Single atomic Au induced dramatic promotion of the photocatalytic activity of TiO2 hollow microspheres

Article abstract of DOI:10.1039/c9cc08578e

Single atomic Au (Au-SA) is firmly anchored on the surfaces of defective TiO₂ (DT) hollow microspheres with oxygen vacancies (Ov), which sharply improves their light-harvesting ability, stimulates charge separation, and facilitates the adsorption and activation of acetone, thus dramatically enhancing their photoreactivity towards acetone oxidation.

Full text of DOI:10.1039/c9cc08578e

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Single atomic Au induced dramatic promotion of the
photocatalytic activity of TiO hollow microspheres
2
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
b
a
c
Zhao Hu , Chao Yang , Kangle Lv* , Xiaofang Li , Qin Li and Jiajie Fan
DOI: 10.1039/x0xx00000x
2
Single atomic Au (SA-Au) is firmly anchored on the surface of deposited TiO photocatalyst, isolated single atom modified
2
TiO usually exhibits superior photoreactivity due to the high
2
defective TiO (DT) hollow microspheres with oxygen vacancy (Ov),
ratio of coordination unsaturated surface atoms to overall
atoms, which therefore can afford more sites to facilitate the
which sharply improves the light-harvesting ability, stimulates the
charge separation, and facilitates the adsorption and activation,
therefore dramatically enhancing the photoreactivity towards
acetone oxidation.
2
, 19,20
interfacial reactions.
However, the high mobility of the
single atoms makes them prefer to aggregate with each other
to reduce the surface energy. Therefore, how to improve the
stability of isolated single atomic site photocatalyst becomes a
hot topic in photocatalysis, but it still remains a great
2
Up to now, TiO is considered as the most typical
2
1, 22
challenge.
semiconductor photocatalyst used for environmental
remediation. However, the large bandgap and quick
recombination of photo-generated electron-hole pairs hamper
Herein, we report a gentle method to prepare single atomic Au
Au-SA) anchored defective TiO -HMSs (DT) using surface
oxygen vacany (Ov) to stabilize Au-SA, and the photoreactivity
of TiO -HMSs was evaluated by photocatalytic oxidation of
acetone (setup in Fig. S1). For comparison, we prepared
perfect TiO -HMSs (PT), Au nanoparticles modified PT (Au-
NP/PT). The detailed processes for the synthesis of TiO
1
-8
its practical applications. To improve the photocatalytic
activity of TiO , many strategies have been used such as
doping TiO with metal and nonmetal elements, coupling
TiO with other semiconductor photocatalyst to form
heterojunction, modifying TiO
transitional metals,13 or introducing surface defects.
Recently, much work has been devoted to hollow structured
TiO photocatalysts, for example, TiO hollow microspheres
TiO -HMSs), due to their unique properties such as good
permeability, high efficient in light utilization, and convenience
(
2
2
9
10
2
2
2
1
1
12
2
with carbon materials,
2
14,15
2
photocatalysts can be seen from the supporting information.
We applied density functional theory (DFT) and in-situ diffuse
reflectance infrared Fourier transform spectra (DRIFTS)
spectrum to study the detailed oxidation processes of acetone
over Au-SA/DT.
2
2
(
2
1
6-18
in filtering and recycling.
range, we successfully prepared TiO
oxygen vacancies (Ov) by simply calcination the mixture of
pristine TiO -HMSs and urea, which exhibit overwhelming
superior photocatalytic activity towards NO oxidation under
To broaden the light-responsive
2
-HMSs with surface
2
2
XRD characterization results show that all TiO -HMSs are pure
anatase phase with a sharp peak at 2θ = 25.3° (Fig 1A), and
only Au-NP/PT sample contains Au nanoparticles with two
small diffraction peaks at 2θ = 38.2° and 44.4°. The absence of
the diffraction peaks of Au nanoparticles for Au-SA/DT sample,
1
5
the irradiation of a visible LED lamp.
Now, single atomic catalysis is emerging as a new frontiers in
photo)catalysis. When compared with nanoparticles
suggesting that surface Ov of TiO
atomic Au. From the SEM (Fig. 1B) and TEM images (Fig. S2),
we can see that these TiO -HMSs have similar morphology in
diameters of about 2-3 um, reflecting that the introduction of
Ov and Au have little effect on the morphology of TiO -HMSs.
