Three-Dimensionally Hierarchical Pt/C Nanocomposite with Ultra-High Dispersion of Pt Nanoparticles as a Highly Efficient Catalyst for Chemoselective Cinnamaldehyde Hydrogenation

Article abstract of DOI:10.1002/cctc.201701301

A monolithic carbon-supported Pt nanocomposite with an interconnected three-dimensionally hierarchical porous carbon framework and ultra-high dispersion of Pt nanoparticles (Pt/3DHPC) is synthesized by using an effective “liquid phase impregnation template” strategy. The obtained Pt/3DHPC possesses rich mesoporosity and a low amount of oxygen-containing functional groups, which notably improve the accessible internal surface area of macropores, number of active Pt sites, and electron transfer ability. When used as a catalyst for the selective cinnamaldehyde (CMA) hydrogenation towards cinnamyl alcohol (CMO), Pt/3DHPC exhibits high CMA conversion (92.7 %) and CMO selectivity (91.1 %) at 1 h reaction time, and the corresponding activity (1553.7 h^?1) greatly surpasses not only the single-sized mesoporous carbon and microporous activated carbon-supported counterparts but also the previously reported Pt catalysts dispersed on other forms of carbon. Furthermore, Pt/3DHPC can be reused at least fifteen times without pronounced decay owing to the strong interaction between Pt and carbon. The present work demonstrates the validity of multiscale control in carbon-supported Pt catalysts by overall consideration of the mass transportation, and the accessibility, quantity, and capability of active sites towards chemoselective hydrogenation of CMA, which is expected to be extended to other catalysis-related processes.

Full text of DOI:10.1002/cctc.201701301

Accepted Article
Title: Three-dimensionally hierarchical Pt/C nanocompsite with ultra-
high dispersion of Pt nanoparticles as a highly efficient catalyst
for chemoselective cinnamaldehyde hydrogenation
Authors: Duo Hu, Qian Wen Fan, Zhi Liu, and Ling Li
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of the final Version of Record (VoR). This work is currently citable by
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the VoR from the journal website shown below when it is published
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Three-dimensionally hierarchical Pt/C nanocompsite with ultra-
high dispersion of Pt nanoparticles as a highly efficient catalyst
for chemoselective cinnamaldehyde hydrogenation
[
a]
[a]
[a]
[a]
Duo Hu, Wenqian Fan, Zhi Liu* and Ling Li*
Abstract: A monolithic carbon-supported Pt nanocomposite with
interconnected three-dimensionally hierarchical porous carbon
framework and ultra-high dispersion of Pt nanoparticles (Pt/3DHPC)
is synthesized using an effective “liquid phase impregnation
template” strategy. The obtained Pt/3DHPC possesses rich
mesoporosity and low amount of oxygen-containing functional
groups, which notably improve accessible internal surface area of
macropores, number of active Pt sites, and electron transfer ability.
When used as catalyst for the selective cinnamaldehyde (CMA)
hydrogenation towards cinnamyl alcohol (CMO), the Pt/3DHPC
exhibits high CMA conversion (92.7%) and CMO selectivity (91.1%)
greatly surpasses not only the single-sized mesoporous carbon and
microporous activated carbon supported counterparts but also the
previously-reported Pt catalysts dispersed on other forms of carbon.
Furthermore, the Pt/3DHPC can be reused at least fifteen times
without pronounced decays due to the strong interaction between Pt
and carbon. The present work demonstrates the validity of multiscale
control in carbon-supported Pt catalysts via overall consideration of
the mass transportation, and the accessibility, quantity and capability
of active sites towards chemoselective hydrogenation of CMA, which
is expected to be extended to other catalysis-related processes.
