Chemical Engineering Journal 249 (2014) 6371

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Chemical Engineering Journal

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PdO loaded TiO2 hollow sphere composite photocatalyst with a high

photocatalytic disinfection efciency on bacteria
Yang Liu a, Qi Li a,, Jingtao Zhang a, Wuzhu Sun a, Shian Gao a, Jian Ku Shang a,b
a
Environment Functional Materials Division, Shenyang National Laboratory for Materials Science, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016,
PR China
b
Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, Urbana, IL 61801, USA

h i g h l i g h t s

g r a p h i c a l a b s t r a c t

 Palladium oxide nanoparticles loaded

titanium oxide hollow sphere

photocatalyst.
 Largely enhanced photocatalytic
disinfection of E. coli bacteria.
 Optimum PdO loading concentration
at 0.4 wt.%.
 Enhancement attributed to both the
hollow structure and the electron
trapping by PdO.
 PdO is better than Pd to trap electrons
because it has a larger work function
than Pd.

a r t i c l e

i n f o

Article history:
Received 5 January 2014
Received in revised form 17 March 2014
Accepted 21 March 2014
Available online 1 April 2014
Keywords:
TiO2 hollow sphere
PdO nanoparticles
Electron/hole separation
Photocatalytic disinfection
Bacteria

a b s t r a c t
PdO loaded TiO2 hollow spheres were synthesized via rst reducing Pd2+ to Pd in ethanol onto TiO2 hollow
spheres by reuxing and then oxidizing Pd to PdO through calcination in air. PdO nanoparticles were
distributed relatively uniformly both on the surface and in the shell/interior of these TiO2 hollow spheres,
to act as potential electron/hole pair separation centers. These PdO loaded TiO2 hollow spheres demonstrated a superior photocatalytic disinfection performance on Escherichia coli bacteria, compared with
the unloaded samples or P25 TiO2 nanoparticles. Their largely enhanced photocatalytic disinfection performance could be attributed to both their unique hollow structure and the electron trapping capability of
loaded PdO nanoparticles. Samples with a series of PdO loading ratios were synthesized and tested to determine the optimum PdO loading ratio, which was found to be 0.4 wt.%. Below the optimum PdO loading,
the photocatalytic disinfection performance increased with the increase of PdO loading ratio, while further
increase of the PdO loading over 0.4% resulted in a deleterious inuence on the PdO enhancement effect.
The photocatalytic performance differences between Pd and PdO modied samples were also investigated.
Samples with 0.4% PdO modication demonstrated a better photocatalytic disinfection effect on E. coli bacteria than samples with 0.4% Pd modication, which could be attributed to their different work functions.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Hollow spheres have received much research attention due to
their specic hollow structure and consequently unique physical
Corresponding author. Address: 72 Wenhua Road, Shenyang, Liaoning Province
110016, PR China. Tel.: +86 24 83978028; fax: +86 24 23971215.
E-mail address: qili@imr.ac.cn (Q. Li).
http://dx.doi.org/10.1016/j.cej.2014.03.087
1385-8947/ 2014 Elsevier B.V. All rights reserved.

and chemical properties in a wide range of technical applications,

such as active-material encapsulation, drug delivery, micro-reactors, lters, piezoelectric transducers, and low dielectric constant
substrates [1]. Hollow spheres of TiO2 are especially interesting because TiO2 has been extensively investigated as a photocatalyst for
both energy conversion and environmental remediation [24]
following the original work of Fujishima and Honda in 1972 in

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Y. Liu et al. / Chemical Engineering Journal 249 (2014) 6371

