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Photocatalytic performance of ZnO nanomaterials for self sensitized

degradation of Malachite Green dye under solar light

Article in Applied Catalysis A General · October 2014

DOI: 10.1016/j.apcata.2014.10.053

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 Applied Catalysis A: General 490 (2015) 42–49

Contents lists available at ScienceDirect

Applied Catalysis A: General

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

Photocatalytic performance of ZnO nanomaterials for self sensitized

degradation of malachite green dye under solar light
Lakshi Saikia a,b,∗ , Diganta Bhuyan a , Mrinal Saikia a,b , Banajit Malakar a ,
Dipak Kumar Dutta a , Pinaki Sengupta a
a
Materials Science Division, CSIR-North East Institute of Science and Technology, Jorhat 785 006, Assam, India
b
Academy of Scientific & Innovative Research, New Delhi, India

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

Article history: ZnO nanomaterials of different morphologies are synthesized by different methodologies. These semicon-
Received 6 August 2014 ductor photocatalysts are potentially explored for self-sensitized photodegradation of malachite green
Received in revised form 14 October 2014 (MG) dye in water in a batch reactor. The effects of various parameters like initial dye concentration, cat-
Accepted 25 October 2014
alyst loading, solution pH, light source on degradation efficiency was also investigated. The experimental
Available online 4 November 2014
results showed substantial reduction of COD, besides removal of colour. The photodegradation of MG
dye followed the pseudo first order kinetics of Langmuir–Hinshelwood model. The hydrothermally syn-
Keywords:
thesized flower shaped homocentric pencil like ZnO nanorod bundles exhibit excellent photocatalytic
Self-sensitized photodegradation
Malachite green dye
activity under solar light. A comparative study of photodegradation efficiency among ZnO nanoparti-
ZnO nanomaterials cles, ZnO nanoparticles (hydrothermal) and flower shaped homocentric pencil like ZnO nanorod bundles
Langmuir–Hinshelwood were also performed. Semiconductor photocatalysis often leads to partial or complete mineralization of
Warburg apparatus organic pollutants. The CO2 gas evolved due to mineralization of MG was determined using Warburg
manometric method under solar light. The possible mechanism of photodegradation under both solar
and UV light were also proposed.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction effects [4,5]. Therefore, it is necessary to find an effective method of

wastewater treatment in order to remove this hazardous dye from
The growing population has led to the increase mainly con- industrial effluents.
tamination of surface and ground water in recent years. Organic A large number of processes have applied for the treatment of
dyes used in textile and food industries are main sources of this dye containing wastewater such as adsorption [6], biological
the environmental contaminations due to their non-bio degrad- treatment [7,8], and heterogeneous photocatalysis [9–13]. In order
ability and high toxicity to aquatic creatures and carcinogenic to decrease the damage caused by organic dye pollution to envi-
effects on humans. Malachite green (MG) (Color Index No. ronment and humans, the use of photocatalyst to degrade organic
42000), also called basic green 4 or Victoria green B, having compounds in contaminated air or water or to convert them into
IUPAC name 4-[(4-dimethylaminophenyl)-phenyl-methyl]-N,N- harmless chemicals has been extensively studied [14]. Therefore,
dimethylaniline with chemical formula C23 H25 N2 Cl, is a green heterogeneous photocatalysis is an interesting area of research as
crystal powder with a metallic luster, highly soluble in water and by this method complete mineralizations of these environmentally
ethanol with blue–green solutions [1]. This dye has been used as hazardous dyes are possible [13].
food colorings additive, dye in the silk, leather, wool, jute, cotton, TiO2 and ZnO nanopowder are generally used as effective
paper and acrylic industry [2,3]. However, MG as well as its reduced and nontoxic semiconductor photocatalysts for the degradation of
form leucomalachite green has adverse effect on reproductive and range of organic chemicals and synthetic dyes. The size and shape
immune system and it shows potential genotoxic and carcinogenic of these photocatalysts are one of the most important factors. There
are many comparative studies about the photocatalytic efficiency
of pollutants between TiO2 and ZnO, which emphasized the effec-
∗ Corresponding author at: CSIR-North East Institute of Science and Technology,
tiveness of TiO2 or ZnO. However, the problem is the great size
Materials Science Division, Jorhat 785006, Assam, India. Tel.: +91 376 2370 081;
discrepancy of the two different kinds of photocatalysts [15–19].
fax: +91 376 2370 011. ZnO has nearly the same wide band gap as TiO2 but in some cases
E-mail address: lakshi saikia@yahoo.com (L. Saikia). it was reported to be a better photocatalyst than TiO2 [20–24]

