Surfactant-Free Synthesis of Ultrafine Pt Nanoparticles on MoS2Nanosheets as Bifunctional Catalysts for the Hydrodeoxygenation of Bio-Oil

Article abstract of DOI:10.1021/acs.langmuir.0c02613

Hydrodeoxygenation (HDO) of bio-oil is a crucial step for improving the bio-fuel quality, but developing highly dispersed Pt-based catalysts with high selectivity for target alkanes remains a great challenge. This study presents a fast surfactant-free method to prepare the MoS2-supported Pt catalyst for HDO. Ultrafine Pt nanoparticles with sizes of <5 nm can be readily grown on chemically exfoliated MoS2 nanosheets (NSs) via the direct microwave-assisted thermal reduction. The obtained Pt NPs/MoS2 composites show excellent catalytic performance in the conversion of palmitic acid, and the best selectivity (also the yield) of hexadecane and pentadecane is 80.56 and 19.43%, respectively.

Full text of DOI:10.1021/acs.langmuir.0c02613

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Article
Surfactant-Free Synthesis of Ultrafine Pt Nanoparticles on MoS2
Nanosheets as Bifunctional Catalysts for the Hydrodeoxygenation of
Bio-Oil
Qicheng Zhang, Danyun Xu, Junmei Liang, Qianqian Lin, Wenchao Peng, Yang Li, Fengbao Zhang,*
and Xiaobin Fan*
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ABSTRACT: Hydrodeoxygenation (HDO) of bio-oil is a crucial step for improving the bio-fuel quality, but developing highly
dispersed Pt-based catalysts with high selectivity for target alkanes remains a great challenge. This study presents a fast surfactant-free
method to prepare the MoS2-supported Pt catalyst for HDO. Ultrafine Pt nanoparticles with sizes of <5 nm can be readily grown on
chemically exfoliated MoS2 nanosheets (NSs) via the direct microwave-assisted thermal reduction. The obtained Pt NPs/MoS2
composites show excellent catalytic performance in the conversion of palmitic acid, and the best selectivity (also the yield) of
hexadecane and pentadecane is 80.56 and 19.43%, respectively.
the synthesis of these NPs typically requires surfactants,14−16
INTRODUCTION
■
and the surfactant residues are difficult to be removed.16,17
Microalgal biomass is a crucial renewable energy resource that
can meet a range of energy requirements.1,2 However,
Besides, the high activity of these NPs, especially the Pt NPs, is
usually accompanied by a low selectivity for complex reactions
like HDO. For example, the Pt NPs may not only catalyze the
hydrogenation of −COOH, −CHO, and CC double bonds
in reactants and intermediates but also the decarbonylation of
aldehydes and alcohols, leading to C atom loss. Recently, many
two-dimensional (2D) materials have been demonstrated to be
an excellent catalyst or catalyst support for many reactions. In
particular, MoS2 itself shows promising applications in the
catalytic hydrodesulfurization18,19 and hydrogen evolution
reaction.20,21 It is interesting to investigate the performance
of the bifunctional Pt NPs/MoS2 catalyst in the complex
microalgae bio-oil prepared by modifying microalgal biomass
has obvious disadvantages. For example, the resultant bio-oil
has a high oxygen content and poor thermal stability, so it is
necessary to remove the oxygen to serve as a replacement of
conventional petrodiesel.3,4 Therefore, catalytic hydrodeoxyge-
nation (HDO) is the crucial step for improving the bio-fuel
quality.5,6
In the past decades, a variety of catalysts for hydro-
deoxygenation have been reported,7−10 and noble-metal-based
catalysts (especially the Pt) have attracted particular attention,
owing to their high activity and excellent resistance to
deactivation through coking. It has been reported that these
metal nanoparticles (NPs) show extraordinary activity in
HDO, and their selectivity in the HDO process is affected by
the particle size. For example, reducing the size of metal