the discovery of the photocatalytic splitting of water on TiO2 electrodes. Since Caruso et al. reported the rst fabrication of TiO2 hollow spheres by templating on polystyrene (PS) spheres in 2001
[5,6], the creation of TiO2 hollow spheres and their applications
in photocatalysis have been intensely studied. Varieties of both
hard and soft templates were subsequently designed [79], and
template-free methods based on Ostwald ripening were also developed to synthesize TiO2 hollow spheres [1014]. Because the multiple reections (scattering) from their specic hollow structure
could result in a better light harvest and the subsequent generation
of more photoelectron/hole pairs, TiO2 hollow spheres usually
demonstrated superior photocatalytic activities over their nanoparticles or solid sphere counterparts [1418].
The electron/hole pair recombination problem is generally
found in photocatalysts, which causes the loss of a large portion
of photo-generated electron/hole pairs before they could react
with electron/hole acceptors to produce reactive oxygen species
(ROS), thus reducing their photocatalytic efciency. To minimize
the electron/hole pair recombination, various materials had been
introduced as electron/hole pair separators to modify pure TiO2
[19]. For example, extensive research efforts had been made on
the use of noble metals or their oxides for the modication of
TiO2 [2034], which could serve as efcient electron/hole pair
separators to largely enhance the photocatalytic performance of
TiO2-based photocatalysts. For TiO2 hollow spheres, modications
had also been examined to further enhance their photocatalytic
performances, including carbon materials modication [36,37],
sulde modication [38], transition metal oxides modication
[39,40], and noble metals modication [4144]. However, to our
best knowledge, there was no report on the use of loaded PdO
nanoparticles to modify TiO2 hollow spheres, while PdO had been
demonstrated as an efcient electron/hole pair separator to largely
enhance the photocatalytic performance of TiO2-based photocatalysts in our previous studies [2730] and a recent report by Ismail
[31]. Furthermore, only limited efforts had been made to examine
the photocatalytic performance difference between noble metal
modications and noble metal oxide modications on TiO2 [32
35], while controversial results were reported in literature.
In this study, TiO2 hollow spheres were synthesized through a
solvothermal method based on the template-free Ostwald ripening
process, and PdO nanoparticles were loaded onto these TiO2 hollow
spheres via rst reducing Pd2+ to Pd in ethanol by reuxing and
then oxidizing Pd to PdO by calcination in air. Samples with a series of PdO loading ratios were synthesized and the PdO loading ratio effect on their structure and optical properties was investigated
by detailed characterizations with SEM, TEM, XRD, XPS, BET and
UVvis spectra. The photocatalytic disinfection of Escherichia coli
(E. coli) bacteria by PdO loaded TiO2 hollow spheres was much faster than that by the unloaded ones. The optimized PdO loading ratio was found at 0.4 wt.%. Below it, the increase of PdO loading
ratio enhanced the photocatalytic disinfection performance, while
further increase over it caused a deleterious effect on the enhancement effect. The photocatalytic performance differences between
Pd and PdO modications on TiO2 hollow spheres were further
investigated, which demonstrated that PdO modication had a better enhancement than Pd modication on the photocatalytic disinfection of E. coli bacteria and it may be attributed to their different
work functions.

Chemical Reagent Co., Ltd. (Shanghai, PR China), and used without

further purication. LB nutrient agar was BR grade and purchased
from Beijing Aoboxing Biotechnology Co., Ltd. (Beijing, PR China).
Deionized water was prepared from a lab ultra-pure water purier.
2.2. Synthesis of TiO2 hollow spheres
Well-dispersed TiO2 hollow spheres were synthesized through
a template-free solvothermal method based on our previous work
[14] as follows. 15 mmol HNO3 was diluted by deionized water to a
total volume of 23 mL, then 1 mmol Ti(SO4)2 was added into the diluted HNO3 solution. After Ti(SO4)2 was dissolved completely,
46 mL n-PrOH was added into the mixture solution to form an
n-PrOH/H2O mixed solvent solution. The solution was transferred
into a Teon-lined autoclave of 90 mL capacity, which was then
sealed, kept in an oven at 180 C for 12 h, and cooled to room temperature afterwards. The obtained precipitate was centrifuged,
washed with water and ethanol for several times, and then dried
at 60 C to obtain the as-synthesized TiO2 hollow spheres.
2.3. Preparation of PdO loaded TiO2 hollow spheres
The synthesis process of PdO loaded TiO2 hollow spheres was
schematically illustrated in Fig. 1. They was prepared via rst
reducing Pd2+ to Pd on TiO2 by reuxing in ethanol and then oxidizing Pd to PdO by calcination in air as follows. PdCl2 was dissolved into deionized water to make a stock solution with
concentration of 10 mg/mL. 0.4 g as-synthesized TiO2 hollow
spheres were dispersed ultrasonically in 200 mL absolute ethanol
for 10 min. A proper amount of PdCl2 solution was then added into
the TiO2 hollow spheres suspension followed by reuxing in ethanol at 70 C for 1 h under vigorous stirring. After reuxing, the suspension was further evaporated and dried at 70 C. This process
was modied from a reported process for Pd-loading onto carbon
materials [45], after which Pd nanoparticles were loaded onto
TiO2 hollow spheres. The dried powder was then calcinated at
600 C for 5 h (heating rate 2 C/min) under air atmosphere in a
mufe furnace to obtain the PdO loaded TiO2 hollow spheres due
to the oxidation of Pd and enhance the degree of crystallinity of
these TiO2 hollow spheres (see Fig. S1 in Supplementary data for
the XRD pattern comparison for TiO2 hollow spheres before and
after the calcination process). Samples with different PdO loading
ratios (0, 0.1, 0.4, 0.7, and 1.0 wt.%, respectively) were synthesized
to obtain the optimized PdO loading ratio.
For comparison purpose, Pd loaded TiO2 hollow spheres
was also prepared as schematically illustrated in Fig. 1. The assynthesized TiO2 hollow spheres were rs calcinated at 600 C in

