Journal of Industrial and Engineering Chemistry 20 (2014) 1584–1590

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Journal of Industrial and Engineering Chemistry

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Au@TiO2 nanocomposites for the catalytic degradation of methyl

orange and methylene blue: An electron relay effect
Mohammad Mansoob Khan, Jintae Lee, Moo Hwan Cho *
School of Chemical Engineering, Yeungnam University, Gyeongsan, Gyeongbuk 712-749, South Korea

A R T I C L E I N F O A B S T R A C T

Article history: Au@TiO2 nanocomposites were used for the catalytic degradation of methyl orange and methylene blue
Received 15 April 2013 by NaBH4. A detail pathway for step by step reduction, oxidation and complete mineralization of
Accepted 4 August 2013 intermediates into the respective end-products was established by UV–vis spectroscopy, chemical
Available online 11 August 2013
oxygen demand, ion chromatography and cyclic voltammetry (CV). CV studies confirmed that the dyes
were reduced and oxidized to the end-products by NaBH4 in the presence of Au@TiO2 nanocomposites
Keywords: and O2, OH and HO2 radicals generated in situ. Results suggest that Au@TiO2 nanocomposites not only
Heterogeneous catalysis
assist in the decolorization of dyes, but also promote their complete mineralization into harmless end-
Electron relay effect
Au@TiO2 nanocomposites
products.
NaBH4 ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
Methyl orange reserved.
Methylene blue

1. Introduction intermediate redox potential between the electron donor and

Metal oxides, mainly TiO2, have attracted attention for
environmental remediation [1,2]. Residual dye contents in textile
wastewater have complex aromatic structures that are difficult to
degrade by a biological treatment. Therefore, over the last few
decades considerable attention has been paid to decomposing
these textile waste dyes by improving the properties of metal
oxides, mainly TiO2, by doping with a range of metals (Au or Ag)
and CNT [3–5]. Several methods have been developed for their
synthesis including physical, chemical and biological methods
[5–8]. Gold-doped TiO2 is attracting tremendous attention because
of its improved characteristics and applications in the catalysis,
alkylation and charge transfer reactions [9–11].
Au/TiO2 prepared by various methods is used for the degrada-
tion of dyes in the presence of UV or visible light [12–15]. NaBH4 is
a well-known reducing agent. Reduction of dyes (MO and MB) by
NaBH4 in the absence of a catalyst is kinetically difficult but
thermodynamically favorable. Nanoparticles can achieve this by
providing an alternate path by reducing the activation energy,
thereby decreasing kinetic barrier, making it kinetically favorable
[16,17]. The electron transfer step plays a dynamic role in the
degradation of dyes because there may be a large redox potential
difference between the electron donor and acceptor species, which
can obstruct electron transfer [16,17]. An effective catalyst with an
* Corresponding author. Tel.: +82 53 810 2517; fax: +82 53 810 4631.
E-mail address: mhcho@ynu.ac.kr (M.H. Cho).
acceptor species can assist in the transfer of electrons, and act as an
electron relay system [17–19]. Several studies have examined the
electron relay effect shown by metal nanoparticles, such as Au, Ag
and Pt for dye reduction [16–20]. To the best of the authors’
knowledge, there are no reports of the simultaneous reduction and
degradation of dyes by NaBH4 in the presence of Au@TiO2
nanocomposites as a catalyst.
The aim of this study is to examine the catalytic properties of
the Au@TiO2 nanocomposites, which help to understand the
mechanism of the heterogeneous catalysis for the reduction and
degradation of dyes. The as-synthesized powdered Au@TiO2
nanocomposites reported earlier [21] were used as a catalyst for
the electron transfer reaction to degrade different classes of dyes
(MO and MB) by NaBH4 because of their higher stability and
relatively well understood physicochemical and electrochemical
processes. Therefore, it is important to investigate this type of
system where the catalyst is a nanocomposite that relays
electrons for the degradation of different classes of dyes with
different characteristics into their respective end-products. In
this study, AuNPs and TiO2 were combined as Au@TiO2
nanocomposites because AuNPs can relay the electrons generat-
ed by BH4 to the dyes and adsorbed O2 at the surface of TiO2,
whereas the O2 adsorbed at the TiO2 surface assists in the in situ
generation of O2 and OH radicals [1,22]. Therefore, the
combined effects of AuNPs at TiO2 to relay electrons and generate
O2 and OH radicals, respectively, helps in the reduction,
oxidation and complete mineralization of dyes into their
respective end-products.