2
can be used to anchor single
(
2
a. Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of
Education, College of Resources and Environmental Science, South-Central
University for Nationalities, Wuhan, hubei Province 430074, China..
E-mail: lvkangle@mail.scuec.edu.cn (K.L. Lv)
2
Tel: +86-27-67841369, Fax: +86-27-67843918
College of Chemistry and Chemical Engineering, Wuhan University of Science and
Technology, Wuhan, 430081, China.
PT sample exhibits little absorption in visible region due to its
large bandgap (Fig. 1C). After introduction of surface Ov, the
absorption edge of TiO -HMSs (DT sample) extends to about
2
550 nm. The absorption of PT extends to the whole visible
region after deposition of Au nanoparticles (Au-NP/PT sample),
possibly caused by the localized surface plasmon resonance
b.
c.
School of Materials Science and Engineering, Zhengzhou University, Zhengzhou
50001, China.
Electronic Supplementary Information (ESI) available: Experimental section,
4
†
characterization of the photocatalysts, nitrogen sorption, FTIR, TEM, EPR, XPS, PL,
photocurrent, EIS, ESR, and DFT calculations. See DOI: 10.1039/x0xx00000x
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2
-HMSs, Au-SA/DT exhibits despite the relatively high Au loading (0.32 wt%, sVeiewe ATrtaicbleleOnSli2ne)
(
LSPR) effect.23 Among all the TiO
the strongest light-harvesting ability. According to the total over DT, only atomically dispersed Au ca
DOS, the band gap of perfect TiO (PT) is 2.2 eV (Fig. 1D), which by aberration-corrected STEM (Fig. 2d), without the presence
is smaller than the experimental value due to the limitations of of any visible nanoparticles or clusters. On the contrary, from
D
n
O
b
I:
e
10
d
.
i
1
r
0
e
3
c
9
t
/
l
C
y
9
o
C
b
C
s
0
e
8
r
5
v
7
e
8
d
E
2
2
4
the known DFT method. When compared with PT and DT, the HAADF-STEM and TEM images, we can clearly observe the
Au-SA/DT has the smallest bandgap due to the formed defect presence of Au nanoparticles over Au-NP/PT sample (Figs. S6-
energy levels of the intermediate state, which therefore makes S8). Then we can conclude that the Ov can be used to anchor
it possess the strongest light harvesting ability. The production atomically dispersed Au. From the X-ray absorption near-edge
of Ov in DT and Au-SA/DT photocatalysts is confirmed by ESR structure (XANES) spectra (Fig. 2e), we can find that the white
4
spectra (Fig. S3), where the Lorentzian line with the line peak of Au-SA/DT is similar to that of HAuCl . From the
corresponding g = 2.003 stems from the Ov trapped extended X-ray absorption fine structure (EXAFS) spectra (Fig.
electrons.2 Interestingly, the intensity of the signal for Ov is 2f), we can compare the short-range local structure of Au. It
5,26
almost kept unchanged for DT even after anchoring of Au-SA.
can be clearly seen the Au–O shell (R = 1.4 Å) and Au–Ti shell
R = 2.3 Å) for Au-SA/DT sample. The Au–Au and Au–Cl
coordination peaks are absent from the EXAFS spectra
compared with Au foil and HAuCl , suggesting the absence of
(
4
Au nanoparticles or clusters in Au-SA/DT sample, consistent
with the HAADF-STEM observation (Fig. 2d).
Fig. 1. XRD patterns (A), SEM images (B), diffuse reflectance
spectra (C), and calculated total density of states (D) of the
Fig. 2. HAADF-STEM image (a) and the corresponding element
mappings for Au (b) and Ti (c) atoms of Au-SA/DT sample.
Single atomic Au sites in HAADF-STEM image highlighted by
red circles (d). L-edge XANES spectra (e) and R-space EXAFS
TiO
nanoparticle deposited TiO
anchored TiO (Au-SA/DT).
2
-HMSs for perfect TiO
2
(PT), defective TiO
(Au-NP/PT) and single atomic Au
2
(DT), Au
2
2
2
magnitudes of TiO -HMSs (f).