http://dx.doi.org/10.1016/j.apcata.2014.10.053
0926-860X/© 2014 Elsevier B.V. All rights reserved.
 L. Saikia et al. / Applied Catalysis A: General 490 (2015) 42–49 43

and ZnO is more suitable for photodegradation of dyes in pres- 2.2.1. Synthesis of ZnO nanoparticles by colloidal precipitation
ence of sunlight which is another advantage for practical use of method
photocatalyst in wastewater treatment [18]. The use of TiO2 for ZnO nanoparticles were synthesized by slight modification
large scale wastewater is not economical so ZnO would be a pos- of method described by Tayebee et al. [29]. 0.5 M zinc acetate
sible replacement of TiO2 because of its low cost. Its efficiency dihydrate solution was prepared in 50 mL absolute ethanol. This
is reported to be particularly noticeable in the advanced oxida- solution was refluxed for 6 h at 80–85 ◦ C under continuous
tion of pulp mill bleaching wastewater [25], the photooxidation of magnetic stirring. Thereafter, the precipitate was collected by
2-phenylphenol and photocatalytic oxidation of phenol [26]. The decantation from the ethanol and dried at room temperature. The
photodegradation of malachite green by heterogeneous photocat- precipitate was then calcined in an electric furnace at 450 ◦ C for
alyst under UV and solar light is reported [9–13], but in most of the 16 h and cooled to room temperature naturally.
cases either the degradation efficiency was less or took longer time
for degradation or in some cases composite materials were used as 2.2.2. Synthesis of ZnO nanoparticles by hydrothermal synthesis
photocatalyst. method
The ZnO nanomaterials of different morphology are reported ZnO nanoparticles were hydrothermally synthesized by modi-
as photocatalyst for degradation of phenol under UV light [27]. fying the method of Baruwati et al. [30]. 2 g of Zn(NO3 ).6H2 O was
Therefore, the present study is to synthesize ZnO nanomaterials of dissolved in mixture of 100 mL double distilled water and 100 mL
different morphology and to study the photodegradation of MG dye ethanol. The pH of the solution was made 9.5 by adding NH3 solu-
under solar light by the synthesized ZnO nanomaterials. The ZnO tion. The reaction mixture was stirred for 1 h and then transferred
nanomaterials of different morphology such as nanoparticles and to a 300 mL Teflon lined steel autoclave and maintained at 110 ◦ C
flower shaped homocentric pencil like ZnO nanorod bundles were temperature for 16 h. The autoclave then cooled at room temper-
synthesized in aerobic and oxygen less hydrothermal condition, ature and the product was washed with double distilled water by
respectively, as oxygen vacancy can affect the photocatalytic activ- centrifugation until the pH become neutral. The product was then
ity of ZnO nanomaterials [28]. The Warburg manometric method filtered and dried in a hot air oven at 80 ◦ C for overnight.
was used for determination of evolved CO2 from complete mineral-
ization of MG dye. The photocatalytic activity of ZnO nanoparticles 2.2.3. Synthesis of flower shaped homocentric pencil like ZnO
was thoroughly studied and comparative study with ZnO nanopar- nanorod bundles by template assisted hydrothermal method
ticles (hydrothermal) and flower shaped homocentric pencil like The flower shaped homocentric pencil like ZnO nanorod bundles
ZnO nanorod bundles are performed. The probable mechanism (hereafter will refer to as ZnO flowers) were synthesized using the
of the photodegradation under solar and UV light are also reported procedure by Bhuyan et al. [31].
proposed.
2.3. Photocatalytic degradation experiment using ZnO
nanomaterials
2. Experimental

