Chemical Engineering Journal 179 (2012) 131–139

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Chemical Engineering Journal

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Carbonate intercalated Zn/Fe layered double hydroxide: A novel photocatalyst

for the enhanced photo degradation of azo dyes
K.M. Parida ∗ , Lagnamayee Mohapatra
Colloids & Materials Chemistry Department, CSIR-Institute of Minerals & Materials Technology, Bhubaneswar 751013, Orissa, India

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

Article history: Zn/Fe layered double hydroxides with different intercalated anions (nitrate, chloride and carbonate)
Received 2 August 2011 as visible-light response photocatalysts were fabricated by co-precipitation method. The as-prepared
Received in revised form 5 October 2011 LDH photocatalysts were characterized by Powder X-ray Diffraction (PXRD), Fourier Transform Infrared
Accepted 21 October 2011
(FT-IR), Thermo Gravimetric/Differential Thermal Analysis (TG/DTA), BET surface area, SEM, TEM and
simultaneously optical absorption spectra. The photocatalytic activity of the catalysts was studied by
Keywords:
degradation of aqueous methyl violet (MV) and malachite green (MG) under solar light. Under optimal
Layered double hydroxide
conditions, among various anions intercalated samples carbonate intercalated Zn/Fe LDH exhibited high-
Intercalation
Co-precipitation
est activity. The kinetics and mechanism of photocatalytic dye degradation over Zn/Fe-CO3 LDH were also
Photocatalyst discussed.
Degradation © 2011 Elsevier B.V. All rights reserved.

1. Introduction
From the viewpoint of environmental issues, the removal of
harmful organic dye compounds is of great interest and impor-
tance [1]. Cationic dyes (malachite green and methyl violet) found
widespread use as colorants in industry and as antimicrobial
agents. Since 1990, researchers found that these azo dyes are highly
toxic, persistent, carcinogenic, and mutagenic [2,3]. It caused irre-
trievable damage to the environment if discharged into water.
Therefore, various attempts were made for its’ removal. Unlike
the conventional biodegradable or activated carbon adsorption
method, photocatalysis especially for TiO2 based photocatalytic
technology offered a powerful oxidation method in the treatment
of bio resistant organic contaminants such as dye wastewater by
converting them into CO2 [4]. Nevertheless, photocatalytic activ-
ity of TiO2 was high enough to meet the need of industrial usages
due to the rapid recombination between photo generated elec-
trons and holes. It is also UV active which makes high running
costs. In addition, it was reported that ZnO exhibited better activ-
ity than TiO2 for the photocatalytic degradation of environmental
pollutants, especially for the decomposition of dyes [5] under
ultraviolet (UV) light. Therefore, the exploration of visible light-
sensitive materials such as metal oxides (TiO2−x Nx ), sulphide (CdS),
nitride (carbon nitride) and mixed oxide (titanium–niobium mixed
oxide) were widely studied [6–9]. Meanwhile, another worth
point of light-driven photocatalyst, iron (III)-based semiconduc-
tors were also drawn increasing attention in recent years, such
∗ Corresponding author. Tel.: +91 0674 2581636 425; fax: +91 0674 2581637.
E-mail address: paridakulamani@yahoo.com (K.M. Parida).
as Fe2 O3 [10] whose application was limited because of their low
stability.
Layered double hydroxides (LDH) received much attention in
the past decades due to their vast applicability such as catalysis,
adsorption, nanotechnology and biotechnology [11–17]. The gen-
eral formula of LDH was represented by M(II)1−x M(III)x (OH)2 Ax/n ,
where M2+ and M3+ are divalent (Mg2+ , Fe2+ , Co2+ , Cu2+ , Ni2+ , Zn2+ )
and trivalent (Al3+ , Cr3+ , In3+ , Mn3+ , Ga3+ , Fe3+ ) metal ions, respec-
tively; A is an intercalate anion (CO3 2− , SO4 2− , NO3 − , F− , Cl− ).
The positive charge generated by the substitution of a part of the
divalent cations by trivalent cations in the brucite-like layers was
compensated by the presence of anions in the interlayer space, so
called anionic clay. The schematic diagram of LDH or anionic clays
presented in Fig. 1(a) LDHs are constituted by sheets of edge shared
M (OH)6 octahedral units in order to build M (OH)2 brucite like
layer structure [18], shown in Fig. 1(b). Silva et al. [19] developed a
novel series of visible active Zn-M (M = Cr, Ti, Ce) LDH photo cata-
lysts for oxygen generation from water and the result showed that
it can be regarded as a “doped semiconductor” in which ‘M (III)’
used as dopant. Recently Angeles et al. [20] reported the photo
assisted activities of Mg/Al layered double hydroxides where the
photo induced electrons in laminar structure of LDH could be easily
captured by hydroxyl groups. Shao et al. demonstrated the poten-
tial applications of Zn/Ti LDH in the field of photocatalysis [21].
In an earlier study, our group reported the photocatalytic activ-
ity of Cu(II) tetrasulphonated phthalocyanine (CuPcTs) intercalated
Zn–Al LDH for methylene blue degradation [22], but no systematic
study was available on the azo dye degradation using Zn/Fe-LDH.
Therefore, in the present study, we concerned to synthesize dif-
ferent anions (chloride, nitrate and carbonate) intercalated Zn/Fe
LDH for effective photocatalytic degradation of azo dyes. These

