Sharma et al. Int. J. Res. Chem. Environ. Vol.

3 Issue 2 April 2013(113-119)

International Journal of Research in Chemistry and Environment

Vol. 3 Issue 2 April 2013(113-119)
ISSN 2248-9649

Research Paper

Use of Nickel Hexacyanoferrate(II) Semiconductor in Photocatalytic Degradation

of Neutral Red Dye
*Sharma Omprakash, Mukesh Kumar and Sharma Mohan Kumar
Department of Chemistry, M. S. J. Govt. (P.G.) College, Bharatpur (Raj.) -321001 INDIA

Available online at: www.ijrce.org

(Received 03rd December 2012, Accepted 16th January 2013)

Abstract: Nickel hexacyanoferrate(II) was synthesised by reaction of potassium hexacyanoferrate and

Nickel Chloride. It was characterised by IR spectra, X-ray diffraction and cyclic voltametry. The
photocatalytic degradation of Neutral red dye was studied using Nickel hexacyanoferrate(II) as
semiconductor under visible light irradiation. The rate of photocatalytic degradation of dye was
observed spectophotometrically. The effect of variation of different parameters like pH, concentration of
dye solution, amount of semiconductor and Intensity of light on the rate of photocatalytic degradation
has been observed and optimum condition for each parameter has also been determined. This
photocatalytic degradation reaction was found to follow pseudo first order kinetics. A tentative
mechanism for the photocatalytic degradation of Neutral red has been proposed.

Keywords: Photocatalyst, Neutral red dye, Nickel hexacyanoferrate(II), Semiconductor (SC), Optical density
(OD).

