the extinction of the solution at 400 nm as a func-
Ni-doped CMC will be referred as CMC and xNi-CMC, respectively tion of time by using Varian Carry 50 spectrophotometer. Similar
(where x is the wt.% of Ni). Films of suitable thickness (50 m) experiments were performed in absence of catalyst and also in pres-
were casted onto stainless steel Petri dishes, and then dried in an ence of Ni2+ -free CMC polymer for comparison. The rate constant (k,
open air at room temperature (about 30 C) for about 6 days until min1 ) was calculated from the slopes of the straight-line portion
solvent was nearly evaporated. of the plots [ln(C0 /C) vs. time].

2.2. Thermal and ac measurements 3. Results and discussion

DTA measurements were carried out using Schimadzu DTG-60H 3.1. Thermal analysis
thermal analyzer. Measurements were carried out under nitrogen
atmosphere (20 ml/min). Measurements of the dielectric constant Fig. 1 shows DTA thermograms of nickel chloride doped sodium
( ) and dielectric loss ( ) in the frequency range of 0.1100 kHz carboxymethyl cellulose composite system from room tempera-
and a controlled temperature range of 30150 C were carried out ture up to 600 C. The different phase transitions and associated
using Hioki 3531 Z Hiester programmable automatic RLC meter. enthalpies are given in Table 1. For pure CMC there is one distinct
Films were cut into square pieces and prepared to t the cell of endothermic phase transitions at 71 C with an enthalpy 60.68 J/g
measuring techniques. The sample was sandwiched between two which is corresponding to glass phase transitions and it is in good
copper electrodes and then tted in designed holder connected to agreement with Su et al. [22]. The thermogram of pure CMC shows
programmable oven with ramp rate of 1 C/min. Temperature was also other three exothermic peaks at 295, 390 and 566 C with asso-
measured using a copper-constant thermocouple kept in perfect ciated enthalpies of 1310, 228.15 and 4780 J/g, respectively. These
Z.M. El-Bahy, K.H. Mahmoud / Spectrochimica Acta Part A 92 (2012) 105112 107

Table 1
Transition temperatures and enthalpy associating each phase transition for Ni-CMC composites.

Sample Glass phase transition New phase transitions

Tg ( C) H (J/g) a
Tp1 ( C) H (J/g) b
Tp2 ( C) H (J/g)

295 1310
CMC 71 60.68 390 228.15
566 4780

304 290.54
516 274.14
5Ni-CMC 66 36.42
525 26.45
570 1470

279 1170
10Ni-CMC 60 208.45
500 5900

389 27.47
20Ni-CMC 83.62 124.56 463 5030
511 475.16

404 160.46
40Ni-CMC 55.42 284.73 202 43.86
525 2780
a
Exothermic peak.
b
Endothermic peak.

peaks are attributed to different degradation processes in Ni-free conductivity processes and therefore it will be labeled as -
CMC [23]. It is noted that the composite samples have glass tran- relaxation. As shown in Fig. 2, the dielectric constant decreases with
sition temperature lower than that of pure polymer except that increasing the frequency over the whole investigated temperatures
for 20Ni-CMC sample which has higher transition temperature. range (30150 C). The increase of  with temperature up to Tg is
This suggests that the segmental mobility of semicrystalline CMC governed mainly by the change in the intra-and inter-molecular
becomes less rigid segments [24]. The changes in the phase transi- interactions. These interactions may involve the alignment or
tion temperatures and associated enthalpies give an indication of rotation of dipoles present in the polymer with the increase of tem-
the structural modication of CMC with NiCl2 . perature. Above Tg , the dielectric constant begins to fall due to the
increase in the chaotic thermal oscillation of the molecules and
3.2. Dielectric properties the diminishing degree of order of the orientation of the dipoles
[27]. Fig. 3 shows the variation of dielectric constant with tem-
3.2.1. Dielectric constant perature for different xNi-CMC composite samples at 1 kHz. No
It is well known that the dielectric polarization in a polymer may relaxation peaks are observed for composite sample 5 and 10Ni-
be due to dipole alignment rotation/motion of the main/segmental CMC. However, the 20Ni-CMC sample yields two relaxation peaks
polymer chain, migration of ions within the material or injection at 72 C and 93 C. In case of 40Ni-CMC sample, other relaxations
from electrodes. Fig. 2 shows the variation of the dielectric con- appeared where a small relaxation peak at 42 C and a higher tem-
stant with temperature at three frequencies 1, 20 and 100 kHz perature relaxation peak occurred at 138 C. However, the glass
for CMC. It can be seen from Fig. 2 that each  (T ) curve reveals transition peak temperature is unaltered and the peak tempera-
three pronounced peaks appearing at 69, 93 and 123 C. The rst ture corresponding to crystalline state is slightly removed to lower
temperature peak is located in the vicinity of the glass transition temperature at 87 C. From the foregoing data, the disappearance
temperature [22] and it is designated to -relaxation. The inter- of relaxation peaks and the appearance of others reect the effect
mediate temperature peak may be assigned to the crystalline state of Ni doping on polymer matrix.
of this material. The high temperature peak is a non-dipolar pro- It is noted that the values of  for all composite samples
cess which is due to the interfacial polarization or space charge are lower than that of pure CMC over whole the temperature
polarization effects [25,26]. The last peak is not always so eas- range. The 40Ni-CMC sample has the highest  value among all
ily visible but it is frequently associated with the onset of ionic