1385-8947/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.cej.2011.10.070
132 K.M. Parida, L. Mohapatra / Chemical Engineering Journal 179 (2012) 131–139
Fig. 1. (a) Schematic diagram of Layered double hydroxide. (b) Structural representation LDH indicating the various octahedral sites of Zn/Fe LDH.
results revealed that Zn/Fe-CO3 photocatalyst was a very perspec-
tive photocatalyst in wastewater remediation. The enhancement
of photocatalytic activity was explained on the basis of electronic
structure of LDH which played an important role for absorption
of visible light, surface hydroxyl groups, pore size distribution
and crystallite size. We opined that our results will stimulate
researchers to work on other members of LDH type of materials.
The dyes used during this study were well suited to harvest visible
light (sunlight) as an economical light source.
2. Experimental
2.1. Materials and methods
Zn (NO3 )2 ·6H2 O obtained from Fisher Scientific and
Fe(NO3 )2 ·9H2 O, ZnCl2 ·6H2 O, FeCl3 ·6H2 O, NH3 , HCl, commercial
Fe2 O3 and ZnO from Merck, were used as received. Methyl vio-
let having IUPAC name N-(4-{bis [4-(dimethylamino)phenyl]
methylidene}cyclohexa-2,5-dien-1-ylidene)-N-methyl
methanaminium chloride, M.W.: 393.958 g/mol, molecular
formula: C24 H28 ClN3 , max :584 nm and malachite green having
IUPAC name 4-[(4-dimethylaminophenyl)-phenyl-methyl]-
N,N-dimethylaniline, M.W.: 364.92 g/mol, molecular formula:
C23 H25 N2 Cl, max : 614 nm and were purchased from Merck, India
and used without further purification. The structure is exemplified
in Scheme 1. Sodium hydroxide and sodium carbonate were
obtained from S.D. Fine Chemical, India. Double distilled water
was used for preparation of various solutions.
The LDH materials used in this study were prepared by co-
precipitation method by keeping the divalent to trivalent molar
ratios 3:1 as the formation of a well crystalline LDH was established
at this proportion by Gasser and Choudhary et al. [23,24]. For Zn/Fe-
NO3 LDH, Zn(NO3 )2 ·6H2 O and Fe (NO3 )2 ·9H2 O salt solution were
mixed in a desired Zn (II)/Fe (III) 3:1 molar ratio and titrated slowly
with the basic solution of 2 M NaOH until the pH reached 10.0
at room temperature maintaining a nitrogen atmosphere. Zn/Fe-
Cl LDH was prepared by the above method by taking ZnCl2 ·6H2 O
and FeCl3 ·6H2 O. For Zn/Fe-CO3 LDH, a reddish-brown solution of
Zn (NO3 )2 ·6H2 O, Fe (NO3 )2 ·9H2 O with Zn/Fe (3:1) was added drop
wise to a vigorously stirred solution of NaOH and Na2 CO3 up to
 K.M. Parida, L. Mohapatra / Chemical Engineering Journal 179 (2012) 131–139 133

