Pd Nanoparticles Supported on Triangle-Shaped La2O2CO3 Nanosheets: A New Highly Efficient and Durable Catalyst for Selective Hydrogenation of Cinnamaldehyde to Hydrocinnamaldehyde

Article abstract of DOI:10.1002/chem.202000741

A catalyst in which Pd nanoparticles are supported on triangle-shaped La₂O₂CO₃ nanosheets exposing predominantly the (001) planes (Pd/La₂O₂CO₃-TNS; where TNS denotes triangular nanosheets)

Full text of DOI:10.1002/chem.202000741

A Journal of
Accepted Article
Title: Triangular-shaped La2O2CO3 Nanosheets Supported
Pd Nanoparticles: A New Highly Efficient and Durable
Catalyst for Selective Hydrogenation of Cinnamaldehyde to
Hydrocinnamaldehyde
Authors: Fei Wang, Yanshuai Bi, Kai Hu, and Xuejiao Wei
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To be cited as: Chem. Eur. J. 10.1002/chem.202000741
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10.1002/chem.202000741
Triangular-shaped La
2
O
2
CO Nanosheets Supported Pd
3
Nanoparticles: A New Highly Efficient and Durable Catalyst for
Selective Hydrogenation of Cinnamaldehyde to
Hydrocinnamaldehyde
Fei Wang,* Yanshuai Bi, Kai Hu, [a] and Xuejiao Wei*[b]
[
a]
[a]
Dedication ((optional))
[
[
a]
b]
Dr. Fei Wang, Yanshuai Bi, Kai Hu
Advanced Catalysis and Green Manufacturing Collaborative Innovation Center
Changzhou University
21 Gehu Road, Changzhou 213164 (China)
E-mail: wangfei@cczu.edu.cn
Dr. Xuejiao Wei
School of Chemical Engineering and Materials
Changzhou Institute of Technology
666 Liaohe Road, Changzhou 213022 (China)
E-mail: weixj@czu.cn
Supporting information for this article is given via a link at the end of the document.((Please delete this text if not appropriate))
Abstract: A triangular-shaped La
predominant (001) planes supported Pd catalyst (Pd/La
TNS) was successfully prepared using a facile solvothermal method.
Pd/La CO -TNS catalysts not only exhibited excellent catalytic
activity and recycling stability for hydrogenation of cinnamaldehyde
2
O
2
CO
3
nanosheets exposed the
with a high dispersion of 73.6 % dispersed on porous nanorods
2 2 3
O CO -
of CeO
2
catalyst exhibit the highest catalytic activity and best
chemoselectivity for hydrogenation of nitroarenes. Tan et al.[
18]
O
2 2
3
2
presented the {100}-faceted CeO nanocubes supported Pd
nanoparticles catalysts exhibited much higher activity than those
{111}-faceted ceria nanooctahedrons and nanorods (enclosed
by {100} and {111} facets) supported Pd nanoparticles for
formaldehyde Oxidation. The same example can be also found
for acid-base oxides supports. Huang et al.[19] reported the
-1
(CAL) to hydrocinnamaldehyde (HCAL) with TOF of up to 41238 h .
This enhanced activity of Pd/La CO -TNS resulted from strong
O
2 2
3
metal-support interactions (SMSI). Structure analysis and
characterization demonstrated that surface oxygen-enriched
La
charge transfer between the Pd nanoparticles and triangle-shaped
La CO nanosheets and increases the electron density of Pd.
Moreover, the modulated electron states of the Pd/La CO -TNS
2
O
2
CO
3
-TNS supports exposed (001) planes was beneficial to
shape effect significantly modified basicity of La
2 2 3
O CO and
improves the performance of Ir/La CO catalyst in the steam
2
O
2
3
2
O
2
3
reforming of glycerol at high temperatures up to 650 ℃ toward a
sustainable hydrogen production.
O
2 2
3
catalysts can enhance the adsorption and activation of hydrogen,
leading to the enhanced hydrogenation activity.
