See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/321378496

Controllable synthesis of 3D hierarchical Co3O4 nanocatalysts with various

morphologies for toluene catalytic oxidation

Article in Journal of Materials Chemistry A · November 2017

DOI: 10.1039/C7TA09149D

CITATIONS READS

248 4,482

9 authors, including:

Quanming Ren Mingyuan Zhang

South China University of Technology Jilin University
31 PUBLICATIONS 1,930 CITATIONS 34 PUBLICATIONS 1,555 CITATIONS

SEE PROFILE SEE PROFILE

Limin Chen Daiqi ye

South China University of Technology South China University of Technology
117 PUBLICATIONS 7,185 CITATIONS 292 PUBLICATIONS 9,958 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Quanming Ren on 23 March 2020.

The user has requested enhancement of the downloaded file.

 Journal of
Materials Chemistry A
View Article Online
PAPER View Journal | View Issue
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.

Controllable synthesis of 3D hierarchical Co3O4

Cite this: J. Mater. Chem. A, 2018, 6,
nanocatalysts with various morphologies for the
498 catalytic oxidation of toluene†
Quanming Ren, a Shengpeng Mo,a Ruosi Peng,a Zhentao Feng,a Mingyuan Zhang,a
Limin Chen,abc Mingli Fu,abc Junliang Wuabc and Daiqi Ye*abc

Received 17th October 2017
Accepted 29th November 2017
DOI: 10.1039/c7ta09149d
rsc.li/materials-a
Three-dimensional (3D) hierarchical Co3O4 nanocatalysts with different morphologies and various exposed
crystal planes were synthesized via a hydrothermal process without the use of a cobalt surfactant precursor
and subsequent direct thermal decomposition. The morphologies obtained include 3D hierarchical cube-
stacked Co3O4 microspheres (C sample), 3D hierarchical plate-stacked Co3O4 flowers (P sample), 3D
hierarchical needle-stacked Co3O4 double-spheres with an urchin-like structure (N sample), and 3D
hierarchical sheet-stacked fan-shaped Co3O4 (S sample), which exhibit high efficiency for the total
oxidation of volatile organic compounds (VOCs). Among them, the C sample exhibits the best activity
with the temperature required for achieving a toluene conversion of 90% (T90%) of approximately 248
C
and the activity energy (Ea) of 80.2 kJ mol1, which is at least 32
C lower than that of the S sample with
a higher Ea of 114.9 kJ mol1 at a space velocity (WHSV) of 48 000 mL g1 h1. The effects of
morphology on the physicochemical properties and catalytic activity of the Co3O4 catalysts are
investigated using numerous analytical techniques. It is concluded that the large specific surface area,
highly defective structure with abundant surface adsorbed oxygen species and rich high valence Co ions
in the C sample are responsible for its excellent catalytic performance. Moreover, no significant decrease
in catalytic efficiency is observed over 120 h at 255
C on the C sample, which indicates that it exhibits
excellent stability for toluene oxidation. Therefore, it shows potential as a non-noble catalyst in practical
applications.

susceptibly to poisoning have greatly limited their practical

1. Introduction
Volatile organic compounds (VOCs) are considered one of the
main atmospheric pollutants, which are not only hazardous to
human health but also harmful to the environment.1,2 To meet
the increasingly stringent environmental regulations on VOCs
emissions, several promising technologies have been proposed
for VOC removal, among which catalytic oxidation is believed to
be one of the most promising methods due to its advantages of
lower operating temperature and less harmful organic by-
products than thermal oxidation.3,4 Catalysts based on
precious metals (platinum,5,6 palladium,7,8 gold,8–11 etc.) exhibit
outstanding catalytic performances at relatively low tempera-
ture, but their high cost, easy sintering and coking, and
a
School of Environment and Energy, South China University of Technology, Guangzhou
510006, China. E-mail: cedqye@scut.edu.cn; Tel: +86 20 3938 0516
b
Guangdong Provincial Key Laboratory of Atmospheric Environment and Pollution
Control (SCUT), Guangzhou 510006, China
c
National Engineering Laboratory for VOCs Pollution Control Technology and
Equipment, Guangzhou 510006, China
† Electronic supplementary information (ESI) available. See
10.1039/c7ta09149d
application.
Therefore, currently there are great efforts to develop metal
oxides, which are promising substitutes for precious metal
catalysts, including mixed metal oxides (such as perovskites12–17
and spinels18,19) and single metal oxides (such as MnOx,20–22
Co3O4 (ref. 2, 9 and 23–25) and CeO2 (ref. 26)). Among them,
tricobalt tetraoxide (Co3O4) is one of the most potential catalysts
in many catalytic reactions, such as water oxidation,27,28 CO
oxidation29–32 and catalytic oxidation of VOCs2,18,33–35 due to its
low-cost, environmentally benign nature, and high catalytic
activity. A tremendous amount of work has been focused on
Co3O4 catalysts with different shapes, including sheets, belts,
cubes, plates and rods, which predominantly expose various
crystal planes and give rise to different catalytic perfor-
mances.11,24,29,36–38 For instance, Hu et al.38 reported that Co3O4
nanosheets ({112} facets) were more reactive than nanobelts
({011} facets) and nanocubes ({001} facets) for the catalytic
combustion of methane. Zhu et al.24 investigated Co3O4 nano-
catalysts with different dimensional architectures for methane
combustion and found that Co3O4 nanoplates manifested
DOI:
excellent catalytic activity, which was attributed to the surface-
adsorbed oxygen species and the highly exposed {112} facets

498 | J. Mater. Chem. A, 2018, 6, 498–509 This journal is © The Royal Society of Chemistry 2018