10000 11 5Ni-CMC

1kHz 10Ni-CMC
20kHz 9
1000 100kHz
20Ni-CMC

40Ni-CMC
7
'

100
'

10
3

0 1
40 60 80 100 120 140 20 40 60 80 100 120 140
Temperature, C Temperature, C

Fig. 2. Temperature dependence of  for pure CMC at different frequencies. Fig. 3. Temperature dependence of  for Ni-CMC composites at 1 kHz.
108 Z.M. El-Bahy, K.H. Mahmoud / Spectrochimica Acta Part A 92 (2012) 105112

8
a
30
0.06
50
60

6
0.04

M''
'

0.02
2

0
0 1.5 2 2.5 3 3.5 4 4.5 5
1.5 2 2.5 3 3.5 4 4.5 5
log (f)
log (f)

Fig. 4. The variation of  with frequency at different temperatures 40Ni-CMC com- 4.5
posite sample. b
4.3

composite samples. The decreasing value of  for composite sam- 4.1


ples than pure CMC may be due to porosity of samples occurred
due to air trapped between Ni particles [28]. It is also noted that 3.9

log (fmax)
the composite samples have progressively increased dielectric con-
stant with increasing Ni content and this is due to increasing the 3.7
number of ionizable charge carriers in the polymer network. CMC
3.5 5Ni-CMC
As representative of all samples, the behavior of dielectric con-
10Ni-CMC
stant  as a function of frequency for the sample 40Ni-CMC was 3.3 20Ni-CMC
measured as shown in Fig. 4. The data were collected in the fre- 40Ni-CMC