Previous reports found that physicochemical interactions
generated by these associations between the metal and the
support can also influence catalytic properties, which have been
[20-23]
linked to the strong metal-support interaction (SMSI).
Guo et
al.[ altered the size regimes of the Ru deposits in Ru/CeO
24]
Introduction
2
assemblies and uncovered the competitive relationship between
SMSI. And Shen et al.[25] reported that Cu/CeO
catalysts are
Supported metal catalysts are the most widely used catalysts in
several important chemical processes and chemical industries
because of high thermal stability, high dispersion of active
2
highly active for the low-temperature water-gas shift and
revealed that the reaction occurs at the copper-ceria interfacial
perimeter due to SMSI. However, from the recent literatures we
found that most of these SMSI phenomena mainly occur on
[
1]
centers and excellent cyclic stability. Most of the supported
[
2]
[3],
metal catalysts use reducible metal oxides (such as CeO
2
[
4]
[5]
[6]
reducible oxides, such as CeO
2 2 2
[26], MnO [27], TiO [28], et al., which
Co3O4 , Fe2O3 , MnO2 , etc.) and acid-base metal oxides
(
Al2O3 , MgO , La2O3 , CaO[10], etc.) as supports. The role of
[
7]
[8]
[9]
was ascribed to their ability to change oxidation states by
exchanging oxygen atoms with the atmosphere and create
oxygen vacancies through the surface oxide and oxide crystal.
oxide supports is mainly embodied in immobilization of the
active component and improvement of the metal dispersion and
surface area.[
11-13]
In recent years, many reports have shown
For acid-base oxide as supports, Shen et al.[29] prepared Cu
that the catalytic activity of supported metal catalysts can be
adjusted by the particle size, shape and composition of the
material concerned.[14-16] Zhang et al.[17] reported Pd clusters
2 2 3
nanoparticles dispersed rod-shaped La O CO catalysts. This
basic support mainly provided substantial amounts of medium-
1
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strength basic sites for the activation of alcohol and directed the
selective dispersion of hemispherical Cu particles. Murata et
TEM, SEM and HRTEM images of as-prepared La CO
2
O
2
3
-TNS
were shown in Figure 2. As expected, the La CO sheets with
2
O
2
3
al.[30] reported Pd/θ, α-Al
O
3
with weak metal-support interaction
triangle shape of regular shape and uniform size were obtained
(Figure 2a). Figure 2b showed shows the typical TEM image of a
single triangular-shaped La O CO nanosheet. Most of the
2 2 3
2
showed a volcano-shaped dependence of the catalytic activity
on the size of Pd particles, and the catalytic activity of the
strongly interacted Pd/γ-Al
2
O
3
increased with the particle size.
nanosheets were about 300-400 nm in length (the distance from
the triangle bottom to the tip). Figure 2c illustrated SEM
From these results we found that the improvement of catalytic
activity is mainly attribute to the acid-base properties of the
support and the size of the metal active center. SMSI effect has
been rarely reported for basic oxide support.
representative image of as-prepared La
thickness of nanosheet is about 22-25 nm. These images
confirmed that the La CO -TNS possess an average bottom
2 2 3
O CO -TNS and the
2
O
2
3
width of 22-25 nm and a length up to 300-400 nm. The single
nanosheet was therefore explored through HRTEM, as shown in
Figure 2d and 2e. Figure 2d showed a highly magnified top-view
Herein, a new highly efficient triangular-shaped La
nanosheets (La CO -TNS) supported Pd catalyst was
successfully prepared. The La CO -TNS mainly exposed
001) planes where oxygen ions terminated (001) surfaces
2 2 3
O CO
2
O
2
3
2
O
2
3
of La
an angle of 60 ° between the adjacent edges correspond to the
3
010) plane and (100) plane of hexagonal La CO ,
2 2 3
O CO -TNS. The lattice spacings of 0.35 and 0.35 nm with
(
generated a stronger electronic interaction with Pd, which
resulted in the highly efficient conversion for cinnamaldehyde
(
2
O
2
respectively. Fast Fourier transformation (FFT) analysis of them
displayed the single-crystalline nature of the nanoplate projected
along the [001] direction. From side-view, the distances of 0.80
nm between fringes in Figure 2e are consistent with the (002)
planes of La O CO . hence, we propose that La O CO -TNS
2 2 3 2 2 3
was composed of two main (001) top and bottom surfaces and
three (100), (010) and (110) side faces, while the shape of the
-1
(
CAL) to hydrocinnamaldehyde (HCAL) with TOF of 41238 h .
