Chemosphere 144 (2016) 1655e1664

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Improved photocatalytic activity of gold decorated differently doped

TiO2 nanoparticles: A comparative study
Nabin Kumar Pal, Carola Kryschi*
Department of Chemistry and Pharmacy and ICMM, Friedrich-Alexander-University of Erlangen-Nuremberg, Erlangen, Germany

h i g h l i g h t s

Undoped, Fe3þ, N and g-Al2O3 doped TiO2 NP-based photocatalysts were engineered.

AuNP decorated, doped or undoped TiO2 photocatalysts operate with visible light.

Methylene blue in water was photocatalytically degraded by visible light.

AuNP decoration and dopants increase the photocatalytic activity of TiO2 NPs.

AuNP decorated, g-Al2O3 doped TiO2 NPs show the highest photocatalytic activity.

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

Article history: In this paper, undoped and several differently doped (with Fe3þ, N, and g-Al2O3) TiO2-nanoparticle-
Received 5 July 2015 based photocatalysts and those covered with ultrasmall gold nanoparticles (AuNPs) were engineered.
Received in revised form Their photocatalytic performance was studied by utilizing them for the liquid-phase decomposition of
2 October 2015
the model dye methylene blue (MB) under visible-light irradiation. The structural, morphological,
Accepted 14 October 2015
Available online xxx
physico-chemical, and optical properties of the photocatalysts were investigated using X-ray diffraction,
X-ray photoelectron spectroscopy, diffuse-reflectance UVeVis absorption spectroscopy, Raman spec-
troscopy and transmission electron microscopy. Photodegradation kinetics of MB was followed by
Keywords:
Doped TiO2 nanoparticles
measuring the absorbance of MB at 664 nm at different irradiation times, whereas the mineralization of
Gold nanoparticles MB was examined by determining the total organic carbon (TOC) content. The photocatalytic activity of
Photocatalyst TiO2 nanoparticles was shown to be significantly increased by introducing dopants into the crystal lattice
Photodegradation and depositing AuNPs on the surface. Among those, g-Al2O3 doped TiO2 nanoparticles covered with
Visible light deposited AuNPs show the best photocatalytic performance. Altogether, the here engineered photo-
Methylene blue catalysts as consisting of doped TiO2 nanoparticles decorated with AuNPs establish novel three-
component nanocomposite systems, where synergetic interactions between surface AuNPs, dopants
and TiO2 were shown to significantly enhance the photocatalytic activity.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction function of a photocatalyst is to convert light energy into chemical

energy. The efficiency of this energy conversion strictly depends on
Nanocrystalline TiO2 has drawn an enormous research attention the ability of the photocatalyst to create stable electronehole pairs,
over the last decade as a photocatalyst, mainly, because of its po- once it absorbs photons of energy higher than the band-gap energy.
tential applications in environmental remediation. Its non-toxicity, TiO2 as having a wide band gap (~3.4 eV for anatase) can only
photostability, high photocatalytic activity, and recyclability make absorb light in the UV and thereupon a very small fraction (2e3%)
TiO2 one of the most promising photocatalyst for various envi- of the solar radiation that arrives at the earth's surface. This prac-
ronmental clean-up applications (Hu et al., 2003; Yu et al., 2005; tically ruled out the use of solar light as an energy source for TiO2
Fujishima et al., 2000; Liu et al., 2011; Silva et al., 2011). The mediated photocatalytic experiments. Moreover, the high electro-
nehole pair recombination rate of TiO2 often results in poor pho-
tocatalytic efficiency. Major efforts are devoted to expand the
* Corresponding author.
photoresponse of TiO2 to longer wavelengths, in order to make the
E-mail address: [Link]@[Link] (C. Kryschi). use of solar energy more efficiently for practical applications (Asahi

[Link]
0045-6535/© 2015 Elsevier Ltd. All rights reserved.
1656 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664