quency range of 0.1100 kHz at different temperatures (30, 50 and 3.1


2.95 3 3.05 3.1 3.15 3.2 3.25 3.3 3.35
100 C). It is observed that the change in  is signicant at low fre-
-1
quencies for all samples. The decrease in dielectric constant with 1000/T, (K )
frequency for the investigated samples at certain temperature may
Fig. 6. (a) The variation of electric modulus with frequency at different temperatures
be attributed to decreasing the number of dipoles which contribute
for 40Ni-CMC composite sample, (b) Plots of log(fmax ) versus reciprocal temperature
to the polarization. The higher values of  at lower frequencies for Ni-CMC composites.
may be ascribed to the space charge and interfacial polarization
as a result of defects and heterogeneity present in the polymer
matrix. It is also noted that the magnitude of the dielectric dis- corresponded to relaxation of amorphous solid systems. This
persion with increasing frequency depends on temperature which relaxation process is non dipolar; it is a result of ionic conductivity.
becomes largely noticeable as the temperature increased toward In 5Ni-CMC sample, a high temperature relaxation peak is observed
the glass transition [29]. at 117 C, while 10Ni-CMC presented two relaxations at 102 and
123 C. In case of 20Ni-CMC, the and crystalline phase transi-
3.2.2. Dielectric loss factor and electric modulus tions were observed at 72 and 111 C. For 40Ni-CMC sample, an
The temperature dependence of  for composite samples under additional low temperature relaxation peak is observed at 42 C.
consideration at 1 kHz is observed in Fig. 5. Three relaxation peaks This low temperature peak was probably related to the so called
are observed in the case of Pure CMC. The rst relaxation peak cor- sub-Tg , which was due either to the local main-chain dynamic
responding to Tg ( relaxation) was observed at 69 C and it was or to different side group motions [30,31]. The electric modulus
attributed to micro-Brownian motion of large chain segments. The formalism M*() will be used to study the relaxation. This formal-
intermediate temperature peak at 93 C may be assigned to the ism is notably suitable to detect electrode polarization phenomena
crystalline state of this material. The later relaxation peak at 123 C and bulk effects as average conductivity relaxation [32]. For the
sake of brevity we represented M for 40Ni-CMC sample only.
100000
M () exhibits low value at low frequencies which may be due to
CMC
CMC large value of capacitance associated with electrodes. M () plots,
10000 C5
5Ni-CMC Fig. 6, show asymmetric maxima at the dispersion region of  ().
C10
10Ni-CMC Regardless prole intensity, the maximum (Mmax  ) shifts to higher
1000 C20
20Ni-CMC frequency with increase of temperature, which suggests the effect
C40
40Ni-CMC
of electrode polarization can be avoided. The peak frequency corre-
100 
sponding to Mmax is known as relaxation frequency fm . When f < fm
''

10 the charge carriers are mobile over large distance and are associated
with the hopping conductivity. For f > fm the carriers are spatially
1 conned to their potential wells, being mobile over short distances
and associated with the relaxation polarization process [33]. Thus
0.1 the peak frequency fm is an indication of transition from long range
to short range mobility and is dened by the condition 2fm  m = 1
0.01
20 40 60 80 100 120 140 where  m is the relaxation time. The asymmetric M peak originates
Temperature, C from the nature of relaxation behavior. This non Debye behavior of
the M spectrum can be associated to the distribution of relaxation
Fig. 5. Temperature dependence of  for Ni-CMC composites at 1 kHz. times.
Z.M. El-Bahy, K.H. Mahmoud / Spectrochimica Acta Part A 92 (2012) 105112 109

0.8

-6

0.6
log(ac(-1cm-1))

-7
0.4

S
CMC
C0
-8
30C 0.2 5Ni-CMC
C5

50C 10Ni-CMC
C10
20Ni-CMC
C20
60C
C40
40Ni-CMC
-9 0
25 30 35 40 45 50 55 60 65
1.5 2 2.5 3 3.5 4 4.5 5
Temperature, C
log ()
Fig. 8. Variation of the exponent s on temperatures for Ni-CMC composites.
Fig. 7. Dependence of  ac on frequency for 40Ni-CMC sample at different temper-
atures.