nanoparticles can significantly improve the selectivity of
aromatic hydrocarbons for phenols HDO.11,12 It has also
been confirmed that particle size can affect the reactivity and
selectivity of fatty acid HDO, and the small metal nanoparticles
are more conducive to the formation of alkanes.13 However,
Received: September 3, 2020
Revised: November 12, 2020
Published: November 23, 2020
https://dx.doi.org/10.1021/acs.langmuir.0c02613
© 2020 American Chemical Society
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Scheme 1. Microwave-Assisted Preparation of Pt NPs/MoS2 Composites without Surfactant
Catalytic Activity Measurements. The catalytic hydrodeoxyge-
nation experiments were carried out in a batch autoclave with a
stirring speed of 300 rpm. In a typical reaction, reactant (palmitic acid,
0.25 g), n-decane (50 mL), and catalyst (0.05 g) were loaded into the
100 mL autoclave (Shanghai Yan Zheng Experimental Instrument,
model YZPR-100(M)). The autoclave was purged with H2 to
completely remove air, and then the hydrogen pressure was increased
to 4 MPa. Normally, the reaction took place at 260 °C for hours (start
timing after the temperature reaches the preset value). But for the
kinetic test reaction, time was calculated from the start of heating. The
liquid-phase products were collected after the reaction and subjected
to component analysis using a gas chromatograph (Agilent
GC6890N) equipped with both an Agilent HP-INNOWax (30 m ×
0.25 mm × 0.25 μm) column and a flame ionization detector.
Conversion of palmitic acid and selectivity of products were
calculated as follows
HDO, despite similar Pt NPs/MoS2 composites have been
reported for other applications.
In this work, we report a strategy to deposit ultrafine Pt NPs
on the chemically exfoliated MoS2 nanosheets (NSs) and study
the performance of the obtained Pt NPs/MoS2 bifunctional
catalyst in HDO. Compared with traditional heating methods,
microwave heating can lead to uniform nucleation and smaller
size and distribution of the nanoparticles.22,23 Using the
microwave-assisted thermal reduction of PtCl2 in the presence
of MoS2 in propylene carbonate (PC), ultrafine Pt NPs with an
average size of <5 nm were well dispersed on the 2D MoS2
(Scheme 1). Notably, we found that this bifunctional catalyst
not only exhibited excellent activity in the conversion of
palmitic acid (model compound of microalgae bio-oil) to
alkanes but also its selectivity of hexadecane could reach over
80%.
moles of converted palmitic acid
moles of palmitic acid in the feed
conversion (%) =
selectivity (%) =
× 100%
EXPERIMENTAL SECTION
■
moles of individual product
moles of total products
× 100%
Materials. MoS2 (bulk, ≥99.5%), palmitic acid (≥99.0%), and n-
decane (≥99.0%) were purchased from Aladdin Chemistry Co., Ltd.
(Shanghai, China). n-Butyllithium/hexane solution (2.5 M solution in
hexanes) was provided from Spcscientific Technology Co., Ltd.
(Nanjing, China). PtCl2 (≥98.0%) was purchased by HWRK
Chemical Co., Ltd. (Beijing, China). Propylene carbonate (PC;
≥99.0%) and n-hexane (≥99.0%) were purchased from Yuanli
Chemical Co., Ltd. (Tianjin, China). All reagents were used as
received without further purification.
Characterizations. The samples were characterized by X-ray
diffraction (XRD; Bruker AXS D8-Focus) with a Cu Kα radiation,
scanning electron microscopy (SEM; Hitachi S-4800) at an
accelerating voltage of 5 kV, energy-dispersive X-ray spectroscopy
(EDX; Hitachi S-4800), transmission electron microscopy (TEM;
JEOL JEM-2100F) at an accelerating voltage of 200 kV, Raman
spectroscopy (Horiba, LabRAM HR Evolution) with 532 nm laser
excitation, X-ray photoelectron spectroscopy (XPS; Thermo
ESCALAB 250XI), Fourier transform infrared (FTIR) spectroscopy
(Nicolet Nexus FTIR spectrometer), and inductively coupled-plasma
optical emission spectrometry (ICP-OES; Varian VISTA-MPX).