-
1
at 1 h reaction time, and the corresponding activity (1553.7 h )
Introduction
[
3]
existing forms. Over the past years, various carbon-supported
As a fundamentally important additive or intermediate in food
industry, perfumery, and pharmaceutical synthesis, cinnamyl
alcohol (CMO) is commonly derived from the selective
[4-10]
Pt (Pt/C) catalysts, including Pt/carbon nanotubes (CNTs),
[
11]
[12-14]
[7, 15-17]
Pt/graphite,
Pt/graphene,
Pt/carbon nanofiber,
[
1]
[18, 19]
[20]
hydrogenation of C=O bond in cinnamaldehyde (CMA).
Pt/carbon aerogel and xerogel,
Pt/ hollow carbon spheres,
Pt/mesoporous carbon,
[
21]
have been investigated for
Unfortunately, the competitive C=C bond hydrogenation in CMA
often occurs simultaneously to form the undesirable by-product
of hydrocinnamaldeyde (HCMA) due to the higher binding
energy of C=O bond than that of C=C bond and more favorable
thermodynamical reduction of C=C bond than that of C=O bond
hydrogenation of CMA towards CMO. Although enhanced
performances in catalytic activity and selectivity can be achieved
with these Pt/C catalysts, they often suffer from some intrinsic
defects: (i) the relatively weak interactions between carbon
scaffold with Pt as well as the sequent Pt detachment during the
(
Scheme.1). Therefore, considerable efforts have been focusing
on promoting the selectivity towards the desired product of CMO. reaction, (ii) low Pt dispersion, (iii) random pore size distribution
Precious metal platinum (Pt) is the most extensively investigated
and seems to be the most effective active specie for the
selective hydrogenation of CMA towards CMO owing to its large
d-band which leads to the strongly repulsive four-electron
interaction with the C=C bond and strongly attractive interaction
with the C=O bond. On the other hand, support is also a
nonnegligible factor to affect the yield of CMO. Carbon materials
have been testified to be one of the best choices as the catalyst
support for heterogeneous reactions in liquid phase due to its
excellent mechanical strength and stability under hydrothermal
conditions, good electronic properties, large surface area for
dispersing active components, easy recovery-refining-recycling
for precious metals, relatively low cost as well as versatile
of catalyst for low efficiency of mass transportation, all of which
enormously inhibit the fully active release of Pt. It is commonly
recognized that chemoselective hydrogenation of CMA is a
complex process involving gas-liquid-solid three-phase interface
behaviour. Therefore, it is very essential to explore new
fabrication methods for the new Pt/C catalyst to solve these
drawbacks.
[
2]
Scheme 1. Possible reaction pathway in hydrogenation of CMA.
In recent years, three-dimensionally hierarchical porous
carbons (3DHPCs) with combined micropore or/and mesopore
throughout a 3D-interconnected macroporous carbon skeleton
have drawn increasing interests owing to their potential
[
a]
D. Hu, W. Q. Fan, Prof. Z. Liu, L. Li
Faculty of Chemistry and Chemical Engineering
Liaoning Normal University
Dalian, Huanghe Road 850#
E-mail: zhiliu@lnnu.edu.cn
applications in catalysis, adsorption, CO
2
capture, energy
lingl@lnnu.edu.cn
[
22-30]
storage/conversion, and drug delivery.
In contrast with the
single-sized pore counterparts (microporous, mesoporous, or
macroporous carbon), the 3DHPCs are expected to combine the
advantages of each pore size regime. Particularly as catalyst
supports, the monolithic macroporous skeleton is mechanically
and thermally stable for facilitating the mass transportation of the
Supporting information for this article is given via a link at the end of
the document.
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ChemCatChem
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reactant and the product molecules. The mesopores in the
macroporous walls can supply larger surface areas for the
nucleation and growth of more active component, leading to
higher activities and better-controlled selectivities, i.e., the
Pt/3DHPC at a low-magnification. It is clearly seen that the
Pt/3DHPC displays a relative intact and solid three-dimensional
arrangement in an interconnected macroporous framework with
distinct skeleton breakages and point defects. At a high-
magnification (white rectangle zone in Figure 1b), the next layer
of channel is highly visible through the macropores (Figure 1c).