exponent s decreases with increasing temperature and its value is


The relaxation process can be modeled by Arrhenius tempera- less than unity, i.e. 0 < s < 1. Parameter s is associated with the mod-
ture dependence as following: ication of network structure and its smaller value signies higher
fm = f0 eE/kT (1) degree of modication [36]. Accordingly these results lead to the
prediction that the correlated barrier hopping (CBH) is the most
where fm is the relaxation frequency at which is maximum, E M suitable mechanism to explain the ac conduction behavior in the
is effective activation energy for relaxation and f0 is the constant considered system [37,38]. In the CBH model [39] the exponent s
parameter characteristic for particular relaxation. The shift in the was found to obey the equation:
frequency of the loss peak is represented as a function of recipro-
cal temperature for all samples, Fig. 6b. The data were tted to a 6kT
S =1 (3)
straight line whose slope is the activation energy. The activation UM kT ln(1/0 )
energies are 0.1, 0.26, 0.37, 0.19 and 0.18 eV for CMC, 5Ni-CMC,
10Ni-CMC, 20Ni-CMC and 40Ni-CMC, respectively. The lower acti- where UM is the maximum barrier height at innite separation,
vation energies for CMC, 20Ni-CMC and 40Ni-CMC samples may which is called the polaron binding energy, i.e. the binding energy
be due to the increase in chain separation and free volume, which of the carrier in its localized sites and  0 is a characteristic relaxation
facilitated dipolar orientation that mainly contributed to polariza- time which is in the order of an atom vibrational period  0 = 1013 s.
tion. For neighboring sites at a separation R, the Coulomb wells overlap,
resulting in a lowering of the effective barrier from UM to value Uh ,
3.2.3. ac Conductivity ( ac ) which for the case of a single electron transition is given by:
Fig. 7 shows the frequency dependence of  ac () at different
e2
temperatures for 40Ni-CMC sample (for the sake of brevity). As can Uh = UM (4)
be seen, each curve displays the conductivity dispersion, which is 4o  R
strongly dependent on frequency at room temperature and show where the hopping distance (R) at frequency is given by:
weaker frequency dependence at higher temperatures. The ac con-
ductivity is a monotonically increasing function of frequency. This e2
type of behavior reveals that the mechanism responsible for ac con- R= (5)
0  [UM kT ln(1/)]
duction could be hopping one. It is found to be consistent with that
observed in many hopping systems [34]. In general, the ac con- For large values of UM /kT, the exponent s becomes [38]:
ductivity as a function of frequency can be represented over many
6kT
decades by AlmondWest type power law of the form: s=1 (6)
UM
s
ac () = tot dc = A (2)
And the lower bound (cut-off) to hopping distance becomes:
where  tot is the total measured conductivity and  dc is the dc
conductivity which is the extrapolation of total conductivity to e2
Rmin = (7)
zero frequency of the ac eld, A is temperature dependent con- o  UM
stant and s is a material and temperature dependent power law
exponent [35]. At low frequencies, random distribution of the ionic Using the values of s derived from Fig. 8 UM is calculated according
charge carriers via activated hopping gives rise to a frequency- to Eq. (6) and listed in Table 2. The values of s and UM changed irreg-
independent conductivity while at higher frequencies, conductivity ularly with polymer composition. The Columbic barrier height Uh ,
exhibits dispersion which increases roughly in a power law fashion hopping distance R and the lower bound (cut-off) Rmin are calcu-
and eventually becomes almost linear at even higher frequen- lated using Eqs. (4), (5) and (7), respectively. It must be remembered
cies [35]. The changeover of the conductivity is shifted toward that the value of the relaxation time () at which electric modulus
higher frequencies with increase in temperature because mobile is maximum is used to calculate R in Eq. (5). The values of ac param-
ions acquire more thermal energy and cross the barrier more eas- eters R, Rmin and Uh at different temperatures are listed in Table 2
ily. The values of the exponent s were derived by calculating the at 1 kHz. It is clear that the values of these parameters change irreg-
slopes of the curves in Fig. 7. ularly with both temperature and composition. This suggests that
Fig. 8 illustrates the variation of the exponent s with tem- the correlated barrier hopping mechanism depends on composition
perature for different composite samples. It is observed that the and temperature of composite matrix.
110 Z.M. El-Bahy, K.H. Mahmoud / Spectrochimica Acta Part A 92 (2012) 105112

Table 2
ac Conductivity parameters at 1 kHz and different temperatures for Ni-CMC composites.

Composite sample T ( C)

30 C 50 C 60 C

R (A) Rmin (A) Uh (eV) UM (eV) R (A) Rmin (A) Uh (eV) UM (eV) R (A) Rmin (A) Uh (eV) UM (eV)

CMC 69 60 0.2 0.26 46 35 0.17 0.22 1.13 0.77 0.17 0.2


5Ni-CMC 156 148 0.27 0.35 140 120 0.29 0.37 135 105 0.29 0.36
10Ni-CMC 154 132 0.36 0.46 128 107 0.36 0.46 154 113 0.32 0.39
20Ni-CMC 80 75 0.46 0.6 132 109 0.3 0.37 123 95 0.3 0.38
40Ni-CMC 134 126 0.26 0.34 104 93 0.23 0.3 39 30 0.22 0.28

2.5
a CMC
5Ni-CMC
10Ni-CMC
2 20Ni-CMC
40Ni-CMC

1.5

ln (C0/C)
1
Scheme 1. Change of the 4-nitrophenol to 4-nitophenolete ion and to 4-
aminophenol.
0.5