Introduction promising technology for solving the problem of

Textile dyes produce huge amount of polluted
effluents that are normally discharged to surface water
bodies and ground water aquifers. This waste water
causes disturbance to the ground water resources. In
spite of many uses, the dyes are toxic and carcinogenic
in nature.Coloured solution containing dyes from
industrial effluents of textile, dyeing and printing
industries may cause skin cancer due to
photosensitisation and photodynamic[1-3]. Adverse
effect of some dyes on environment and human such
as skin, lungs and other respiratory disorders are also
reported [4-6]. Most of the dyes used in the textile
industries are stable to light and non biodegradable [7].
Thus it is necessary to treat waste water before
discharging it into the ground water resources.
Dyes waste water has been traditionally
treated by physical or chemical techniques[8] including
flocculation, adsorption, membrane filtration,
electrolysis, ion exchange, electro kinetics, coagulation
advanced chemical oxidation photo-catalysis etc. But,
most of these methods have difficulty in practical use.
Recently, semiconductor photocatalysis has
emerged as an alternative to conventional methods.
Semiconductor photocatalysis has been predicted as a
113
environmental pollution. Photocatalyst are used to
degrade organic pollutants in water to less harmful
inorganic materials [9].
Various photocatalyst like oxides[10-13],
sulphides[14,15], combination of sulphides of two
metals[3,16], oxides of two metals[17,18] are used to
decolourise different dyes. Luan et al[19] established
the Structural, photophysical and photocatalytic
properties of novel Bi2AlVO7 and used it as
photocatalyst for the photochemical degradation of
methylene blue dye. Nanoparticles of CaZnO2
synthesized by Gopalappa et al[20] were used in solar
photocatalytic degradation of azo dye acid orange-7.
Yaneyama et al[21] studied the photocatalytic reduction
of dichromate ions using WO3 powder in acidic range.
Shyama and Arakawa[22] have used Zirconium dioxide
as photocatalyst in photocatalytic decomposition of
water and photocatalytic reduction of carbon dioxide.
Now different transition metal complexes are
also used as photocatalyst for phocatalytic degradation
of various dyes and organic compounds. D. Sachdeva
et al[23] and S. Sharma et al[24] used ammonium
phospomolybdate as photocatalyst for the
photochemical degradation of Fast green and Janus
 Sharma et al. Int. J. Res. Chem. Environ. Vol.3 Issue 2 April 2013(113-119)
green B respectively. Potassium trioxalatoferrate(III)
used by Jhala et al[25] for the decolourisation of neutral
red dye. In our previous study copper
hexacyanoferrate(II)[26] and Nickel
hexacyanoferrate(II)[27] established as semiconductor
in photocatalytic degradation of Amidoblack-10B.
In the present study Nickel
hexacyanoferrate(II) was used as Semiconductor in the
photocatalytic degradation of Neutral red dye. Since it
is water insoluble complex, thus after treatment of
polluted water, it is easy to remove semiconductor.
Now, treated water may be recycled in the same
factory or reused in other applications such as other
industries or agriculture, in which less quality of water
is required.
Neutral red is a basic dye of the azine series.
It is widely used as a biological stain for a variety of
purposes including the demonstration of gonococci
and other intracellular Gram-negative bacteria, for the
supravital staining of blood, differentiation of living
and dead cells etc. and it is also used as an indicator(
pH 6.8-8.0, pinkish- red-brown- yellow). It is also
used for desensitizing photographic emulsions [28].
Neutral red Dye
Material and Methods
Chemicals: Neutral red dye [LobaChemie], Nickel(II)
Chloride[Merck], Potassium hexacyanoferrate(II)
[Merck], Sulphuric acid(BDH) and Sodium
hydroxide(Merck) are used in present investigation.
Double distilled water was used for the preparation of
solutions.
Apparatus and Instruments: Electronic balance
(Citizen Scale Model-CY 204), Digital pH meter
(Systronics Model - 335) and Spectrophotometer
(Systronics Model-106), were used for the
measurement weight of different chemicals, pH and
absorbance (OD) of dye solution respectively.200W
tungsten lamp (Philips) was used for irradiation.
Infrared studies of the complex were performed by
FTIR (Jasco -6100, Mumbai,India) from Pune
University, Maharashtra.X-ray diffraction spectrum of
Ni(HCF) were performed by using XRD pro
Panalytical system ( Dept. of physics university of
Rajasthan, Jaipur).Cyclic voltamgram of complex
were obtained by using a BAS CV 50W
electrochemical analyzing system .
Synthesis characterisation of Nickel
114
hexacyanoferrate(II): For the preparation of Nickel
hexacyanoferrate(II), 0.1M solution of Potassium
hexacyanoferrate and 0.1M Nickel(II) chloride were
prepared. Then added Potassium hexacyanoferrate
(167ml, 0.1M) solution slowly into Nickel chloride
(500ml, 0.1M) solution, with constant stirring
according to the method used by Kourim et al [29] and
also used by Tanveer et al [30]. The reaction mixture
was heated on a water bath at 600C about 2-3 hrs and
kept as such for 24 hrs at room temperature. Brownish
green precipitate was obtained.
The precipitate obtained was filtered and
washed thoroughly with doubly distilled water and
then dried in an oven at 600C.Nickel ferrocyanide was
characterised by elemental and spectral studies. It is
fairly stable in acids like HNO3, HCl, H2SO4etc and
base like NaOH, KOH etc. The prepared Nickel
hexacyanoferrate(II) was characterized by IR spectra.
IR Spectral data of Nickel ferrocyanide shows a broad
peak about 3447 cm-1, which is characteristics of OH
group and water molecule. Thus, some water
molecules are associated with this complex, also a
peak at around 1637 cm-1 is due to HOH bending. A
sharp intense peak at 2129 cm-1 and a broad peak at
519 cm-1 are the characteristics of cyanide coordinated
to a metal transition ion [31,32] and Fe-C stretching[33]
respectively. A broad band about500cm-1 is obtained,
which may be due to polymerisation of metal nitrogen
bond.
The synthesised complex was also examined
by XRD. X-ray diffraction measurements have been
performed by using Panalytical system having CuK,
as a radiation source of wave length = 1.5406A0
within the 2theta ranging from10 0 to 79.980(Figure 1).
Figure 1: XRD of Ni (HCF)
The clarity and sharpness of the X-ray peaks
indicate that complex is a highly crystalline in nature.
Lattice parameters for this complex are obtained as,
a=4.9168, b=9.963, c=12.234 and = = = 900, thus
 Sharma et al. Int. J. Res. Chem. Environ. Vol.3 Issue 2 April 2013(113-119)

for this complex crystal system is found as

orthorhombic lattice type. Results and Discussion
Typical Run: In order to examine the photocatalytic
activity of Nickel hexacyanoferrate(II) the
photochemical degradation of Neutral red dye has
been investigated at max= 520nm. Optical density of
irradiated solution was noted at 20 minute time
interval and graph is plotted between exposure time
and 1+logOD, which is obtained as straight line, linear
behaviour of curve shows that photocatalytic bleaching
of Neutral red dye with Nickel hexacyanoferrate (II)
follows pseudo first order kinetics. The rate constant K
for the reaction was determined using the expression