Paper
of the Co3O4 nanoplates. Xie et al.29,39 reported that Co3O4
nanorods with predominantly exposed {110} planes not only
exhibited excellent catalytic activity for CO oxidation at
a temperature as low as 77
C but also remained stable in
a moist stream (moisture 3–10 ppm) of normal feed gas, which
was ascribed to the abundant active Co3+ sites for CO adsorp-
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
tion on the surfaces through preferentially exposed reactive
{110} planes. Ma and co-workers11 reported that mesoporous
Co3O4 with the most exposed {110} facets displayed higher
catalytic activity for ethylene oxidation than Co3O4 nanosheets
with {112} facets, in which the {110} planes were composed
mainly of Co3+ cations and provided sufficient sites for ethylene
and oxygen adsorption. Based on these reports, it is meaningful
and signicant to research the characteristics of Co3O4 catalysts
with different shapes in the toluene oxidation reaction and
whether the three-dimensional (3D) architecture of 3D-Co3O4
can increase the catalytic activity at low temperature. To the best
of our knowledge, there are only a few reports about the fabri-
cation of various types of 3D hierarchical Co3O4 morphologies
for the catalytic oxidation of toluene. For example, Xia et al.35
and Garcia et al.40 fabricated 3D ordered mesoporous Co3O4
using KIT-6 as a hard template for toluene oxidation, which
exhibited excellent catalytic performances due to its high
surface area and abundant oxygen adsorbed species as well as
low-temperature reducibility. Yan et al.25 reported the synthesis
of 3D hierarchical Co3O4 nanoower clusters using a hydro-
thermal method with polyvinylpyrrolidone (PVP), which had
a high toluene conversion rate due to the abundant Co3+ cations
and high relative concentration surface-adsorbed oxygen on the
Co3O4 nanoower surface. Bai et al.36 fabricated a Co3O4-HT-
CTAB sample with a porous nanowire-like morphology, which
manifested a higher catalytic performance due to its large
surface area and high surface oxygen species concentration, as
well as good low-temperature reducibility. Obviously, hard
templates and so templates play an important role in
controlling the 3D hierarchical Co3O4 morphology. However, it
remains a challenge to absolutely remove templates in as-
synthesized samples and preserve their initial morphology.
Herein, we report a series of morphology-controlled 3D
hierarchical Co3O4 nanocatalysts with various exposed crystal
planes via a hydrothermal process without the use of a cobalt
surfactant precursor and subsequent direct thermal decompo-
sition for toluene oxidation, including 3D hierarchical cube-
stacked Co3O4 microspheres, plate-stacked Co3O4 owers,
needle-stacked Co3O4 double-spheres with an urchin-like
structure, and sheet-stacked fan-shaped Co3O4. The aim of
this study is to systematically investigate the correlation
between the morphologies of the Co3O4 samples and their
catalytic performances via various analytical techniques.
2. Experimental
2.1 Catalyst preparation
All chemicals were analytical grade and used without further
purication. The precursors were synthesized under hydro-
thermal conditions. In a typical synthesis, 15.0 mmol of
Co(NO3)2$6H2O was dissolved in 70 mL of deionized water.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Journal of Materials Chemistry A
Aer stirring for 30 min, a certain amount of urea was added to
the above solution. Aer stirring for another 30 min, the ob-
tained homogeneous solution was transferred to a 100 mL
Teon-lined stainless-steel autoclave. The autoclave was sealed
and maintained at 100
C for 12 h in an electron oven. Aer-
ward, the autoclave was cooled naturally to room temperature
(RT). Subsequently, the product was collected and washed with
deionized water and ethanol several times by centrifugation,
and then, dried at 80
C overnight and calcined in static air at
a heating ramp of 1
C min1 from RT to 300
C and maintained
at 300
C for 3 h. Next, 40–60 mesh catalyst pellets were
prepared by compressing the oxide powders into akes in
a hydraulic press (Specac), then crushing and sieving.
The amount of reagents and different hydrothermal condi-
tions required for the synthesis of the various samples are as
follows:
Synthesis of 3D hierarchical cube-stacked Co3O4 micro-
spheres (C sample). 15.0 mmol of Co(CH3COO)2$4H2O,
30 mmol of urea, 70 mL of ethylene glycol (EG), at 180
C for
12 h in an electron oven.
Synthesis of 3D hierarchical plate-stacked Co3O4 owers (P
sample). 15.0 mmol of Co(NO3)2$6H2O, 30 mmol of urea, 70 mL
of methanol, at 180
C for 12 h in an electron oven.
Synthesis of 3D hierarchical needle-stacked Co3O4 double-
spheres with an urchin-like structure (N sample). 15.0 mmol
of CoCl2$6H2O, 75 mmol of urea, 70 mL of deionized water, at
100
C for 12 h in an electron oven.
Synthesis of 3D hierarchical sheet-stacked fan-shaped Co3O4
(S sample). 15.0 mmol of Co(SO4)2$7H2O, 75 mmol of urea,
70 mL of deionized water, at 100
C for 12 h in an electron oven.
2.2 Catalyst characterization
The morphologies of the samples were characterized via eld-
emission scanning electron microscopy (SEM) using an elec-
tron microscope (SEM, ZEISS). The microstructures of the
samples were recorded on a transmission electron microscope
(TEM, JEOL JEM-2010F) at an accelerating voltage of 200 kV. The
crystalline structure of the catalysts was obtained by X-ray
diffraction (XRD) (Bruker D8 ADVANCE diffractometer) with
Cu Ka radiation (40 kV, 40 mA, scanning step ¼ 0.02
). The
specic surfaces area and pore size distributions of all the
samples were determined with the N2 adsorption/desorption
method according to the Brunauer–Emmett–Teller (BET) and
Barrett–Joyner–Halenda (BJH) methods, respectively. The N2
adsorption–desorption isotherms of the samples were
measured via N2 adsorption at 196
C on an automatic surface
analyzer (Micromeritics ASAP 2020). Before measurement, each
sample was outgassed at 120
C for 3 h. Raman spectroscopy
was performed on a LabRAM HR system (HYJ) with a CCD
detector and a spectral resolution of 1 cm1. A 532 nm laser was
employed as the excitation source with an 1800 groove mm1
grating and 80 holes. The laser power was maintained at 6 mW,
and the exposure time was 60 s. In addition, the wavenumber
region measured was from 100 to 850 cm1. X-ray photoelectron
spectroscopy (XPS) analysis was performed using a Thermo
ESCALAB 250Xi electron spectrometer with Al Ka (hv ¼ 1486.8
J. Mater. Chem. A, 2018, 6, 498–509 | 499

Journal of Materials Chemistry A
eV) as the excitation source. The binding energies of all the
elements were referenced to the C 1s line at 284.8 eV from
carbon impurities. Temperature-programmed reduction in H2
(H2-TPR) and temperature-programmed desorption of O2 (O2-
TPD) were performed on a chemisorption analyzer (Micro-
meritics AutoChem II2920) equipped with a thermal conduc-
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
tivity detector (TCD) and a mass quadrupole spectrometer. For
H2-TPR, 50 mg catalyst was rst treated under an Ar ow (30
mL min1) at 300
C for 1 h to remove physically adsorbed
molecules, and then cooled down to room temperature.
Subsequently, the gas was switched to a ow of 10 vol% H2/Ar
(30 mL min1) in the tube and the sample was heated to 800
C
at a ramp of 10
C min1. For O2-TPD, 50 mg catalyst was rst
treated under an He ow (30 mL min1) at 300
C for 1 h to
remove physically adsorbed molecules, and then cooled to room
temperature. Then, the gas was switched to a ow of 5 vol% O2/
He (30 mL min1) in the tube for 1 h, followed by purging with
pure He at the same temperature for 30 min to remove the
unabsorbed O2 molecules. Then, the catalysts were heated from
room temperature to 750
C at 10
C min1 in pure He (30
mL min1).
2.3 Catalytic evaluation
The catalytic activity of the catalysts was evaluated in a xed-
bed quartz tubular micro-reactor (6 mm i.d., 500 mm length)
at atmospheric pressure under steady-state conditions. To
minimize the effect of hot spots, 100 mg (40–60 mesh)
catalyst and 400 mg of quartz sand (40–60 mesh) were mixed
well and placed in the quartz reactor with quartz wool packed
at both ends of the catalyst bed. The reactant gases
(1000 ppm toluene, 20 vol% O2/N2) passed through the
reactor at a rate of 80 mL min1, and the corresponding
space velocity (SV) was 48 000 mL g1 h1. The concentration
of reactant and product gases was analyzed using an online
gas chromatograph (GC-2014C, Shimadzu) equipped with
a ame ionization detector (FID) and the concentration of
CO2 in the outlet gas was monitored by another FID with
a conversion furnace to convert CO 2 to CH4. Before the outlet
products were measured by the gas chromatograph at a given
temperature 8 times, the toluene oxidation reaction was
stabilized for 15 min. The catalytic activity of the samples
was evaluated using the temperature (T50% and T90%)
required to achieve toluene conversions of 50% and 90%,
respectively. The range of catalytic activity testing tempera-
tures was 180
C to 260
C. The complete conversion of
toluene (htoluene) was calculated according to the following
equation:
Ctoluene;in  Ctoluene;out
htoluene ¼  100
Ctoluene;in
The specic toluene reaction rate dtoluene (mol (m2 s)1) was
calculated according to the following equation:
Ntoluene  Xtoluene
stoluene ¼
SBET
500 | J. Mater. Chem. A, 2018, 6, 498–509
View Article Online
Paper
1
Xtoluene ¼ log htoluene (3)
1
100
where, Ctoluene,in (ppm), Ctoluene,out (ppm), Ntoluene (mol s1) and
SBET (m2 g1) are the concentrations of toluene in the inlet and
outlet gas, toluene gas ow rate and surface area, respectively.
The stability of the C sample was evaluated at 255
C for 120 h
under the same reaction conditions (1000 ppm toluene, 20 vol%
O2/N2, 48 000 mL g1 h1).
3. Results and discussion
3.1 Structural and textural properties of the catalysts
The structural properties of the catalysts were determined via X-
ray diffraction (XRD) using the JCPDS les as a reference. Fig. 1
shows the XRD patterns of the four samples calcined at 300
C.
The positions and relative intensities of the main diffraction
peaks of all samples are relatively similar. The diffraction peaks
located at 19.0
, 31.3
, 36.8
, 38.5
, 44.8
, 59.4
and 65.2