1226-086X/$ – see front matter ß 2013 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jiec.2013.08.002
 M.M. Khan et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 1584–1590
2. Experimental
2.1. Materials
MO, MB, sodium citrate, KCl and NaBH4 (Duksan Pure
Chemicals Co. Ltd. South Korea); TiO2 (P25; Degussa), and
chloroauric acid (HAuCl4nH2O; n = 3.6) (Kojima Chemical, Japan)
were used as received. All solutions were prepared in de-ionized
water prepared using a water purification system (PURE ROUP 30,
Hanascience, South Korea).
2.2. Methods
A UV–VIS–NIR spectrophotometer (VARIAN, Cary-5000, USA)
was used to measure the absorbance. The COD was determined
using a COD analyzer kit (HACH kit, USA), and ion chromatography
(Dionex, DX-600, USA) was used to measure the NO3 and SO42
concentrations. CV was performed on a potentiostat (VersaSTAT 3,
AMETEK, USA) using Ag/AgCl, Pt gauze and plain carbon paper as
the reference, counter and working electrodes, respectively. The
solutions of MO and MB in the CV experiments were approxi-
mately 3.97  105 M and 4.10  105 M, respectively, with 0.5 M
KCl as the supporting electrolyte. In each case, the sweep begins
from the positive to negative potential.
2.3. Synthesis of Au@TiO2 nanocomposites
Au@TiO2 nanocomposite was synthesized, as reported earlier
[21,23]. Briefly, 5 mM TiO2 was dispersed in 200 mL DI water and
pretreated with UV light (l = 254 nm) for 3 h. To this solution,
2.5 mM HAuCl4 was added drop-wise and the pH was maintained
at pH 9 using 0.1 M NaOH. The color of the reaction mixture was
whitish-golden yellow. Subsequently, 0.1 g sodium citrate was
added and N2 gas was sparged for 5 min to maintain the inert
atmosphere. The reaction mixture was sealed and left for stirring
with UV irradiation for 10 h. At the end, the color of the reaction
mixture changed to brownish-purple with some precipitation. The
resulting suspension was centrifuged and the catalyst was
obtained for further use.
2.4. Degradation of dyes
Three separate sets of experiments were performed for MO and
MB. In set 1, the as-synthesized Au@TiO2 catalyst was used,
whereas sets 2 and 3 were control sets. In set 1, 20 mL MO
(13 mg/L) or 20 mL MB (13 mg/L), and 2 mg Au@TiO2 catalyst were
mixed in a vial and sonicated for 5 min in the dark. Subsequently,
2 mL of a 0.1 M NaBH4 was added and the resulting mixture was
stirred. In set 2, 20 mL MO or 20 mL MB, and 2 mg TiO2 was mixed
in a vial and sonicated for 5 min in dark. Afterwards, 2 mL of a
0.1 M NaBH4 was added and the resulting mixture was stirred. In
set 3, 20 mL MO or 20 mL MB and 2 mL 0.1 M NaBH4 were added
and stirred. All three sets of reactions were observed for 12 min.
The rate of dye degradation was monitored by taking 2 mL samples
from each set every 2 min, centrifuging them (except for set 3),
removing the catalyst and recording the UV–vis spectra.
As a control experiment, TiO2 (P25) was used and considered as
the reference catalyst. Typically the catalytic activity of any new
material is compared with that of pure TiO2 as a standard. Each
experiment examining the catalytic activities of Au@TiO2 nano-
composites and TiO2 was performed in triplicate.
2.5. Stability and reusability of the Au@TiO2 nanocomposites
A preliminary test for stability was performed by suspending
the Au@TiO2 nanocomposites in water followed by sonication for
1585
1 h. Possible AuNPs leaching in the solution was monitored by UV–
vis spectrophotometry, which revealed the stability of the
Au@TiO2 nanocomposites and its potential use as a catalyst. The
reusability of the Au@TiO2 nanocomposite was tested after
removing the catalyst by centrifuge. The isolated catalyst
(Au@TiO2 nanocomposites) was washed with DI water, dried in
an oven at 110 8C and reused for a second run to check its catalytic
activity with the MO and MB solutions under the same conditions.
2.6. COD measurement
The COD for MO and MB degraded solutions were measured
using the Reactor Digestion Method on a HACH kit DR/2500,
Method 8000 (HACH, USA).
3. Results and discussion
The Au@TiO2 nanocomposites were synthesized and character-
ized as discussed in a previous report [21,23]. The catalysts were
then used for the degradation of MO under UV light irradiation and
showed enhanced photocatalytic activity [21]. The advantage of
this method is that it helps in the formation of very small size (2–
5 nm) of the AuNPs on TiO2 and were distributed uniformly. The
overall size of the Au@TiO2 nanocomposites was 20–30 nm, which
is suitable for the catalytic activity and electron transfer [21]. In