Scheme 1. Structure of methyl violet and malachite green.

pH 10.0. The resulting precipitate was filtered. The solid washed

thoroughly with deionized water and dried at 80 ◦ C for 24 h.

2.2. Photocatalytic reaction

The photocatalytic decolourization of methyl violet and mala-

chite green were performed taking 20 ml of 100 ppm solution in
100 ml Pyrex flask containing 0.02 g of catalyst. The solution was
exposed to sunlight at room temperature (33 ± 2 ◦ C) and agitated
with a magnetic stirrer. All the experiments were performed in
duplicate during the first half of May 2010 (sunny days), from
10:00 a.m. to 13:00 p.m. (radiation). The average light intensity was
around 10,4000 Lx measured by using LT lutron Lx-101A digital
light meter at every half an hour. The light intensity was found
nearly constant during the experiments with minor variation. After
irradiation, the suspension was centrifuged and the content of
methyl violet and malachite green was analysed quantitatively by
measuring the absorbance at 584 nm and 614 nm by using UV-Vis
spectrophotometer (Varian Cary 100 model EL 96043181) and the
blank reaction was also carried out by the same procedure without Fig. 2. X-ray diffraction patterns of (a) Zn/Fe-Cl LDH, (b) Zn/Fe-NO3 LDH and (c)
adding any catalyst. The decolourization of malachite green and Zn/Fe-CO3 LDH.
methyl violet due to adsorption was also measured by carrying out
similar experiments in dark.
Experiments were also performed in the presence of quenchers using Cu-K␣ radiation ( = 1.5418 Å) with a step size of 0.02◦ and
such as benzoquinone and dimethyl sulphoxide (DMSO) to find out 4 s per scan. The Fourier transform infrared (FTIR) spectra of the
the role of photogenerated oxidative species such as superoxide samples were recorded on a Varian FTIR spectrophotometer (FTS-
and hydroxyl radicals. Each quencher solution was prepared using 800) at room temperature taking KBr as the reference in the range
chemical of reagent grade (purity of 99%) with double distilled of 400–4000 cm−1 . The TG-DTA thermograms were recorded on
water. Perkin-Elmer thermal analysers in the temperature range from 30
to 800 ◦ C at a heating rate of 10 ◦ C/min in nitrogen atmosphere.
2.3. Laboratory analyses N2 adsorption–desorption isotherms were measured at 77 K by
ASAP-2020 (Micromeritics) system from which the surface area
Layered double hydroxide was identified by Powder X-Ray (BET) values were calculated. SEM images were obtained using
Diffraction (PXRD) patterns on a Rigaku XRD-600 diffractometer HITACHI 3400 N microscope. Transmission electron microscope

Table 1
Cell parameters, BET surface area, Pseudo first order reaction rate constant and t1/2 for MG and MV with different LDH photocatalysts.

