Direct growth of defect-rich MoO3-x ultrathin nanobelts for efficiently catalyzed conversion of isopropyl alcohol to propylene under visible light

Article abstract of DOI:10.1039/c5ta08603e

We report a robust and highly active photocatalyst for the C₃H₆ evolution reaction that is constructed by surfactant-free growth of oxygen vacancy-rich MoO_3-x ultrathin nanobelts. Under visible-light irradiation, the new catalyst can selectively (95% selectivity) dehydrate isopropyl alcohol into C₃H₆ with yields above 98%.

Full text of DOI:10.1039/c5ta08603e

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Direct growth of defects-rich MoO3-x ultrathin nanobelts for
efficiently catalyzed conversion of isopropyl alcohol to propylene
under visible light
Received 00th January 20xx,
Accepted 00th January 20xx
a
b
a
a
a
a
b
DOI: 10.1039/x0xx00000x
Hua Bai, Wencai Yi, Junfang Li, Guangcheng Xi,* Yahui Li, Haifeng Yang and Jingyao Liu*
www.rsc.org/
7
-12
We report a robust and highly active photocatalyst for C
3
H
6
owing to their unique chemical and physical properties.
evolution reaction that is constructed by surfactant-free growth of Orthorhombic phase molybdenum oxide has been recognized
oxygen vacancy–rich MoO3-x ultrathin nanobelts. Under visible- as one of the most promising semiconductor materials for
light irradiation, the new catalyst can selectively (95% selectivity) applications in lithium batteries, sensors, light-emitting diodes,
dehydrate isopropyl alcohol into C
3
H
6
with yields above 98 %).
and photocatalysts owing to its unique layered structure and
3-15
1
environmental friendliness.
In particular, oxygen vacancies-
Propylene is one of the most important raw materials for
chemical industry. Currently, catalytic or steam cracking of
fossil feedstocks is the most commonly used method for the
preparation of propylene in industry. However, with the
increasing demands for energy and the depletion of non–
renewable fossil feedstocks, more and more attention has
been paid to alternative and renewable sources for fuels and
chemicals. It is known that alcohols, such as ethanol, propanol,
and isopropyl alcohol can be easily prepared by the biomass
rich MoO3-x is of great interest owing to its unusual oxygen
defect structure and novel properties in the nanometer
1
6,17
regime.
Since Wang et al. reported the synthesis of
ultrathin MoO3-x single-wall nanotubes with a diameter of 6
1
8
nm by a thiol-assisted hydrothermal method, ultrathin MoO3-
one-dimensional and two-dimensional nanostructures have
been prepared by various solution–phase methods, such as
x
1
9-21
bioligand– and surfactant–assisted routes.
However,
complete removal of the surfactant or organic ligand
molecules from the ultrathin nanostructure surface is almost
impossible. For both fundamental investigations on the
ultrathin nanostructure itself and technological applications,
the presence of residue from the synthesis on the surface may
1
-3
conversion technology. Such biomass conversion technology
offers inexhaustible energy source since plants as the raw
materials are renewable. With increased availability and
reduced cost of bio-alcohols, conversion of the bio–based
feedstocks to highly valuable fuels and chemicals has been an
2
2
be
a
significant drawback.
It can be predicted that
4
,5
especially important research issue. Currently, research on
alcohol conversion to value–added chemicals focuses mainly
on ethanol dehydration to ethylene, or ethanol
dehydrogenation to acetaldehyde and then to acetone via
Aldol–condensations pathways, while for other types of
researchers will have opportunity to research the natural
chemical and physical properties of nanoscaled MoO3-x raised
by oxygen vacancies once the ultrathin nanostructures with
clear surfaces are received.
In this communication, we report the clean preparation of
ultrathin MoO3-x nanobelts that are efficient in the
photocatalytic conversion of isopropyl alcohol to propylene by
visible light. The ultrathin MoO3-x Nanobelts were prepared by
6
alcohol dehydration have rarely been reported. Generally,
high reaction temperature (200–400 °C) are necessary in these
reported methods.