The voids are interconnected through open window, reflecting
that the surface of the catalyst has a very enriching porosity. The
macroporous size is ~180 nm, suggesting the occurrence of
striking shrinkage of the PMMA templates during pyrolysis,
which is possibly caused by the melting and carbonization of the
[
31]
confinement effect of mesopore. Conventionally, there are two
typical approaches for fabricating the 3DHPCs. One is a two-
[
32, 33]
step carbonization-activation method with coalderivatives,
[
34, 35]
[36, 37]
organic polymer,
or biomass
as carbon sources, and
the other is the liquid phase impregnation template (LPIT)
strategy, which involves filling the void space of a porous
template with a variety of carbon-containing precursors followed
by solidification of the precursors, removal of template, and
PMMA microspheres and the sintering of the produced samples.
[
38-42]
[44]
pyrolysis under an inert atmosphere.
For the latter, it can be
envisaged that the desired metal active species may be directly
introduced into the 3DHPC solid-state nanoarchitecture through
using the mixed solution containing corresponding metal salt
and organic sol-gel as precursor to infiltrate the template, and
thereby leads to a high metal dispersion and a uniform
metal/carbon (host/guest) constitution. Moreover, the spatial
hindrance caused by the carbon matrices can strictly prevent the
aggregation, growth, and detachment of the metal active species
during reaction. Although some of the active species might be
entrapped or encapsulated by the carbon matrices resulting in
the inaccessible to the reactant molecules and thus decreasing
the intrinsic high catalytic activity of catalyst, the hierarchical
micropores or/and mesopores in the walls of the macroporous
framework would potentially ensure the catalytically active sites
to be approached easily as much as possible and afford stability
a
b
c
[43]
under repetitive recycling.
On the basis of the above elaboration, we for the first time
report the synthesis of a novel 3DHPC-supported Pt (Pt/3DHPC)
nanocomposite by means of a multi-component (resorcinol-
formaldehyde
hydrochloroplatinic acid) infiltration of polymethyl methacrylate
PMMA) templates followed by a direct pyrolysis process. The
resol,
triblock
copolymer
F127,
and
(
as-prepared Pt/3DHPC possesses pore-hierarchical structure
with an ultra-high Pt dispersion. Pt nanoparticles with an
average size of 1.57 nm can be directly introduced into the
carbon matrices, and F127 acts as a structure-directing agent to
create mesopores in the 3DHPC skeletons and increase surface
area for active sites. When the Pt/3DHPC is used as the catalyst
in the selective liquid-phase hydrogenation of CMA, it exhibits
higher CMA conversion and CMO selectivity than those of the
single-sized mesoporous and microporous carbon-supported Pt
counterparts (Pt/MC and Pt/MAC).
Results and Discussion
Figure 1a depicts the SEM image of the PMMA templates. It is
observed that the PMMA templates have a uniform spheres
arrays with an average diameter around 270 nm in a face-
centered cubic close packed in a large-scale. No significant
disordered region is observed over the entire surface. The
Pt/3DHPC catalyst is obtained by filling the void of the colloidal
Figure 1. Typical SEM images of the PMMA template (a), Pt/3DHPC catalyst
at a low-magnification (b), and Pt/3DHPC catalyst at a high-magnification (c).
PMMA templates with RF resol solution containing H
2 6 2
PtCl ·6H O.