et al., 2001; Wang et al., 2009; Zhang et al., 2010a, b). The two most of Au nanostructure-decorated TiO2 nanowire electrodes can be
convenient approaches for improving the photocatalytic perfor- effectively enhanced for photoelectrochemical water oxidation in
mances of TiO2 are either metal-ion (e.g. Fe3þ, Co3þ, Sn4þ, Mo5þ, the entire UVevisible region by adopting different shapes of the
Sr2þ, Cr3þ) doping or doping with non-metallic elements (e.g. N, decorating Au nanostructures (Pu et al., 2013). Rodriguez-Gonzalez
C, P) (Devi et al., 2010; Dholam et al., 2009; Yang et al., 2004; et al. reported that gold supported titania-alumina mixed oxide
Sakthivel and Kisch., 2003; Yoong et al., 2009). Metal-ion dopants exhibits a much higher photocatalytic activity for the decomposi-
can act as electron or hole traps and thereupon, may significantly tion of methyl-tert-butyl ether (MTBE) than comparable AuTiO2 or
alter the electronehole pair recombination rate. Among various AuTiO2 (P25) nanoparticles (Rodriguez-Gonzalez et al., 2008).
transition metal ions, Fe3þ is considered to be an interesting dopant In this contribution, the main emphasize was given to improve
for TiO2 (Wu et al., 2010; Kazutaka Obata et al., 2014) as Fe3þ (79 the visible light photocatalytic activity of differently modified TiO2
pm) has a similar size like that of Ti4þ (75 pm). Hence Fe3þ ions can by incorporating AuNPs (size 4.4e6.9 nm) on its surface. For a
be easily incorporated into the crystal lattice of TiO2. The reason for comparative study, a cation (Fe3þ), an anion (N), and a metal oxide
the enhanced photocatalytic efficiency of iron-doped TiO2 is (g-Al2O3) were used for modifying TiO2. The photocatalytic per-
believed to be due to the direct influence of the dopant on the formance of these photocatalysts was investigated for the degra-
intrinsic properties of TiO2 as being the band-gap energy, electro- dation of the methylene blue (MB) dye under visible-light
nehole pair recombination, particle size, and interfacial electron irradiation. The cooperative impact of surface deposition with
transfer rate (Zhu et al., 2006; Adan et al., 2007). Doping with non- AuNPs and the different dopants in the TiO2-based system was
metals such as carbon, nitrogen, and sulfur were found to be studied. In addition, the effects of the catalyst-loading concentra-
effective as well in enlarging the photoresponse of TiO2 (Burda tion and the initial dye concentration on the photocatalytic effi-
et al., 2003; Kachina et al., 2012; Nasir et al., 2013; Zhang et al., ciency were also investigated.
2014). These non-metal dopants are commonly introduced onto
the lattice oxygen site to affect the valence band of TiO2. Among 2. Experimental
them nitrogen is the most promising one because its p states can
contribute to the band gap narrowing by effectively mixing with O 2.1. Chemicals
2p of TiO2. In case of other non-metal dopants this mixing requires
very high formation energy mainly because of their large ionic Titanium (IV) n-butoxide (VERTEC® TNBT, 98%) was obtained
radius as compared to oxygen. Coupling TiO2 with metal oxides from Alfa Aesar, TiO2 (IV) P25 (nanopowder, average particle size
such as Al2O3, ZrO2, and WO3 is another way to improve the pho- 21 nm,  99.5% trace metal basis) from Evonic Degussa, titanium
tocatalytic efficiency of TiO2 (Wang et al., 2006; Gao et al., 2006; (IV) oxide, anatase (nanopowder, 99.8% trace metal basis) from
Yan et al., 2008; Pal and Kryschi, 2015). However, in many cases Aldrich, g-alumina (nanopowder, < 50 nm particle size) from
the modified TiO2 was found not to exhibit the expected photo- Aldrich, hydrogen tetrachloroaurate (III) trihydrate (99.5% p.a)
catalytic efficiency which occurs mainly because of low doping from Roth, iron (III) nitrate nonahydrate (99.99%) from Aldrich,
concentration and the generation of charge recombination centers ammonium hydroxide (30% NH3, 99.9%) from Aldrich, urea (98%)
in the lattice. Therefore, further modification is necessary to from Alfa Aesar, sodium hydroxide (ACS reagent,  97% pellets)
modulate the electronic structure of TiO2 and to achieve improved from Aldrich, methylene blue (dye content  82%) from Aldrich,
charge separation. Chen et al. demonstrated an approach to ethanol (anhydrous,  99.8%) from Aldrich. All materials and sol-
enhance solar absorption by introducing disorder in the surface vents were used as received from the suppliers without further
layers of nanophase TiO2 through hydrogenation (Chen et al., 2011). purification. Throughout the experiments ultrapure water (Milli-Q)
Zhang et al. reported of a new graphene-TiO2 composite catalyst with a resistivity of 18 MU cm was used.
system which shows largely improved photocatalytic efficiency for
the methylene blue degradation (Zhang et al., 2010a, b). Among 2.2. Synthesis of Fe3þ- doped TiO2 nanoparticles (FeeTiO2)
other strategies to extent the photoresponse of TiO2 to visible re-
gion, one that attracted considerable attention has been the Iron-doped TiO2 nanoparticles were prepared by a simple
deposition of gold nanoparticles (Kamat, 2002; Bootharaju and impregnation method. In a typical synthesis, about 5 g of TiO2 (P25)
Pradeep, 2013, Naya et al., 2013, Silva et al., 2011). Gold nano- and 90 mg of Fe(NO3)3*9H2O were mixed in 5 ml of milli-Q
particles in such a system are expected to act as a co-catalyst as well deionised water to get a slurry. The slurry was gently stirred at
as a sink for the photoinduced charge carriers. Moreover, due to the 100  C, until the excess water was completely evaporated. The solid,
existence of characteristic surface plasmon resonance (SPR) ab- thus obtained, was washed with absolute ethanol several times and
sorption band of gold nanoparticles (AuNPs), when deposited on centrifuged to remove the excess Fe3þ and NO-3 ions being present
the TiO2 surface they can act as photosensitizers for the excitation in the reaction mixture. The solid was then dried at 80  C overnight
of TiO2 under visible light irradiation via transferring electrons and grounded to a fine powder and finally calcined at 350  C in a
from photoexcited metals to TiO2. This effect increases the con- static oven for 4 h, to obtain the iron-doped TiO2 nanoparticles.
centration of the trapped charge carriers under visible light irra-
diation and as a consequence it enhances the photocatalytic 2.3. Synthesis of nitrogen-doped TiO2 nanoparticles (NeTiO2)
activity. However, until now, only limited reports are available on
applications of such plasmonic photocatalysts (Yogi et al., 2008; Nitrogen-doped TiO2 was prepared by hydrolysing titanium (IV)
Sangpour et al., 2010; Dozzi et al., 2009; Primo et al., 2011). Few n-butoxide using an aqueous ammonia solution. In a typical syn-
recent studies demonstrated that AuNPs deposition on TiO2 sub- thesis, 18.75 ml of 30% ammonium hydroxide was drop-wise added
strates can increase the photocatalytic performance when to 25 ml of titanium (IV) n-butoxide under vigorous stirring at room
compared to that of pure TiO2 (Zanella et al., 2002; Wang et al., temperature. A white gel was immediately formed. The gel was
2012; Subramanian et al., 2003). Recently Shi et al. synthesized then aged for another 24 h under gentle stirring at room temper-
gold nanoisland loaded TiO2 photoelectrode and reported that the ature. The solid precipitate thus obtained was centrifuged, in order
photocurrent generation and photocatalytic activity depends on to remove the excess solvent. This procedure was followed by
the interfacial structural geometry between the Au nanoisland and drying at 120  C for at least 3 h and was finally calcined at 450  C at
TiO2 (Shi et al., 2013). Pu et al. demonstrated that the photoactivity a rate of 2  C/min for 3 h.
 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664 1657