correspond to the (111), (220), (311), (222), (400), (511) and (440)
planes of the spinel Co3O4 phase (JCPDS Card no. 42-1467,
space group: Fd3 m (no. 227)), respectively.41–44 Also, no peaks
from other phases or impurities are observed in the patterns of
the Co3O4 samples. In addition, the crystallite size was calcu-
lated from the Co3O4 (311) diffraction peak by applying the
Scherrer equation,45 and shown in Table 1. It can be observed
that the crystallite size of the C, P, S samples is relatively similar
with sizes in the range of 16–18 nm, and approximately half that
of the N sample (30 nm), which is attributed to the different
shapes of the Co3O4 samples due to the various preparation
conditions.
The N2 adsorption–desorption isotherms and the pore size
distributions of the Co3O4 catalysts prepared by various
methods are illustrated in Fig. 2. Obviously, classical type-IV
isotherms are obtained, and all the isotherms have a typical
hysteresis loop,46,47 which is oen associated with a mesoporous
architecture (the average pore size is between 11.3 and 36.1 nm
(calculated by the Barrett–Joyner–Halenda (BJH) method)) in all
the Co3O4 samples. The textural properties in terms of BET
(1)
(2)
Fig. 1 XRD patterns of the prepared Co3O4 catalysts.
This journal is © The Royal Society of Chemistry 2018
 View Article Online

Paper Journal of Materials Chemistry A

Table 1 Crystallite size, textural properties and conversion of toluene on the synthesised Co3O4 samples

Temperature
Crystallite Surface area Pore volume Average pore reduction Co3+/(Co3++Co2+) Oads/(Oads + Tb90% Ea
Sample sizea (nm) (m2 g1) (cm3 g1) size (nm) peak (
C) (%) Olatt) (%) Tb50% (
C) (
C) (kJ mol1)

C 16 83.1 0.27 11.3 87, 238, 323 62.5 55.5 240 248 80.2
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.

P 18 58.8 0.26 16.4 87, 244, 328 58.9 53.5 243 254 91.0
N 30 25.9 0.24 36.1 101, 284, 368 55.9 51.3 250 259 98.7
S 17 53.2 0.29 17.3 288, 390 49.6 47.9 >280 >280 114.9
a
Calculated from Dc ¼ Kl/b cos(q) (Scherrer equation) based on Co3O4 (311). b Reaction conditions: WHSV ¼ 48 000 mL g1 h1, mcat ¼ 0.1 g, T ¼
180–280
C.

surface area, pore volume and average pore size are listed in
Table 1. It is obvious that the pore volume of all the samples is
approximately 0.27 cm3 g1. Moreover, it can be observed that
the surface areas of the P and S samples are 58.8 and 53.2 m2
g1, respectively, which are approximately two times higher
than that of the N sample (25.9 m2 g1). However, the C sample
(83.1 m2 g1) shows the largest surface area among the samples.
The differences in the surface area of the Co3O4 samples result
from the various morphologies obtained from the various
synthetic conditions to some extent.
The morphologies of the four samples before and aer
calcination at 300
C were characterized via scanning electron
Fig. 2 N2 adsorption–desorption isotherms (a) and pore size distri-
butions calculated from the desorption branch (b) of the as-synthe-
sized Co3O4 catalysts.
microscopy (SEM) (Fig. 3). It can be clearly seen that the C
sample exhibits a uniform and spherical morphology with a size
of approximately 18 mm (Fig. 3(a)). In this sample each 3D
hierarchical cube-stacked Co3O4 microsphere is composed of
aggregated cubes with a size of 180–200 nm, as shown in the top
right corner inset in Fig. 3(b). Aer calcination this morphology
is considerably stable (Fig. 3(c)). Before calcination, the P
sample (Fig. 3(e–f)) presents the desired plate-stacked ower-
like morphology, and its size and shape subtle change due to
calcination (Fig. 3(g)). It is noted that the morphology of the 3D
hierarchical needle-stacked Co3O4 double-spheres with an
urchin-like structure was composed of a substantial number of
needles (Fig. 3(i–j)). Aer calcination this morphology was
essentially preserved, although the needlepoints were not so
well-dened (Fig. 3(k)) compared to before calcination. Finally,
micrographs of the 3D hierarchical sheet-stacked fan-shaped
sample (S sample) before (Fig. 3(m–n)) and aer calcination
(Fig. 3(o)) are shown. The fan-like S sample is composed of
substantial sheets, and the length, width and thickness of each
sheet are about 13 mm, 4 mm and 100 nm, respectively. For the S
sample, its 3D structure is homogeneous and thermally stable.
Moreover, schematic illustrations of the C, P, N and S samples
are depicted in Fig. 3(d), (h), (l), and (p), respectively. Briey, the
morphology of each Co3O4 sample, which corresponds to the
cobalt precursor calcined at 300
C, is essentially preserved.
To acquire a deeper understanding of the structure of the as-
prepared Co3O4 catalysts, transmission electron microscopy
(TEM) and high-resolution transmission electron microscopy
(HRTEM) analyses of the four samples were performed, as
shown in Fig. 4. The TEM and HRTEM images of the C sample
are shown in Fig. 4(a–d). As can be seen from Fig. 4(a),
a substantial number of well-dened faces of the Co3O4 cubes
accumulate to form a microspherical structure. The selected
area electron diffraction (SAED) pattern in the top le corner
inset in Fig. 4(b) demonstrates that the C sample has a poly-
crystalline structure.48,49 Fig. 4(c) shows the lattice-resolved
HRTEM image, which was recorded from the dotted rectan-
gular area in Fig. 4(b). Both the (202) and (0–22) crystal planes
with the d-spacing of 0.290 nm and interfacial angle of 60
can
be clearly observed in Fig. 4(c). Also, the corresponding FFT
image spot array is shown in Fig. 4(d), which can be indexed as
the [111] zone axis. Therefore, the main exposed facets of the 3D
hierarchical cube-stacked Co3O4 microspheres should be {111}
facets, as also indicated by Yu et al.50