Figure 1b depicts the typical SEM image of the resulting
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Figure 2a reveals the N
2
adsorption-desorption isotherms and
carbonization of the RF resol, whereas the mesopores with a
broad distribution of 2-50 nm and a maximum peak at 3.7 nm is
contributed from the aggregation of cross-linked carbon particles
and the templating function of F127. In the macroporous range
of >50 nm, the macropores predominantly center at 183 nm,
collaborating well with the SEM observation. The Pt/MC shows a
typical type IV isotherm with sharp capillary condensation steps
the corresponding PSDs of the Pt/3DHPC, Pt/MC, and Pt/MAC
catalysts. It is found that the isotherm of Pt/3DHPC exhibits a
combined characteristic of type I with type II. At the very low
P/P
presence of some micropores. The existence of a distinct H2
type hysteresis loop at medium P/P (0.2-0.8) and no clear
adsorption plateau at P/P ≈ 1.0 imply the presence of huge
amounts of mesopores and macropores, respectively.
0
, the adsorption amount increases sharply, indicating the
0
[
49]
0
0
at a P/P = 0.4-0.8, characteristic of mesoporous materials.
[
45-48]
As
The relative PSD is narrowly centered at around 6.2 nm (Figure
2c). The Pt/MAC presents a typical type I isotherm and a broad
microporous distribution of 0.4-2 nm, reflecting its essentially
microporous structure (Figure 2d). Table 1 summarizes the
detailed textual properties of the three catalysts. The Pt/3DHPC
shown in Figure 2b, the Pt/3DHPC possesses well-developed
pore system with detectable sizes from 0.4 and 400 nm. The
micropores with sizes of 0.4-2 nm and multiple peaks at 0.62,
0
.86, 1.25, 1.46, 1.76 nm are possibly generated from the
2
-1
3
-1
p
exhibits a SBET of 668 m g and a V of 0.57 cm g . Its Vmeso
3
-1
and Vmic are 0.46 and 0.06 cm g , respectively, which are
stemmed from the present of mesopores and micropores in the
macropore walls of the HPC, further indicating its hierarchically
porous structure. In contrast with the Pt/3DHPC, the Pt/MC has
2
-1
3
-1
p
a lower SBET of ~573 m g and a smaller V of 0.38 cm g with
3
-1
3
-1
a Vmeso of 0.37 cm g and a tiny Vmic of 0.01 cm g , further
verifying its single mesoporosity. The Pt/MAC possesses typical
textural properties of microporous materials with a high SBET of
2
-1
3
-1
1
337 m g and a large V
p
of 1.24 cm g . The corresponding
Vmeso is almost negligible. In addition, ICP results demonstrate
that the exact Pt contents in the three catalysts is 2.8 wt.%, 3.1
wt.%, and 3.0 wt.%, respectively.
Table 1. Textural properties of the Pt/3DHPC, Pt/MC, and Pt/MAC catalysts.
S
m
BET
-1
V
meso
V
mic
V
p
Pt content
(wt.%)
Catalyst
2
3
-1
3
-1
3
-1
(
g )
(cm g )
(cm g )
(cm g )
Pt/3DHPC
Pt/MC
668
573
0.46
0.37
-
0.06
0.01
1.23
0.57
0.38
1.24
2.8
3.1
3.0
Pt/MAC
1337
Figure 3 records the XRD patterns of the Pt/3DHPC, Pt/MC,
and Pt/MAC catalysts. For the three samples, there are two
o
o
typical broad diffraction peaks at 2θ = ~22 and ~43 indexed as
[
50, 51]
amorphous carbon structure.
Both Pt/MC and Pt/MAC
o
o
o
exhibit distinct diffraction peaks at 2θ = 39.8 , 46.3 , and 67.5 ,
which are assigned to the (111), (200), and (220) planes of Pt(0)
face-centered cubic structure (JCPDS 04-0802), respectively.
There is no evidence of peak related to the oxide of Pt, implying
2 6 2
that the Pt precursor (H PtCl ) is completely reduced by H
treatment. The average particle sizes of Pt estimated by the
Scherrer equation are 5.68 and 3.47 nm for Pt/MC and Pt/AC,
respectively. Intriguingly for the Pt/3DHPC, no characteristic
diffraction peaks belonging to Pt species are detected. Such a
phenomenon is possibly due to the low content of Pt (2.8 wt.%)
or the high dispersion of Pt nanoparticles with small sizes in the
3DHPC framework.