Catalyst Lattice parametersa (nm)a Crystallite BET surface Pore volume Pore diameter Kapp (min−1 ) R2 t1/2 (min)
size (nm)b area (m2 /g)b (cm3 /g)b (nm)b

d0 0 3 ‘c’ ‘a’ MV MG MV/MG MV MG

Zn/Fe-CO3 0.77 2.34 0.354 28 56 0.18 19 0.036 0.032 ≥0.9 19 24

Zn/Fe-Cl 0.79 2.38 0.353 29 69 0.2 16 0.012 0.009 57 76
Zn/Fe-NO3 0.78 2.36 0.355 31 60 0.3 22 0.008 0.007 86 98
a
Calculated from XRD patterns.
b
Measured from N2 isotherms.
134 K.M. Parida, L. Mohapatra / Chemical Engineering Journal 179 (2012) 131–139

images were carried out by TEM FEI, TECNAI G2 20, and TWIN at
200 kV. The samples for electron microscopy were prepared by dis-
persing the powder in ethanol and coating a very dilute suspension
on carbon-coated Cu grids and the images were recorded by using
a Gatan CCD camera. The resolution was set at 4 cm−1 . The UV–vis
DRS spectra of the samples were recorded in a UV–vis spectropho-
tometer (Cary 100 model EL 96043181). Pellets of 2 mm thickness
were prepared taking 0.05 g of sample and boric acid together. Boric
acid was used here as a reference material since it was not optically
active and no absorption maxima present between 200 and 750 nm.
The spectra were recorded in the range of 800–200 nm.

3. Results and discussion

3.1. Structural characteristics of LDHs

Fig. 2 shows the XRD patterns of Zn/Fe-Cl, Zn/Fe-NO3 and Zn/Fe-

CO3 LDHs coded as ‘a’ ‘b’ and ‘c’. The measured XRD patterns of all
the LDHs fitted well to layered double hydroxide with basal reflec-
tions of planes h k l (0 0 3), (0 0 6), (0 1 2), (0 1 5), (1 1 0) and (1 1 3) Fig. 3. FTIR of (a) Zn/Fe-Cl LDH, (b) Zn/Fe-NO3 LDH and (c) Zn/Fe-CO3 LDH.

[25]. As the nucleation and precipitation processes were very much

controlled by slow addition of alkali, formation of free hydroxides
M (OH)3 byproduct was not observed in the XRD pattern. This indi-
cated the formation of a well crystallized LDH. The basal spacing of
the carbonate containing LDH (7.8 Å) was slightly lower than that
of Zn/Fe-NO3 LDH (7.89 Å) and Zn/Fe-Cl LDH (7.9 Å) as expected
on the basis of the higher charge density of the carbonate. The unit
cell parameters c and a, listed in Table 1, were obtained by Bragg’s
law, assuming hexagonal stacking. The ‘a’ values remained almost
constant for all the compounds; however, the ‘c’ values depend
both on the size and the charge of the anion. The average crystallite
size (D) of LDHs was determined by employing the Scherrer’s
formula (Eq. (1)) and were listed in Table 1, where  is the wave-
length of the X-ray (Cu-K␣), ˇ is the full width at half-maximum
of the diffraction peak, K is a shape factor (0.94), and  is the angle
of diffraction. Crystallite size is one of the important factors which

Fig. 4. TG and DTA of (a) Zn/Fe-Cl LDH, (b) Zn/Fe-NO3 LDH and (c) Zn/Fe-CO3 LDH.
 K.M. Parida, L. Mohapatra / Chemical Engineering Journal 179 (2012) 131–139 135