2. Experimental
2.1. Materials and chemicals
Ti(SO4)2 (96%), HNO3 (65%), n-PrOH (99%), PdCl2 (59%, count as
Pd), and absolute ethanol (99.8%) were purchased from Sinopharm

Fig. 1. Schematic illustration of the synthesis processes of PdO and Pd loaded TiO2
hollow spheres, respectively.

Y. Liu et al. / Chemical Engineering Journal 249 (2014) 6371

air for 5 h to enhance its degree of crystallinity, and then Pd nanoparticles were loaded on these calcinated TiO2 hollow spheres by
the reuxing process as mentioned above. The detailed characterization analysis of these Pd loaded TiO2 hollow spheres could be
found in Supplementary data.
2.4. Characterization of PdO loaded TiO2 hollow spheres
SEM images were obtained on a Leo-Supra-35 scanning electron
microscope (Carl Zeiss, Oberkochen, Germany). TEM images and
SAED pattern were taken on a JEOL-2100 transmission electron
microscope (JEOL, Tokyo, Japan). XRD patterns were examined on
a D/MAX-2004 X-ray powder diffractometer (Rigaku, Tokyo, Japan)
using Cu Ka radiation. XPS spectra were recorded on an Escalab
250 X-ray photoelectron spectrometer (Thermo Fisher, Waltham,
USA) with Al Ka X-ray source. The BrunauerEmmettTeller
(BET) data was measured by nitrogen adsorptiondesorption isotherms on an Autosorb-1 surface area and pore size analyzers
(Quantachrome, Boynton Beach, USA). The optical absorbance
was determined from the diffuse reectance measurements on a
UV-2550 UVvis spectrophotometer (Shimadzu, Kyoto, Japan)
using BaSO4 as the reference.
2.5. Photocatalytic disinfection of E. coli
Wild type E. coli (ATCC 15597, the American Type Culture
Collection, Manassas, VA, USA) were used for photocatalytic disinfection experiments. After overnight culture, the cells were diluted
to a cell suspension of ca. 108 cfu/mL in buffer solution (0.05 M
KH2PO4 and 0.05 M K2HPO4, pH 7.0) for further use. All solid or
liquid materials had been autoclaved for 30 min at 121 C before
use. A xed concentration of 1 mg photocatalyst/mL E. coli suspension was used in the experiments. 10 mg photocatalyst with 9 mL
buffer solution was rst injected into a sterile 60 mm  15 mm
Petri dish and was dispersed ultrasonically for 5 min. Then, 1 mL
E. coli suspension (ca. 108 cfu/mL) was added into the Petri dish,
so that the initial E. coli concentration used in the photoctalytic disinfection experiments was ca. 107 cfu/mL. The Petri dish was exposed to a UV light irradiation from a 300 W Xe arc lamp (PLSSXE300, Beijing Trusttech Co., Ltd., Beijing, China) with a 365 nm
band pass lter (300 < k < 400, kmax = 365 nm). The light intensity
measured at 365 nm was 3 mW/cm2. At regular time intervals,
100 lL of the cell suspensions were withdrawn in sequence. After
appropriate dilutions in buffer solution, three aliquots of 100 lL
suspensions was spread onto three agar medium plate, respectively, and incubated at 37 C for 18 h. Then, the number of viable
cells in terms of colony-forming units was counted. The comparison experiments in the dark with the photocatalyst and under light
illumination only without photocatalyst were also carried out
when other experiment conditions were the same.
3. Results and discussion
3.1. Morphology and micro-structure of PdO loaded TiO2 hollow
spheres
TiO2 hollow spheres with 1 wt.% PdO loading were chosen as
the representative for the investigation of the morphology and
micro-structure details of PdO loaded TiO2 hollow sphere composite photocatalyst. Fig. 2a shows a lower magnication SEM image
of the sample. It could be observed that these PdO loaded TiO2 hollow spheres were well-dened and the loading of PdO nanoparticles did not affect their specic hollow sphere structure. They
were relatively uniform in size, and their diameter was 2 lm.
Fig. 2b shows a higher magnication SEM image of a single PdO