Figure 2. N
2
-sorption isotherms (a) and corresponding pore size distributions
of the Pt/3DHPC, Pt/MC, and Pt/MAC catalysts (b-d).
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C-C (284.6 eV)
a
Pt/3DHPC
b
Pt 4f7/2
Pt/3DHPC
Pt 4f5/2
Pt (0)
Pt (0)
C-O (285.7 eV)
C=O (287.7 eV)
O=C-O (289.0 eV)
+
Pt
+
Pt
2
80
282
284
286
288
290
292
294
68
70
72
74
76
78
80
Binding energy (eV)
Binding energy (eV)
c
Pt 4f7/2
Pt/MC
d
Pt 4f5/2 Pt/MC
C-C (284.6 eV)
Pt (0)
C-O (285.7 eV)
+
Pt
Pt (0)
+
Pt
C=O (287.7 eV)
O=C-O (289.0 eV)
Figure 3. XRD patterns of the Pt/3DHPC, Pt/MC, and Pt/MAC catalysts.
Since the uncertainty of Pt valence, XPS is conducted to
further identify the chemical state of Pt atoms as well as the
elemental composition and heterocarbon components in the
Pt/3DHPC, Pt/MC, and Pt/MAC catalysts, as shown in Table 2
and Figure S3. In the wide XPS survey spectra (Figure S3),
there are three predominant peaks at around 74 eV (Pt 4f), 285
eV (C1s), and 531 eV (O1s), respectively, indicating the
existence of not only the host carbon atoms but also Pt and O
dopant atoms without evidence of impurities. On the high-
resolution scan of the three catalysts (Figure 4a, 4c, and 4e), the
asymmetric C 1s spectra can be deconvoluted into four
2
80
282
284
286
288
290
292
294
68
70
72
74
76
78
80
Binding energy (eV)
Binding energy (eV)
e
f
Pt 4f7/2
Pt 4f5/2
Pt (0)
Pt/MAC
Pt/MAC
C-C (284.6 eV)
Pt (0)
C-O (285.7 eV)

Pt
+
C=O (287.7 eV)
O=C-O (289.0 eV)
+
Pt
2
80
282
284
286
288
290
292
294
68
70
72
74
76
78
80
Binding energy (eV)
Binding energy (eV)
2
individual component peaks, i.e., the sp -hybridized C (C-C,
Figure 4. XPS spectra of C 1s (a, c, and e) and Pt 4f (b, d, and f) of the
284.6 eV), the carboxyl, hydroxyl or ether C (C–O, 285.7 eV),
Pt/3DHPC, Pt/MC, and Pt/MAC catalysts.
the carbonyl or quinonyl C (C=O, 287.7 eV), and the carboxylate
[52]
or lactone C (O=C–O, 289.0 eV), respectively.
The C–C
δ+
to Pt chemical state that anchored with the oxygen-containing
functional groups on the carbon surface (Pt-O-C). The relative
atomic percentages of the Pt (0) and Pt from the XPS spectra
are also listed in Table 2. For the Pt/3DHPC (Figure 4b), Pt (0)
exists in a high portion of 87.3%, and the left of 12.7% exists as
Pt-O-C. Li et al. ever fabricated a Pt/graphene catalyst for
hydrogenation of CMA through a deposit-chemical reduction
method and achieved excellent catalytic performances with a
CMA conversion of 92% and a CMO selectivity of 88% in
functional group is the predominant carbon component (81.1%)
in the Pt/3DHPC, other carbon species including the C-O (8.5%),
C=O (5.1%), and O=C–O (5.3%) are presented with relatively
low quantity (Table 2). Contrarily, the quantities of carbon atoms
singly or doubly coordinated with oxygen atoms increase
remarkably (7.8-19.3%) in both Pt/MC and Pt/MAC,
[54]
δ+
2
accompanying with the decrease of the sp -hybridized C (53.7-
60.8%) accordingly. These results indicate that most of oxygen-
containing functional groups on the carbon surface of the
Pt/3DHPC synthesized by the LPIT strategy have been
thermally reduced during the RF resol pyrolysis with the
stepwise-formed carbon itself as the reducing agent. While for
the Pt/MAC and Pt/MC synthesized with the conventional
support impregnation, there is still a certain amount of oxygen-
containing functional groups on the carbon surface even after
o
[14]
isopropanol under 10 bar H
2
, 60 C, and 4 h.