Inorganic nanostructures with ultrathin diameter or
thickness (less than 2 nm) and even one unit cell size, have
attracting much research attention in the past few years,
a
simple one–pot solution–phase method (see the
experimental section). In a typical procedure, molybdenum
acetylacetonate was dissolved in distilled water, and the
obtained solution was transferred to a teflon–lined stainless–
steel autoclave and heated at 180 °C for 20 h. A blue flocculent
a
Nanomaterials and Nanoproducts Research Center, Chinese Academy of precipitate was collected, washed, dried in air, and obtained in
Inspectionand Quarantine, No. 11, Ronghua South Road, Beijing, 100123, China.
Email: xiguangcheng@caiq.gov.cn
a yield of approximately 100%. The product is insoluble in
b
water and in acid (HCl, pH 0), and has a high specific surface
International Joint Research Laboratory of Nano-Micro Architecture Chemistry,
Institute of Theoretical Chemistry, Jilin University, Changchun 130023, P. R. China.
Electronic Supplementary Information (ESI) available: Experimental procedure,
XRD patterns, TEM and HRTEM images, energy-dispersive X-ray spectra, UV-vis
spectra, X-ray photoelectron spectroscopy (XPS), and EDS. See
DOI: 10.1039/x0xx00000x
2
area of 201 m /g (Figure S1).
The most important structural characteristic of
orthorhombic phase molybdenum oxide is its structural
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The ultrathin MoO3-x nanobelts show unusual photophysical
properties, as indicated by ultraviolet–visible–near infrared
(
UV–Vis–NIR) absorption spectroscopy (Figure 2a). It is well
known that commercial MoO with a wide band gap (3.1 eV)
requires high energy UV light to activate it. However, a very
3
–
strong absorption peak with a center of 550 nm present in the
visible and near infrared regions of the absorption spectrum
gives clear evidence that the MoO3-x nanobelts consist of a
2
2
large number of oxygen vacancies,
demonstrated by electron spin resonance (ESR) spectrum
Figure S4). This result is very different from those 1D and 2D
MoO3-x nanostructures synthesized by surfactant–assisted
which is also
(
1
8,20
methods. For those MoO3-x nanostructures obtained via
surfactant–assisted methods, their absorption peaks often
18,20
appear in the NIR infrared region.
It is also noted that Chen
Figure 1. (a) XRD pattern of the as-prepared MoO3-x sample, inset: crystal structure of et al. reported the surfactant–free synthesis of 20–30 nm thick
orthorhombic molybdenum oxide. (b,c) SEM and TEM images of the ultrathin MoO3-x
MoO
nanosheets with a LSPR peak center at about 680
3
23
-x
nanobelts. (d) HRTEM image and corresponding FFT pattern of the ultrathin nanobelts.
nm, which may be the first observation of the visible LSPR in
MoO3-x nanostructures. Compared with the value reported by
Chen et al., the result obtained by our experiments
experienced a significant blue shift of 130 nm. To the best of
our knowledge, the strong absorption below 600 nm
wavelength has not been reported for molybdenum oxide.
Moreover, this absorption peak may be the shortest
wavelength of semiconductor LSPR even though compared
with other typical plasmonic semiconductor nanostructures
anisotropy (inset in Figure 1a), which can be considered as a
layered structure parallel to (010). Distorted MoO6
octahedrash are four corners to form a plane and two planes
join together by sharing octahedral edges to form a single
layer. The layers stack up along the [010] direction by van der
Waals forces. The high crystallinity and phase purity of the
resultant samples were confirmed by XRD (Figure 1a). Our XRD
15-17
pattern is consisted with previous reports.