As expected, all samples have similar Brunauer-Emmett-Teller
2
-1
(
(
BET) surface area (about 80-100 m g ) and pore structures
Fig. S4 and Table S1). Therefore, BET surface area is not the
key factors affecting the photoreactivity of TiO
prepared TiO -HMSs contain Ti, O and small amount of C
elements with binding energies of 458 (Ti 2p), 529 (O 1s) and
84 (C 1s), respectively (Fig. S5A). The C element is ascribed to
2
-HMSs. All the
2
2
the residual carbon from the adventitious hydrocarbon in XPS
instrument itself.15 From the high resolution XPS spectra, we
can see that both the binding energies of Ti 2p (Fig. S5B) and O
1
s (Fig. S5C) reduce after introduction of Ov, which is due to
1
5
the higher electronic density in Ov regions. The presence of
Au in Au-SA/DT and Au-NP/PT samples are confirmed from the Fig. 3. The electronic local function (ELF) (a) and charge
corresponding high resolution XPS spectra in Au 4f region (Fig. difference distribution of Au-SA/DT photocatalyst (charge
S5D), where two peaks with binding energies of 83.4 and 87.1 accumulation in blue and charge depletion in yellow).
eV are corresponding to the orbital energies of Au 4f7/2 and Au
4f
5/2 , respectively. 27
The electronic local function (ELF) result also supports the
formation of Ti-Au-Ti bonds at the single atomic Au site (Fig.
To disclose the fine structure and distribution of Au in Au- 3a). From the calculated charge difference distribution result,
SA/DT sample, high-angle annular dark-field scanning TEM we can clearly see the electrons transfer from surrounding Ti
(
HAADF-STEM) is performed. From Fig. 2a, we can observe the to single atomic Au in Au-SA/DT photocatalyst, activating the
finely dispersed gold on the surface of TiO
2
-HMSs. Surprisingly, single atomic Au due to the increased electronic density (Fig.
2
| J. Name., 2012, 00, 1-3
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3
b). The optimized atomic models of TiO
introduction of Ov results in a stretched length of neighboring and Au-SA/DT sample, respectively (Ta
Ti atoms (Ti1 and Ti2) that are around the Ov site from 3.77 to average life time of the carriers for Au-SA/DT also indicates the
.73 Å. However, this distance slightly reduces to 4.49 Å after severely retarded recombination of carriers. As Au-SA/DT
anchoring single atomic Au. That is to say, the anchored single photocatalyst exhibits the strongest light-harvesting ability (Fig.
2
shows that the carriers are 1.13, 2.34, 1.96 and 2.67 ns for PT, DViTew, AArutic-lNe OPn/lPinTe
DO
b
leI: 10
S
.
1
10).39
T
/C
h
9
e
CClo
0
n
8
gest
57
8
E
4
atomic Au can stabilize the structure of defective TiO
2
(Fig. S9). 1C) and has the longest average life time of photo-generated
carriers (Fig. S13B), it is not hard to understand the superior
photocatalytic activity of Au-SA/DT among all the
Photocatalytic oxidation of acetone under UV irradiation is
used to evaluate the photoreactivity of the TiO -HMSs
photocatalysts (Fig. 4A). It can be seen that the introduction of
Ov or Au-NPs separately has little effect on the photoreactivity
photocatalysts. Consistent with the results of PL spectra, Au-
SA/DT photocatalyst performs the highest photocurrent (Fig.
S13C) and smallest arc radius on the Nyquist plot in the high
frequency range of the electrochemical impedance
spectroscopy (Fig. S13D), suggesting its quickest interfacial
charge transfer to the electron donor/acceptor.
2
2
of TiO -HMSs towards acetone oxidation. However, the
photoreactivity of DT greatly improves after anchored with Au-
SA, exceeding that of PT by a factor of 3.1. The decomposed
acetone soars from 67.8 ppm to 214.2 ppm within 60 min
when Au-SA/DT is used as photocatalyst instead of PT (Fig. 4B). Both hydroxyl radicals (•OH) and superoxide radicals (•O
The photoreactivity of Au-SA/DT is also much higher than that important reactive oxygen species (ROSs) that are responsible
-) are
2
5
,7,8
of other photocatalyst. For example, only 90 ppm and 160 for the oxidation of organic pollutants.
ppm of acetone can be decomposed when P25 TiO and high- the radicals-trapping experiments (Fig. S14). Under UV
energy TiO nanosheets are used as photocatalyst, respectively irradiation for 5 min, both the signals of the DMPO trapped
Table S3). In addition, Au-SA/DT also exhibits excellent photo- •OH and •O
stability. Its photocatalytic activity is almost kept unchanged weak. However, after loading TiO
even repeated used for 5 times (Fig. S10). We also SA, the intensities of the signals for the trapped •OH and •O
systematically studied the effect of Au-SA loading amount on radicals greatly improve, and Au-SA/DT exhibits the strongest
the photoreactivity of defective TiO -HMSs (Fig. S11). It can be signals, suggesting its excellent photocatalytic activity.