They believed
that the large fraction (61%, determined by XPS) of Pt (0) sites
on the surface of the catalyst played an important role in
obtaining the high CMO selectivity. In contrast, the present
Pt/3DHPC possesses a higher potion of Pt (0) (87.3%), which
should be conducive to the enhancement of CMO selectivity
potentially. Quite different from the Pt/3DHPC, the portions of Pt-
O-C in the Pt/MC and Pt/MAC increase remarkably (Figure 4d
and 4f), accounting for 43.7% and 33.9%, respectively. The
the following
H
2
reduction (Table S2), which is highly
disadvantageous to the dispersion of Pt. A more insightful
understanding of this issue will be discussed in the following
section for Pt XPS.
δ+
higher percentages of Pt on surfaces of Pt/MC and Pt/MAC are
presumably originated from the higher concentration of oxygen
species on their surfaces, as aforementioned in the C 1s spectra
section. It tends to believed that a support with rich surface
oxides may accelerate the increase of Pt particle size because
the surface oxides can weaken the interaction between Pt and
support, and thereby leading to a lower resistance to surface
Figure 4b, 4d, and 4f show the XPS spectra of Pt 4f in the
Pt/3DHPC, Pt/MC, and Pt/MAC catalysts. These spectra present
two broad peaks, which can be fitted into two pairs of doublets
with a spin-orbit splitting of 4f7/2 and 4f5/2 states, respectively.
The major doublet with binding energies of 71.2 (Pt 4f7/2) and
[53]
74.5 (Pt 4f5/2) eV is attributed to metallic Pt (0), whereas the
[55]
migration of Pt particles.
As a result, large sizes of Pt particle
minor one at 72.2 (Pt 4f7/2) and 75.6 (Pt4f5/2) eV can be assigned
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would be formed on the support containing rich surface oxides. Based on these analyses, we therefore infer that the sizes of Pt on
the 3DHPC might be much smaller than those on the MC and MAC. This would benefit the selective hydrogenation of CMA towards
CMO.
Table 2. Distribution of functional groups derived from the XPS data in the Pt/3DHPC, Pt/MC, and Pt/MAC catalysts.
Relative atomic percentage (%)
Heterocarbon
Relative atomic percentage (%)
Sample
δ+
C-O
C=O
O-C=O
C-C
component (%)
Pt (0)
Pt
Pt/3DHPC
Pt/MC
8.5
5.1
5.3
8.9
7.8
81.1
53.7
60.8
18.9
46.3
39.2
87.3
56.3
66.1
12.7
43.7
33.9
18.1
16.9
19.3
14.5
Pt/MAC
Figure 5 illustrates the representative TEM images of the
Pt/3DHPC, Pt/MC, and Pt/MAC catalysts. In the Pt/3DHPC
a
b
(
Figure 5a), the interconnected networks of three-dimensional
structures with overlapped pores can be clearly observed. In its
partial magnified image (Figure 5b), the macroporous diameter
is observed to be around 180 nm, in good agreement with its
SEM observation. Pt nanoparticles are ultra-highly dispersed in
the macropore walls of the carbon framework without any
aggregations into large clusters, as seen by the tiny, spherical,
and black spots. Further high-resolution TEM investigation
reveals that the distance between two adjacent lattice planes of
the spots is measured approximately to be 0.227 nm (Figure 5d),
[56]
coinciding well with the Pt (111) plane of crystalline Pt.