Preparation of Chemically Exfoliated MoS2 Nanosheets.
Chemically exfoliated MoS2 nanosheets were prepared by sonication-
assisted lithium intercalation method from bulk MoS2.24 Bulk MoS2
(1 g) was transferred into a 25 mL Schlenk flask, and n-butyllithium/
hexane solution (10 mL, 2.5 M) was injected into it under an argon
(Ar) atmosphere. The mixture was sonicated for 3 h with an
ultrasonic bath (AS3120B) at 120 W output power. Then, the
dispersion was retrieved by centrifugation and washed with hexane to
remove residual n-butyllithium. After that, the precipitations were
washing repeatedly with water and redispersed in PC to obtain
monolayer MoS2 nanosheet (ex-MoS2) dispersion (1 mg mL−1).
Preparation of Pt NPs/MoS2 Composite. Pt NPs/MoS2
composite was synthesized by microwave-assisted method. In brief,
PtCl2 was dispersed in PC by sonication to form a 5 mg mL−1
solution, which was added dropwise to MoS2/PC under magnetic
stirring. Stirring was continued for more than 30 min. Subsequently,
the mixture (30 mL) was subjected to microwave irradiation for a
certain time using a 2.45 GHz microwave oven (Shanghai Sineo,
model MAS-II) under an Ar atmosphere, with magnetic stirring and
output power of 500 W.
RESULTS AND DISCUSSION
■
Figure 1 shows the XRD patterns of the ex-MoS2-MW and Pt/
MoS2-MW-X. Compared with the standard spectrum of MoS2
crystal (JCPDS No. 37-1492), a new (001) peak at 2θ ≈ 7.98°
is clearly observed in the ex-MoS2-MW sample, attributed to
the separation between the MoS2 nanosheets in the dried
restacked films. Besides, the disappearance of the (00l) peaks
of raw bulk MoS2 (Figure S1a) in the ex-MoS2-MW reveals
that the long-range stacking order of the nanosheets along the c
axis was destroyed. This indicates that MoS2 effectively
exfoliated into the essentially single layers.25,26 For the Pt/
MoS2-MW-X composites, two obvious peaks appear at 39.7
and 46.3°, which are assigned to the (111) and (200) peaks of
Pt NPs, respectively. Besides, the (001) peak of the MoS2 shifts
to lower angles, attributed to the presence of Pt NPs, which
hinders the restacking of MoS2 NSs. Calculated by the Scherrer
According to the radiation time of 5, 10, and 30 min, the obtained
composites were denoted as Pt/MoS2-MW-X. Microwave-irradiated
pure ex-MoS2 was denoted as ex-MoS2-MW.
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3d3/2) (Figure 3c).31 The appearance of Mo6+ peaks is due to
the inevitable surface oxidation of MoS2 nanosheets during
exfoliation. The S 2p peak in Figure 3d can be deconvoluted
into two peaks at 162.0 and 163.2 eV, corresponding to the S
2p3/2 and S 2p1/2. Note that the characteristic peak of S 2p is
red-shifted by 0.2 eV relative to pure MoS2 (Figure S2),
attributed to the interaction between Pt and S. Besides, no
detectable signal is found in the range of 195.0−215.0 eV
(Figure S2c,d), which means that the sample surfaces are free
of chlorine.32,33 Therefore, the influence of chlorine ligands on
the surface of Pt can be excluded.
The typical SEM images of unloaded ex-MoS2-MW (Figure
4a) showed an agglomeration of nanosheets with crumpling
features, which is completely different from the layered
structure of the raw bulk MoS2 (Figure S1b), supporting
that the MoS2 was successfully exfoliated. Abundant restacking
MoS2 nanosheets with the lateral size of 1.5−3.0 μm can be
clearly observed. After the loading of Pt NPs, the Pt/MoS2-
MW-X composites (Figures 4b and S3) show similar
morphologies, maintaining a perfect sheet structure of the
exfoliated MoS2 nanosheets. In Figures 4c−f and S3c−j, the
corresponding SEM and EDX elemental mapping support the
uniform distribution of Mo, S, and Pt elements in the
composites.