This journal is © The Royal Society of Chemistry 2018 J. Mater. Chem. A, 2018, 6, 498–509 | 501

Journal of Materials Chemistry A
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
Fig. 3 SEM images of the synthesized Co3O4 samples before (a, b, e, f, i, j, m and n) and after calcination at 300
C (c, g, k and o). C, cube-stacked
sample (a, b, c and d); P, plate-stacked sample (e, f, g and h); N, needle-stacked sample (i, j, k and l); and S, sheet-stacked sample (m, n, o and p).
The TEM and HRTEM images of the P sample are illustrated
in Fig. 4(e–f). It can be observed that this sample maintains the
shape of its precursors with a plate-like structure (Fig. 3(e)), and
the SAED pattern in the top le corner inset in Fig. 4(f) indicates
that the P sample has a polycrystalline structure. The FFT spot
patterns, as shown in Fig. 4(h), can be well indexed as the (2–20)
and (111) crystal planes of 3D hierarchical plate-stacked
Co3O4 owers along the [110] zone axis. The lattice-resolved
HRTEM image (Fig. 4(g)) shows the (2–20) and (111) crystal
planes with d-spacings of 0.290 and 0.467 nm, respectively, and
45
interfacial angle, which conrm that the 3D hierarchical
plate-stacked Co3O4 owers have primarily {110} exposed facets.
Fig. 4(i–j) present the TEM images of the N sample. A tiny
branch-free standing Co3O4 needle is shown in Fig. 4(i), and the
SAED pattern is shown in the top le corner inset in Fig. 4(j),
which demonstrate that the N sample has a polycrystalline
structure. In the lattice-resolved HRTEM image (Fig. 4(k)), (1–
13) crystal planes with a d-spacing of 0.243 nm, interfacial
angles of 50.4
and 64.8
toward the (1–31) and (220) crystal
planes, respectively, can be observed. The bright spot array can
be distinctly observed from the corresponding FFT image
(Fig. 4(l)), which can be well indexed as the [110] zone axis.
Therefore, {110} is the dominant exposed facet of the 3D
502 | J. Mater. Chem. A, 2018, 6, 498–509
View Article Online
Paper
hierarchical needle-stacked Co3O4 double-spheres with an
urchin-like structure.
The sheet-like Co3O4 TEM image (Fig. 4(m)), and electron
diffraction rings in the top le corner inset in Fig. 4(n) reveal
that the S sample possesses a polycrystalline structure. The
lattice fringe spacing of 0.459 and 0.276 nm correspond to the
(11–1) and (2–20) crystal planes of the 3D hierarchical sheet-
stacked fan-shaped Co3O4, respectively. Also, an interfacial
angle of 90
can be distinctly observed in Fig. 4(o). In addition,
the rectangle spot array of the FFT pattern is shown in Fig. 4(p),
which demonstrates that the dominant exposed facet of the 3D
hierarchical sheet-stacked fan-shaped Co3O4 is the {112}
facet.38,51,52
Moreover, Fig. 5 shows the atomic structure of an ideal Co3O4,
in which the framework of the CoO4 tetrahedra and CoO6 octa-
hedra obtained using the Diamond 3.2 soware. Additionally, the
surface atomic congurations of Co3O4 with {111}, {110}, and
{112} crystal planes are also illustrated in Fig. 5.
3.2 Chemical states and redox behavior
To obtain further insight into the composition and chemical
state on the surface of the prepared bulk oxides, the XPS spectra
This journal is © The Royal Society of Chemistry 2018

Paper
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
Fig. 4 TEM, HRTEM, fast-Fourier-transform (FFT), lattice and selected area electron diffraction (SAED) images of the Co3O4 samples: C, cube-
stacked sample (a–d); P, plate-stacked sample (e–h); N, needle-stacked sample (i–l); and S, sheet-stacked sample (m–p).
of Co 2p and O 1s are shown in Fig. 6, and the XPS data are
summarized in Table 1. The Co 2p XPS spectra of the four Co3O4
samples are illustrated in Fig. 6(a). The main peak at the
binding energy of about 780.0 eV is characteristic of Co(2p3/2)
with Co3+ (779.6  0.1 eV) and Co2+ (781.3  0.2 eV). The
shoulder peak at the binding energy of about 795.0 eV, which
was deconvoluted into two components peaks of Co3+ (794.6 
0.1 eV) and Co2+ (796.3  0.2 eV), is attributed to the corre-
sponding Co(2p1/2).36,53 It is well-known that the spin–orbit
splitting value for Co3+ compounds is 15.0 eV.1,23 It can be
observed that the preparation method obviously inuences the
surface content of Co3+ (Co3+/(Co3++Co2+)) in the Co3O4 cata-
lysts, and their relative surface content of Co3+ vary in the order
of C > P > N > S. Fig. 6(b) shows the O 1s XPS spectra of the Co3O4
This journal is © The Royal Society of Chemistry 2018
View Article Online
Journal of Materials Chemistry A
catalysts, which were tted into three components peaks at
529.7, 531.1, and 533.2 eV, corresponding to surface lattice
oxygen (Olatt) species, surface adsorbed oxygen (Oads) species,
and chemisorbed water (Ow), respectively.37,54,55 The relative
surface content of Oads (Oads/(Oads + Olatt)) decreased as follows:
C > P > N > S. The abovementioned results reveal that the
surface Co3+ and Oads species on the Co3O4 samples with
different shapes affect their catalytic efficiency. In accordance
with the conclusions of Bai et al. and Zhao et al.,7,36 the C sample
with the more surface Co3+ and Oads species exhibits a higher
catalytic performance.
Raman scattering is extensively used as a powerful tool for
studying defects.56 The Raman spectra of the Co3O4 samples are
shown in Fig. 7. Typically, the ve Raman bands in the range of
J. Mater. Chem. A, 2018, 6, 498–509 | 503