65

loaded TiO2 hollow sphere, which clearly demonstrated its hollow

nature from the hole on its shell. The shell was highly porous, and
was composed of ne nanoparticles. Fig. 2c shows the TEM image
of a single PdO loaded TiO2 hollow sphere, which further demonstrated its hollow structure. The shell thickness was 250 nm,
which was in accordance with the SEM observation. Fig. 2d shows
its corresponding SAED pattern, which indicated that these PdO
loaded TiO2 hollow spheres had polycrystalline anatase structure.
No diffraction spot of PdO could be easily identied in this pattern
because the PdO loading ratio was too low to form diffraction spots
with enough intensity to be observed. To directly observe the
loaded PdO, higher magnication TEM observations on the hollow
sphere edge were conducted. Some ne nanoparticles of several
nanometers in diameter with darker color could be observed on
nanoparticles of few tens of nanometers with lighter color. For
example, Fig. 2e shows the view of the part of the hollow sphere
with higher magnication which was marked using a box in
Fig. 2c. The ne nanoparticle pointed by an arrow had a darker color, compared with those larger nanoparticles around with lighter
color. Fig. 2f shows the corresponding HRTEM image of this ne
nanoparticle. One set of lattice planes could be clearly observed,
which demonstrated its well-crystallized nature. The d-spacing
was determined at 0.215 nm, corresponding to the (1 1 0) plane
of PdO. These observations suggested that these ne nanoparticles
with darker color were PdO nanoparticles, which were loaded on
TiO2 hollow spheres successfully with our synthesis approach.

3.2. Crystal structure and composition of PdO loaded TiO2 hollow

spheres
Fig. 3a shows the XRD patterns of PdO loaded TiO2 hollow
spheres with different PdO loading ratios. Their major diffraction
peaks belonged to the anatase TiO2 phase (JSPDS No. 21-1272)
and were mostly identical. After the calcination process at
600 C, all ve samples were highly crystallized, which was benecial for photocatalytic performance due to the lack of defects. An
additional weak diffraction peak at 2h34 could be observed for
samples with 0.4%, 0.7%, and 1.0% PdO loading ratios, respectively,
and its intensity increased with the increase in the PdO loading ratio. Fig. 3b shows the enlarged XRD patterns with 2h range from
30 to 36, from which this additional weak diffraction peak could
be distinguished more clearly. Its peak position was found at 2h
33.84, which could be assigned to PdO (1 0 1) diffraction peak
(JSPDS No. 41-1107), the strongest diffraction peak of PdO. This
observation was in accordance with the HRTEM observation demonstrated in Fig. 2f. No obvious PdO (1 0 1) XRD peak could be identied in the XRD diffraction pattern of sample with 0.1% PdO
loading ratio, which could be attributed to the very low PdO ratio
below or close to the XRD detection limitation.
Fig. 3c shows the XPS survey spectra of PdO loaded TiO2 hollow
spheres with different PdO loading ratios, which further conrmed
the existence of Ti, O, and Pd in PdO loaded TiO2 hollow spheres. C
1s peak was also observed due to the widespread presence of carbon in the environment. Fig. 3d shows the high-resolution XPS
scans over Pd 3d peaks, from which Pd peaks could be easily identied for samples with 0.4%, 0.7% and 1.0% PdO loading ratios,
respectively, and the intensity of Pd peaks increased with the increase of PdO loading ratio. The binding energy of Pd 3d5/2 and
3d3/2 were 336.5 eV and 341.8 eV, respectively, which further
conrmed that palladium existed as PdO in these samples. This
observation was in accordance with the HRTEM and XRD observations. No obvious Pd 3d peak could be identied in the XPS scan
over the sample with 0.1% PdO loading ratio, which may be attributed to this very low PdO ratio below or close to the XPS detection
limitation.