this study, the same Au@TiO2 nanocomposites were used as a
catalyst for reduction followed by degradation of the two different
classes of dyes (MO and MB) by NaBH4. These dyes were selected
based on the following two factors. First, these dyes have different
colors in their oxidized and reduced forms, and their major
absorption bands do not overlap with the plasmon band of AuNPs.
Second, the reduction of these dyes is thermodynamically favorable
but kinetically unfavorable. In the present case, TiO2 serves a four-
fold function in the Au@TiO2 nanocomposites: (i) provides support
for AuNPs; (ii) assists in the electron transfer from BH4 ions to
dyes via AuNPs; (iii) assists in the in situ generation of O2 and OH
radicals from the adsorbed oxygen at its surface, and (iv) plays an
important role in avoiding the aggregation of AuNPs during the
catalytic process. NaBH4 were used as a reducing agent because the
efficiency of the BH4 ions is associated with its high electron
injection capacity [24]. O2 is an electron-capturer that can produce
O2, an important intermediate species [25]. Some studies showed
that O2 adsorbed at the surface of TiO2 by accepting the electrons
can be converted to O2 and may later interact with H2O and
generate OH radicals, which is quite energetic and can effectively
mineralize the reduced dyes [5,16,22,25,26].
3.1. MO and MB degradation and its measurements
Fig. 1(a) and (b) shows the UV–visible absorption spectra of MO
and MB degradation by NaBH4 in the presence of Au@TiO2
nanocomposites, TiO2 and NaBH4 only. The spectra show that
NaBH4 alone does not cause any appreciable change in the
reduction of the dyes, indicating a small decrease in MO and MB
absorbance. TiO2 is a well-known catalyst that increased the rate of
reduction/decomposition of MO and MB, as is apparent from the
decrease in absorbance. Nevertheless, TiO2 alone cannot help to
reduce/degrade the dyes completely. Finally, Au@TiO2 nanocom-
posites in the presence of NaBH4 catalyze the reaction, which leads
to the removal of MO and MB; the absorbance became almost zero
and 0.3 in the case of MO and MB, respectively. This suggests that
Au@TiO2 nanocomposites act as a very good electron transfer
system that catalyzes the reactions by reducing the activation
energy.
Fig. 1(a) shows the complete disappearance of the MO peak
at 464 nm in the case of reaction catalyzed by Au@TiO2
1586 M.M. Khan et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 1584–1590
Fig. 1. UV–visible spectra of (a) methyl orange and (b) methylene blue, degraded by NaBH4 in presence of Au@TiO2 nanocomposites and TiO2.
nanocomposites, which indicates the complete reduction of MO
compared to TiO2 and NaBH4 only [6]. According to that report,
if only the reduction of MO takes place then peak at 290 nm
should increase because of hydrazine derivatives [6]. On the
other hand, in the case of MO + Ag@TiO2 + NaBH4, the intensity
of the peak at 290 nm appears to decrease, which suggests that
the simultaneous reduction, oxidation and mineralization of the
intermediates had taken place. This was further confirmed by
COD (Fig. 4a), ion chromatography and CV (Fig. 6a). On the other
hand, in case of MO with NaBH4 only, the intensity of the peak at
290 nm increased, which indicates that only the reduction of
MO takes place in the absence of Au@TiO2 nanocomposites [6].
This shows that the Au@TiO2 nanocomposites catalyze the
reaction and degrade the dye. Fig. 1(b) shows a significant
decrease in the absorbance peak of MB in the case of the reaction
catalyzed by Au@TiO2 nanocomposites compared to TiO2 and
NaBH4 only. Yogi et al. [14,27] and Fu et al. [15] reported that
the peaks at 300 nm and 660 nm almost disappeared when MB
was decomposed completely. In this case, both the absorption
peak at 300 nm and 660 nm decreased, which shows the
reduction, oxidation and finally the mineralization of MB
intermediates. This was confirmed further by COD (Fig. 4b),
ion chromatography and CV (Fig. 6b).
Fig. 2(a) and (b) shows the comparative catalytic percentage
degradation of MO and MB by NaBH4 in the presence of Au@TiO2
nanocomposites, TiO2 and NaBH4 only. The initially sharp increase
in the percentage degradation of the dyes is probably due to the
adsorption of MO and MB on the surface of the Au@TiO2
nanocomposites. The average degradation in terms of the
Fig. 2. Percentage degradation of (a) methyl orange and (b) methylene blue by NaBH4 in presence of Au@TiO2 nanocomposites and TiO2.
percentage of MO and MB in solution was calculated using the
following formula:
 