The photocatalytic (PC) activity of ZnO nanomaterials were eval-

2.1. Materials and method
uated for photodegradation of aqueous solution of MG dye under
solar light. In a typical experiment, 100 mL of 0.2 g L−1 MG dye solu-
All chemicals are analytical grade and used as purchased with-
tion was taken in a glass reactor and 0.2 g L−1 of ZnO nanoparticles
out further purification. Zinc acetate dihydrate (Alfa Aesar), Zinc
were added as photocatalyst. The reaction mixture was stirred in
nitrate hexahydrate (Sigma Aldrich), Ethanol (Merck), Ammonia
dark for 20 min to establish the adsorption–desorption equilibrium
(Rankem), Polyethylene glycol-4000 (SRL), malachite green dye
of the dye molecules and dissolved oxygen with the catalyst surface.
(purchased from local firm).
Then the reaction was carried out for 100 min because no further
The crystalline phases of ZnO nanomaterials were identi-
degradation was observed after that. The catalyst was recovered
fied by XRD technique. XRD pattern were recorded in the
by centrifugation. In solar light, the reaction was done during sum-
2 range of 20–80◦ with an automated X-ray diffractome-
mer season (between 11 AM and 2 PM during which fluctuation
ter (Model ULTIMA IV, Rigaku, Japan) using Cu K␣ radiation
of solar intensity is usually minimum). Photolysis experiment of
( = 1.5418 Å) at a scan rate of 4◦ min−1 . FTIR spectra were
MG dye in absence of photocatalyst under solar light was carried
recorded using a FTIR spectrophotometer (Model spectrum-
out by aforementioned procedure. The effect of UV light sources on
100, Perkin Elmer, USA) in the frequency range 400–4000 cm−1
photodegradation of MG dye was studied for only one time using
as KBr pellet. The absorbance spectra were recorded at room
ZnO nanoparticles as photocatalyst. UV irradiation was carried out
temperature using a UV–visible spectrophotometer (Model Shi-
with a 30 W (UV-C, 254 nm) mercury lamp (Philips), which was put
madzu 1601 pc) as aqueous dispersion and Photoluminescence
above the batch photoreactor. The distance between dye solution
(PL) was done in a Shimadzu, Spectrofluorophotometer, RF-
and UV source was 20 cm.
5301. The morphology of the samples were examined using
The degradation efficiency (%) was determined using the follow-
Hitachi S-4800 field emission scanning electron microscopy
ing relation.
(FE-SEM). The Brunauer–Emmett–Teller (BET) surface areas of
the materials were measured in a N2 adsorption–desorption C0 − C A0 − A
%Degradation = × 100% = × 100%
machine (Autosorb-1, Quantachrome, USA). pH values were C0 A0
measured with EUTECH pH 700 instrument. The O2 -TPD
where C0 is the initial concentration of dye and C is the concentra-
measurement was performed in a Micromeritics ASAP 2910
tion of dye after photo irradiation and A0 and A are absorbance of
instrument.
dye before and after photocatalytic reaction. The degradation effi-
ciency was measured at 617 nm peak of MG dye which appears in
2.2. Synthesis of ZnO nanomaterials the visible region. The pH of the aqueous solution of MG dye is 5.2.
Using the same experimental procedure we have also investigated
ZnO nanomaterials were synthesized by colloidal precipitation this reaction by varying the catalyst loading, initial concentration of
method, hydrothermal synthesis method (without template) and dye and solution pH using ZnO nanoparticles under solar light. Pho-
template assisted hydrothermal method. tocatalytic activity of ZnO nanoparticles (hydrothermal) and ZnO
44 L. Saikia et al. / Applied Catalysis A: General 490 (2015) 42–49

flowers were also investigated under solar light and compared with
ZnO nanoparticles.