has vital role for the catalytic activity. Here the crystallite size
followed the trend of Zn/Fe-NO3 > Zn/Fe-Cl > Zn/Fe-CO3 .
K
D= (1)
ˇ cos 
The FT-IR spectra of Zn/Fe-Cl, Zn/Fe-NO3 and Zn/Fe-CO3 LDHs
are shown in Fig. 3. The absorption bands below 1000 cm−1
were M–O vibration modes of LDH and the patterns were very
similar for the three LDHs. The ϑH–O–H Bending and ϑO–HSym
bands in these compounds appeared in the ranges 1610–1630 and
3440–3470 cm−1 , respectively. The spectrum of Zn/Fe-CO3 LDH
showed an intense band at around 1370 cm−1 associated with the
carbonate ion, whilst that of Zn/Fe-NO3 LDH showed an intense
band at 1384 cm−1 associated with the nitrate ion and 868 cm−1
corresponded to Cl− ion vibration in Zn/Fe-Cl LDH [26]. The TG-
DTA curves of Zn/Fe-Cl, Zn/Fe-NO3 and Zn/Fe-CO3 LDHs presented
in Fig. 4 may be divided into two well-differentiated regions. An
endothermic peak relating to the dehydration of the physisorbed
water molecules from the external surface of the LDH was noticed
in the temperature range150–250 ◦ C. The second region, ranging
from 350 to 600 ◦ C corresponded to the weight loss due to the
dehydroxylation and de-carbonation reactions [27,28].
Nitrogen adsorption–desorption isotherms at 77 K for Zn/Fe-Cl,
Zn/Fe-NO3 and Zn/Fe-CO3 LDHs are revealed in Fig. 5. For Zn/Fe-
NO3 and Zn/Fe-Cl, the isotherms were of type IV with a broad H3
type hysteresis loop (P/P0 ) > 0.4 indicating mesoporous solids with
slit-shaped irregular pores [29]. According to IUPAC classification,
Zn/Fe-CO3 , followed type IV isotherm with H2 hysteresis loop indi-
cating mesoporous and regular with narrow pore size distribution.
As the binding strength of the divalent anion with a basic layer was
more than that of the monovalent anion, the surface are followed
the pattern Zn/Al-Cl ≥ ZnAl-NO3 ≥ ZnAl-CO3 (Table 1). Though sur-
face area, pore size and pore volume were slightly different, but
Zn/Fe-CO3 showed improved photocatalytic activity due to well
defined pore size distribution. SEM images (Fig. 6) of the prepared
LDHs indicated that all were agglomerated and possessed plate-
like morphology lying on top of one another [30]. These aspects
were typical for hydrotalcites prepared by co-precipitation method.
The TEM micrograph and the selected area electron diffraction
(SAED) pattern (Fig. 7) showed that all prepared LDHs were crys-
tallites, plate like morphology and uniformity in nature. This could
be attributed to a homogeneous and slow nucleation process [31].

3.2. Photo absorption properties

It is well-known that light absorption by the materials and the

migration of the light-induced electrons and holes are the key fac-
tors controlling a photocatalytic reaction which is relevant to the
electronic structure of the material. In principle, the photo absorp-
tion of the photocatalyst depends on the mobility of electron–hole
pairs, which determines the probability of electrons and holes to
reach reaction sites on the surface of the photocatalyst. The photo
absorption properties of all LDH materials detected by UV–vis DRS
are illustrated in Fig. 8. It could be seen that the absorbance of the
semiconductors extended to the visible light region. For a crys-
talline semiconductor; it is known that the optical absorption near
Fig. 5. N2 adsorption–desorption curves of (a) Zn/Fe-Cl LDH, (b) Zn/Fe-NO3 LDH and
the band edge followed the equation,
(c) Zn/Fe-CO3 LDH.
n/2
˛h = K(h − Eg ) (2)
where ˛, , K, and Eg are the absorption coefficient, light fre- near the band edge. When this method was used, the n value was
quency, proportionality constant, and band gap, respectively. In the determined as 1, indicating the directly allowed optical transition.
equation, ‘n’ decides the characteristics of the transition in a semi- Second, plot (˛h)2/n vs. h and then evaluated the band gap Eg by
conductor [32]; 1 or 3 for a direct allowed transition and 4 or 6 for extrapolating the linear region straight line to the h axis intercept
an indirect transition and determined by the following steps: first, by means the value of n.
plot ln(˛h) vs. ln(h − Eg ), using an approximate value of Eg , and It was remarkable that the band gap of LDHs were estimated
then determined the value of n with the slope of the straightest line to be 2.16, 2.2, and 2.4 eV for Zn/Fe-CO3 , Zn/Fe-Cl and Zn/Fe-NO3
136 K.M. Parida, L. Mohapatra / Chemical Engineering Journal 179 (2012) 131–139

Fig. 6. SEM images of (a) Zn/Fe-Cl LDH, (b) Zn/Fe-NO3 LDH and (c) Zn/Fe-CO3 LDH.