Ao  At
h¼  100% (1)
Ao
where h is the rate of degradation of MO and MB in terms of
percentage, Ao is the initial absorbance of dyes solution and At is the
absorbance of the dyes at time t [21,28]. Au@TiO2 nanocomposites
catalyzed >95% and 84% degradation of MO and MB, respectively,
which is much higher than that of TiO2 as well as other reports [3].
Fig. 3(a) and (b) shows a plot of ln(C0/C) vs. time for the catalytic
degradation of MO and MB by NaBH4 in the presence of the
Au@TiO2 nanocomposites, TiO2 and NaBH4 only. The first-order
kinetic model derived from the Langmuir–Hinshelwood kinetic
equation was used to quantify the catalytic efficiency of the
Au@TiO2 nanocomposites by calculating the respective first-order
rate constants (k) according to the following equation:
 
C0
ln ¼ kt (2)
C
where C0 and C are the initial and reaction concentrations of MO
and MB at time t, respectively [21,29]. The linear regression plots
fitted well, from which the slopes of each plot were calculated and
used to obtain the first-order rate constants (k). The k for MO
degradation were found to be kAU@TiO2 ¼ 3:89  103 s1 , kTiO2 ¼
3:90  104 s1 and kNaBH4 ¼ 2:95  104 s1 . The k for MB
degradation were kAU@TiO2 ¼ 2:60  103 s1 , kTiO2 ¼ 1:26 
103 s1 and kNaBH4 ¼ 8:03  104 s1 . The k represents the
 M.M. Khan et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 1584–1590 1587

Fig. 3. Kinetics of catalytic degradation of (a) methyl orange, and (b) methylene blue by NaBH4 in presence of Au@TiO2 nanocomposites and TiO2. Graph fitted with linearity
from which rate constants were determined.

Fig. 4. Kinetics of COD disappearance for (a) methyl orange, and (b) methylene blue degradation by NaBH4 in presence of Au@TiO2 nanocomposites and TiO2.