3. Result and discussion

3.1. Catalyst characterization

The powder XRD of the ZnO nanoparticles, ZnO nanoparticles

(hydrothermal) and ZnO flowers was recorded in Rigaku Ultima IV
X-ray diffractometer (Fig. 1). The diffraction peaks of the samples
are indexed which corresponds to the hexagonal wurtzite structure
of ZnO (JCPDS No. 36-1451) with lattice constants of a = 0.325 nm
and c = 0.521 nm. No traces of other impurities like Zn(OH)2 was
observed.
Photoluminescence (PL) spectra are effective way to study the
effect of morphology on the electronic, optical and photochemical
property of semiconductor like ZnO. The synthesized ZnO nanopar-
ticles, ZnO nanoparticles (hydrothermal) and ZnO flowers show a
strong and sharp emission peak at 390 nm (Fig. 2). This UV emission
is usually referred as UV band edge emission which originates from
the recombination of the free excitons through an exciton–exciton
collision process [32]. The weak and broad blue emission band at Fig. 2. Photoluminescence spectra of ZnO nanoparticles, ZnO nanoparticles (hydro-
thermal) and ZnO flowers (inset 468 nm and 550 nm peaks of the PL spectra).
468 nm is a deep level emission (DLE) originates from the oxygen
vacancies or interstitial zinc ions of ZnO nanomaterials [33]. A broad
green emission band was observed at 550 nm for all ZnO nanomate- bands around 3426 and 1598 cm−1 are due to surface adsorbed
rials which may be ascribed to the existence of defect such as singly O H stretching and bending mode of vibration for ZnO nanoparti-
ionized oxygen vacancies [34,35]. The PL intensity of the green cles and the strong absorption band at 421 cm−1 is characteristic
emission band of ZnO flowers is greater than ZnO (hydrothermal) vibration mode of Zn O bonding [36]. For ZnO nanoparticles
and ZnO (colloidal) nanoparticles, respectively, which indicate (hydrothermal) the two band around 3429 and 1604 cm−1 are due
more surface oxygen vacancies of the ZnO flowers. This result to the O H stretching and bending mode of vibration and a strong
suggests that low temperature template assisted hydrothermal band appears at 539 cm−1 is due to Zn O bonding [37]. Similarly,
synthesis of ZnO flowers at oxygen less environment is respon- the bands appear around 3429, 1589 and 419 cm−1 are because of
sible for the high quantity of surface oxygen vacancies in ZnO O H stretching, bending and Zn O bonding, respectively, for ZnO
flowers than ZnO nanoparticles (hydrothermal) and ZnO nanopar- flowers.
ticles, respectively. Some recent works reported that surface The max of UV–visible spectra for as synthesized ZnO nanopar-
oxygen defect related vacancies can significantly affect the pho- ticles, ZnO nanoparticles (hydrothermal) and ZnO flowers were
toluminescence (PL) and photocatalytic (PC) properties of ZnO found at 369, 375 and 388 nm respectively (Fig. S2, ESI) The calcu-
nanostructures [28]. lated band gaps energy for these wavelengths are 3.37 eV, 3.31 eV
The FT-IR spectra for ZnO nanoparticles, ZnO nanoparticles and 3.20 eV, respectively [29]. The ZnO flowers show a very broad
(hydrothermal) and ZnO flowers are shown in Fig. S1, ESI. The broad visible absorption peak. The BET specific surface areas measured
for ZnO nanoparticles, nanoparticles (hydrothermal) and flowers
are found to be 12, 22 and 27 m2 g−1 , respectively.
The FE-SEM images of as-synthesized ZnO nanomaterials are
depicted in Fig. 3. It is clear from Fig. 3(a) and (b) that ZnO nanopar-
ticles synthesized by both colloidal precipitation and hydrothermal
synthesis methods produce almost uniformly distributed spherical
shape particles. From Fig. 3(c) and (d) for flower shaped pencil like
ZnO nanorod bundles, it is seen that flower-like clusters grow in
several directions and have symmetrical arms in level direction.
Every arm consists of few nanorods with almost uniform diameter
and average length about 3 ␮m. The nanorod bundles are highly
disperse in the space without any aggregation among nanorod bun-
dles and have approximately uniform morphology with diameter
of 250–300 nm and length up to 2 ␮m. It is also observed that ZnO
flowers are composed of symmetric nanorod bundles extending
radially from the center. Every rod has a sharp pencil like tip in
comparison with its base the length is up to 2 ␮m.
To further clarify our claim that hydrothermal method creates
more surface oxygen vacancies, O2 -TPD of the ZnO nanoparticles
(hydrothermal) was performed. It is observed that ZnO nanopar-
ticles (hydrothermal) exhibited a narrow peak at 375 ◦ C with
quantitative O2 adsorption of 0.055 mmol g−1 (Fig. S3, ESI). As
the powder XRD pattern of ZnO nanoparticles (hydrothermal)
confirmed the presence only ZnO crystalline phase without any
Fig. 1. XRD patterns of (a) ZnO nanoparticles, (b) ZnO nanoparticles (hydrothermal)
impurity so the peak at O2 -TPD confirmed that O2 was adsorbed
and (c) ZnO flowers. on ZnO and it must have surface oxygen vacancies [28,38].
 L. Saikia et al. / Applied Catalysis A: General 490 (2015) 42–49 45