2.4. Synthesis of g-Al2O3 modified TiO2 nanoparticles (Al2O3eTiO2)

g-Al2O3 modified TiO2 nanoparticles were prepared via a facile

surface solegel process. First, about 3 g of pre-heated (heated for
12 h at 125  C) g-Al2O3 was loaded inside a tightly sealed round
bottom flask fitted with a reflux condenser. After purging the flask
with dry argon for 15 min, 4 ml of titanium (IV) n-butoxide, 20 ml of
anhydrous toluene, and 20 ml of anhydrous methanol were trans-
ferred one by one into the flask. The whole mixture was then
refluxed at 90  C for about 3 h. After the completion of the reaction,
a precipitate was obtained which was filtered, repeatedly washed
with absolute ethanol and finally with deionised water. The as-
synthesized product was then dried at 80  C inside a static oven
for 12 h followed by calcination at 400  C in air flow for 3 h.

2.5. AuNPs deposition

Before the gold deposition was carried out, doped and undoped
TiO2 nanoparticles were dried in air at 100 C for at least for 24 h.
Because of the light-sensitive nature of the gold precursor, all gold
deposition reactions were performed in the absence of light. Gold
deposition was performed using a simple deposition-precipitation
method. Typically about 1 g of the support (doped or undoped TiO2)
was dispersed in 100 ml aqueous solution of HAuCl4  3H2O
(30 mg, corresponding to a theoretical gold loading of 1.5 wt. %).
The solution temperature was slowly increased to 80  C, and the pH
was adjusted to a value of 9 using a 0.42 M urea solution. The re-
action was then carried out for another 16 h at the constant tem-
perature of 80  C under gentle stirring. After the completion of the
reaction the precipitate was separated from the solution mixture by
centrifugation and was repeatedly washed with deionised water
and then with absolute ethanol to remove the chloride ions. The
solid precipitate was then dried under vacuum at room tempera-
ture for 24 h and finally calcined at 300  C at a rate of 10  C/min for Fig. 1. (a); Spectrum of the light source used in the photocatalytic experiments. (b);
4 h in air. The gold concentrations in all the synthesized photo- Diffuse reflectance UVeVis absorption spectra of pristine TiO2 (P25) (a), NeTiO2 (b),
catalysts were determined by chemical analysis. All the prepared FeeTiO2 (c), Al2O3eTiO2 (d), Au/NeTiO2 (e), Au/FeeTiO2 (f), and Au/Al2O3eTiO2 (g)
photocatalysts.
photocatalysts were stored at room temperature under vacuum in a
desiccator, under exclusion of daylight.
sphere attachment, and BaSO4 was used as a reference. X-ray
2.6. Photodegradation of MB diffraction analyses were carried out at room temperature
employing a Philips PW1800 diffractometer with monochromic
The as-prepared photocatalysts were employed for the liquid- high-intensity CuKa radiation (l ¼ 154.18 pm). The samples were
phase decomposition of MB. First, an aqueous suspension of MB scanned in the 2q range of 20 e80 . The surface morphologies and
(25 ml, 5 ppm) and the photocatalysts (20 mg) were mixed in a particle sizes were determined employing transmission electron
100 ml Pyrex glass vessel and were stirred for 30 min in the dark to microscopy (TEM) (Zeiss EM 900) operating at 120 kV accelerating
allow the adsorptionedesorption equilibrium to be reached. The voltage and high-resolution transmission electron microscopy
suspension was then irradiated under a 150 W tungsten-halogen (HRTEM) (Phillips CM 300) operating at 300 kV accelerating
lamp (average intensity measured as 60 mW/cm2) selected as the voltage, respectively. The samples for both, TEM and HRTEM, were
visible-light source (Fig. 1a). A cut-off filter was inserted between prepared by drop-casting 5 ml of the ethanolic suspension of the
the lamp and the reaction vessel in order to eliminate light with prepared photocatalysts onto an ultrathin carbon coated copper
wavelengths shorter than 420 nm. The distance between the light grid (300 mesh) that was subsequently dried in vacuum at 25  C for
source and the vessel was maintained at 10 cm throughout the 2 days. The chemical composition and oxidation state of the pre-
reaction. A 3 ml of aliquot was taken at various time intervals, pared photocatalysts were investigated with X-ray photoelectron
centrifuged to isolate the solid catalyst and subsequently analyzed spectroscopy (PHI 5600 XPS spectrometer). Monochromatic Al Ka
using UVeVis absorption spectroscopy. The percentage of the MB (E ¼ 1486.7 eV) light was used as the X-ray source. Raman mea-
photodegradation was calculated using the formula (1At/ surements were performed at room temperature using a FT-Raman
Ao)  100%, where Ao is the absorbance at 664 nm of the initial MB (Bruker, RFS 100IS) spectroscopy using Nd-YAG laser (l ¼ 1064 nm)
solution before irradiation, At is the absorbance of the MB solution for excitation. Typically 150 scans were performed for each sample
at 664 nm which was measured after distinct time intervals. with a 4 cm1 resolution. BET-specific surface areas (SBET) of the
samples were determined through nitrogen adsorption at 77 K
2.7. Analytical methods (Micromeritics ASAP 2010). Prior to the BET measurements, the
powders were degassed at 250  C for 3 h. The actual gold content
Diffuse reflectance UVeVisible (DRUVeVis) absorption spectra and the amount of different dopants in the prepared photocatalysts
of the prepared photocatalysts were recorded using an UVeVis were determined using inductively coupled plasma-atomic
spectrophotometer (PerkinElmer Lambda 2) with an integrating
1658 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664