catalytic activity of the catalyst. The higher the k value, the faster
the degradation of MO and MB, hence, better catalytic activity of
the Au@TiO2 nanocomposites. In the case of MO, the Au@TiO2
nanocomposites showed an approximately 9.93 and 13.16 times
higher reaction rate than TiO2 and NaBH4, respectively. In contrast,
in the case of MB, the Au@TiO2 nanocomposites showed an
approximately 2.06 and 3.23 times higher reaction rate than TiO2
and NaBH4, respectively. It was also observed that the catalytic
activities of our Au@TiO2 nanocomposites was much better than
other previously reported Au/TiO2 [12,13].
After the catalytic reaction, the degraded MO and MB solution
was analyzed for NO3 and SO42 ions after centrifuging and
removing the catalyst. In the case of MO, the amount of NO3 and
SO42 ions in the degraded solution were 0.09 mg/L and 0.21 mg/L,
whereas in the case of MB, the amount of NO3 and SO42 ions in
the degraded solution were 0.04 mg/L and 0.19 mg/L, respectively.
This supports the proposed mechanism (Fig. 5) and proves that MO
and MB had been degraded and mineralized by NaBH4 in the
presence of Au@TiO2 nanocomposites as a catalyst to their
respective end-products.
The reused Au@TiO2 nanocomposites showed similar catalytic
activity for the degradation of MO and MB solutions as the fresh
Au@TiO2 nanocomposites. Essentially, the same plots in Figs. 1–3
were obtained. Moreover, after two consecutive uses, the catalyst
showed similar catalytic activity to the fresh Au@TiO2 nanocom-
posite. This shows that the Au@TiO2 nanocomposites can be used
repeatedly. This confirmed the stability and reusability of Au@TiO2
nanocomposites.