Moreover, after five consecutive cycles Pd/La CO -TNS still
2
O
2
3
maintain the same activity and selectivity. Structure analysis and
characterizations revealed that morphology-induced SMSI
2 2 3
between Pd and La O CO -TNS remarkably enhanced the
catalytic activity.
2 2 3
La O CO nanorod was assumed to be a square block that was
terminated by two (001) flat planes, two (110) side planes, and
two (110) end planes, as illustrated in previous reported.[29]
Results and Discussion
2 2 3
Figure 1 presented XRD pattern of as-prepared La O CO -TNS
support. These peaks at about 26 º, 27 º, 31 º, and 45 º for
La CO -TNS can be indexed to (100), (101), (103), and (110)
phases, which corresponding to hexagonal phase of La CO
JCPDS Card No. 37-0804).[31] No other peaks were found,
indicating that as-prepared sample were pure La CO phase.
After deposition of Pd, distinguished characteristic peaks due to
La CO are observed for Pd/La CO -TNS catalysts.
a
2
O
2
3
2
O
2
3
(
2
O
2
3
2
O
2
3
2
O
2
3
However, no Pd peak was observed, which was probably
attributed to the fact that Pd nanoparticles were high-dispersed
on suface of La O CO -TNS.
2 2 3
b
d
c
e
Pd/La O CO -TNS
2
2
3
La O CO -TNS
2
2
3
1
0
20
30
40
50
60
2
Theta (degree)
2 2 3 2 2 3
Figure 1. XRD patterns of as-prepared La O CO -TNS and Pd/La O CO -
TNS samples.
Figure 2. TEM (a, b), SEM (c) and HRTEM (d, e) images of as-prepared
La CO triangular nanosheets.
2
O
2
3
2
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A closer examination of the as-obtained Pd/La
catalyst by high-resolution TEM (HRTEM) images showed that
Pd nanoparticles are uniformly dispersed on La CO -TNS with
2 2 3
O CO -TNS
a
b
2
O
2
3
regular shape and no significant formation of aggregates was
found (Figure 4a-d). These images reveal that size of Pd
nanoparticles was about 4-5 nm. The lattice distance with a
spacing of 0.22 nm and 0.35 nm correspond to the (111) plane
(
001)
c
d
of metallic Pd and the (010) and (100) planes of La
support, which confirmed that Pd nanoparticles had been
successfully loaded on La CO -TNS. HAADF-STEM images
and corresponding EDX-elemental mapping images of top-view
and side-view of Pd/La CO -TNS on edge of carbon lattice
2 2 3
O CO
(110)
(010) or (100)
2
O
2
3
Figure 3. (a) Hexagonal unit of La
(
O
2 2
CO
3
crystal. Perspective views from (b)
CO
2
O
2
3
001), (c) (110), (d) (010) or (100) planes of the crystal structure of La
2
O
2
3
.
were presented in Figure 4e and 4f, respectively. There are
three elements in the sample: O (blue), La (orange) and Pd
(
yellow). Obviously, Pd locates averagely on every surface of
La CO -TNS. Because the top and bottom surface area
account for about 70 % of the total area, this La CO -TNS
2 2 3
Previous reported presented that La O CO has a hexagonal
2
O
2
3
structure where each La3+ cation is surrounded by seven oxygen
anions: four in tetrahedral and three in octahedral coordinations
2
O
2
3
supported Pd structure is expected to have a large distribution of
surface-exposed Pd atoms over top and bottom surface of
La O CO -TNS.