Fig. 3. FE-SEM images of (a) ZnO nanoparticles, (b) ZnO nanoparticles (hydrothermal), (c) ZnO flowers and (d) one individual ZnO flower.

3.2. Photocatalytic activity available active catalytic sites of ZnO nanoparticles and donated
more electrons to the conduction band of ZnO nanoparticles. But
ZnO nanomaterials are efficiently tested as photocatalyst for beyond 0.2 g L−1 of dye concentration, a decrease in degrada-
self sensitized degradation of MG dye under solar light. The effect tion efficiency was observed which may be due to competition
of different parameters such as catalyst loading, dye concentra- of adsorption between dye molecules and dissolved O2 into the
tion, solution pH on photodegradation was evaluated using ZnO catalyst surface. As O2 molecules is the electron acceptor in the
nanoparticles under solar light. photocatalytic reaction, therefore, lesser the O2 adsorbed than the
dye on the catalyst surface, lesser is the degradation efficiency as
3.2.1. Effect of the catalyst loading well as rate constant [40]. Otherwise, a fixed amount of catalyst
The study of the effect of catalyst loading on photodegradation is provides a fixed amount of reactive radical which is not enough to
important for its use for practical purpose. Experiments were car- degrade a higher concentration of dye [41].
ried out using different amount of ZnO nanoparticles from 0.1 to
0.5 g L−1 and keeping the MG dye concentration fixed at 0.2 g L−1 . 3.2.3. Influence of pH
The optimum amount of catalyst for the highest photodegrada- The influence of different pH (4, 7 and 10) value on the degrada-
tion efficiency was found to be 0.2 g L−1 (Fig. 4). In principle, the tion efficiency of MG was investigated (Fig. S5, ESI). The natural pH
amount of catalyst is proportional to the number of active radical value of MG solution was found to be 5.2. The pH value was adjusted
like • OH and O2 • which rapidly degraded the adsorbed MG dye. using dilute HCl or dilute NaOH solution for the experiment.
Above 0.2 g L−1 of the catalyst amount, the degradation efficiency It was observed that the degradation efficiency was mini-
was decreased rather than increased; this may be due to the aggre- mum (58.59%) at pH 4. On the other hand, degradation efficiency
gation of the catalyst at higher concentration which decreases the increases at pH 10 to its maximum value (93.09%). The probable
total active sites of the catalyst for adsorption of dye molecules. reason of this difference can be explained as adsorption of MG on
Moreover, higher amount of catalyst can create turbidity which catalyst surface is dependent of its surface charge. As ZnO has high
reduces the penetration of light through the solution by scatter- zero point charge (zpc), so at pH < pzpc , ZnO surface is positively
ing the light and it results in the deactivation of the active catalyst charged (at acidic pH ) which decreases the active sites available for
molecules by colliding with ground state molecules [39]. adsorption of a cationic dye like malachite green. At pH > pzpc , the
ZnO surface is negatively charged (at pH 10). Therefore at alkaline
3.2.2. Effect of the initial dye concentration: pH , the number of surface hydroxyl group at ZnO was increased
The effect of initial concentration of MG dye on degradation effi- which facilitates adsorption of MG as well as its self sensitized
ciency was studied by varying the dye concentration from 0.05 to degradation [42].
0.4 g L−1 , keeping the catalyst concentration fixed at 0.2 g L−1 . The
degradation efficiency of MG dye under solar light was increased 3.2.4. Kinetic study
with increasing dye concentration up to 0.2 g L−1 (Fig. S4, ESI), prob- The kinetic study of degradation of MG was done by tak-
ably at this concentration more dye molecules are adsorbed on ing the different initial concentration of MG range from 0.05
46 L. Saikia et al. / Applied Catalysis A: General 490 (2015) 42–49