emission spectroscopy (ICP-AES) (Perkin Elmer Plasma 400). The

degradation kinetics of MB blue was monitored by measuring the
absorbance at 664 nm using a spectrophotometer (Perkin Elmer
Lambda 2), whereas the mineralization of the dye was monitored
by measuring the total organic carbon content (TOC) using a Shi-
madzu TOC 5000A analyzer by directly injecting the aqueous
solution.

3. Results and discussion

3.1. Characterization of the prepared photocatalysts

The diffuse reflectance UVeVis absorption spectra of pristine

TiO2 nanoparticles (P25), differently doped TiO2 and those of AuNPs
covered doped TiO2 photocatalysts was measured and shown in
Fig. 1b. In case of pure TiO2 P25, the primary absorbance was
determined to be around 400 nm (~3.1 eV) which is attributed to
the indirect electronic band-to-band transition. However, a signif-
icant enhancement of light absorption at a wavelength in the range
of 400e700 nm and a red shift of the absorption edge were
observed for all doped TiO2 photocatalysts. The origin of the
enhanced visible-light absorption due to doping is mainly because
of the formation of additional dopant energy levels in between the
valence and conduction band of TiO2. The lower-energy electronic
transitions from the dopants energy level to the conduction band of
doped TiO2 shift the absorption edge towards longer wavelengths.
In case of iron-doped TiO2 Adan et al. proposed that transitions of
3d electrons of Fe3þ to the conduction band of TiO2 give rise to a
band centered at 400 nm and therewith, contribute to the
enhanced visible-light absorption of iron-doped TiO2 nanoparticles
(Adan et al., 2007). Furthermore, the absorption spectra of all
AuNPs loaded doped TiO2 photocatalysts show a broad absorption
peak located at 550 nm which corresponds to the surface plasmon
resonance of AuNPs.
The actual gold content and the amount of various dopants in
different photocatalysts were determined by ICP-AES and are pre- Fig. 2. (a); The XRD patterns of TiO2 (P25) (a), anatase TiO2 (b), Au/TiO2 (P25) (c),
sented in Table 1. The gold deposition with 1.5 wt. % on pristine and NeTiO2 (d), Au/NeTiO2 (e), FeeTiO2 (f), and Au/FeeTiO2 (g). (b); XRD patterns of pure
doped TiO2 nanoparticles yielded as values for the real gold content g-Al2O3 (black solid line) and Au/Al2O3eTiO2 (red solid line). (For interpretation of the
in Au/P25, Au/FeeTiO2, Au/NeTiO2, and Au/Al2O3eTiO2 0.85, 0.79, references to color in this figure legend, the reader is referred to the web version of this
article.)
0.72 and 0.90 respectively. The result shows that the actual content
of gold is slightly lower than that predicted from the starting
material. (111) planes of the rutile phase respectively. The TiO2 (P25) nano-
The X-ray diffraction patterns of the synthesized photocatalysts particles loaded with AuNPs (Au/P25) exhibit almost the same
were measured (Fig. 2) to examine the effect of the AuNPs depo- diffraction pattern (Fig. 2a) as that of pristine TiO2 P25 as consisting
sition and doping on the phase structure and the phase composi- of the characteristic peaks of the anatase and the rutile phase. In
tion of the photocatalysts. In case of pristine TiO2 P25 nanoparticles case of iron-doped TiO2 (FeeTiO2) nanoparticles peaks identifying
signatures identifying the anatase and rutile phases were observed both, the anatase and rutile phase, were observed. However, no
(Fig. 2a), where the peaks at 25.33 , 37.92 , 48.16 , 54.02 , 55.20 , significant characteristic peaks for iron were found in the diffrac-
62.81, 68.81, 70.28 were assigned to the (101), (004), (200), tion patterns. This suggests that for iron-doped TiO2 nanoparticles,
(105), (211), (204), (105), (220) planes of the anatase phase, and the Fe3þ ions were incorporated into the crystal lattice of TiO2 where
peaks at 27.32 , 36.16 , 41.28 were attributed to the (110), (101),

Table 1
Textural properties of different photocatalysts and Au and other dopant concentrations.