1.5
PNP 0
0 min 0 10 20 30 40
1.2 1 min Time, min
PAP 2 min
Absorbance, a.u

3 min
0.9 0.8
5 min
7 min b
0.7
10 min
0.6
0.6

0.3 0.5
k, min-1

0.4
0
0.3
210 260 310 360 410 460
Wavelength, nm 0.2

Fig. 9. Time dependence of the UVvis spectra of 4-NP reduction by 20%Ni-CMC at 0.1
30 C by NaBH4 .
0
0 10 20 30 40
3.3. The catalytic activity of the prepared samples Ni ratio, Wt %

The preliminary experiment on the reduction of 4-nitrophenol Fig. 10. (a) Pseudo rst-order plots of 4-NP reduction by NaBH4 in presence of Ni2+ -
CMC with different Ni2+ ratios at 30 C. (b) Correlation between the Ni2+ ratio and
by NaBH4 indicates that no hydrogenation reaction occurs in the the rst order rate constant (k).
absence of the catalyst, conrming the absence of any noncatalytic
reduction of the organic substrate. In this investigation Ni2+ ion
was incorporated in CMC polymer and demonstrated the use of rst order plots [ln(C0 /C) vs. time] of the 4-NP reduction over Ni-
these composite systems in the reduction 4-NP to 4-AP in pres- CMC with different Ni2+ ratios (ca. 040%). It can be seen that
ence of an excess amount of aqueous NaBH4 . A red shift of the there is an induction period in the beginning of the reaction which
peak from 317 nm to 400 nm with a small shoulder at 260 nm has decreases with increasing the Ni ratio. The rate constant values, k
been observed immediately after the addition of NaBH4 . This is (min1 ), calculated from the slope of the straight line portion of the
because of the formation of 4-nitrophenolate ion under alkaline rst order plots, are listed in Table 3 and were plotted against the
conditions caused by NaHB4 (pH > 11), Scheme 1. After addition of Ni2+ ratio as shown in Fig. 10b. The k value was minimum for 5Ni-
the Ni2+ -CMC catalyst, a continuous fading of the solution color and CMC and it increased with increasing the Ni2+ ratio. The absence of
a continuous decrease of the adsorption maxima at 400 nm and the any catalytic activity in absence of Ni2+ and the clear dependence
shoulder at 260 nm due to the reduction of 4-NP to 4-AP, Scheme 1. of the catalytic activity on the Ni2+ ratio indicate that the Ni2+ ions
As the reaction progressed, new band formation at 295 nm was are the active sites of the present reaction.
observed and increased with reaction time. This new peak is noth-
ing but the characteristic peak of the 4-AP [40] as shown in Fig. 9 3.3.2. The inuence of the amount of catalyst
conrming the reduction of 4-NP into 4-AP. As previously mentioned, the catalyst 5Ni-CMC exhibited the
least catalytic activity. Therefore, in an attempt to increase its activ-
3.3.1. Effect of Ni2+ ratio in CMC ity, the effect of the amount of Ni-CMC on the reduction of 4-NP was
The inuence of Ni2+ ratio incorporated in CMC on the catalytic studied, and the time change of 4-NP concentration are shown in
activity toward the reduction of 4-NP by NaBH4 , was studied using Fig. 11a. The rate constant values (k, min1 ) as a function of the
the above mentioned experimental conditions. Fig. 10a shows the catalyst mass are presented in Table 3. It is clear that, the reduction
Z.M. El-Bahy, K.H. Mahmoud / Spectrochimica Acta Part A 92 (2012) 105112 111

Table 3 0
The change in the rate constant of the catalytic reduction of 4-NP with different
reaction parameters.
-1
Ni ratio (wt.%) Temp ( C) Mass (g/l) k (min1 ) Ea (kJ mol1 )

0 30 0.2 0
-2
25 0.2 0.010

ln k
0.1 0.01
0.2 0.017 -3
30 0.4 0.111 5Ni-CMC
5 145.1
0.6 0.112 10%Ni-CMC
10Ni-CMC
0.8 0.113 -4
35 0.2 0.070 20Ni-CMC
20%Ni-CMC