2 2 3
(
Figure 3a).[29] As mentioned above, La
2
O
2
CO
constructed by in-plane (001) surfaces and side (100), (010) and
110) planes. Density-functional theory calculations identified
3
-TNS was
(
that the {110}, {010} and {100} planes were made up of O and
La atoms whereas the {001} plane contained O and C atoms
only (Figure 3b-d). The surface area of the {001} planes was
3
d5/2
Pd/La O CO -TNS
2
2
3
3
d3/2
Pd(0)
about 70 % of the total surface area, so La
2 2 3
O CO -TNS mainly
exposed (001) plane, made up of O and C atoms, while for the
Pd(II)
(
2 2 3
110) plane of La O CO -NR takes up 40 percent of the total
surface.[
29]
Pd/La O CO -NR
2
2
3
346
344
342
340
338
336
334
332
330
Binding Energy (eV)
2 2 3
Figure 5. Pd 3d region of XPS spectra of as-prepared Pd/La O CO -TNS and
Pd/La CO -NR samples.
2
O
2
3
Pd 3d region of XPS spectra of as-prepared Pd/La
2 2 3
O CO -TNS
and Pd/La CO -NR samples was showed in Figure 5, which
2
O
2
3
f
are deconvoluted into two pairs of doublets. The peaks at 334.8
and 340.1 eV are assigned to the binding energies of Pd(0) 3d5/2
and 3d3/2, and these at 335.9 and 341.3 eV are attributed to
Pd(II) oxidation state 3d5/2 and 3d3/2, respectively, possibly due
to the oxidation when exposed to air.[32] The binding energy of
Figure 4. (a, b, c, d) HRTEM images of as-prepared Pd/La
HAADF-STEM images and corresponding EDX-elemental mapping images (e)
top-view and (f) side-view of Pd/La CO -TNS on edge of carbon lattice.
2 2 3
O CO -TNS.
metallic Pd(0) 3d5/2 of Pd/La
energy by 0.7 eV compared with Pd/La
weakened 3d electron binding for Pd in the Pd/La
which likely results from partial electron transfer from La
TNS to Pd. This electron transfer would increase the electron
2
O CO
2
3
-TNS shifted to lower binding
CO -NR, indicating
CO -TNS,
CO
2
O
2
3
O
2 2
3
2
O
2
3
2
O
2
3
-
3
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FULL PAPER
density of Pd and enhance the penetration of outer-layer
electrons to the inner layer, which changed the binding energies
and substantially enhanced the catalytic activity.[33]
catalyst showed two reduction peaks in the temperature region
of -10-850 oC. The peaks at high temperature regions can be
attributed to the reduction of lattice oxygen of La O CO -TNS
2 2 3
support (not shown), whereas the sharp reduction peak below
Temperature-programmed desorption of CO
Temperature-programmed reduction of H (H
as-prepared Pd/La CO -TNS and Pd/La
were shown in Figure 6 and Figure 7. Figure 6 showed that two
obvious peaks at 110 oC and 280 oC appeared, which were
2
(CO
-TPR) profiles of
CO -NR catalysts
2
-TPD) and
0 oC could be ascribed to the reduction of PdO (to the Pd0)
5
x
2
2
and the surface adsorbed oxygen species[30] and the
2
O
2
3
2
O
2
3
2 2 2 3
corresponding H consumption of Pd/La O CO -TNS catalyst
-1
was 238 μmol g , which was almost two time larger than the
-1
theoretical amount for reducing Pd(II) to Pd(0) (96 μmol g ). The
attribute to weak and medium strong basic sites of La
corresponding to surface OH groups and La-O site pairs,
respectively.[34] Compared with Pd/La
CO -NR, as-prepared
Pd/La CO -TNS catalyst exhibited smaller amount of weak
and medium-strong basic sites (0.13 mmol g ).These results
suggested that Pd/La CO -TNS and Pd/La CO -NR
2 2 3
O CO ,
extra H
from La
2
consumption was caused by the oxygen back-spillover
CO -TNS to Pd. In addition, the amount of H
2
O
2
3
2
2
O
2
3
consumption for this peak for as-prepared Pd/La
2
O
2
CO
CO
3
3
-NR was
2
O
2
3
-1
190 μmol g , which was lower than Pd/La
2
O
2
-TNS,
-1
suggesting that a larger amount of high-valence palladium and
higher adsorbed oxygen species concentration existed in the
2
O
2
3
2
O
2
3
catalysts possessed different surface atomic arrangement.