The successful dispersion of Pt NPs was further confirmed
by the TEM (Figures 4g,h and S4), which shows the good
dispersion of abundant nanoparticles with irregular shapes over
the translucent MoS2 nanosheet. Statistical analysis shows that
the average size of these nanoparticles on Pt/MoS2-MW-10 is
4.67 nm. And the average sizes of Pt/MoS2-MW-5 and Pt/
MoS2-MW-30 are 3.73 and 4.97 nm, respectively (Figure
S4e,c). A close look at the individual nanoparticles (Figure 4h)
shows an interplanar spacing of 0.225 nm, corresponding to
the (111) planes of face-centered cubic (FCC) Pt, in line with
the XRD results. Besides, the spacings of 0.230 nm match well
with the (103) facet of MoS2 nanosheet, indicating that the Pt
NPs are tightly bonded to the MoS2 nanosheet via their (111)
plane.28,34
Figure 1. XRD patterns of ex-MoS2-MW and Pt/MoS2-MW-X. Note
that there are some minor peaks between 20 and 30° in all of the
XRD patterns that come from the sample cell for the XRD
characterization.
formula, the average sizes of the Pt NPs on Pt/MoS2-MW-X
are 4−4.5 nm.
As shown in Figure 2a, the coexistence of E1g and weak E21g
proves that ex-MoS2 is 1T (trigonal) phase.24,27 The
superlattice structure of 1T-MoS2 also leads to the appearance
of J1, J2, and J3 peaks, which disappear after the microwave
irradiation (Figure 2b). The samples after the irradiation only
exhibit distinct Raman signals of the characteristic in-plane E21g
and out-of-plane A1g modes of MoS2, confirming the 1T to 2H
(hexagonal) phase change. Compared with the ex-MoS2-MW,
the Pt/MoS2-MW-X composite shows an obvious blue shift
(∼4 cm−1) of the E21g vibration, which is sensitive to the built-
in strain of MoS2. This result implies that the surface
modification of Pt NPs may cause the lattice distortion of
MoS2, which increases the vibration energy.28,29
The formation of Pt/MoS2-MW-X composites was further
confirmed by XPS spectra. The characteristic peaks of C 1s, O
1s, Pt 4f, Mo 3d, and S 2p are observed in the survey region
(0−1200 eV) (Figure 3a). Figure 3b shows that the Pt 4f7/2
and Pt 4f5/2 peaks can be deconvoluted into two independent
components with a separation of binding energy around 0.9
eV, corresponding to Pt0 and Ptδ+. The presence of positively
charged Pt ions should be attributed to surface oxidation and
the dynamic electron transfer of Pt clusters to MoS2.30 In line
with previous studies, the Mo 3d spectra mainly consist of
peaks at around 229.1 (Mo4+ 3d5/2) and 232.3 eV (Mo4+
Catalytic hydrodeoxygenation of palmitic acid was then used
to evaluate the performance of these Pt/MoS2-MW-X
composites in HDO, and the performance of the different
samples under the optimum reaction conditions (4 MPa H2,
260 °C, 4 h) is summarized in Figure 5. With pure ex-MoS2,
the conversion is ∼96%, but the sum of hexadecanol and
hexadecene constitutes more than 50% of the products.
However, the conversion quickly goes to 100% after the
Figure 2. Raman spectra of (a) ex-MoS2 and (b) ex-MoS2-MW and Pt/MoS2-MW-10. Note that different Raman intensities were observed under
the same characterization conditions with 532 nm laser excitation.
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Figure 3. (a) XPS spectra of the Pt/MoS2-MW-10 and the high-resolution XPS (b) Pt 4f spectrum, (c) Mo 3d and S 2s spectrum, and (d) S 2p
spectrum.