40 0.2 0.140 40Ni-CMC


40%Ni-CMC

-5
25 0.2 0.030 3.18 3.22 3.26 3.3 3.34
10
30 0.2 0.076
122.5 1000/T, (K-1)
35 0.2 0.202
40 0.2 0.310
Fig. 12. ln k 1/T graphs for 4-NP reduction using 0.6 g/l of the different catalysts.
25 0.2 0.250
30 0.2 0.352
20 40.7 reaction of 4-NP increases gradually with increasing the amount
35 0.2 0.433
40 0.2 0.560 of catalyst until 0.6 g/l after which, the addition of more amount
25 0.2 0.440
of catalyst will not be useful. This is clear also from the plot of k
30 0.2 0.700 (min1 ) values against the mass of the catalyst (g/l), Fig. 11b. The k
40 26.5
35 0.2 0.714 value increases with increasing the catalyst mass until 0.4 g/l after
40 0.2 0.770 which a plateau was obtained. Moreover, the conversion values of
4-NP after 20 min reaction were 7, 20, 72, 78 and 80% for the catalyst
masses of 0.1, 0.2, 0.4, 0.6 and 0.8 g/l, respectively. From foregoing
results, it is concluded that the proper amount of catalyst which
is sufcient to accomplish the reaction under the studied reaction
a 1.4 conditions is in the range of 0.40.6 g/l.

1.2
3.3.3. The inuence of reaction temperature
The pseudo-rst order rate constant values (k, min1 ) for the
1
reduction of 4-NP with the synthesized (540%)Ni-CMC catalysts
Absorbance, a.u

were calculated in the temperature range of 2540 C and the data


0.8
are listed in Table 3. The activation energy values were calculated
using the well-known Arrhenius equation:
0.6 E 
a
ln k = ln A (8)
0.4 0.1 gm/l RT
0.2 gm/l
0.4 gm/l where k is the rate constant, Ea is the activation energy, R is the ideal
0.2 0.6 gm/l
0.9 gm/l gas constant (8.314 J K1 mol1 ) and T is the absolute temperature.
* 0.8 gm/l
The Ea was calculated from the plot (ln k vs. 1/T), Fig. 12, and the data
0 are listed in Table 3. From the calculated values of Ea , it is clear that
0 10 20 30 40
the Ea values for 20 and 40Ni-CMC were 40.8 and 26 kJ mol1 which
Time, min
in coherence with the data obtained by Sahiner et al. [21] while
the activation energy values for 5 and 10Ni-CMC were relatively
b high (ca. 122 and 145 kJ mol1 , respectively) compared to the other
0.12 samples. This is due to the relatively low activity of these samples
that needs higher activation energy to proceed the reaction.

4. Conclusions
0.08
k, min-1

Thermal characteristics of nickel chloride doped carboxymethyl


cellulose lms have been assessed by DTA method. Nickel act as a
plasticizer for pure polymer where it reduces its glass transition.
0.04
Different relaxation processes appeared via dielectric spectroscopic
analysis. The -relaxation process exhibited Arrhenius behav-
ior with low activation energies. In the high temperature range
0
(100 C), the relaxation is detected. The correlated barrier hop-
0 0.2 0.4 0.6 0.8 ping model (CBH) was found to be the most suitable mechanism for
Catalyst mass. gm/l interpretation of ac conduction of the investigated samples. Pure
CMC has no catalytic activity toward the reduction of 4-NP in pres-
Fig. 11. (a) Pseudo rst-order plots of 4-NP reduction by NaBH4 in presence of dif- ence of NaBH4 as hydrogen source. Incorporating Ni2+ into CMC led
ferent amounts of 5%Ni2+ -CMC at 30 C. (b) Correlation between the mass of the
to the reduction of 4-NP to 4-AP and the catalytic activity increased
catalyst and the rst order rate constant.
proportionally with increasing the Ni ratio. The activation energy of
the reaction over 40Ni-CMC sample was found to be 26 kJ mol1 ,
112 Z.M. El-Bahy, K.H. Mahmoud / Spectrochimica Acta Part A 92 (2012) 105112

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