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Y. Liu et al. / Chemical Engineering Journal 249 (2014) 6371

Fig. 2. (a) SEM image of 1 wt.% PdO loaded TiO2 hollow spheres; (b) SEM and (c) TEM images of a hollow sphere, respectively; (d) SAED pattern of the hollow sphere in (c); (e)
TEM image of the box area in (c) with a higher magnication; and (f) HRTEM image of the arrow marked particle in (e).

The relative element composition ratio of Pd/Ti was determined

by XPS analysis, and it was converted to PdO/TiO2 weight ratio for
comparison with the nominal one used in the synthesis process.
The XPS measured values in samples with 0.4%, 0.7% and 1.0% nominal PdO loading ratios were 0.5831%, 0.8317% and 1.0526%,
respectively, slightly higher than the nominal values. XPS is a surface elemental analysis technique, which provides elemental information within a shallow layer from the material surface. It is easy
to understand that the surface enrichment of PdO loadings would
happen from the loading process. However, if PdO nanoparticles
were only loaded on the outermost surface of these TiO2 hollow
spheres, the PdO/TiO2 weight ratio obtained from XPS analysis
should be much higher than the nominal values. Since the TiO2

hollow sphere shell was highly porous, PdCl2 solution could enter
the porous shell and the interior void of TiO2 hollow spheres,
which would result in a more dispersed distribution of PdO nanoparticles both on the surface and in the shell/interior of these TiO2
hollow spheres, and be benecial to the electron/hole pair separation process.

3.3. Calcination and PdO-loading effects on the structure of PdO loaded

TiO2 hollow spheres
The calcination and PdO-loading effects on the structure of PdO
loaded TiO2 hollow spheres were summarized in Table 1. The

Y. Liu et al. / Chemical Engineering Journal 249 (2014) 6371

67

Fig. 3. (a) XRD patterns of PdO loaded TiO2 hollow spheres; (b) enlarged XRD patterns of PdO loaded TiO2 hollow spheres with 2h from 30 to 36; (c) XPS survey spectra of
PdO loaded TiO2 hollow spheres; and (d) high-resolution XPS scans over Pd 3d peaks of PdO loaded TiO2 hollow spheres.

Table 1
The average crystallite size and BET data.
Sample

Average
crystallite
size
(nm)

Specic
surface
area
(m2/g)

Total
pore
volume
(cm3/g)

As-synthesized
TiO2 hollow spheres
0%
PdO(x%)-loaded TiO2
hollow spheres
0.1%
0.4%
0.7%
1.0%

12.3

125.9

0.208

6.6

25.7
24.6
23.9
23.4
21.5

35.0
37.7
38.9
40.6
41.2

0.194
0.190
0.198
0.202
0.209

22.2
20.17
20.33
19.87
20.31

Average
pore
size
(nm)

average crystallite size of TiO2 was calculated by the Scherrers

equation [46]:

D 0:9k=b cos h

25.7 nm and their specic surface area subsequently decreased

to 35.0 m2/g. However, they could still keep their hollow structure
with a similar pore volume (0.194 cm3/g) and a much larger average
pore size (22.2 nm). The loading of PdO had an inhibition effect on
the grain growth of these TiO2 hollow spheres during the calcination, as demonstrated by the decrease of average crystallite size
with the increase of PdO loading ratio. This observation also suggested that the loading of PdO occurred not only on the surface
but also in the shell/interior of these TiO2 hollow spheres as XPS
analysis indicated. Otherwise, the inhibition effect could not be so
obvious if PdO nanoparticles were only loaded on the outermost
surface of these TiO2 hollow spheres. The increase of specic surface
area with the increase of PdO loading ratio could be attributed to
both the decrease of average crystallite size as well as additional
surfaces from PdO nanoparticles. It was also found that the loading
of PdO did not obviously affect the total pore volume and average
pore size.