Journal of Materials Chemistry A
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
Fig. 5 Surface atomic configurations in the {111} (a), {110} (b), and {112}
(c) planes of Co3O4.
100–850 cm1 at 193, 471, 514, 615, and 683 cm1, correspond to
the different modes of crystalline Co3O4.7,57 The Raman peaks
centered at 193, 514 and 615 cm1 are associated with F2g
symmetry. Specically, the band at approximately 193 cm1 is
attributed to the F2g(1) symmetry of the tetrahedral sites (CoO4) of
the crystalline Co3O4 phase. The band at 471 cm1 is assigned to
Eg symmetry, and the strong band at 683 cm1 is attributed to A1g
symmetry, corresponding to the octahedral sites (CoO6) of the
crystalline Co3O4 phase.2,56 Moreover, it is noteworthy that the A1g
symmetry in the C, P, and N samples at 674 cm1, 677 cm1, and
678 cm1, respectively, are lower than that (683 cm1) of the S
sample. Generally, a red shi in the A1g symmetry towards a lower
frequency suggests that a catalyst possesses a highly defective
structure,7 which is benecial to activate absorbed oxygen mole-
cules to active oxygen species, especially in the C sample.
504 | J. Mater. Chem. A, 2018, 6, 498–509
View Article Online
Paper
Fig. 6 XPS spectra of the Co3O4 catalysts.
Hydrogen temperature programmed reduction (H2-TPR) was
employed to investigate the oxidation–reduction properties of
the Co3O4 samples with different morphologies, as illustrated in
Fig. 8(a). The reduction proles essentially present two peaks,
which correspond to a two-step reduction process. According to
previous literature, the rst peak centered at approximately
250
C is associated with the reduction of Co3+ ions to Co2+ with
a concomitant structural change to CoO, whereas the second
peak located at 350
C is ascribed to the subsequent reduction
of CoO to metallic cobalt.7,57 Obviously, the intensity of the
reduction peak at around 250
C for the C sample is greater than
that of the other three samples, which indicates that the C
sample possesses a greater quantity of Co3+ ions, which is
consistent with the XPS analysis. In addition, it can be distinctly
observed that in all cases, Co3O4 is reduced completely into
metallic cobalt at 450
C. Simultaneously, it can also be seen
that the reduction behavior strongly depends on the various
morphologies of the samples to a certain extent. Compared with
the reduction features of the S sample, a weak reduction peak
for the C, P and N samples can be observed at 87–100
C, which
is ascribed to the very active oxygen species on their surface. In
other words, the molecular oxygen species adsorbed on the
oxygen vacancies.57,58 These results are in accordance with the
Raman analysis. Besides, the N and S samples exhibit a peak the
temperature of 284–288
C, whereas the P sample exhibited
This journal is © The Royal Society of Chemistry 2018

Paper
a peak at a slightly higher temperature (244
C). Furthermore,
the good reducibility of the C sample is conrmed by its low-
temperature reduction peak at about 238
C. All these nd-
ings clearly manifest that the reducibility is particularly
enhanced for the C sample due to its larger amount of adsorbed
oxygen species and rich Co3+ cations, which are also evidenced
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
by the XPS analysis.
To investigate the interaction between the adsorbed oxygen
species and Co3O4 surface, O2-TPD experiments were carried
out over the Co3O4 catalysts starting from 50
C to 750
C. As
illustrated in Fig. 8(b), four types of oxygen species are observed
at the temperature ranges of 80–120
C, 120–450
C, 450–700
C
and at above 700
C, which are assigned to molecular oxygen
species adsorbed on oxygen vacancies (Ov), surface adsorbed
oxygen ions (Oads), surface lattice oxygen (Olatt,s), and bulk
phase lattice oxygen (Olatt,b), respectively.46,58 Obviously, the
desorption peak at approximately 100
C for the C, P and N
samples belong to the molecular oxygen desorbed from the
oxygen vacancies of the Co3O4 catalysts, which is lower than that
of the S sample. This result is in accordance with the Raman
and H2-TPR analyses. The C sample exhibits much larger inte-
gration desorption peak areas and lower desorption tempera-
tures in comparison to the other samples. Generally, the larger
the corresponding desorption peak area of surface-active
oxygen species in the low-temperature range, the higher the
catalytic ability for oxidation reactions.11 Therefore, the signif-
icant desorption behavior of O2 on the C sample demonstrates
that the amount and mobility of oxygen species are obviously
enhanced, which is benecial for toluene oxidation.
3.3 Catalytic performance
The toluene conversion over the Co3O4 catalysts as a function of
reaction temperature under the conditions of toluene concen-
tration ¼ 1000 ppm and GHSV ¼ 48 000 mL g1 h1, as shown
in Fig. 9(a). In order to compare the activity data easily, the
temperatures for 50% and 90% toluene conversion (T50% and
T90%) are summarized in Table 1. It must be pointed out that
toluene conversion in the absence of any catalyst (only quartz
sand loaded to the microreactor) was not observed below
280
C. The catalytic activity of toluene oxidation decreased in
Fig. 7 Raman spectra of the Co3O4 catalysts.
This journal is © The Royal Society of Chemistry 2018
View Article Online
Journal of Materials Chemistry A
the order: C > P > N > S. Apparently, among all the catalysts, the
C sample is the most active achieving T50 and T90 toluene
conversion at 240
C and 248
C, which are 10
C and 11
C
lower than that of the N sample, respectively. Moreover, the P
sample exhibits slightly lower catalytic activity in comparison to
C sample. Nevertheless, the S sample presents poor catalytic
activity at the test temperatures. Substantial differences are
distinctly evident depending on the sample obtained via various
synthetic conditions, which reveals that the morphology of the
catalyst plays an important role, and thus is a key factor for
obtaining a highly active Co3O4 catalyst. The catalytic activities
of the typical samples for toluene oxidation are summarized in
Table 2. Obviously, the catalytic activity over the C sample is
much better than that in previous literature, such as Co3O4-T2
(T90% ¼ 257
C),25 3DOM LSCO (T90% ¼ 260
C),59 Co3O4
microspheres (T90% ¼ 285
C),10 Pd/Co3AlO (WIE) (T90% ¼ 272


C),60 0.99Au/3DOM Co3O4 (T90% ¼ 275
C)8 and 6.4Au/bulk
Co3O4 (T90% ¼ 277
C).9
Catalytic activity can be evaluated by comparing the apparent
activation energy (Ea) values of different catalysts, where the
sample with a lower Ea value exhibits superior catalytic activity.
A dimensionless Weisz–Prater (W–P) parameter less than 0.3,
an effectiveness factor higher than 0.95 and reaction order of 1
provide sufficient conditions for overcoming the signicant
pore diffusion limitations.68 At a toluene conversion less than
20%, the Weisz–Prater criterion (NW–P) values were calculated,
Fig. 8 H2-TPR profiles of the synthesized Co3O4 samples (a) and O2-
TPD profiles of the synthesized Co3O4 samples (b).
J. Mater. Chem. A, 2018, 6, 498–509 | 505
 View Article Online

Journal of Materials Chemistry A Paper

Ntoluene  htoluene
gtoluene ¼ (4)
Wcat
  
Ea
gtoluene ¼ kc ¼ A exp  c (5)
RT

where, Wcat, g, k, A, and Ea are the catalyst weight (g), reaction

Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.