Sample SBET m2/g Mean pore size (nm) crystallitea size (nm) Au (wt %)b N (wt %)b Fe (wt %)b Al (wt %)b

TiO2 (anatase) 64 23.2 24 e e e e

TiO2 (P25) 54.3 17.5 21 e e e e
Au/P25 59.0 11.2 19.5 0.85 e e e
FeeTiO2 132.1 8.1 18.2 e e 0.15 e
NeTiO2 82.2 4.9 20.4 e 0.1 e e
Al2O3eTiO2 223.2 12.1 17.6 e e e 0.30
Au/NeTiO2 85.9 4.6 18.8 0.72 0.09 e e
Au/FeeTiO2 141.2 9.4 17.5 0.79 e 0.12 e
Au/Al2O3eTiO2 231.3 10.7 15.8 0.90 e e 0.23
a
Determined using DebyeeScherrer equation.
b
Determined using inductively coupled plasma-atomic emission spectroscopy (ICP-AES) technique.
 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664 1659

they substitute Ti4þ ions. On the other hand, the XRD pattern of
nitrogen-doped TiO2 (NeTiO2) nanoparticles may be mainly
assigned to the anatase phase. However, prominent diffraction
peaks of the respective dopant along with characteristic peaks of
anatase TiO2 were observed for g-Al2O3 doped TiO2 nanoparticles
(Fig. 2b). The peaks at the 2q values of 19.01, 32.27, 36.43, 45.28,
61.16 and 67.20 were assigned to the (111), (220), (311), (400), (511)
and (440) diffractions of g-alumina. The characteristic diffractions
for gold, however, could not be detected for AuNPs decorated pure
and doped TiO2 nanoparticles. This may be due to significantly low
gold content (<1 wt %) below the detection limit and their homo-
geneous dispersion on the surface of the TiO2 and doped TiO2
supports. The average crystallite sizes of all samples were estimated
using the DebyeeScherrer equation (Eq. (1)) and are presented in
Table 1.

D ¼ Kl=b cos q (1)

where b is the full width at half maximum (FWHM) of the

diffraction peak emerging from the (101) plane of anatase titania
and the (440) plane of g-Al2O3, K ¼ 0.89 is a coefficient, q is the
diffraction angle, and l is the X-ray wavelength of the CuKa
radiation.
All the prepared doped TiO2 samples show large BET-specific
surface area (SBET) when compared with pure anatase TiO2 and
TiO2 P25, among which alumina doped TiO2 exhibits the highest
SBET (223.2 m2/g) (Table 1). Moreover, these samples shows more or
less similar SBET values when they have surface AuNPs, implies that
surface area of these samples was not greatly influenced by the
introduced AuNPs.
Fig. 3 presents the Raman spectra of the pristine TiO2 P25
nanoparticles, differently doped TiO2, and AuNPs decorated doped
TiO2 photocatalysts. For pristine TiO2, five Raman-active peaks at
143.27 cm1 (Eg), 197 cm1 (Eg), 397.84 cm1 (B1g), 516.46 cm1
(A1g þ B1g), 638.92 cm1 (Eg) are ascribed to anatase, whereas the
very weak peak at 445.23 cm1 is characteristic for the rutile
structure (Fig. 3 a). The B1g mode corresponds to an OeTieO Fig. 3. (a); Raman spectra of pure anatase TiO2 (a), TiO2 P25 (b), Au/P25 (c), FeeTiO2
bending vibration, and the TieO stretching vibration has A1g and Eg (d), Au/FeeTiO2 (e), NeTiO2 (f), Au/NeTiO2 (g), Al2O3eTiO2 (h), and Au/Al2O3eTiO2 (i).
symmetry. The prominent peaks of the observed Raman spectra of (b); representative Eg Raman active mode of different photocatalysts (a: anatase TiO2,
the AuNPs decorated, doped TiO2 photocatalysts resemble that of b: TiO2 P25, c: Au/P25, d: FeeTiO2, e: Au/FeeTiO2, f: NeTiO2, g: Au/NeTiO2, h:
Al2O3eTiO2, and i: Au/Al2O3eTiO2).
the TiO2 (P25) nanoparticles and that of anatase TiO2. This suggests
that surface modification with AuNPs does not alter the crystal
structure of TiO2. However, in comparison with P25 and pure in the TiO2 lattice (Fig. 4b). A slightly higher O1s binding energy
anatase TiO2, for AuNPs decorated, doped TiO2 nanoparticles we (530.9 eV) for the g-Al2O3 doped TiO2 photocatalyst was observed.
observed a noticeable shift to higher wavenumbers and in addition, This increase in the binding energy is attributed to the larger O1s
peak broadening for the Eg mode at 141 cm1 (Fig. 3b). Both, the binding energy of g-Al2O3 (531.8 eV), when compared to the O1s
shift and broadening of the peak, presumably arise from doping binding energy of TiO2 (530.2 eV). The observed binding energy can
and the smaller crystallite size of doped TiO2 nanoparticles. Obvi- be assumed as the average value of the O1s binding energy with
ously, doping of TiO2 nanoparticles destroys the TieOeTi symmetry contributions from both, g-Al2O3 and TiO2. The Au 4f7/2 and Au 4f5/2
to some extent which affects the force constants of the involved binding energies at 82.86 eV and 86.48 eV for Au/TiO2, at 82.5 eV
vibrational modes and thus, causes a shift of certain Raman modes. and 86.20 eV for Au/NeTiO2, at 82.45 eV and 86.1 eV for Au/
Moreover, no Raman lines due to iron oxide, nitrogen or alumina Al2O3eTiO2, and at 82.35 eV and 86.1 eV for Au/FeeTiO2 nicely
were found which is consistent with the results obtained from the coincide with the binding energy values of elemental Au (Fig. 4c).
XRD measurements. According to XPS hand books and other published work (Dozzi
The as-synthesized photocatalysts were further examined using et al., 2009; Primo et al., 2011; Wang et al., 2012), the binding en-
X-ray photoelectron spectroscopy (XPS) to investigate the ergy values of Au 4f7/2 and Au 4f5/2 for metallic gold are reported to
elemental compositions and oxidation states of the elements on the be 84.0 eV and 87.2 eV, respectively. The shift of the Au 4f peak to
surface (Fig. 4). With respect of the XPS peaks of the Ti 2p, although lower binding energy values which was observed here for the
there are slight differences in the binding energies of Ti 2p1/2 and Ti prepared photocatalysts indicates strong interactions between the
2p3/2 among different photocatalysts, they are all still in good AuNPs and the doped and undoped TiO2 nanoparticles. The Fe 2p
agreement with the actual binding energy values of Ti4þ (Fig. 4a). XPS spectrum of Fe3þ-doped TiO2 contains an extremely low con-
The slightly lower binding energy of Ti 2p for the doped TiO2 tent of iron in the support surface. The binding energy values of Fe
nanoparticles indicates that the TiO2 lattice is modified to some 2p3/2 and Fe 2p1/2 with 712.80 eV and 726.12 eV, respectively,
extent by incorporating dopants. The O1s binding energies of all the suggest that the iron is present in the oxide state (Fig. 4d).
samples appear around 530 eV which is typical for bulk oxide ðO2  Þ
1660 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664