The diffraction
(such as CuS2-x, CuSe2-x, CuTe2-x, WO3-x, TiO2-x, Al-ZnO, and Si)
peaks of the XRD pattern for the sample can be readily indexed
to be orthorhombic with lattice constants of a = 3.962 Å, b =
which usually appear in the NIR–mid infrared (MIR) region
2
5-33
(Table S1 in Supporting Information).
From the view point
13.85 Å, c = 3.697 Å (JCPDs, No. 05–0508). No peaks of any
of energy conversion, the visible-LSPRs with higher energy are
more promising and efficient way compared with the NIR-
LSPRs.
other crystalline phases were detected, indicating the high
purity of the MoO3-x ultrathin nanobelts.
Scanning electron microscopy (SEM) image shows that the
as–synthesized sample is composed of 1D nanostructures with
large aspect ratio and lengths of up to several micrometers
(Figure 1b). Transmission electron microscope (TEM) image
show that the as-synthesized 1D nanostructures are composed
of ultrathin MoO3-x nanobelts with width of 20-30 nm and
lengths of up to several micrometers (Figure 1c). From the
vertical view (marked by arrows in Figure 1c), the standing
ultrathin MoO3-x nanobelts show a wire-like morphology due to
its ultrathin thickness. The thickness of the nanobelts is only
about 1.45 nm. The high–resolution TEM (HRTEM) image
Figure 2. a) UV-Vis-NIR absorption spectrum and b) Mo3d XPS spectra of the oxygen
(Figure 1d) shows that the ultrathin MoO3-x nanobelts are
vacancies-rich MoO3-x ultrathin nanobelts and Mo-500-60 min.
highly crystallized. The fringe spacing of 0.18 nm (shown in the
inset of Figure 1d) agrees well with the spacing of the (002)
We speculate this significant blue shift of LSPR absorption
peak may be attributed to its very high concentration oxygen
vacancies contained in the ultrathin MoO3-x nanobelts. Control
experiments show that the color of a MoO3-x sample gradually
changed from vivid blue in the original sample to white in the
final sample (Figure S5) once the sample was oxidized by
heating the MoO3-x nanobelts in air at 500 °C for 60 min. The
corresponding absorption spectrum of the white sample
3
plane of orthorhombic MoO . The diffraction spots of the
corresponding FFT pattern (indexed as the [010] zone) can be
indexed as the 200 and 002 reflections (inset of Figure 1d),
clearly demonstrating that the growth direction of the
nanobelts is [001], the top/bottom surfaces of the belts are
(
010) and the side surfaces are (100). Energy–dispersive X–ray
spectroscopy (EDS) confirms that the sample only contains Mo
and elements (Figure S2). Furthermore, the Fourier
O
(marked as Mo-500-60 min) shows a little red shift, and no
transform infrared (FTIR) spectrum exhibits the clear surface of
our sample (Figure S3).
absorption is present in the visible and near infrared regions,
which indicates that the oxygen vacancies contained in the
nanobelts disappear after oxidizing with heated air. In
2
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with the Mo-500-60 min, indicating that MoO3-x ultrathin
nanobelts should be better semiconductor material for solar
light harvesting. For a better understanding on the light
harvesting by MoO3-x ultrathin nanobelts, the photocurrent
responses under different illumination conditions are
examined. Under UV or visible light, the MoO3-x nanobelts also
show the higher photocurrent density compared with Mo-500-
6
0 min (Figure 3b-c). The enhanced photocurrent responses of
MoO3-x ultrathin nanobelts as compared with Mo-500-60 min
should be related to the introduction of oxygen vacancies. As
an evidence, photoluminescence (PL) spectra recorded at an
excitation wavelength of 300 nm demonstrated this hypothesis
(Figure S8). The PL emission spectrum of the MoO3-x ultrathin
nanobelts recorded at -10 °C shows an strong blue emission
band at 2.87 eV (435 nm), which originate from the presence
of oxygen vacancies or defects. Figure S8 also reveals that the
ultrathin MoO3-x nanobelts lower PL intensity compared with
the Mo-500-60 min, suggesting the recombination of photo-
generated electron-hole pairs is effectively suppressed upon
Figure 3. Photocurrent response of the oxygen vacancies-rich MoO3-x ultrathin the introduction of oxygen vacancies, which accordingly results
nanobelts under the illumination of (a) full-spectrum light (200-2000 nm), (b) UV light
35
in higher photocurrent responses. Very interestingly, the
(
200-420 nm), (c) visible light (420-780 nm), and (d) NIR light (780-2000 nm).