(a) 90 (b)
-1
0.1 gL 86
85 -1
0.2 gL
-1 84
0.3 gL
80 -1
0.4 gL 82
-1
75 0.5 gL
% Degradation

% Degradation
80
70
78
65
76
60 74

55 72

50 70

45 68
20 40 60 80 100 0.1 0.2 0.3 0.4 0.5
-1
Irradiation time(min) Catalyst loading (gL )

Fig. 4. (a) Effect of catalyst loading on photodegradation efficiency of MG dye under solar light, initial concentration 0.2 g L−1 and initial pH 5.2. (b) Catalyst loading plotted
against % degradation of MG dye under solar light.

(a) (b)
2.1
0.014

1.8
0.012

1.5
k (min-1)
ln (C0 /C)

0.010

1.2

0.008
0.9

0.006
0.6

20 40 60 80 100 0.00 0.08 0.16 0.24 0.32 0.40

Irradiation time (min) Dye Concentration (gL-1)

Fig. 5. (a) Pseudo first order reaction kinetics curves for photodegradation of MG dye with different initial concentration, () 0.05 g L−1 , ( ) 0.1 g L−1 , ( ) 0.2 g L−1 , ( )
0.3 g L−1 , ( ) 0.4 g L−1 , initial pH 5.2, catalyst loading 0.2 g L−1 . (b) Plot of different initial dye concentration against the rate constant for photodegradation of MG dye.

to 0.4 g L−1 . The kinetic curves for degradation of MG was nanoparticles under UV light as a light source (93.75%) and low-
(Fig. 5(a)) follows pseudo first order kinetics represented by the est in case of photolysis experiment (4.88%). At dark condition
Langmuir–Hinshelwood equation as follows: and under solar light the degradation efficiency were 16.32% and
C  85.29%. This result suggests that ZnO nanoparticles efficiently catal-
0 ysed the degradation of MG in presence of both UV and solar light.
ln = kapp t
C

where C0 is the initial concentration (g L−1 ) of MG before irradi-

ation, C is the final concentration (g L−1 ) of MG after irradiation,
kapp is the apparent rate constant (min−1 ), t is the irradiation time
(min). The apparent rate constants (kapp ) for photodegradation of
MG were determined from the experimental data (Fig. 5(b)) using
linear regression. It was observed that the values of degradation
efficiency for different initial concentration of MG are consistent
with the kinetic data.