Fig. 4. XPS spectra for the Ti 2p (a); O 1s (b); Au 4f (c); Fe 2p (d); N1s (e) and Al 2p (f) binding energy regions of different photocatalysts.

Moreover, the 13.41 eV separation between the Fe 2p1/2 and Fe 2p3/ was observed. The lowered binding energy may be due to the
2 peaks further confirms the presence of Fe3þ ions. The nitrogen 1s presence of Ti which has a stronger electron affinity than Al.
core level in Au/NeTiO2 appears as a single peak at 399.56 eV which The TEM and HRTEM images of the photocatalysts are shown in
can be attributed to the anionic N of the OeTieN bond (Fig. 4e). Fig. 5. The micrographs of these photocatalysts showed that AuNPs
This N1s binding energy value is significantly higher than that of are homogeneously deposited on the surface of doped and undo-
N1s (397 eV) that arises from chemisorbed nitrogen. Moreover, ped TiO2. The mean size of the AuNPs deposited on the Au/TiO2
there is no indication of TiN formation as evident form XRD and (P25), Au/FeeTiO2, Au/NeTiO2 and Au/Al2O3eTiO2 photocatalysts
also no Ti3þ peaks in the XPS suggesting that the N 1s peak at were found to be 6.9 nm, 5.6 nm, 5.8 nm and 4.4 nm, respectively.
399.56 eV in nitrogen modified photocatalyst may be assigned for The HRTEM images confirm that the AuNPs and TiO2 nanoparticles
substitutional nitrogen. In case of Au/P25, Au/FeeTiO2, and Au/ are highly crystalline in nature. Furthermore, the AuNPs turned out
Al2O3eTiO2, no nitrogen signal was observed in N 1s region of XPS as being slightly smaller when deposited on doped TiO2 nano-
spectra which ruled out the possibility of any nitrogen contami- particles than those on undoped TiO2. This indicates an effect of the
nants from urea in the prepared photocatalysts (data are not support on the growth kinetics of AuNPs during the deposition
shown). Urea treatment was also not found to introduce any N in process.
Au/NeTiO2, as there is rarely any change in the N 1s peak intensity
after urea addition. C1s peak at around 284.6 eV were found in all
survey spectra, corresponding to carbon impurities arising prob- 3.2. Photocatalytic degradation of the methylene blue (MB) dye
ably from the background of XPS test or the residual precursors. For
Au/Al2O3eTiO2, the Al 2p peak appears at a binding energy value of The photocatalytic activities of the photocatalysts were studied
73.7 eV which indicates the presence of Al3þ (Fig. 4f). In comparison by measuring the percentage of decomposition of MB in aqueous
with the binding energy of Al 2p (74.2 eV) in pure g-alumina, a solution under visible-light irradiation. MB is a photostable dye and
0.5 eV reduction in the binding energy of Al 2p in the photocatalyst cannot be degraded in the absence of any photocatalyst under UV
or visible-light irradiation. In the presence of a catalyst the reaction
 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664 1661

Fig. 5. TEM (a: Au/TiO2 P25; b: Au/NeTiO2; c: Au/FeeTiO2; d: Au/Al2O3eTiO2) and HRTEM (e: Au/TiO2 P25; f: Au/NeTiO2; g: Au/FeeTiO2; h: Au/Al2O3eTiO2) images of different
photocatalysts.