MoO3-x ultrathin nanobelts also show noticeable photocurrent
responses under near-infrared illumination, in great contrast
to Mo-500-60 min (Figure 3d). The observed photocurrent
responses under near-infrared illumination should come from
LSPR induced by the abundant oxygen vacancies. On the basis
of photocurrent responses under different illumination
conditions, we could come to the conclusion the introduction
of oxygen vacancies to molybdenum oxide nanobelts can not
only promote full-spectrum, UV, and visible light harvesting
but also create near-infrared light harvesting.
contrast, after the oxygen vacancy concentration of the MoO3-x
ultrathin nanobelts was increased by NaBH4 reduction, a
stronger visible-LSPR peak located at 516 nm was detected
(Figure S6). The change in the valence of Mo atoms in the
ultrathin nanobelt surface before and after oxidation could be
further characterized by using X–ray photoelectron
spectroscopy (XPS; Figure 2b). For the MoO3-x ultrathin
nanobelts, four peaks corresponding to Mo3d could be seen in
the XPS spectrum. Two peaks observed at 232.8 and 235.9 eV
6
+
Because crystal defects often give rise to unexpected results
in chemical reactions, we investigated the photochemical
activity of the oxygen-vacancy-rich MoO3-x nanobelts by the
photochemical dehydration of isopropyl alcohol (IPA,
CH CH(OH)CH ) vapor in a gas-solid system. The ultrathin
correspond to Mo , and the other two peaks at 231.9 and
5+ 20
34.9 eV are assigned to Mo . For the sample Mo-500-60
2
min, two sharp peaks of Mo3d can be seen in the spectrum,
6
+
which is a typical feature of Mo . At the same time, two peaks
can also be clearly identified from the O1s core level spectra
shown in Figure S7: one peak at 529.8 eV is deemed as the
oxygen bond of Mo-O-Mo, while the other located at 531.4 eV
can be attributed to the O-atoms in the vicinity of an O-
3
3
MoO3-x nanobelts achieved efficient propylene (C H )
3
6
production from isopropyl alcohol vapor on illumination with
visible light (λ > 420 nm) in the absence of noble-metal co-
catalysts such as Pt and Au (Figure 4a). The average formation
3
4
vacancy. As for the Mo-500-60 min, no obvious O-vacancy
mode was detected. The XPS spectra clearly demonstrated
that after oxidizing with heated air, the valence of Mo has
-1 -1
rate of C H is about 5.75 mmol g h . Besides C H , only 3%
3
6
3 6
(molar ratio) of other compounds (such as carbon dioxide and
6
+
acetone) were produced, which suggests that the selectivity of
this photochemical reaction is very high. Because the
equilibrium temperature of the photochemical reaction
system was about 50 °C, control experiments were carried out
to detect the influence of temperature on product formation.
The experimental results indicated that only very small
amount of C3H6 (0.18 mmol g-1h-1) was detected when the
reactions were performed in the dark at 50 °C, that is, the
dehydration of isopropyl alcohol almost cannot be started in
the absence of light. To further support that the present
catalytic reaction proceeds through light absorption within
ultrathin MoO3-x nanobelts, we also examined the dependence
completely changed into Mo . This means that the oxygen
vacancies contains in the ultrathin nanobelts disappeared after
oxidation with heated air, which also explains the disappearing
of the absorption peak in the absorption spectra.
The photoelectrochemical properties of the ultrathin MoO3-x
nanobelts are examined by means of photocurrent responses.