Fig. 7. A representative low magnification TEM image (a) Zn/Fe-Cl LDH, (b) Zn/Fe-NO3 LDH and (c) Zn/Fe-CO3 LDH and the corresponding selected area diffraction pattern
of image (d) Zn/Fe-Cl, (e) Zn/Fe-NO3 and (f) Zn/Fe-CO3 LDH.

respectively indicating narrower band gap of Zn/Fe-CO3 compared

to that of Zn/Fe-Cl and Zn/Fe-NO3 . This implied that the photo
absorption of Zn/Fe-CO3 was stronger than that of other two owing
to synergetic effect of carbonate, which resulted in a higher photo-
catalytic activity of than that of Zn/Fe-Cl and Zn/Fe-NO3 [33–36].

3.3. Photocatalytic activities

Fig. 8. UV–vis diffuse reflectance spectra of (a) Zn/Fe-Cl, (b) Zn/Fe-NO3 and (c)
Zn/Fe-CO3 LDH.
3.3.1. Effect of pH
The effect of pH on the photocatalytic degradation of basic dyes
(MG and MV) was studied in the range 5–10 at 0.1 g/L dye con-
centration and 1 g/L photocatalyst loading. The result showed that
the rate of decolourisation decreased in the pH range 5–9 and then
increased with increasing pH up to 10.0 (Fig. S1). It is well known
that the photocatalytic degradation of dye is a complicated process
in which its adsorption on the catalyst surface is the first step. The
photocatalytic performance of LDHs was attributed to the surface
electrical properties due to different interlayer anions. The superior
surface potential of the Zn/Fe-LDHs facilitated the dye adsorption,
which is beneficial to promote the transfer of the light-generated
 K.M. Parida, L. Mohapatra / Chemical Engineering Journal 179 (2012) 131–139 137

charge carriers (OH groups) to the surface. Therefore, Zeta poten-

tial was recommended to shed light on the surface potential of
various LDHs, which closely related with the photocatalytic per-
formance. The pHs of isoelectric point or points of zero charge
(pzc) of LDHs were 8.7, 8.5, and 8.4 for Zn/Fe-CO3 , Zn/Fe-Cl and
Zn/Fe-NO3 , respectively. At pHpzc the interaction between the pho-
tocatalyst particle and the dye molecule is minimal due to absence
of electrostatic forces. At pH > pzc, the surface would be negatively
charged and the electrostatic attraction effect between the nega-
tively charged catalyst surface and the hydroxyl radicals favored
the decomposition of dye molecules [37]. Moreover, the pH of the
dye solution greatly influenced the degradation process. So, we
conducted photocatalytic degradation of dyes at pH 10.