kinetics of the photodegradation of MB was examined by detecting with pristine TiO2 (P25), the AuNPs decorated TiO2 nanoparticles
the decay of the absorption of MB at 664 nm. The decrease of the show a significantly higher photocatalytic activity under visible-
MB concentration (5 ppm) when irradiated with a tungsten- light irradiation among which the Au/Al2O3eTiO2 catalyst ex-
halogen lamp in the presence of a photocatalyst (0.8 g/L) is hibits the best performance. The removal of MB in percentage due
shown as a function of the irradiation time (Fig. 6a). In comparison to the action of various supported photocatalysts under identical
1662 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664

experimental conditions is demonstrated in Fig. 6b. The efficiencies where r is the rate of dye mineralization being proportional to the
of the AuNPs decorated, doped and undoped TiO2 photocatalysts coverage q, which becomes proportional to the dye concentration
were found to rank in the following order: Au/ [MB] at low concentrations. k is the first-order rate constant, and K
Al2O3eTiO2 > AuFeTiO2 > Al2O3eTiO2 > Au/NeTiO2> is the adsorption coefficient. Eq. (2) can be re-written as:
AuP25 > FeeTiO2 > NeTiO2 > TiO2 (P25) > TiO2 anatase.
The rate of the photocatalytic reactions was evaluated applying 1 1 1
the kinetic model developed by Langmuir and Hinshelwood. The
¼ þ (3)
r k kK½MB
photocatalytic oxidation of various dyes (including MB) obeys the
LangmuireHinshelwood kinetics which is given by the following The constants k and K can be obtained from the intercept and
equation: slope of the straight line that is formed when 1/r is plotted as
function of 1/[MB]. [MB] is varied as a function of the irradiation
kK½MB time. The rate constants, r, of the MB photodegradation reaction
r ¼ kq ¼ ; (2) performed over various photocatalysts are obtained as 0.065 min1
1 þ K½MB
for TiO2 anatase, 0.107 min1 TiO2 P25, 0.197 min1 (Au/P25),
0.187 min1 for FeeTiO2, 0.172 min1 for NeTiO2, 0.251 min1 for

Fig. 6. (a); MB photodegradation in aqueous solution over various photocatalysts under visible-light irradiation at a photocatalyst loading concentration of 0.8 g/L and an initial MB
concentration of 5 ppm (b); percentage removal of MB using different photocatalysts under visible-light irradiation for 40 min: (A) photolysis; (B) anatase TiO2; (C) TiO2 (P25); (D)
NeTiO2; (E) FeeTiO2; (F) Al2O3eTiO2; (G) Au/P25; (H) Au/NeTiO2; (I) Au/FeeTiO2; and (J) Au/Al2O3eTiO2. (c); TOC removal in the reaction systems during visible light irradiation of
MB over various photocatalysts. The effect of the photocatalyst loading concentration (d) and the initial MB concentration (e) on the degradation rate of MB under visible-light
irradiation. In these experiments Au/Al2O3eTiO2 was used as the photocatalyst.
 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664 1663