3.2.5. Effect of different light conditions

Effect of different light sources (Solar light, UV light and at
dark condition) on photodegradation of MG dye in presence of
ZnO nanoparticles as photocatalyst was studied (Fig. 6). A pho-
tolysis experiment for photodegradation of MG dye in absence
of catalyst under solar light was also performed (Fig. 6). It was Fig. 6. Effect of different light source on photodegradation efficiency of MG dye;
observed that degradation efficiency of MG was highest for ZnO intial concentration 0.2 g L−1 , catalyst loading 0.2 g L−1 .
 L. Saikia et al. / Applied Catalysis A: General 490 (2015) 42–49 47

Fig. 7. (a) Comparative photodegradation of MG dye by ZnO nanoparticles, ZnO nanoparticles (hydrothermal) and ZnO flowers under solar light. (b) Rate constant for
comparative photodegradation of MG dye by ZnO nanoparticles, ZnO nanoparticles (hydrothermal) and ZnO flowers under solar light.

3.2.6. Comparative study of ZnO nanomaterials as photocatalysts

• •
The comparative study for self sensitized photodegradation of OH or O2− + MGads → Degraded Product
MG dye using ZnO nanomaterials as photocatalyst was investigated
(Fig. 7(a)). Among the all three synthesized ZnO nanomaterials, the • • •
OH orO2− + MGads
+
→ Degraded Product
hydrothermally synthesized ZnO flowers and ZnO nanoparticles
(hydrothermal) show better photocatalytic activity for degradation The surface adsorbed MG was excited by absorbing solar light
of MG dye than ZnO nanoparticles synthesized by colloidal pre- and donates its electrons to the conduction band of ZnO nanoma-
cipitation method. The rate constant for photodegradation of MG terials. These electrons were scavenged by surface adsorbed O2 to
using ZnO nanoparticles, ZnO nanoparticles (hydrothermal) and generate O2 •− . The O2 •− can react with surface adsorbed H2 O to
ZnO flowers were found to be 0.014, 0.017 and 0.023 min−1 , respec- form H2 O2 which is ultimately converted to • OH (Fig. 8(a)). The sur-
tively (Fig. 7(b)). Among all three synthesized ZnO nanomaterials, face adsorbed MG radical cation or surface adsorbed MG dye can
ZnO flowers exhibited the highest photocatalytic (PC) activity and undergo degradation by O2 •− and • OH. As soon as a dye molecule
also it has the highest surface oxygen vacancy which was confirmed degrades another dye molecule will adsorbed on ZnO surface and
from PL spectra (Fig. 2). It was reported that PL spectra and PC activ- the photocatalytic cycle was continued (Fig. 8(a)).
ity of ZnO nanomaterials are interrelated [28,38,43,44]. The ZnO
flowers synthesized by template assisted hydrothermal method in
oxygen less environment generates high quantity of surface oxygen (a)
vacancies which leads to the adsorption of higher quantity O2 on
ZnO surface. These surface adsorbed O2 can scavenge an electron
donated by the photosensitized MG dye to the conduction band
of ZnO nanomaterials to produce O2 • . The O2 • generally unstable
in aqueous solution and generates • OH radicals which are largely
responsible degradation of MG dye [45]. The UV visible spectra
of comparative photodegradation study among ZnO nanomaterials
were depicted in Fig. S6, ESI.