Pt/MoS2-MW-X toward hexadecane increases first and then
decreases with the extension of microwave irradiation time. At
the same time, the percentage of hexadecane in alkane
products continued to decline (line chart in Figure 5b). Pt/
MoS2-MW-10 exhibits the best performance, and its selectivity
(also the yield) toward hexadecane and pentadecane is 80.56
and 19.43%, respectively. Note that long-term radiation results
in larger Pt NPs, which have been demonstrated by XRD
(Figure 1) and TEM (Figures 4g and S4). According to
previous studies, larger Pt NPs should facilitate the decarbon-
ylation (DCO) process35−37 and result in the increase of
pentadecane.
Kinetic studies show that the hexadecanol and hexadecanal
emerge in the initial stage and then disappear after 5 h (Figure
6), which is the characteristic of intermediate products. In
addition, hexadecane and pentadecane were produced at the
same rate at the beginning, indicating that the HDO process
proceeds simultaneously along the two different reaction paths.
After that, the hexadecanal and hexadecene remained at a low
Figure 4. SEM images of (a) ex-MoS2-MW and (b) Pt/MoS2-MW-
percentage during the first 4 h, suggesting that the dehydration
10. (c) SEM image and the corresponding (d−f) EDX elemental
of hexadecanol is a rate-controlling step. The kinetic data of
mapping of Mo, S, and Pt of Pt/MoS2-MW-10. (g, h) TEM images of
the other samples are shown in Figure S5, and a similar trend
Pt/MoS2-MW-10. The inset in (g) shows Pt NPs particle size
to Pt/MoS2-MW-10 is presented. The ex-MoS2 shows good
hexadecane selectivity but low conversion efficiency in a
reaction time of 4 h, and a large amount of intermediate
hexadecanol is observed. The introduction of Pt NPs can
accelerate the conversion of hexadecanol, while the molar ratio
of hexadecane/pentadecane decreases, especially for large Pt
NPs in Pt/MoS2-MW-30.
To further probe the mechanisms involved, the adsorption
of palmitic acid on the catalyst was analyzed by FTIR
spectroscopy. First, 0.1 g of Pt/MoS2-MW-10 was stirred with
20 mL of a 0.05 M n-hexane solution of palmitic acid at room
histograms; the dotted line represents the average size.
growth of Pt NPs on the MoS2 nanosheet, and the distribution
of the products varies in the Pt/MoS2-MW-X catalysts with
different microwave irradiation times. In particular, the
intermediate products (hexadecanol and hexadecane) com-
pletely disappear in the Pt/MoS2-MW-10 catalysts and the
highest selectivity of the most desirable product (hexadecane)
is achieved among the four catalysts.
Detailed analysis of the selectivity of alkanes is shown in
Figure 5b, where the histogram shows that the selectivity of the
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Figure 5. (a) Conversion (%) of palmitic acid and product composition (%) after hydrogenation over different catalyst samples. (b) Composition
(histogram, %) of alkanes and percentage (line chart, %) of hexadecane in alkanes over different catalyst samples. Reaction conditions: hexadecane
(0.25 g), n-decane (50 mL), catalyst (0.05 g), 4 MPa H2, 260 °C, 300 rpm.
results mean that palmitic acid can be successfully adsorbed on
the catalysts. However, the characteristic peak of the palmitic
acid at 1705 cm−1 (the stretching vibration of CO in
−COOH) disappears and a new peak at 1563 cm−1 emerge
which can be assigned to the stretching vibration of the CO
of the carboxylates. Note that the formation of carboxylates has
been proven to be an important intermediate for the HDO of
fatty acids in previous reports.39,40
Based on these results and related literature,41−43 the
possible reaction network and mechanisms are outlined in
Scheme 2. In brief, the palmitic acid adsorbed on the MoS2
Scheme 2. Proposed (a) Reaction Network and (b)
Reaction Mechanism of Palmitic Acid HDO over the Pt/
MoS2-MW-X Catalyst
Figure 6. (a) Conversion of palmitic acid and yields of products as a
function of reaction time over Pt/MoS2-MW-10 catalyst and (b) an
enlarged representation of the initial region.
temperature for 12 h.38,39 The catalysts were collected, washed
with n-hexane, and then dried for further characterizations.