Al2O3eTiO2, 0.265 min1 (Au/FeeTiO2), 0.242 min1 (Au/NeTiO2), scales with the electron deficiency of the deposited AuNPs. The
and 0.360 min1 (Au/Al2O3eTiO2). smaller the AuNPs sizes are, the larger the electron deficiency will
The photocatalytic mineralization of organic carbon of MB was become which results into increased photocatalytic activity. Several
examined by detecting the total organic carbon (TOC) as function of previous literatures reported of a critical AuNPs size <5 nm for the
the irradiation time, [TOC] ¼ f(t) (Fig. 6c). The decomposition and maximum photoactivity of gold supported catalysts (Orlov et al.,
mineralization curves were well fitted to an exponential decay 2007; Haruta, M., 1997). Similar behavior of small nanosized gold
curve which suggests first-order kinetics. Fig. 6c demonstrates that particles in the oxidation of CO was also reported by Haruta, who
about 50 min of visible-light irradiation is required to almost show that AuNPs with size smaller than 5 nm are the most active
completely mineralize MB over the Au/Al2O3eTiO2 photocatalyst. (Haruta, M; 1997). On the other hand when the AuNPs size
For an irradiation time of 40 min the mineralization level of MB is > 5 nm, the gold electron deficiency diminishes which make it
reached values of 22.1%, 31%, 37%, 59%, 45.3%, 55.5%, and 72% for less capable to effect the recombination rate of the electronehole
TiO2 (P25), NeTiO2, FeeTiO2, Al2O3eTiO2, Au/TiO2 (P25), Au/ pair. In our case, the TEM and HRTEM images clearly evidence that
NeTiO2, and Au/FeeTiO2, respectively. The significantly enhanced the AuNPs deposited on Al2O3eTiO2 exhibited smaller sizes
photoactivity of the AuNPs decorated, doped TiO2 nanoparticles is (average size 4.4 nm) than that for Au/FeeTiO2 and Au/NeTiO2. This
attributed to the synergetic impact of dopants and AuNPs on the explains the significantly higher photoactivity of the Au/
electronic and structural properties of the TiO2 nanoparticles. Al2O3eTiO2 photocatalyst when compared to the other photo-
While the incorporation of dopant ions into the lattice may result catalysts. The highest photocatalytic activity was observed for Au/
into the creation of trap and mid-gap states, the deposition of Al2O3eTiO2 with 1.5% AuNPs loading: about 99.5% of the MB dye
AuNPs modifies the surface structure and functionality and there- was degraded after 50 min of the reaction under visible-light
upon, increases the surface reactivity. In addition to the chemical irradiation. Any increase in AuNPs loading hardly changes the.
composition of doped TiO2 nanoparticles the crystallite size may However, a slight decrease of the photocatalytic performance was
also have a great influence in determining the dynamics of the e/ observed for an AuNPs loading above 5 wt. %. The higher content of
hþ recombination process. For pristine TiO2 (P25) the light ab- gold on the photocatalyst surface should not only affect the ab-
sorption capacity can be drastically increased by doping when sorption properties but also may provide the creation of additional
resulting in the formation of appropriate mid-gap states. The rate- recombination centers for the electronehole pairs which lowers
determining process in photocatalytic reactions of this type is the the photoactivity.
electron transfer from the catalyst surface to adsorbed oxygen The effect of the photocatalyst loading concentration on the
molecules. The increased visible-light absorption of Al2O3eTiO2, photodegradation rate was examined by performing a series of
when compared to FeeTiO2 and NeTiO2, provides enhanced rates experiments using different Au/Al2O3eTiO2 concentrations ranging
of electrons and holes migration to the catalyst surface. In addition, from 0.2 g/L to 1 g/L. The initial MB concentration was kept iden-
the bulk e/hþ recombination rate is significantly suppressed in tical. The observed photodegradation rates for various catalyst
Al2O3eTiO2 because of its smaller crystallite size (17.2 nm, Fig. 5 d, concentrations are shown in Fig. 6d. Generally, the photocatalytic
h). Owing to its smaller crystallite size, Al2O3eTiO2 has a relatively activity of a photocatalyst depends on the number of active sites
large surface area as evident from BET surface area (SBET: 223.2 m2/ present on the catalyst surface. The availability of the active sites
g) and thus, allows more and more gold nanoparticles to be increases with the photocatalyst loading concentration when risen
deposited on its surface. Moreover, alumina can serve as an efficient up to 0.8 g/L. However, an increase of the photocatalyst loading
electron accepting species since it is more acidic than TiO2. Alumina concentration beyond 0.8 g/L is associated with increased light
is known to improve the electronic properties of TiO2 by modifying scattering. Light scattering will reduce the number of photons
the crystal lattice and surface structure to some extent. available for the photocatalytic reactions, and thereupon reduce the
To understand the impact of AuNPs on the photocatalytic ac- photodegradation rate.
tivity of the different photocatalysts, the MB photodegradation Effects of the initial MB concentration on the photocatalytic rate
reaction was performed once in the presence of doped TiO2 were also investigated by carrying out a series of experiments at
nanoparticles without any surface AuNPs and another time, in the different initial MB concentrations when all other experimental
presence of AuNPs covered, doped TiO2. Apparently, the AuNPs parameters were kept identical. The photocatalyst used for this
deposition causes a much higher visible-light activity in compari- study was Au/Al2O3eTiO2 at a loading concentration of 0.8 g/L. The
son with the uncovered TiO2 surface. The significantly increased experimental data showed that the photodegradation rate
photoactivity of AuNPs covered, doped TiO2 nanoparticles is un- decreased with the rise of the initial MB concentration (Fig. 6e). A
derstood to arise from the improved charge separation. Subse- reduction of the photodegradation rate to about 25% was observed
quently to the photo-generation of excitons the charge separation when the initial MB concentration was scaled up from 5 ppm to
occurs via the transfer of the conduction-band electrons from the 10 ppm. This change of the photodegradation rate is explained with
TiO2 surface to adsorbed oxygen molecules. Surface AuNPs as acting the increased light absorption due to the MB molecules which re-
as an efficient sink for the conduction-band electrons increase the duces the excitation density at the photocatalyst surface and
separations between electrons and holes and therefore, consider- therewith, the formation of reactive hydroxyl and superoxide
ably facilitate the electron transfer to adsorbed oxygen. The radical which are required for the photodegradation of MB.
adsorbed oxygen molecules will be oxidized to superoxy radicals
that oxidize water so that finally hydroxyl radicals will be formed 4. Conclusion
which oxidize MB and therewith provide the decomposition of the
dye. Furthermore, under visible-light irradiation AuNPs exhibit Here in this contribution we explored the photocatalytic activity
surface plasmons. Plasmonic AuNPs, when deposited on TiO2 sur- of AuNPs decorated, differently doped and undoped TiO2 nano-
faces, cause a small negative shift in the quasi-Fermi energy level of particle based photocatalysts for the visible-light mediated degra-
the TiO2 bulk. This also enlarges the charge separation in the dation of MB in water. The as-prepared AuNPs decorated, doped
photocatalyst and therewith enhances the efficiency of the inter- TiO2 photocatalysts exhibited a much better visible-light photo-
facial charge-transfer process. The photocatalyst becomes highly response and consequently evolved higher photocatalytic effi-
reductive in nature which is associated with an enhanced photo- ciency when compared with pristine TiO2 and doped TiO2 with
catalytic performance. The reductive nature of the photocatalyst AuNP-free surfaces. Among various photocatalysts, Au/Al2O3eTiO2
1664 N.K. Pal, C. Kryschi / Chemosphere 144 (2016) 1655e1664

showed the best performance for the MB photodegradation: MB over TiO2 catalysts doped with Fe. Appl. Catal. B Environ. 160e161, 200e203.
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was degraded for about 99.5% in just 50 min under visible-light
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Sakthivel, S., Kisch, H., 2003. Daylight photocatalysis by carbon-modified titanium
Support of the Deutsche Forschungsgemeinschaft (graduate dioxide. Angew. Chem. Int. Ed. 42 (40), 4908e4911.
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