4. Mechanism

4.1. In solar light

ZnO cannot absorb solar light directly due to its band gap (b)
∼3.37 eV [46], but when a colored organic compound is present,
a sensitized photocatalytic process is able to operate. Huang et al.
reported dye sensitized photodegradation [47] which follows the
radical mechanism. Similarly, the MG dye can also act as a pho-
tosensitizer [48] and it was adsorbed on ZnO surface during the
photodegradation experiment.
+ •
MGads ∗ +ZnO → MGads + ZnO(e− ) λ 〈 390

•
O2 + e−
cb
→ O2−

•
O2− + e−
cb
+ 2H+ → H2 O2

• Fig. 8. Mechanism of MG dyes photodegradation using ZnO nanomaterials as pho-

H2 O2 → 2 OH tocatalyst under (a) solar light and (b) UV light.
48 L. Saikia et al. / Applied Catalysis A: General 490 (2015) 42–49

Table 1
COD values of MG dye solution before and after photodegradation reaction.

Catalyst Before treatment COD (mg L−1 ) After treatment COD (mg L−1 ) Photodegradation efficiency (%)

ZnO nanoparticles 356 69.63 80.44

ZnO nanoparticles (hydrothermal) 356 58.03 83.68
ZnO flowers 356 32.50 90.87

4.2. In UV light and ZnO flowers under solar light was confirmed by measuring
the CO2 production using Warburg apparatus. The Warburg mano-
ZnO can absorb UV light ( < 390 nm) and generate metric method generally used for biological samples to measure
electron–hole pairs. These photogenerated electron and hole gas absorption as well as gas production [49]. In a typical pro-
pairs can migrate into the catalyst surface and react with surface cedure, an experiment was conducted with 4 mL of 0.2 g L−1 MG
adsorbed O2 to form O2 •− . In absence of O2 these electrons and dye solution and 0.002 g ZnO nanomaterials as photocatalyst. The
holes will recombine. The O2 •− can react with surface adsorbed ZnO flowers generated much more CO2 gas than ZnO nanoparti-
H2 O to form H2 O2 which is responsible for generation of • OH cles (hydrothermal) and ZnO nanoparticles (Fig. 9). These results
radical. The • OH is a potent indiscriminant oxidizing agent which strongly resemble with the previously found better photocatalytic
possibly responsible for degradation of most of the surface activity of ZnO flowers than ZnO nanoparticles (hydrothermal) and
adsorbed MG (Fig. 8(b)). The h+ can also react with the surface ZnO nanoparticles. The evolved gas was confirmed to be CO2 as
adsorbed H2 O to form • OH radical and in alkaline pH , h+ can react BaCO3 precipitate formed by adding BaCl2 solution to KOH solution
with − OH to generate • OH. removed from the center wells of the Warburg vessels by using CO2
free water.
(390 nm)
ZnO −→ ecb − + hvb +

O2 + ecb − → O2 •− 6. Determination of COD

O2 •− + ecb − + 2H+ → H2 O2 The COD of MG dye was estimated before and after photodegra-
dation reaction. The COD is used as a measure of the oxygen
equivalent of the organic content in a sample that is susceptible
H2 O2 → 2• OH
to oxidation to CO2 and H2 O by a strong oxidant. The COD was
estimated using dichromate reflux method [50]. The initial dye
h+ +− OH → • OH concentration and catalyst loading taken for COD measurement
was 0.2 g L−1 and 0.02 g L−1 , respectively. The COD of the MG was
h+ + H2 O → • OH + H+ determined for solar light photodegradation. The photodegrada-
tion efficiency from COD measurement can be determined by the
•
• OH or O2− + MGads → Degraded Product following equation [51] which shows the reduction of COD after
degradation and is in good agreement with the previously deter-
mined data by UV method (Table 1).
5. Determination of CO2 production from the
mineralization of malachite green dye InitialCOD − FinalCOD
Photodegradation = × 100%
InitialCOD
The complete mineralization of MG dye by photocatalytic degra-
dation using ZnO nanoparticles, ZnO nanoparticles (hydrothermal)

Fig. 9. Comparative CO2 production studies using Warburg manometric method for Fig. 10. Reusability study of ZnO nanoparticles for photodegradation of MG dye
photodegradation of MG dye using ZnO nanomaterials. under solar light.
 L. Saikia et al. / Applied Catalysis A: General 490 (2015) 42–49 49

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