rate (mmol g1 s1), rate constant (s1), pre-exponential factor,

Fig. 9 Catalytic performance (a) and Arrhenius plots (b) of the
synthesized Co3O4 catalysts for toluene oxidation under the following
conditions: toluene ¼ 1000 ppm, 20 vol% O2/N2 and WHSV ¼
48 000 mL g1 h1.
which are much less than 0.3. Therefore, there is no signicant
mass transfer limitation in our catalytic systems. It has been
reported that toluene combustion follows rst-order kinetics at
toluene concentrations under excess oxygen57,69 with the
equations:
and apparent activation energy (kJ mol1), respectively. The k
values were calculated from the reaction rates and reactant
conversions under various reaction temperatures.
As shown in Fig. 9(b), the linear plots of the Arrhenius results
reveal that the toluene oxidation only remains in the kinetically
controlled region at a conversion of less than 20%. Based on the
slopes of the Arrhenius plots, the Ea values were calculated, as
summarized in Table 1. The results indicate that the Ea values
follow the order: S (114.9 kJ mol1) > N (98.7 kJ mol1) > P
(91.0 kJ mol1) > C (80.2 kJ mol1). Obviously, the catalytic
activities follow an inverse trend with respect to the Ea values.
Therefore, the results conrm that the C sample exhibits the
highest catalytic activity for toluene combustion among the
samples. It is well known that Co3O4 nanocatalysts with
different shapes and highly exposed different crystal planes
inuence toluene catalytic combustion. Herein, we cannot
ignore that the C, P, N, and S samples have predominantly
exposed {111}, {110}, {110}, and {112} facets, respectively. It is
clearly observed that there are signicant differences in the
surface areas of the Co3O4 samples. Therefore, it is necessary to
normalize the specic toluene reaction rate to the specic
surface area of the various Co3O4 nanocatalysts, as shown in
Fig. 10(a), which follows the order N > P > C > S. In other words,
the catalytic activity order for toluene oxidation of these crystal
planes follows {110} > {111} > {112} on the premise of excluding
the effect of surface specic area. The fact that the {110} crystal
plane exhibits the best catalytic oxidation activity is consistent
with the conclusion by Xie and co-workers,29 who reported that
Co3O4 nanorods with predominantly exposed {110} planes

Table 2 Main data reported on VOCs over related cobalt oxide catalysts

Surface area VOC conc.

Samples (m2 g1) VOC type (ppm) WHSV (mL g1 h1) T50% (
C) T90% (
C) Ref. no.

Co3O4-HT 41.9 Toluene 1000 20 000 241 260 47

Co3O4 microspheres 17.4 Toluene 1000 20 000 266 285 10
7.4Au/Co3O4 22.4 Toluene 1000 20 000 242 250 10
6.4Au/bulk Co3O4 8.7 Toluene 1000 20 000 244 277 9
LaMnO3 32.5 Toluene 1000 20 000 254 278 61
0.99Au/3DOM Co3O4 36.2 Toluene 1000 40 000 268 275 8
8.4Au/3DOM Co3O4 27.0 Toluene 1000 40 000 251 260 62
Co3O4-T2 21.0 Toluene 1000 37 500 234 257 25
Pd/Co3AlO (WIE) 42 Toluene 800 30 000 252 272 60
Ce–Co EM 1 : 2 109 Toluene 260 60 000 237 253 63
0.12 Ag/Mn2O3-redn 75–80 Toluene 1000 40 000 225 250 64
Mn–Co (1 : 1) 27.9 Toluene 1000 30 000 236 249 65
3DOM LSCO 31.5 Toluene 1000 20 000 240 260 59
6.55Au/Fe2O3 18.9 Toluene 1000 20 000 200 260 66
8MnOx/3DOM LSMO 22.9 Toluene 1000 20 000 240 254 67
C 83.1 Toluene 1000 48 000 240 248 Present work

506 | J. Mater. Chem. A, 2018, 6, 498–509 This journal is © The Royal Society of Chemistry 2018

Paper
exhibited excellent activity for CO oxidation at temperatures as
low as 77
C, which is ascribed to the abundance of active Co3+
sites for CO adsorption on its surfaces due to the preferentially
exposed reactive {110} planes.
Moreover, much attention was paid to investigating the
stability of the C sample when operating at constant tempera-
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
ture for a relatively prolonged time on stream. As shown in
Fig. 10(b), no signicant decrease in catalytic efficiency was
observed for a period of 120 h at 255
C. To better understand
this good catalytic stability, all the catalysts were characterized
via XRD, BET and SEM aer three consecutive runs. As shown in
Fig. S1,† the chemical composition and phase structure of the
spent Co3O4 catalysts were well retained, and no peaks from
other phases or impurities are observed in the patterns of the
spent Co3O4 catalysts. It can be observed from Table S1† that
the crystallite size of the spent Co3O4 catalysts slightly
decreased compared with that of the fresh catalysts. Addition-
ally, the N2 adsorption–desorption isotherms and pore size
distributions of the spent Co3O4 catalysts are illustrated in
Fig. S2.† Also, the textural properties in terms of BET surface
area, pore volume and average pore size are listed in Table S1.†
Obviously, there is no signicant decrease in the surface area,
pore volume and average pore of the spent Co3O4 catalysts. The
SEM images in Fig. S3† show that the morphologies of the spent
Co3O4 catalysts were essentially preserved. Specically, aer
Fig. 10 Specific reaction rate of toluene oxidation over Co3O4 cata-
lysts (a) and reaction stability with time for toluene oxidation over the C
catalyst at 255
C, reaction conditions: toluene ¼ 1000 ppm, 20 vol%
O2/N2, WHSV ¼ 48 000 mL g1 h1 (b).
This journal is © The Royal Society of Chemistry 2018
View Article Online
Journal of Materials Chemistry A
three consecutive runs, the structural, textural and morpho-
logical features of the Co3O4 catalysts remained almost the
same. Fig. S4† shows the toluene conversion curves versus
temperature during three consecutive runs, where the three-run
curves overlap very well, which indicates that the C and N
samples were stable aer reacting three times. Therefore, it is
reasonable to deduce that the excellent stability of the
morphology and structure of the catalysts ensures their catalytic
stability in toluene oxidation.
It is noteworthy that the catalytic activity on Co3O4 is related
to various aspects, such as morphology, surface area, oxygen
vacancies and reducibility. Generally, a catalyst with a higher
surface area shows better catalytic activity. Thus, the C sample
exhibited the highest activity at lower temperatures due to its
highest surface area. Moreover, the defective structure of spinel
Co3O4 plays an important role in generating oxygen vacancies
on the surface, which is benecial to accelerate adsorption,70
thus giving rise to the formation of surface adsorbed oxygen
species. On the other hand, the surface adsorbed oxygen species
on catalysts easily desorb, which are believed to play the major
role in the complete oxidation.71 Based on the results from the
Raman (Fig. 7) and XPS spectra (Table 1), the structural defects
and abundant surface adsorbed oxygen species in the C sample
are responsible for its high catalytic performance in the oxida-
tion of toluene. Furthermore, low temperature reducibility
enhanced the catalytic performance of this catalyst.72 Under the
reaction conditions, toluene is oxidized, which is accompanied
with a transformation from Co3+ and Co2+. Meanwhile, the
content of high-valence metal ions increases, thus the chemical
potential and reactivity of oxygen adjacent to the metal ions are
promoted. Specically, the distribution of cobalt oxidation
states has a distinct inuence on the catalytic performance.19
From the results of the H2-TPR (Fig. 8(a)) and XPS spectra (Table
1), it can be seen that the C sample with the best reducibility
and highest surface content of Co3+ (Co3+/(Co3+ + Co2+)) exhibits
the best catalytic activity.
4. Conclusions
In summary, Co3O4 nanocatalysts with different morphologies
and different exposed crystal planes were successfully synthe-
sized via a hydrothermal process without a cobalt surfactant
precursor and subsequent direct thermal decomposition. The
morphologies obtained included 3D hierarchical cube-stacked
Co3O4 microspheres (C sample), 3D hierarchical plate-stacked
Co3O4 owers (P sample), 3D hierarchical needle-stacked
Co3O4 double-spheres with an urchin-like structure (N
sample), and 3D hierarchical sheet-stacked fan-shaped Co3O4 (S
sample). As conrmed by HRTEM analysis, they primarily have
exposed {111}, {110}, {110}, and {112} crystal planes, respec-
tively. The catalytic efficiency of toluene oxidation decreased in
the order C > P > N > S due to the largest specic surface area
and highly defective structure of the C sample, giving rise to
more surface adsorbed oxygen species. Besides the abundant
Co3+ cationic species on the surface of C sample are benecial
for toluene oxidation. Moreover, we observed that the specic
toluene reaction rate normalized to the specic surface area of
J. Mater. Chem. A, 2018, 6, 498–509 | 507