1
3.4. Optical Properties of PdO loaded TiO2 hollow spheres

where k is the average wavelength of the X-ray radiation (Cu Ka,

k = 0.15418 nm), b is the line-width at half-maximum peak position,
and h is the diffracting angle. The BET surface area was measured by
N2 adsorptiondesorption isotherms, and the total pore volume and
average pore size were derived from the BarrettJoynerHalenda
(BJH) model. TiO2 hollow spheres obtained after the solvothermal
process had a ne average crystallite size of 12.3 nm, a high specic surface area of 125.9 m2/g, and a porous structure, all of
which are benecial for the loading of various modications and
make these TiO2 hollow spheres ideal substrates for the synthesis
of composite photocatalysts. During the calcination, the average
crystallite size of these TiO2 hollow spheres increased to

The optical properties of these PdO loaded TiO2 hollow spheres

were investigated by measuring the diffuse reectance spectra.
From the reectance data, optical absorbance could be approximated by the KubelkaMunk function, as given by Eq. (2):

FR

1  R2
2R

where R is the diffuse reectance [47]. Fig. 4 shows the optical

absorbance of these PdO loaded TiO2 hollow spheres, compared
with TiO2 hollow spheres. All samples had the absorption edge at
380 nm, which came from the light absorption of TiO2. When

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Y. Liu et al. / Chemical Engineering Journal 249 (2014) 6371

PdO loading was present, these TiO2 hollow spheres had an extra
small absorption shoulder up to 600 nm coming from the absorbance of PdO. With the increase of PdO loading ratio, the intensity
of this absorption shoulder increased gradually.
3.5. Photocatalytic disinfection of E. coli cells by PdO loaded TiO2
hollow spheres
The photocatalytic activities of these PdO loaded TiO2 hollow
spheres were evaluated by their disinfection of E. coli under UV
irradiation (k = 365 nm). The initial E. coli concentration was ca.
107 cfu/mL, and 1 mg photocatalyst/mL E. coli suspension was used
in the disinfection experiment. The survival ratio of E. coli was
determined by the ratio of Nt/N0, where N0 and Nt are the numbers
of colony-forming units at the initial and each following time interval, respectively. Fig. 5a shows the survival ratio versus the treatment time by PdO loaded TiO2 hollow spheres with different
loading ratios. With only UV irradiation at 365 nm and no photocatalyst presence, the survival ratio of E. coli was kept at 100%
(not shown in Fig. 5a). Thus, the UV light used in the photocatalytic
disinfection experiment had no bactericidal effect on E. coli cells.
Control experiments were also conducted in the dark with the
presence of photocatalysts (shown in Fig. 5a with 0.4% PdO loaded
TiO2 hollow spheres as a representative). Without the UV irradiation, no bactericidal effect was observed for all these photocatalysts, which suggested that PdO loaded TiO2 hollow spheres
could not disinfect E. coli cells by just themselves.
When illuminated by UV light, all these photocatalysts demonstrated distinct bactericidal effect on E. coli cells. Compared with
the two control experiments, it is clear that the bactericidal effect
demonstrated by these samples came from their photocatalytic
behavior activated by the UV illumination. Without PdO loading,
unloaded TiO2 hollow spheres demonstrated just a moderate photocatalytic disinfection effect on E. coli cells under UV illumination.
After 2 h treatment, the survival ratio of E. coli cells just dropped to
40%. The disinfection efciencies of PdO loaded TiO2 hollow
spheres were much better than that of the unloaded ones. The increase of PdO loading ratio initially enhanced the photocatalytic
disinfection performance of these PdO loaded TiO2 hollow spheres,
while its further increase after a critical ratio had a deleterious
effect on its enhancement effect. With just 0.1% PdO loading, the
survival ratio of E. coli cells largely dropped to 3  106 after
2 h treatment, which was over ve magnitudes lower than that
of E. coli cells treated by TiO2 hollow spheres under the same
experiment conditions. The sample with 0.4% PdO loading demonstrated the best bactericidal effect among all these samples. After
100 min treatment by this sample, the survival ratio of E. coli cells
had a 7-log decrease, which reached the detection limit of the plate

Fig. 4. Optical absorbance spectra of PdO loaded TiO2 hollow spheres.