Fig. 5. Proposed mechanism for the catalytic reduction, oxidation and finally mineralization of MO and MB by NaBH4 in presence of the Au@TiO2 nanocomposites into
respective end-products. O2(ads) is the adsorbed oxygen at TiO2 surface which leads to the formation of O2, OH and HO2.
1588 M.M. Khan et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 1584–1590
3.2. Kinetics of COD disappearance
Fig. 4(a) and (b) presents kinetic plots of the COD disappear-
ance, which shows the catalytic degradation of the MO and MB by
NaBH4 in the presence of the Au@TiO2 nanocomposites, TiO2 and
NaBH4 only. Each plot shows a decrease in the COD. The decrease in
COD in the case of MO/MB + Au@TiO2 + NaBH4 was much higher
than the decrease in MO/MB + TiO2 + NaBH4 and MO/MB + NaBH4.
The kinetic curves for the MO and MB degradation by NaBH4 in the
presence of Au@TiO2 nanocomposites showed an approximately
sigma shape, indicating that it is related to the formation of the
final end-products [30]. This pattern means that during the first
step of the process, where the solution is still colored, there is only
a small decrease of the COD because the dye molecules may have
decomposed to lower molecular weight compounds that still
contribute to the COD of the solution. After decolorization of the
solution, the COD decreased sharply (the linear segment of the
sigmoid curve) corresponding to the oxidation of most stable
compounds. This suggests that almost complete mineralization of
the intermediates had taken place [30]. The inflection point in case
of MO and MB corresponds to a reaction time of 6 and 8 min,
respectively, which may be due to aromatic ring opening with the
transient formation of intermediates followed by the evolution of
CO2. The degradation leads to the conversion of organic carbon to
gaseous CO2 as well as the conversion of nitrogen and sulfur
heteroatoms to nitrate and sulfate ions, respectively [29,31].
The mechanism of reduction, oxidation followed by the
mineralization of MO and MB by NaBH4 is different from the
pathway implicated under U.V. or visible light radiation [28,29].
The UV–visible spectra (Fig. 1a and b), kinetics of the catalytic
degradation plot (Fig. 3a and b), and kinetics of the COD
disappearance plot (Fig. 4a and b) showed that TiO2 alone in the
presence of BH4 ions reduces the MO and MB partially, whereas
the Au@TiO2 nanocomposites facilitates the reduction, oxidation
and further mineralization of the dyes. In addition, the disappear-
ance patterns of MO and MB were different. This might be due to
the different molecular structure of the dyes and their reactivities
with the Au@TiO2 nanocomposites and O2 and OH radicals, which
are the main oxidizing agents. On the other hand, the degree of the
electrostatic attraction and rate of reduction depends on the nature
of the dye (charge, hydrophobicity, presence of donor atom and
reduction potential). This is mainly due to the negative charge
accumulated on the Au@TiO2 nanocomposites and charged organic
dyes, which are attracted toward it through electrostatic interac-
tions [32]. In the case of MO, the rate of reduction was high
compared to MB. This suggests that the electrostatic interaction of
the Au@TiO2 nanocomposites with MO is higher than MB. The
lower rate of MB reduction might be due to the hydrophobicity of
MB (due to the four methyl groups) which hinders physical contact
of the Au@TiO2 nanocomposites with MB [32].
The reduction of the dye by NaBH4 did not occur to a
considerable extent in the absence of metal nanoparticles due to
the kinetic barrier [16–19,25]. A catalyst is needed to relay the
electron from NaBH4 to the dye. The catalytic process can be
explained by an electrochemical mechanism, where the AuNPs
supported on TiO2 acts as an electron relay for the oxidant and
reductant, and electron transfer occurs via the metal nanoparticles
[19]. In the present system, Au@TiO2 nanocomposites act as an
electron relay, assisting in the transfer of electrons from BH4 ions
to the dyes, thereby causing the reduction of the dyes. The BH4