According to previous analysis, due to surface (110) planes
exposed mainly, which were made up of O and La atom,
2 2 3
Pd/La O CO -TNS sample. The above results demonstrate that
the reducibility of the supported Pd-based sample was
dependent on the support morphology. Compared to
Pd/La
2 2 3
O CO -NR catalyst showed large amount of weak and
2 2 3
Pd/La O CO -NR catalysts, higher hydrogen consumption might
-1
medium-strong basic sites (0.21 mmol g ), which confirmed that
be due to a stronger interaction between a larger amount of
oxygen enrichment on surface of Pd/La
2
O
2
CO
3
-TNS catalyst.
coordination-unsaturated surface PdO
x
2 2 3
and La O CO -TNS.
1
00
100
80
60
40
20
0
Pd/La O CO -TNS
2
2
3
a
Pd/La O CO -NR
2
2
3
8
6
4
2
0
0
0
0
0
CAL Conversion
HCAL Selectivity
5
0
100
150
200
250
300
350
400
0
.5
1.0
1.5
2.0
2.5
3.0
Temperature (degree)
Reaction time (h)
1
00
100
80
60
40
20
0
Figure 6. CO
2
-TPD profiles of as-prepared Pd/La
2
2 3
O CO -TNS and
Pd/La CO -NR catalysts.
2
O
2
3
b
8
6
0
0
PdO/La O CO -TNS
2
2
3
PdO/La O CO -NR
40
2
2
3
CAL Conversion
HCAL Selectivity
2
0
0
0
.5
1.0
1.5
2.0
2.5
3.0
Reaction time (h)
Figure 8. CAL hydrogenation performance over (a) Pd/La
Pd/La CO -TNS catalysts. Reaction conditions: CAL (1 mL), ethanol (20
mL), catalyst (100 mg), H (1.0 MPa), temperatue: 353 K.
2 2 3
O CO -NR and (b)
2
O
2
3
0
10
20
30
40
50
60
70
80
2
Temperature (degree)
Figure 7. -TPR profiles of as-prepared PdO/La
H
2
2
O
2
3
CO -TNS and
The catalytic activity of CAL hydrogenation on the Pd/La
TNS and Pd/La CO -NR catalysts was evaluated and the
reaction time dependence of CAL conversion and HCAL
selectivity was shown in Figure 8. Compared with Pd/La CO
NR catalyst, Pd/La CO -TNS exhibited significantly excellent
catalytic activity on CAL hydrogenation and it accelerates quickly
2 2 3
O CO -
PdO/La CO -NR catalysts.
2
O
2
3
2
O
2
3
2
O
2
3
-
H
2
-TPR was used to investigate the reducibility and nature of
noble metal sites of the Pd/La CO -TNS catalysts, and the H
TPR profile was shown in Figure 7. The Pd/La CO -TNS
2
O
2
3
2
O
2
3
2
-
2
O
2
3
4
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Chemistry - A European Journal
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Figure 10. Arrhenius plot of the reaction rate of CAL hydrogenation on the
Pd/La O CO -TNS catalyst at 323-373 K.