K = 2.303 x Slope

The results for a typical run are presented in

table: 1 and graphically represented in Figure: 3

Figure 2: Cyclic Voltammogram of Ni(HCF) in
ammonia solution Scan rate 100mV/Sec.
Cyclic voltametric measurements were carried
out using a BAS CV 50W electrochemical analyzing
system (E1/2 measured to an accuracy of 1.0 mv).
Cyclic voltagram of complex was recorded in
ammonia solution. A three electrode configuration
composed of Pt-disk working electrode, a pt-wire
counter electrode and Ag/AgNO3 reference electrode
was used for measurement.
Effect of pH: The pH is the most important factor
which affects the photochemical degradation of
Neutral red dye. The effect of pH on the photocatalytic
degradation of Neutral red dye was studied in the pH
range 3.0 to 6.0, keeping all other factor identical. The
results are represented in the table: 2 and graphically
presented in Figure: 4.
Table 1
[Neutral red] = 6.2x10-5M, Amount of SC=0.150g
Light intensity = 51.0 mWcm-2, pH=4.5

In the above cyclic voltammogram, in forward Time(min) OD 1+logOD

scan (from -1.0 to 0.5V) two oxidation peaks were 0 0.887 0.9479
observed having peak potentials (EP)-0.41168 and 20 0.753 0.8768
0.12543V.Where as, in reverse scan (potential from 40 0.714 0.8537
0.5 to -1.0V) tworeduction peak were observed at (EP) 60 0.595 0.7745
-0.14313 and 0.63141V. These are corresponding to 80 0.474 0.6758
one electron exchange [34] between Fe+2 and Fe+3. 100 0.442 0.6454
Thus, this complex[35] may be used as oxidant or 120 0.397 0.5988
reductant in photochemical reactions depending on the K=1.157x10-4 Sec-1
nature of dye and reaction conditions.

Procedure of photochemical degradation of Neutral Table 2: Effect of pH

red dye: 1.0x10-3 M Neutral red dye solution was [Neutral red]=6.2x10-5M, SC=0.150g
prepared by dissolving 0.2888g of neutral red dye in Light intensity = 51mW cm-2
1000mL of doubly distilled water and it was used as
stock solution and further diluted as and when pH K x 104(Sec-1)
required. The desired pH of the solution was adjusted
3.0 0.217
by adding previously prepared standardised solutions
of H2SO4 and NaOH and measured by a digital pH 3.5 0.821
meter. 0.150g of Nickel hexacyanoferrate(II) was 4.0 1.065
added to 50.0mL 6.2 x 10-5M Neutral red dye solution. 4.5 1.157
Irradiated was carried out by a200W tungsten lamp. A 5.0 1.106
water filter was used to remove thermal degradation. 5.5 0.719
The optical density of this solution was recorded at 6.0 0.497
regular time interval by spectrophotometer. Before
measuring OD Nickel hexacyanoferrate (II) (SC) was
removed with the help of centrifuging machine.

115
 Sharma et al. Int. J. Res. Chem. Environ. Vol.3 Issue 2 April 2013(113-119)

Table 3
Effect of Neutral red concentration
SC = 0.150g pH = 4.5Light intensity = 51mWcm-2

[Neutral red] x 105M Kx104(Sec-1)

5.0 0.615
5.2 0.709
5.4 0.869
5.6 0.931
5.8 0.989
6.0 1.081
6.2 1.157
6.4 1.125
6.6 1.077
Figure 3: A Typical run
6.8 0.953

Figure 4: Effect of pH

It has been observed that the optimum rate of

bleaching of Neutral red dye with Nickel hexacya-
noferrate(II) was obtained at pH=4.5. The rate of pho-
tocatalytic bleaching of neutral red dye decreases with
decrease in the pH below the optimum value. This
behaviour may be explained on the basis that as the pH
was lowered (pH = < 4.5) the surface of the semico-
nductor becomes slightly positively charged and the
dye molecule may becomes protonated causing a force
of repulsion between the surface of semiconductor and
the protonated dye molecules. This will decrease the
rate of reaction on the other hand, the rate of photo-
catalytic bleaching of neutral red dye also decrease
with increase in the pH above the optimum value. This
may be due to the fact that at higher pH (pH = > 4.5)
the OH- ions are absorbed on the surface of semic-
onductor making it negatively charged and as a result,
the anionic dye molecule will experience a force of
repulsion causing a decrease in the rate of reaction.
Effect of Neutral red dye concentration: The
concentration of neutral red dye solution also affects
the rate of photochemical bleaching. The effect of
variation of neutral red concentration on the rate of
reaction was also studied by using different
concentration solutions of neutral red. The results are
reported in table: 3 and graphically presented in Fig: 5
116
Figure 5: Effect of Dye Concentration
It has been observed that the rate of
photocatalytic bleaching increases with an increase in
the concentration of the dye up to 6.2x10-5M. This
behaviour may be explained on the basis that as the
concentration of neutral red dye was increased, more
dye molecule will be available for excitation and
consecutive energy transfer, hence increase in the rate
of photochemical bleaching was observed. On the
further increase in the concentration of dye (above
6.2x10-5M), the rate of photochemical bleaching
decreases. This is probably due to the fact that after
certain limits of dye concentration, dye molecule
present in the upper layer of the solution will absorb a
major portion of light. This will prevent the incident
light to reach the dye molecule in the bulk of solution.
Thus, high concentration of dye acts as a filter for the
incident light and hence at higher concentration, the
rate of bleaching of dye decreases.
Effect of amount of semiconductor: The amount of
SC also affects the rate of photcatalytic bleaching of
dye. The effect of amount of Nickel
hexacyanoferrate(II) powder on the rate of
photocatalytic bleaching of neutral red dye was
 Sharma et al. Int. J. Res. Chem. Environ. Vol.3 Issue 2 April 2013(113-119)