ions were nucleophilic, whereas the dyes were electrophilic in
nature with respect to the Au@TiO2 nanocomposites. Nucleophilic
ions can donate electrons to metal nanoparticles, whereas an
electrophile can capture the electrons from the metal particles
[19]. BH4 ions and the dyes were adsorbed simultaneously on the
surface of metal nanoparticles when they were in close proximity,
and electron transfer from BH4 ions to the dyes can occur via
AuNPs [19,24]. According to Jiang et al. BH4 reacts with AgNPs to
produce a negatively charged layer around the AgNPs [19]. BH4
ions are well known for electron generation and charging AuNPs
[24,32–34]. A similar reaction should occur with AuNPs, and the
Au@TiO2 nanocomposites will become surrounded by a layer of
negative charge (electrons), as shown by reaction (I) [19,32–34].
BH4  þ Au@TiO2 þ 3H2 O ! BO3 3 þ ðAu@TiO2 Þ8 þ 10Hþ (I)
The adsorbed O2 at the surface of TiO2, in the presence of any
electron providing source (such as BH4), can generate O2 and OH
radicals, [4,14–16,22,25–29,35]. These radicals are quite energetic
and can easily mineralize the dyes [22,26–37]. As reported by Tian,
the Fermi energy of the metal particles increases with decreasing
size due to the quantum size effect, the AuNPs with an appropriate
size might possess an energy level between the conduction band of
TiO2 and the adsorbed O2 [13]. Therefore, the electrons can be
captured by AuNPs and be transferred to the O2 adsorbed at the
TiO2 surface for the formation of O2 and later OH [5,22,26]. When
the AuNPs are too large or small, electrons cannot be transferred to
O2 or any other electrophile. Therefore, AuNPs with the appropri-
ate size are effective for improving the catalytic activity. From a
previous report, the size of AuNPs at TiO2 were in the range of
2–5 nm, which is effective for the transfer of electrons produced by
BH4 ions to the dyes, adsorbed O2 molecule for the formation of
O2 and OH radicals [5,22–29,33].
TiO2-based catalytic oxidation in water is not selective
compared to oxidation in the pure organic gaseous or liquid phase
of aliphatic or aromatic hydrocarbons [29]. In water, O2 and OH
radicals are formed, which are highly active oxidizing species but
non-selective agents that can be generated according to reactions
(II)–(VII). The resulting radicals, mainly O2 and OH, being very
strong oxidizing agents, can oxidize most of the dyes or
intermediates into their mineral end-products [5,14–16,22–
29,35]. The transient in situ formation of O2, OH and HO2
radicals occurs according to the following reactions [5,14–16,22–
29]:
ðO2 Þads þ ! O2  (II)
O2  þ Hþ ! HO2  (III)
O2 þ Hþ þ ! HO2  (IV)
2HO2  ! H2 O2 þ O2 (V)
H2 O2 þ ! OH þ  OH (VI)
H2 O2 þ O2  !  OH þ OH þ O2 (VII)
3.3. Mechanism for MO and MB mineralization
Fig. 5 presents a common and general proposed mechanism for
MO and MB degradation. In the case of the reduction/degradation
of MO and MB by NaBH4 in the presence of Au@TiO2 nanocompo-
sites as a catalyst, these dyes may be protonated to form
protonated and cationic species (Dye+) through reaction (VIII)
[6,15]. MO and MB can form reduced and protonated MO
(hydrazine derivatives) and MB (leuco methylene blue, LMB),
respectively. The functional group of these dye molecules might be
adsorbed at the surface of the Au@TiO2 nanocomposites. As soon as
BH4 ions provide electrons to the Au@TiO2 nanocomposites, these
electrons accumulate at the AuNPs and become trapped by
adsorbed oxygen molecules to form O2 and OH radicals
[5,14,15,22,26]. These radicals then react with the functional
group of adsorbed MO and MB, and destroy the molecular
 M.M. Khan et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 1584–1590
structure of the dyes via reactions (IX)–(XIII) to produce the
mineralized end-products [22–27,30].
MO & MB þ n þ nHþ ! protonated and reduced MO & MB ðDyeþ Þ
Dyeþ þ HO ! Dye þ  OH
Dye þ 2 OH ! H2 O þ oxidation products
Dyeþ þ O2  ! DO2 ! mineralized products
Dyeþ þ 2HO2  ðor OHÞ ! DO2 ! mineralized products
Overall reaction:
protonated and reduced MO & MB ðDyeþ Þ þ O2  ;  OH or HO2 
! respective mineralized end-products