Clear C−H vibration peaks can be observed on the treated Pt/
MoS2-MW-10 (Figure 7). Among them, the characteristic peak
at 2954 cm−1 corresponds to the asymmetric stretching
vibration of C−H in −CH3, the peaks at 2918 and 2850
cm−1 correspond to the asymmetric and symmetric stretching
vibration of C−H in −CH2−, and the peak at 1467 cm−1
corresponds to the deformation vibration of C−H. These
and Pt will convert into aldehyde via C−O hydrodeoxygena-
tion. Subsequently, the formed hexadecanal is further hydro-
deoxygenated to hexadecanol, which transforms into hexade-
cene by the dehydration process. In the final step, the CC of
hexadecene is further hydrogenated to form hexadecane, while
the minor product of pentadecane is obtained from the DCO
reaction on the larger Pt NPs.
CONCLUSIONS
In summary, we report a simple and efficient method for the
quick growth of ultrafine Pt NPs on exfoliated MoS2
■
Figure 7. FTIR spectra of Pt/MoS2-MW-10 with (red) and without
(blue) palmitic acid adsorption treatment.
nanosheets through the microwave-assisted method without
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any surfactant. A systematic study on the catalytic performance
of the obtained Pt/MoS2-MW-X composites in the palmitic
acid HDO suggests the synergistic catalytic effect of MoS2 and
Pt NPs, and their selectivity toward the hexadecane can reach
over 80%. The strategy here may be readily modified to grow a
wide range of metal nanoparticles on MoS2 nanosheets and
find promising applications in different reactions.
Tianjin University, Tianjin 300072, People’s Republic of
China; orcid.org/0000-0003-3003-9857
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.langmuir.0c02613
Notes
The authors declare no competing financial interest.
ASSOCIATED CONTENT
ACKNOWLEDGMENTS
■
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.langmuir.0c02613.
This study was supported by the National Natural Science
Funds (No. 21878226).
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catalysts (PDF)
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Fengbao Zhang − School of Chemical Engineering and
Technology, State Key Laboratory of Chemical Engineering,
Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin University, Tianjin 300072, People’s
Republic of China; Email: fbzhang@tju.edu.cn
Xiaobin Fan − School of Chemical Engineering and
Technology, State Key Laboratory of Chemical Engineering,
Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin University, Tianjin 300072, People’s
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Authors
Qicheng Zhang − School of Chemical Engineering and
Technology, State Key Laboratory of Chemical Engineering,
Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin University, Tianjin 300072, People’s
Republic of China
Danyun Xu − School of Chemical Engineering and Technology,
State Key Laboratory of Chemical Engineering, Collaborative
Innovation Center of Chemical Science and Engineering,
Tianjin University, Tianjin 300072, People’s Republic of
China
Junmei Liang − School of Chemical Engineering and
Technology, State Key Laboratory of Chemical Engineering,
Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin University, Tianjin 300072, People’s
Republic of China
Qianqian Lin − School of Chemical Engineering and
Technology, State Key Laboratory of Chemical Engineering,
Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin University, Tianjin 300072, People’s
Republic of China
Wenchao Peng − School of Chemical Engineering and
Technology, State Key Laboratory of Chemical Engineering,
Collaborative Innovation Center of Chemical Science and
Engineering, Tianjin University, Tianjin 300072, People’s
Republic of China; orcid.org/0000-0002-1515-8287
Yang Li − School of Chemical Engineering and Technology,
State Key Laboratory of Chemical Engineering, Collaborative
Innovation Center of Chemical Science and Engineering,
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