We measured the photocurrent response in a three-electrode
electrochemical cell with Ag/AgCl as the reference electrode
and Pt wire as the counter electrode (see Experimental Section
in Supporting Information). The photocurrent responses for all
samples under dark are very low, while obvious current
responses could be discerned from 0.1 to 1.0 eV (vs Ag/AgCl)
under full-spectrum light (Fig. 3a). The ultrathin MoO3-x
nanobelts show the higher photocurrent density compared
of the rate of C
3
H
6
evolution on the wavelength of incident
evolution
light. As shown in Figure S9, the maximum of C
3 6
H
rates is obtained when 540 nm incident light was used, which
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Figure 5. Adsorption structure of isopropyl alcohol on (a) MoO nanobelts and (b) on
MoO3-x nanobelts; (c) Charge-density difference for isopropyl alcohol adsorption on
the MoO3-x nanobelts, Isosurfaces calculated at 0.004e/Å3; (d) DOS of MoO3-x after
isopropyl alcohol adsorption.
-1 -1
very lower (0.85 mmol g h ). Finally, no C H were detected
3
6
when Mo-H O -2 h was used as the catalyst, the surface of
2
2
6+
which was completely oxidized into Mo by H O (Figure S10),
2
2
thus suggesting that MoO is not active for photocatalytic C H
3 6
3
evolution. These experimental results demonstrated
unambiguously that oxygen vacancies in the samples play a
very important role in the photocatalytic C H evolution under
3
6
visible light.
In order to clarify the underlying mechanism for the high
photochemical activity of the ultrathin MoO3-x nanobelts, we
also studied the isopropyl alcohol adsorption structures and
energies on the ultrathin MoO3-x nanobelts at the DFT+U level
3 6
Figure 4. (a) Time courses of C H production over the as-synthesized MoO3-x ultrathin
(see Supporting Information of adsorption energies
nanobelts under visible light (λ > 420 nm) and in the dark at 50 °C. (b) UV/Vis
absorption spectra of the molybdenum oxide samples obtained by oxidation with H
for different time periods. (c) Time courses of C production over the molybdenum
oxide samples with different oxygen-vacancy concentrations.
calculations for details, Figure S11-12). Seen from Figure 5a,
2 2
O
isopropyl alcohol is weakly physisorbed over the perfect MoO3
3 6
H
nanobelts, with adsorption energy of -0.10 eV and no strong
preference for a particular surface site. While as the creation
5
+
is a high match with the LSPR central wavelength. Therefore,
the formation of C H is really based on a photopromoted
of an O-vacancy on molybdenum oxide nanobelt, Mo is
exposed, which leads to a much stronger adsorption of
isopropyl alcohol molecule through O at the defect site of
MoO3-x nanobelt (Figure 5b). The calculated adsorption energy
becomes -1.29 eV. At the same time, the greatly enhanced
adsorption make the C-O bond length of isopropyl alcohol
increase of 0.047Å, reaching 1.487 Å, which reduce the
breaking energy of carbon-oxygen bond of isopropyl alcohol.
Furthermore, the plot of the contour surface of the charge-
density difference for the isopropyl alcohol adsorption is
shown in Figure 5c. The further Bader charge analysis suggests
that the electrons are transferred from the hydrogen to
oxygen in hydroxyl of isopropyl alcohol and from IPA to
surface. The charge–charge interaction between isopropyl
alcohol and MoO3-x may account for the enhanced adsorption
ability of isopropyl alcohol. In addition, the band gap of the
ultrathin MoO3-x nanobelt is further reduced from 1.917 eV
before isopropyl alcohol adsorption to 1.374 eV after isopropyl
3
6
dehydration of isopropyl alcohol. To our knowledge, the
photochemical conversion of isopropyl alcohol into C H over
3
6
MoO3-x under visible light has not been reported to date.