seen that the photoreactivity of Au-SA anchored defective
TiO -HMSs increases first and then decreases, and all Au-SA
modified defective TiO -HMSs exhibit higher photoreactivity
Here we performed
2
2
-
(
2
radicals in suspensions of PT and DT are very
-HMSs with Au-NP and Au-
2
-
2
2
2
2
than Au-NP/PT photocatalyst.
DFT calculation results show the adsorption energy of acetone
over Au-SA/DT is -0.41 eV, much larger than that over PT (-0.30
eV) and DT samples (-0.23 eV), which indicate that Au-SA/DT
exhibits stronger adsorption to acetone when compared with
PT and DT photocatalysts (Fig. S12). The stronger adsorption
will facilitate the activation of acetone. Larger Bader charge (-
0
.04 e) of the adsorbed acetone over Au-SA/DT is observed
than that over PT (-0.01 e) and DT photocatalysts (-0.02 e).
Fig. 5. In-situ DRIFTS recording the adsorption (A and B) and
photocatalytic oxidation process (C and D) of acetone over Au-
SA/TiO under a mixed gas flow of acetone and O .
2 2
Fig. 4. Photocatalytic oxidation of acetone over different TiO
2
-
HMSs (A) and comparison of the photoreactivity (B).
The time dependent dark adsorption of acetone over Au-
SA/DT is recorded by in-situ DRIFTS (Fig. 5A and Fig. 5B), where
-
1
the negative bands at 3698 cm is related to the depletion of
Ov can act as an electron trap. Then, it is not strange to see a
reduced photoluminescence (PL) intensity of DT than that of
PT (Fig. S13A). When compared with Au-NP/PT, Au-SA/DT
sample possesses lower PL intensity, which infers that the
introduction of SA-Au can sharply retards the recombination of
photo-generated carriers, improving the photoreactivity. The
retarded recombination of carriers is further confirmed by
transient PL spectra (Fig. S13B). The average lift time of the
adsorbed acetone, and the positive bands at 3008, 2974, 2957,
1
2
930, 1366 and 1238 cm- are corresponding to the
2
8
-1
molecularly adsorbed acetone. The peak at 1720 cm can be
2
9
assigned to the ν(C=O) vibration mode of adsorbed aldehyde.
Both formaldehyde and acetaldehyde are plausible
intermediates of acetone photocatalytic oxidation, and they
could account for the band at 2870 cm which is characteristic
of the ν(CH) vibration of aldehyde molecules. Therefore,
−1
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acetaldehyde is very likely to form during adsorption acetone.
The peak centering at 1745 cm− could correspond to formic
acid. However, the possible formation of acetic acid cannot be
ascertained, because the corresponding ν(CO) band overlaps
with that of the acetone. In addition, we can observe the
typical IR absorption peak of bicarbonates featuring at 1225
cm . Consequently, we can conclude the oxidation of acetone
over Au-SA/DT photocatalyst occurs in the dark. The
assignments of the absorption peaks are shown in Table S4.
Notes and references
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DOI: 10.1039/C9CC08578E
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photocatalytic oxidation of acetone begins, and the in-situ
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stronger such as the peak centering at 1745 cm , indicating a
rapid accumulation of formic acid. In order to verify the above
conclusions, we calculated the reaction path of acetone over
Au-SA/DT photocatalyst and the corresponding reaction
energy is obtained using Dmol3 module. Fig. S15 presents the
changes of the free energy in reactions, from which we can see
that the rate-determining step (RDS) for acetone oxidation is
the decomposion of formic acid with an energy barrier of 1.22
eV. The reactions involved in acetone oxidation are listed in
Table S5. Based on the in-situ DRIFTS and calculation, we
proposed the oxidation pathway of acetone over Au-SA/DT
2
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This work was supported by the National Natural Science
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Conflicts of interest
2
070.
There are no conflicts to declare.
4
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TOC
Surface oxygen vacancy (Ov) is used to stabilize single atomic Au on the surface of
TiO hollow microspheres (TiO -HMSs), sharply improving its photoreactivity
2
2
towards acetone oxidation.