studied. The results are reported in table: 4 and neutral red dye increases on increasing the intensity of
graphically presented in Fig: 6. light. It may be explained on the basis that as the light
intensity is increased the number of photons striking
Table 4 per unit area of SC are also increased. This will result
Effect of amount of semiconductor in a corresponding increase in the rate of
[Neutral red]=6.2x10-5M pH=4.5 photocatalytic bleaching of neutral red dye. However,
Light intensity = 51mWcm-2 higher intensities are avoided due to thermal effect.
Amount of SC in gram Kx104(Sec-1)
0.050 0.578 Table 5
0.075 0.705 Effect of light intensity
0.100 0.816 [Neutral red]=6.2x10-5M, pH=4.5, SC = 0.150g
0.125 0.928
0.150 1.157 Light intensity i Kx104(Sec-1)
0.175 1.146 n mWcm-2
0.200 1.160 35 0.685
0.225 1.158 38 0.731
41 0.778
44 0.861
47 0.929
50 1.052
51 1.157

Figure 6: Effect of amount of Semiconductor

From above data, it has been observed that

rate of photocatalytic degradation of dye is increases
with increase in the amount of Nickel
hexacyanoferrate (II) up to 0.150g. But beyond 0.150g Figure7: Effect of light Intensity
the rate of reaction remains almost constant. It may be
explained on the fact that, as the amount of Mechanism: On the basis of experimental
semiconductor is increased exposed surface area of SC observation, a tentative mechanism has been proposed
will also increased, thus more radiation will be for bleaching of neutralred by Nickel
absorbed by SC, thus an increase in the rate of reaction hexacyanoferrate(II).
is observed. But, after this certain limiting amount of 1 1
SC (0.150g), if the amount of SC was further increased Dye0 + h Dye1(Singlet excited state)
it will not contribute in the exposed surface area. This 1 3
is also confirmed by using reaction vessel of different Dye1 Dye1(Triplet excited state)
dimension. Thus, after certain amount of SC, the SC + h e + h+ or SC+
-

saturation point like behaviours is observed. 3

Effect of intensity of light: The effect variation of
light intensity on the rate of photocatalytic bleaching
of neutral red dye was also observed. The results are
reported in table: 5 and graphically presented in Figure
6.
As indicated from the above data, it has been
observed that rate of photocatalytic degradation of
117
Dye1 + e- Leuco-Dye
Leuco-Dye Product
When solution of dye, neutral red, was
exposed to light in presence of semiconductor Nickel
hexacyanoferrate(II); initially, the dye molecules,
present in singlet ground state(1Dye0), absorb the
radiation of suitable wavelength and then excited to
 Sharma et al. Int. J. Res. Chem. Environ. Vol.3 Issue 2 April 2013(113-119)
their first excited singlet state(1Dye1). These excited
singlet molecules were converted to the triplet excised
state through inter system crossing (ISC).
Semiconductor also absorb light to excite its electron
from valence band to conduction band; thus, leaving
behind a hole in the balance band. The electron of the
SC will reduce the dye molecule to its colourless
Leuco form which is ultimately degraded into final
products.
Conclusion
Neutral red dye can be successfully degrading
using nickel hexacyanoferrate(II) semiconductor under
visible light irradiation. Thus, Nickel hexacyanoferrate
(II) may act as a photocatalyst quite effectively to
photodegrade different dye molecules to colourless
less toxic products.
Acknowledgement
The authors are thankful to Prof. Suresh C.
Ameta, Director, Pacific College of Basic and Applied
Sciences, Pacific University, Udaipur for helpful
discussions and valuable suggestions. Authors are also
thankful to the principal, M.S.J. Govt. College,
Bharatpur for providing laboratory facilities. We are
also thankful to Mr. Deepak Rajawat for Cyclic
voltammetric studies from Dayalbagh Deemed
University, Agra and also Dr Balram Sharma for
performing and analysing XRD spectrum.
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