We then investigated the effect of the concentration of
oxygen vacancies on the photochemical dehydration of
2 2
isopropyl alcohol. By adjusting the H O treating time, a series
of molybdenum oxide samples with different oxygen-vacancy
concentrations was prepared. UV–Vis–NIR absorption spectra
show the oxygen-vacancy concentrations of the samples
gradually reduced as the oxidation time increased (Figure 4b).
Figure 4c shows the rate of C
oxide catalysts with different concentrations of oxygen
vacancies. After oxidizing for 0.5 h, the activity of C
evolution on the sample is reduced down to 32% (1.84 mmol g
3 6
H evolution on molybdenum
3 6
H
-
1
-1
h ). After oxidizing for 1 h, the sample still shows activity in
photochemical C evolution, but the rate of C evolution is
3
H
6
3 6
H
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alcohol adsorption (Figure 5d), consistent with the high activity
of MoO3-x nanobelt observed in experiments.
Chen, Z. Y. Zhou, F. X. Ruan, Z. L. Yang, N. F. Zheng, Nat.
Nanotechnol. 2011, 6, 28-32.
Y. F. sun, Z. H. sun, s. Gao, H. Cheng, Q. H. Liu, J. Y. Piao, T.
7
8
Based on the experimental and calculated results, it can be
rationally concluded that the oxygen vacancies contained in
the ultrathin nanobelts play a crucial role in the formation of
Yao, C. Z. Wu, S. L. Hu, S. Q. Wei, Y. Xie, Nat. Commun. 2012
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H. H. Duan, N. Yan, R. Yu, C. R. Chang, G. Zhou, H. S. Hu, H.
,
3
C
3
H
6
, which may markedly increase the number of catalytically
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active sites on their surfaces and facilitate the adsorption of
organic molecules on these sites. From the point of view of
catalytic kinetics, the stronger adsorption between oxygen
vacancy and isopropyl alcohol molecule may generate
9
1
0
unexpected affinity interaction, and therefore, reduces the 11 a) L. Q. Mai, B. Hu, W. Chen, Y. Y. Qi, C. S. Lao, R. Yang, Y.
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1
1
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the strong LSPR effect result from the large quantity of oxygen
vacancies make the oxygen vacancies-rich MoO3-x nanobelts
highly efficient photocatalytic conversion agent. As we known,
3
4
5
Z. Y. Yin, X. Zhang, Y. Q. Cai, J. Chen, J. I. Wong, Y. Y. Tay, J.
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3
5
the instantaneous temperature of LSPRs can reach 1000K,
1
1
which offers enough energy for the isopropyl alcohol
dehydration reaction.
To evaluate stability of the MoO3-x ultrathin nanobelts, the
reaction was allowed to proceed for a total 30 h with
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intermittent evacuation every 5 h. Continuous C
3
H
6
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,
4
with no apparent decrease in its photocatalytic activity was
clearly observed (Figure S13). After the reactions, the structure
and morphology of the catalysts is not apparently change
1
1
7
8
(Figure S14-15).
1
2
9
0
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,
1
Conclusions
In summary, ultrathin MoO3-x nanobelts were successfully
synthesized by a very simple one-pot solution method. The
ultrathin nanobelts contain a large number of oxygen
vacancies, which lead them to possess much strong visible-
LSPR absorption and greatly enhanced photocurrent responses
9
2
1
under UV light, visible light, and even NIR light irradiation. As a 22 T. Nutz, M. Haase, J. Phys. Chem. B 2000, 104, 8430.
2
2
2
3
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3 6
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COMMUNICATION
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Oxygen Vacancies-Rich MoO3-x Ultrathin nanobelts with diameters less than 1.5 nm
and aspect ratios larger than 1000 have been synthesized without using any
surfactants. The as-synthesized ultrathin MoO3-x nanobelts show remarkable
capability in photocatalytic conversion of isopropyl alcohol to propylene depending
on its high adsorption energy and strong localized surface plasmon resonance
caused by large quantities of oxygen vacancies.