This shows that the dyes (MO and MB) and BH4 ions adsorbed
simultaneously on the Au@TiO2 nanocomposites and are electro-
philic and nucleophilic in nature with respect to the Au@TiO2
nanocomposites, respectively. As a consequence, electron charge
transfer can occur from the BH4 ion to the dyes via the Au@TiO2
nanocomposites [24]. The AuNPs on the TiO2 substrate can act as
electron traps, and these state-trapped electrons can be transferred
effectively to the adsorbed O2 via the AuNPs to form O2, OH and
HO2 radicals [5,14–16,22–26]. Finally, these radicals assist in the
mineralization of intermediates formed during catalytic degrada-
tion into the final mineralized end-products.
The catalytic efficiency of a metal nanoparticle for an electron-
transfer process is closely related to the size-dependent redox
properties [13,17–19]. As a general rule, the rate of the catalytic
reaction should be determined by the concentration of the catalyst,
the difference in potential between the reductant adsorbed on
metal particles and the oxidant used. The redox potential of a metal
nanoparticle increases with decreasing size [17,37]. For a given
concentration of Au@TiO2 nanocomposite, the smaller the size of
the particles, the more negative the potentials of Au@TiO2
nanocomposites are, which causes a larger potential difference
between the Au@TiO2 nanocomposites and dyes, and hence higher
catalytic activity [37].
As mentioned above, the catalytic reduction rate of a dye is
closely related to the difference in the potential between the metal
particles and dyes. The catalytic reaction rate increases with
increasing difference between the two potentials. In solution, the
Fermi potential of a metal particle is related to the properties of the
micro-environment [19]. An electrophile can produce a positive
Fig. 6. Cyclic voltammetry profile of (a) methyl orange, and (b) methylene blue solutions with Au@TiO2 nanocomposites, 0.1 M NaBH4 and 0.5 M KCl with scan rate 0.1 V/s at 0,
6 and 12 min.
1589
shift in the Fermi potential of the metal particles. In contrast, a
negative shift in the Fermi potential will occur when a nucleophile
is added. In the initial stages of the catalytic reaction, Au@TiO2
nanocomposites are surrounded by dye molecules, and the Fermi
(VIII) potential of the Au@TiO2 nanocomposites is relatively high. After
adding sodium borohydride, BH4 ions will adsorb gradually onto
(IX) the surface of the Au@TiO2 nanocomposites through competitive
adsorption, resulting in a decrease in the Fermi potential of the
(X) Au@TiO2 nanocomposites. Therefore, in the initial stage of the
reaction, the catalytic reduction rate of the dyes is slow due to
(XI) the lack of BH4 ions on the surface of the Au@TiO2 nanocompo-
sites and the small potential difference between the Au@TiO2
(XII) nanocomposites and dyes. With increasing reaction time, a larger
number of BH4 ions accumulate around the surface of Au@TiO2
nanocomposites, and the potential difference of the Au@TiO2
nanocomposites and the dyes are also increased. As a result, the
reaction rate increases.
(XIII)
3.4. Electrochemical study of the catalytic degradation of MO and MB
The electron transfer mechanism among BH4, Au@TiO2
nanocomposites and dyes were confirmed by CV, which was
performed to examine the electron transferability of the Au@TiO2
nanocomposites as well as the reduction and oxidation potentials
of MO and MB. According to the proposed mechanism, the in situ
generation of O2 occurs by the reduction of adsorbed O2
molecules, as clearly observed in the voltammograms of MO
and MB. Fig. 6(a) and (b) shows the CV profile of MO and MB for its
reduction and oxidation peaks as well as the reduction of adsorbed
O2 molecules to O2 radicals. In each case, three voltammograms
were recorded at different times e.g. 0, 6 and 12 min. In addition, in
each case, a shift in the peak was observed after scanning for 0, 6
and 12 min, which might be due to the cleavage of MO and MB
molecules to their respective intermediates. The features (peak
shape) observed upon the addition of Au@TiO2 nanocomposites to
the MO and MB solutions were attributed to the electrochemical
activity of the catalyst. In the case of MO degradation, the
reduction potential of O2 was 2.08 V, 1.77 V and 1.45 V at 0, 6 and
12 min (Fig. 6a), respectively. The reduction potential of O2 is
known to be 0.8 V, which may also depend on the system [38].
The reduction potential of MO (Fig. 6a) was 0.75 V, 0.80 V and
0.56 V at 0, 6 and 12 min respectively. Similarly, the oxidation
potential of MO was 0.65 V, 0.53 V and 0.13 V at 0, 6 and 12 min,
respectively [39]. In the case of MB (Fig. 6b), the reduction
potential of O2 was 1.93 V, 1.77 V and 1.68 V at 0, 6 and 12 min,
respectively [38]. The reduction potential of MB (Fig. 6b) was
1.37 V and 0.866 V at 0 min, 1.11 V and 0.68 V at 6 min and 1.059 V
1590 M.M. Khan et al. / Journal of Industrial and Engineering Chemistry 20 (2014) 1584–1590
and 0.66 V at 12 min. Similarly, the oxidation potential of MB was
0.47 V, 0.33 V and 0.70 V at 0, 6 and 12 min, respectively [40,41].
CV showed that the concentration of both dyes decreased with
time because the peak current (ipc) decreases with time. This
means that the dyes are degraded with time. The separation
between the anodic and cathodic peak increased with time. This
suggests that the electron transfer kinetics has increased, which
might be because of the in situ formation of different anions,
reduction and decomposition of dyes. This indicates that MO and
MB are reduced, oxidized and finally mineralized by the NaBH4 in
presence of Au@TiO2 nanocomposites and in situ generated O2,
 [12] B. Zhu, K. Li, Y. Feng, S. Zhang, S. Wu, W. Huang, Catal. Lett. 118 (2007) 55.
OH and HO2 radicals.
4. Conclusion
The catalytic properties of the Au@TiO2 nanocomposites in
reducing and degrading MO and MB to their end products by
NaBH4 at room temperature were investigated. This shows that the
Au@TiO2 nanocomposites has enhanced catalytic activity due to
the pretreatment of TiO2 with U.V. light and the uniform
deposition of small (2–5 nm) AuNPs at the TiO2. The catalytic
degradation of dyes followed first-order kinetics according to the
Langmuir–Hinshelwood model. UV–visible, COD and ICP (NO3
and SO42) analyses further supports the degradation of the dyes.
CV provided further electrochemical evidence that MO and MB
were reduced and degraded to their respective mineralized end-
products by NaBH4 in the presence of the Au@TiO2 nanocompo-
sites and in situ generated O2, OH and HO2 radicals. Therefore,
Au@TiO2 nanocomposites might be a good tool for the reduction
and mineralization of diluted textile dye wastewater and polluted
water. Au@TiO2 nanocomposites also showed extremely high
stability and reusability under similar experimental conditions.
Acknowledgement
This study was supported by the Basic Science Research
Program through the National Research Foundation of Korea
(NRF) funded by the Ministry of Education, Science and Technology
(grant no: 2012R1A1A4A01005951).
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