Fig. 5. The photocatalytic disinfection curves of E. coli under UV irradiation

(365 nm) by (a) PdO loaded TiO2 hollow spheres with different loading amounts,
compared with that in the dark with the presence of 0.4% PdO loaded TiO2 hollow
spheres, (b) by P25 TiO2 nanoparticles, 0.4% Pd loaded TiO2 hollow spheres, and
0.4% PdO loaded TiO2 hollow spheres.

counting method under the current experiment conditions. When

the PdO loading ratio was further increased to 0.7% and 1.0%, the
survival ratio of E. coli cells gradually increased, while it was still
over four magnitudes lower after 2 h treatment than that of
E. coli cells treated by TiO2 hollow spheres under the same experiment conditions.
3.6. Photocatalytic disinfection performance comparison between PdO
loaded TiO2 hollow spheres and Pd loaded TiO2 hollow spheres
Fig. 5b shows the survival ratio versus the treatment time by
the 0.4% PdO loaded sample under UV irradiation, compared with
that by Degussa P25 TiO2 nanoparticles and 0.4% Pd loaded TiO2
hollow spheres, respectively. After 2 h treatment by Degussa P25
TiO2 nanoparticles, the survival ratio of E. coli cells just dropped
to 30%, only slightly better than the unloaded TiO2 hollow
spheres. Under the same experiment conditions, the survival ratio
of E. coli cells dropped to 3  104 by the treatment of 0.4% Pd
loaded TiO2 hollow spheres, which was much better than that by
Degussa P25 nanoparticles. However, its photocatalytic disinfection effect was still much worse compared with that by 0.4% PdO
loaded TiO2 hollow spheres. After 100 min treatment by 0.4%
PdO loaded TiO2 hollow spheres, the survival ratio of E. coli cells
dropped to 107, which was about 5 magnitudes lower than that
by 0.4% Pd loaded TiO2 hollow spheres after 100 min treatment

Y. Liu et al. / Chemical Engineering Journal 249 (2014) 6371

(102). Thus, the comparison demonstrated clearly that PdO

modication had a much better enhancement effect than Pd modication on TiO2 hollow spheres for the photocatalytic disinfection
of E. coli bacteria. These PdO loaded TiO2 hollow spheres also had a
good stability during the photocatalytic process as demonstrated
in their recycling experiments (see Supplementary data for
details).
3.7. Photocatalytic performance enhancement analysis
The enhanced photocatalytic activities of PdO loaded TiO2 hollow spheres could be attributed to both their unique hollow structure and the electron trapping capability of loaded PdO
nanoparticles as schematically illustrated in Fig. 6. As demonstrated in Fig. 6a, the incident light could generate multiple reections in the hollow interior voids, which had been veried in
various reports before [1418]. So it could have a better light harvest and thus more photogenerated electronhole pairs could be
created. This explained why unloaded TiO2 hollow spheres could
have a comparable photocatalytic activity with Degussa P25 TiO2
nanoparticles under UV illumination, although their specic surface area was just about 60% as that of Degussa P25 TiO2
nanoparticles.
To have a good photocatalytic activity, photogenerated electronhole pairs must separate effectively and diffuse to the photocatalyst surface to react with the target reactants. The loaded PdO
nanoparticles dispersed on the surface, shell and interior void of
TiO2 hollow spheres could serve as efcient electron trapping centers (Fig. 6b), which made it possible for more holes to diffuse to
their surface and react with water and oxygen to produce ROS such
as OH radicals. OH radical was reported as the main oxidant that
inactivates bacteria on TiO2 [48]. Thus, PdO loaded TiO2 hollow