3.3.2. Photolysis, control experiments and photocatalysis

reactions
Three sets of photocatalytic reactions were performed using
LDHs. First, the experiments without photocatalyst under visible
light irradiation resulted in a small amount of MV (0.9%) and MG
(1.1%) degradation indicating photolysis reaction. Next the control
experiments performed in the dark condition for 1 h, indicated the
adsorption of dyes on the active sites of the catalyst. It could be
seen that an equilibrium state of dye (MG and MV) adsorption was
reached within 1 h. The percentage of adsorption of dyes followed
the order: Zn/Fe-Cl (23%) > Zn/Fe-NO3 (21%) > Zn/Fe-CO3 (18%) for
MV and Zn/Fe-Cl (24%) > Zn/Fe-NO3 (22%) > Zn/Fe-CO3 (20%) for MG
in commensurate with that of surface area. Then the solution was
stirred under visible light irradiation for photocatalytic reaction.
All three LDH photocatalysts showed higher activities compared
to ZnO (∼40%) and Fe2 O3 (∼45%) for degradation of MV and MG
under solar light irradiation (Fig. 9(a) and (b)). In comparison with
the photocatalytic activities of different LDHs, the carbonate inter-
calated LDH showed highest photocatalytic activity (99%, 98.5%)
compared to chloride intercalated LDH (75%, 72%) and nitrate inter- Fig. 9. Photolysis, adsorption and photocatalytic degradation of (a) MV (b) MG in
calated LDH (66%, 64%) for MV and MG degradation after 2 h of aqueous solution (100 ppm) with all as prepared LDHs, ZnO and Fe2 O3 .
reaction. The spectra of both the dyes (methyl violet and malachite
green) are presented in Fig. 10(a) and (b), respectively, where it
confirmed that Kapp was enhanced in the carbonate, then chloride
could be seen that the dyes were almost completely decolourised
intercalating LDH followed by nitrate.
after 2 h.
The reuse, regeneration and stability of a novel photocatalyst
In addition, we performed the kinetics of MV and MG dye
had significant impact on the removal process, hence made the
degradation over ZN/Fe-CO3 photocatalyst. It illustrates the photo
application of the materials more economical. Here, the catalysts
catalytic degradation of dyes as a function of irradiation time in the
(after completion of dye degradation) were regenerated by cen-
presence of different LDHs which followed Langmuir–Hinshelwood
trifuging in water and ethanol solutions (two times with each) for
model [38] as expressed in Eq. (3).
complete cleaning of the catalysts. Then the catalysts were dried at
−dC 80 ◦ C for 10 h and reused for another cycle keeping the concentra-
r= = Kr KC = Kapp C (3) tion of dyes and photocatalyst constant. Even after five cycles, no
dt
remarkable change in the dye degradation activity was observed as
where r is the degradation rate of dyes, Kr is the reaction rate con- shown in Fig. S2(a) and (b). This indicated the stability of the LDH
stant, C is the reactant concentration. When C was very small, then photocatalysts.
KC was negligible; so that Eq. (1) became first order kinetic. Setting
Eq. (3) under initial conditions of photocatalytic procedure, (t = 0, 3.4. Mechanism and discussion on visible light photocatalytical
C = C0) , it became Eq. (4). reaction using LDHs
C0
ln = Kapp t (4) According to the experimental results, a possible mechanism
C
was proposed and discussed as followed. The photocatalytic pro-
C0 was the initial concentration of dye and C was the concentration cess started with the activation of a catalyst by radiation with
at time ‘t’. By using Eq. (4), we calculated the apparent rate constant higher energy than that of the band gap of catalyst. In this case,
from the gradient of the graph of ln(C0 /C) verses irradiation time. the excited electrons of d5 Fe: 3d ions in FeO6 octahedron were
The apparent rate constant of photocatalytic activity was indepen- promoted from the valence band to the conduction band yielding
dent of adsorption and the concentration of the dye remaining in holes and photo generated electrons. The photo generated holes
the solution. The variations of ln(C0 /C) as a function of irradiation (hVB + ) reacted with water to form hydroxyl radicals (OH• ) and also
time are given in Fig. 11(a) and (b) for MV and MG respectively and the photo generated electrons (eCB − ) absorbed by dioxygen to form
the corresponding Kapp (kinetic constant), t1/2 parameters (time superoxide (O2 −• ) radicals, which were highly oxidizing species.