Journal of Materials Chemistry A
the various Co3O4 followed the order N > P > C > S. In other
words, the specic toluene reaction rate of these crystal planes
for toluene oxidation follows the order {110} > {111} > {112}. In
addition, for the C sample, no signicant decrease in catalytic
efficiency was observed over 120 h at 255
C, which indicates
that the 3D hierarchical cube-stacked Co3O4 microspheres
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
exhibit excellent catalytic activity and stability for toluene
oxidation. Therefore, it might be a potential non-noble catalyst
in practical applications.
Conflicts of interest
There are no conicts to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (No. 51378218, 51108187, 21207039 and
50978103), the Fundamental Research Funds for the Central
Universities, and Natural Science Foundation of Guangdong
Province, China (Grant No. 2014A030310431 and
2016A030311003).
Notes and references
1 Z. Zhu, G. Lu, Z. Zhang, Y. Guo, Y. Guo and Y. Wang, ACS
Catal., 2013, 3, 1154–1164.
2 X. Wang, Y. Liu, T. Zhang, Y. Luo, Z. Lan, K. Zhang, J. Zuo,
L. Jiang and R. Wang, ACS Catal., 2017, 7, 1626–1636.
3 H. Huang, Y. Xu, Q. Feng and D. Y. C. Leung, Catal. Sci.
Technol., 2015, 5, 2649–2669.
4 H. Sun, Z. Liu, S. Chen and X. Quan, Chem. Eng. J., 2015, 270,
58–65.
5 R. Peng, S. Li, X. Sun, Q. Ren, L. Chen, M. Fu, J. Wu and
D. Ye, Appl. Catal., B, 2018, 220, 462–470.
6 Y. T. Lai, T. C. Chen, Y. K. Lan, B. S. Chen, J. H. You,
C. M. Yang, N. C. Lai, J. H. Wu and C. S. Chen, ACS Catal.,
2014, 4, 3824–3836.
7 S. Zhao, F. Hu and J. Li, ACS Catal., 2016, 6, 3433–3441.
8 S. Xie, J. Deng, S. Zang, H. Yang, G. Guo, H. Arandiyan and
H. Dai, J. Catal., 2015, 322, 38–48.
9 Y. Liu, H. Dai, J. Deng, S. Xie, H. Yang, W. Tan, W. Han,
Y. Jiang and G. Guo, J. Catal., 2014, 309, 408–418.
10 H. Yang, H. Dai, J. Deng, S. Xie, W. Han, W. Tan, Y. Jiang and
C. T. Au, ChemSusChem, 2014, 7, 1745–1754.
11 Z. M. Chun Yan Ma, J. J. Li, Y. Gang Jin, J. Cheng, G. Qing Lu
and S. Z. Q. Zheng Ping Hao, J. Am. Chem. Soc., 2010, 132,
2608–2613.
12 C. Zhang, Y. Guo, Y. Guo, G. Lu, A. Boreave, L. Retailleau,
A. Baylet and A. Giroir-Fendler, Appl. Catal., B, 2014, 148–
149, 490–498.
13 J. Zhang, D. Tan, Q. Meng, X. Weng and Z. Wu, Appl. Catal.,
B, 2015, 172–173, 18–26.
14 S. Royer, D. Duprez, F. Can, X. Courtois, C. Batiot-Dupeyrat,
S. Laassiri and H. Alamdari, Chem. Rev., 2014, 114, 10292–
10368.
508 | J. Mater. Chem. A, 2018, 6, 498–509
View Article Online
Paper
15 L. Z. Jiguang Deng, H. Dai, H. He and C. T. Au, Ind. Eng.
Chem. Res., 2008, 47, 8175–8183.
16 A. Worayingyong, P. Kangvansura, S. Ausadasuk and
P. Praserthdam, Colloids Surf., A, 2008, 315, 217–225.
17 S. Rousseau, S. Loridant, P. Delichere, A. Boreave,
J. P. Deloume and P. Vernoux, Appl. Catal., B, 2009, 88,
438–447.
18 S. Mo, S. Li, J. Li, Y. Deng, S. Peng, J. Chen and Y. Chen,
Nanoscale, 2016, 8, 15763–15773.
19 S. Mo, S. Li, W. Li, J. Li, J. Chen and Y. Chen, J. Mater. Chem.
A, 2016, 4, 8113–8122.
20 W. Tang, X. Wu, D. Li, Z. Wang, G. Liu, H. Liu and Y. Chen, J.
Mater. Chem. A, 2014, 2, 2544–2554.
21 Z. Sihaib, F. Puleo, J. M. Garcia-Vargas, L. Retailleau,
C. Descorme, L. F. Liotta, J. L. Valverde, S. Gil and
A. Giroir-Fendler, Appl. Catal., B, 2017, 209, 689–700.
22 W. Si, Y. Wang, S. Zhao, F. Hu and J. Li, Environ. Sci. Technol.,
2016, 50, 4572–4578.
23 J. González-Prior, R. López-Fonseca, J. I. Gutiérrez-Ortiz and
B. de Rivas, Appl. Catal., B, 2016, 199, 384–393.
24 Y. Sun, J. Liu, J. Song, S. Huang, N. Yang, J. Zhang, Y. Sun
and Y. Zhu, ChemCatChem, 2016, 8, 540–545.
25 Q. Yan, X. Li, Q. Zhao and G. Chen, J. Hazard. Mater., 2012,
209–210, 385–391.
26 J. M. López, A. L. Gilbank, T. Garcı́a, B. Solsona, S. Agouram
and L. Torrente-Murciano, Appl. Catal., B, 2015, 174–175,
403–412.
27 H. Y. Wang, S. F. Hung, H. Y. Chen, T. S. Chan, H. M. Chen
and B. Liu, J. Am. Chem. Soc., 2016, 138, 36–39.
28 M. Zhang, M. de Respinis and H. Frei, Nat. Chem., 2014, 6,
362–367.
29 X. Xie, Y. Li, Z. Q. Liu, M. Haruta and W. Shen, Nature, 2009,
458, 746–749.
30 Z. Ren, V. Botu, S. Wang, Y. Meng, W. Song, Y. Guo,
R. Ramprasad, S. L. Suib and P.-X. Gao, Angew. Chem., Int.
Ed., 2014, 53, 7223–7227.
31 L. Lukashuk, K. Föttinger, E. Kolar, C. Rameshan,
D. Teschner, M. Hävecker, A. Knop-Gericke, N. Yigit, H. Li,
E. McDermott, M. Stöger-Pollach and G. Rupprechter, J.
Catal., 2016, 344, 1–15.
32 H.-C. C. Hung-Kuan Lin, H.-C. Tsai, S.-H. Chien and
C.-B. Wang, Catal. Lett., 2003, 88, 169–174.
33 H. Wang, C. Chen, Y. Zhang, L. Peng, S. Ma, T. Yang, H. Guo,
Z. Zhang, D. S. Su and J. Zhang, Nat. Commun., 2015, 6, 7181.
34 M. A. Carreon, V. V. Guliants, L. Yuan, A. R. Hughett,
A. Dozier, G. A. Seisenbaeva and V. G. Kessler, Eur. J. Inorg.
Chem., 2006, 2006, 4983–4988.
35 Y. Xia, H. Dai, H. Jiang and L. Zhang, Catal. Commun., 2010,
11, 1171–1175.
36 G. Bai, H. Dai, J. Deng, Y. Liu, F. Wang, Z. Zhao, W. Qiu and
C. T. Au, Appl. Catal., A, 2013, 450, 42–49.
37 K. Wang, Y. Cao, J. Hu, Y. Li, J. Xie and D. Jia, ACS Appl.
Mater. Interfaces, 2017, 9, 16128–16137.
38 L. Hu, Q. Peng and Y. Li, J. Am. Chem. Soc., 2008, 130, 16136–
16137.
39 X. Xie and W. Shen, Nanoscale, 2009, 1, 50–60.
This journal is © The Royal Society of Chemistry 2018