2 2 3
at 0.5 h, and a complete conversion is achieved at about 1 h. In
the current reaction process, high conversion of CAL (90%) and
high selectivity of HCAL (92%) were achieved after 0.5 h of
reaction time. In addition, we also expressed the activity as
turnover frequency (TOF) per mmol surface metal Pd. The
Conclusion
-1
Pd/La
contrast to 1251 h for the Pd/La
results were the one of highest activity for reported
2 2 3
O CO -TNS catalyst exhibits a TOF = 41238 h in
-1
In summary, we have developed
a
new triangle-shaped
Pd nanoparticles
2 2 3
O CO -TNS) catalyst presenting the best catalytic activity
2
2 3
O CO -NR. This performance
La
(Pd/La
2 2 3
with TOF of up to 41238 h than Pd/La O CO -NR catalyst and
2
O
2
CO
3
nanosheets
supported
heterogeneous hydrogenation catalysts, such as Pd@TNT 35],
[
-1
Pd-NMC[36]
PdWN/SBA-15[37] and so on.[38-43] This result
,
other previous reported and excellent recycling stability for
selective hydrogenation of CAL to HCAL. It was also the first
indicated that morphology effect of La
modify the reaction rate of CAL hydrogenation.
2 2 3
O CO support can
time that triangle-shaped La
as support for heterogeneous catalytic reactions. This
enhanced activity of Pd/La O CO -TNS resulted from strong
2 2 3
O CO was synthesized and used
The catalytic reusability of Pd/La
2
O
2
CO
3
-TNS investigated in a
a
five-run recycling test was shown in Figure 9. No apparent
decline of conversion and selectivity happens, reflecting stable
activity during the reuse process, which further confirmed that
SMSI play important roles in promoting catalytic activity. As
shown in Figure 10, Kinetic measurements identified that
2
2
3
metal-support interactions (SMSI). Structure analysis and
characterization demonstrated that surface Oxygen-enriched
La
charge transfer between the Pd nanoparticles and triangle-
shaped La CO nanosheets and increases the electron
density of Pd. Moreover, the modulated electron states of the
Pd/La CO -TNS catalysts can enhance the adsorption and
2 2 3
O CO -TNS supports exposed (001) planes was beneficial to
activation energies of Pd/La
2
O
2
CO
3
-NR was about 100.6 kJ mol-
2
O
2
3
1
-1
whereas Pd/La
2
O
2
CO
3
-TNS was just only 50.9 kJ mol . It was
observed that morphology-induced SMSI between Pd and
La CO -TNS with the abundant surface oxygen improve
2
O
2
3
2
O
2
3
activation of hydrogen, leading to the enhanced hydrogenation
activity. These discoveries not only open up the development of
a new basic oxide supported metal catalyst through morphology-
controlled synthesis, but also extend application of the SMSI in
basic oxide.
reducibility and oxygen mobility and increased the catalytic
activity.
1
00
8
6
4
2
0
0
0
0
0
Acknowledgements ((optional))
This work was financially supported by the National Natural
Science Foundation of China (No. 21802008, 21503023) and
Advanced Catalysis and Green Manufacturing Collaborative
Innovation Center, Changzhou University.
CAL Conversion
HCAL Selectivity
2 2 3
Keywords: Pd/La O CO • triangular-shaped nanosheets •
1
2
3
4
5
cinnamaldehyde hydrogenation • Strong metal-supports
Recycle number
interaction
Figure 9. Recycling test of the used Pd/La
2
O
2
CO
3
-TNS catalyst for CAL
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[
1]
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[
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2 2 3 2 2 3
A triangular-shaped La O CO nanosheets exposed the predominant (001) planes supported Pd catalyst (Pd/La O CO -TNS) was
successfully prepared, which exhibited highly active and recycling ability for hydrogenation of cinnamaldehyde with TOF of up to
-1
4
1238 h . Existence of morphology-induced strong metal and basic support interaction state in Pd/La
2 2 3
O CO -TNS significantly
enhances reaction activity.
7
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