69

spheres showed a superior photocatalytic activity than the unloaded TiO2 hollow spheres as demonstrated in their photocatalytic disinfection of E. coli cells. An optimized PdO loading ratio
was found to be 0.4 wt.% for the best photocatalytic performance,
and similar behavior of noble metal/metal oxide loadings had been
reported in various noble metal/metal oxide loaded photocatalysts
[2027,31,33]. A small amount of noble metal/metal oxide loadings could enhance the activity of the photocatalyst, while a higher
amount would not further enhance its activity and usually cause a
reverse effect. This phenomenon could be attributed to their different roles in the photocatalytic process. When the loading ratio is
proper, they usually exist as ne nanoparticles and serve as efcient electron trapping centers. The trapped electrons could easily
diffuse to their surface to react with the electron acceptors. When
the loading radio is higher than the optimized value, their crystallite size usually is larger. They could also act as recombination centers, detrimental to photocatalysis by hindering or avoiding the
electrons to react with the electron acceptors in the environment
[2224,27,31,33].
Controversial results existed in literature on the photocatalytic
performance difference between noble metal modications and
noble metal oxide modications on TiO2 [3235]. For example,
Lee and Choi [32] had reported that Pt-loaded TiO2 had better photocatalytic degradation performance on several chlorinated organic compounds than PtO-loaded TiO2. However, Lalitha et al. [33]
observed that Ag2O-loaded TiO2 showed a superior photocatalytic
hydrogen production activity than Ag-loaded TiO2, and Yang
et al. [34,35] recently also found that PtO-loaded TiO2 showed
superior photocatalytic hydrogen production activity than Ptloaded TiO2. In our work, TiO2 hollow spheres with either PdO
modication or Pd modication had been calcined at 600 C for
5 h, so the matrixes of these two composite photocatalysts were
comparable. Thus, the observed photocatalytic disinfection effect
differences in Fig. 5b must come from the different modications
of PdO and Pd. When PdO and Pd were loaded on TiO2 surface, a
pn junction and a metal-n junction were formed at the PdO/
TiO2 and Pd/TiO2 interfaces, respectively. The work function of
TiO2 is 4.2 eV [21], the work function of Pd is 5.12 eV [49], while
the work function of PdO could reach values up to 7.9 eV depending on the surface orientation and termination as estimated theoretically by Rogal et al. [50]. Due to the work function difference,
the photo-generated electrons could readily transfer from TiO2 to
PdO or Pd, while they could be trapped by PdO more easily than
Pd because PdO has a work function signicantly higher than that
of Pd. Thus, PdO modication could have a better electronhole
separation capability than Pd modication, benecial for its
enhancement on the photocatalytic performance of these TiO2 hollow spheres. Schifano et al. [51,52] had reported that H2O2 treatment promoted the formation of PdO at the Pd/ZnO interface,
which largely enhanced the performance of rectifying contacts.
We believe that the easier electron ow from ZnO to PdO should
account for their observed performance enhancement of rectifying
contacts, similar to the observed better photocatalytic disinfection
by PdO modication in the current study.

4. Conclusions

Fig. 6. Schematic illustrations for (a) the multiple reections in the hollow sphere
and (b) the electron/hole pair separation in the composite photocatalyst. (Note: A
refers to an electron acceptor which could accept surface photoelectrons, while D
refers to an electron donor which could donate electron and react with surface
holes).

In summary, PdO loaded TiO2 hollow spheres were synthesized,

which demonstrated a superior photocatalytic disinfection performance on E. coli bacteria, compared with the unloaded samples
and Degussa P25 TiO2 nanoparticles. Through this process, PdO
loadings were distributed relatively uniformly both on the surface
and in the shell/interior of these TiO2 hollow spheres, making them
effective electron/hole pair separation centers and subsequently
enhancing the photocatalytic performance of these loaded

70

Y. Liu et al. / Chemical Engineering Journal 249 (2014) 6371

samples. A very small PdO loading ratio of 0.4 wt.% was found to
effectively optimize the photocatalytic performance of this composite photocatalyst material system. Their largely enhanced photoctalytic disinfection performance could be attributed to both
their unique hollow structure and the electron trapping capability
of loaded PdO nanoparticles. It was also found that PdO modication had a better photocatalytic performance enhancement on
these TiO2 hollow spheres than Pd modication, which may be
attributed to their different work functions.
Acknowledgements
The experimental assistance on E. coli culture by Ms. Mian Song
and Ms. Shuang Jiao was greatly appreciated. This study was supported by the National Natural Science Foundation of China (Grant
No. 51102246), the Knowledge Innovation Program of Institute of
Metal Research, Chinese Academy of Sciences (Grant No.
Y0N5A111A1), the Youth Innovation Promotion Association, Chinese Academy of Sciences (Grant No. Y2N5711171), and the Scientic Research Foundation for the Returned Overseas Chinese
Scholars, State Education Ministry, PR China.
Appendix A. Supplementary material
Supplementary material associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/j.cej.
2014.03.087.
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