required to degrade half of the initial concentration of dye) and LDHs also acted as doped semiconductor and Fe+3 exhibited to
regression relative coefficient values are given in Table 1, which be more effective dopant for enhancing the photocatalytic activity
138 K.M. Parida, L. Mohapatra / Chemical Engineering Journal 179 (2012) 131–139
Fig. 10. Absorption changes in photocatalytic degradation of (a) MV and (b) MG in
different time over Zn/Fe-CO3 sample under visible light radiation.
[39] by shifting the light absorbance towards visible range. Also the
hydroxide groups present in LDH surface captured the photo pro-
duced holes (h+ ) consequently preventing the recombination of the
hole and electron as a result improved the photocatalytic activity
[40]. Compared to all intercalated LDHs, Zn/Fe-CO3 showed more
activity due to some factors as discussed below. The important fac-
tors were crystallite size, i.e. small crystallite size (detected from
XRD pattern and Scherrer’s formula), facilitated the rapid transfer
of photoelectrons from bulk to the surface, which could effectively
inhibit the recombination between photoelectrons and holes, lead-
ing to improved photo activity [41]. Another factor influenced the
activity was pore size distribution as disused previously where as
an extra factor was band gap energy. We observed that the red
shift of Zn/Fe-CO3 and Zn/Fe-Cl as compared to Zn/Fe-NO3 , was due
to the effect of carbonate and chloride ions in the interlayer. The
lower activities of ZnO and Fe2 O3 were owing to that, ZnO photo-
catalyst activated only under UV irradiation because of their large
band gap, which greatly limits their application in environmental
decontamination as solar spectra only contain 5% of UV and in the
case of Fe2 O3 the limitations over photocatalytic applications con-
sist of the low band gap energy (2.2 eV), poor conductivity and high
electron-hole Therefore, it is crucial to explore by surface modifica-
tion for efficient photocatalytic response. The tentative mechanism
for photocatalytic degradation (mineralization) of azo dyes may be
proposed as follows:
Catalyst + h → Catalyst (eCB − + hVB + ) (5)
Catalyst (hVB + ) + H2 0 → Catalyst + H+ + OH• (6)
Fig. 11. Pseudo-first order kinetics of (a) MV (b) MG for Zn/Fe-CO3 LDH.
Dye + OH• → Dye product (DP) (7)
− −•
Catalyst (eCB ) + O2 → Catalyst + O2 (8)
O2 −• + Dye → Dye product (DP) (9)
The formation of oxidative intermediate species such as super-
oxide (O2 −• ) and hydroxyl radicals (OH䊉 ) under photo-reaction
conditions and their role in the dye degradation process was inves-
tigated indirectly with the use of appropriate quenchers of these
species such as benzoquinone (BQ) [42] and dimethyl sulphoxide
(DMSO) [43]. In Fig. S3, a comparison study was made between the
original decolourization of MV, MG dyes and solutions obtained
after addition of millimolar concentrations of quenchers in the ini-
tial dye solution.
4. Conclusions
Zn/Fe LDHs with different intercalated anions were synthesized
by co-precipitation method. The prepared LDHs showed higher
photocatalytic activity for degradation of azo dyes (methyl vio-
let and malachite green) compared to commercial ZnO and Fe2 O3
under solar light irradiation. This result implies that Fe+3 ions
located in the FeO6 octahedrons of Zn/Fe LDH structure played
an important role in the absorption of visible light, suggesting a
new route to design visible-light-driven photocatalysts. The car-
bonate intercalated LDH showed highest photocatalytic activity
compared to other anion intercalated LDHs and neat ZnO and Fe2 O3 .
The synergy of average crystallite size, well-defined mesoporosity
with narrow and regular pore size distribution and also band gap
energy are the factors responsible for higher activity. This work
 K.M. Parida, L. Mohapatra / Chemical Engineering Journal 179 (2012) 131–139
may provide useful informations on development of some effec-
tive LDH catalysts for degradation of pollutants under visible-light
irradiation for wastewater treatment.
Acknowledgement
The authors are thankful to Prof. B.K. Mishra, Director, Institute
of Minerals & Materials Technology (IMMT), Bhubaneswar, for his
constant encouragement and kind permission to publish this paper.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.cej.2011.10.070.
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