Paper
40 T. Garcia, S. Agouram, J. F. Sánchez-Royo, R. Murillo,
A. M. Mastral, A. Aranda, I. Vázquez, A. Dejoz and
B. Solsona, Appl. Catal., A, 2010, 386, 16–27.
41 X. W. Lou, D. Deng, J. Y. Lee, J. Feng and L. A. Archer, Adv.
Mater., 2008, 20, 258–262.
42 X. Liu, Q. Long, C. Jiang, B. Zhan, C. Li, S. Liu, Q. Zhao,
Published on 29 November 2017. Downloaded by South China University of Technology on 01/02/2018 08:17:23.
W. Huang and X. Dong, Nanoscale, 2013, 5, 6525–6529.
43 J. Wang, N. Yang, H. Tang, Z. Dong, Q. Jin, M. Yang,
D. Kisailus, H. Zhao, Z. Tang and D. Wang, Angew. Chem.,
Int. Ed., 2013, 52, 6417–6420.
44 D. Zhang, J. Zhu, N. Zhang, T. Liu, L. Chen, X. Liu, R. Ma,
H. Zhang and G. Qiu, Sci. Rep., 2015, 5, 8737.
45 T.-Y. Wei, C.-H. Chen, H.-C. Chien, S.-Y. Lu and C.-C. Hu,
Adv. Mater., 2010, 22, 347–351.
46 B. Bai, H. Arandiyan and J. Li, Appl. Catal., B, 2013, 142–143,
677–683.
47 B. Bai and J. Li, ACS Catal., 2014, 4, 2753–2762.
48 G. Cheng, T. Kou, J. Zhang, C. Si, H. Gao and Z. Zhang, Nano
Energy, 2017, 38, 155–166.
49 D. Wang, Q. Wang and T. Wang, Inorg. Chem., 2011, 50,
6482–6492.
50 X. Y. Yu, Q. Q. Meng, T. Luo, Y. Jia, B. Sun, Q. X. Li, J. H. Liu
and X. J. Huang, Sci. Rep., 2013, 3, 2886.
51 J. Mu, L. Zhang, G. Zhao and Y. Wang, Phys. Chem. Chem.
Phys., 2014, 16, 15709–15716.
52 Z. Fei, S. He, L. Li, W. Ji and C. T. Au, Chem. Commun., 2012,
48, 853–855.
53 Z. Feng, W. Bao, X. Xu, X. Ma, J. Zhan and Y. Yin,
ChemNanoMat, 2016, 2, 946–951.
54 S. Seefeld, M. Limpinsel, Y. Liu, N. Farhi, A. Weber, Y. Zhang,
N. Berry, Y. J. Kwon, C. L. Perkins, J. C. Hemminger, R. Wu
and M. Law, J. Am. Chem. Soc., 2013, 135, 4412–4424.
55 W. Song, A. S. Poyraz, Y. Meng, Z. Ren, S.-Y. Chen and
S. L. Suib, Chem. Mater., 2014, 26, 4629–4639.
This journal is © The Royal Society of Chemistry 2018
View publication stats
View Article Online
Journal of Materials Chemistry A
56 Q. Liu, L.-C. Wang, M. Chen, Y. Cao, H.-Y. He and K.-N. Fan,
J. Catal., 2009, 263, 104–113.
57 B. de Rivas, R. López-Fonseca, C. Jiménez-González and
J. I. Gutiérrez-Ortiz, J. Catal., 2011, 281, 88–97.
58 Y. Yu, T. Takei, H. Ohashi, H. He, X. Zhang and M. Haruta, J.
Catal., 2009, 267, 121–128.
59 X. Li, H. Dai, J. Deng, Y. Liu, Z. Zhao, Y. Wang, H. Yang and
C. T. Au, Appl. Catal., A, 2013, 458, 11–20.
60 P. Li, C. He, J. Cheng, C. Y. Ma, B. J. Dou and Z. P. Hao, Appl.
Catal., B, 2011, 101, 570–579.
61 Y. Liu, H. Dai, J. Deng, L. Zhang, Z. Zhao, X. Li, Y. Wang,
S. Xie, H. Yang and G. Guo, Inorg. Chem., 2013, 52, 8665–
8676.
62 S. Xie, H. Dai, J. Deng, Y. Liu, H. Yang, Y. Jiang, W. Tan, A. Ao
and G. Guo, Nanoscale, 2013, 5, 11207–11219.
63 S. A. C. Carabineiro, X. Chen, M. Konsolakis, A. C. Psarras,
P. B. Tavares, J. J. M. Órfão, M. F. R. Pereira and
J. L. Figueiredo, Catal. Today, 2015, 244, 161–171.
64 J. Deng, S. He, S. Xie, H. Yang, Y. Liu, G. Guo and H. Dai,
Environ. Sci. Technol., 2015, 49, 11089–11095.
65 Z. Qu, K. Gao, Q. Fu and Y. Qin, Catal. Commun., 2014, 52,
31–35.
66 W. Han, J. Deng, S. Xie, H. Yang, H. Dai and C. T. Au, Ind.
Eng. Chem. Res., 2014, 53, 3486–3494.
67 Y. Jiang, J. Deng, S. Xie, H. Yang and H. Dai, Ind. Eng. Chem.
Res., 2015, 54, 900–910.
68 S. Oyama, X. Zhang, J. Lu, Y. Gu and T. Fujitani, J. Catal.,
2008, 257, 1–4.
69 G. B. M. Casas-Cabanas, D. Larcher, A. Lecup, V. Giordani
and J.-M. Tarascon, Chem. Commun., 2009, 21, 1939–1947.
70 X. Pan, M. Q. Yang, X. Fu, N. Zhang and Y. J. Xu, Nanoscale,
2013, 5, 3601–3614.
71 N. Bahlawane, Appl. Catal., B, 2006, 67, 168–176.
72 L. F. Liotta, G. Di Carlo, G. Pantaleo, A. M. Venezia and
G. Deganello, Appl. Catal., B, 2006, 66, 217–227.
J. Mater. Chem. A, 2018, 6, 498–509 | 509