On
counting 800 nanoparticles, the average size of the Pt
nanoparticles is calculated to be ~1.57 nm, as shown in the
corresponding size distribution histogram (Figure 5c). By
contrast, Pt nanoparticles supported on MAC have a relatively
poor dispersion, and the average particle size is enlarged to be
c
d
~3.25nm (Figure 5f and 5h). While for the Pt/MC, most of Pt
nanoparticles are severely aggregated to large regiments onto
the surface of MC as the yellow circular rings shown. The
average particle size excluding the agglomerates is calculated to
be ~5.53 nm (Figure 5e and 5g). This is presumedly attributed to
the weak confinement effect of mesopore caused by the
conventional support impregnation. With the additional
observation of electron dispersion spectroscopy, the ultra-highly
dispersed Pt element in the 3DHPC framework is further verified
e
f
(
Figure S4). Through the TEM observation, the Pt/3DHPC
apparently possesses better Pt dispersion than the others,
confirming the presumption of XRD observations (Figure 3) and
in good coherence with the XPS analyses (Figure 4). The
features of ultra-high dispersion and fine size of Pt nanoparticles
of the Pt/3DHPC are critical for the enhancement in catalytic
activity. Also, such phenomenon indicates that the LPIT strategy
used in our case can effectively prevent the aggregation of Pt
nanoparticles for the synthesis of Pt/3DHPC, i.e., Pt
nanoparticles are thermally stable. In the 3DHPC skeleton with
uniform Pt-carbon constitution, carbon phase can limit the space
for the growth of Pt nanoparticles and act as a nanoglue to
prevent the Pt nanoparticles from aggregating and sintering, and
thereby resulting in an ultra-high dispersion of Pt nanoparticles
even after the pyrolysis.
g
h
Figure 5. Representative TEM images the Pt/3DHPC catalyst at a low-
magnification (a) and a high-magnification (b); particle size distribution of the
Pt/3DHPC catalyst (c); high-resolution TEM image of the Pt/3DHPC catalyst
(d); TEM image (e) and particle size distribution (g) of the Pt/MC catalyst; TEM
image (f) and particle size distribution (h) of the Pt/MAC catalyst.
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In order to further monitor the surface active sites and the
much lower than that over the Pt/3DHPC (38.7%). On the
contrary, its selectivity towards HCMO is the highest (40.6%)
amongst the three catalysts, which is possibly attributed to the
abundant microporous texture of the MAC (Table1) as discussed
in Ref. 59. These micropores are huge obstacles for the
effective diffusion of intermediate products of CMO from the
catalyst, resulting in its successive hydrogenation to the
saturated alcohol (HCMO). The Pt/MC with typical mesoporous
structure makes the mass transportation relatively easier and
shows a somewhat better CMO selectivity (53.4%). Based on
these data, the calculated TOF value in terms of the amount of
intrinsic information regarding dispersion, H
are acquired on the Pt/3DHPC, Pt/MC, and Pt/MAC catalysts.
As summarized in Table 3, the H uptakes on the three samples
2
-chemisorption data
2
is 41.9, 14.3, and 23.8 µmol/gcat, respectively, following the order
Pt/3DHPC > Pt/MAC > Pt/MC. The calculated Pt dispersions
(
DPt), 75.2%, 24.6% and 38.2%, also present the same
sequence. Additionally, the dispersions are very close to those
estimated with the average particle sizes by TEM (DTEM
=
[
57]
1
.133/dTEM).
Because one
H
atom stoichiometrically
2
chemisorbed on one Pt surface active site, the more H uptakes,
the more the number of the active sites has on the catalyst
surface. This implies that the Pt nanoparticles loaded on the
-1
yielded CMO is 1553.7 h , 1.3 and 2.7-fold of the Pt/MC (1224.0
-1
-1
h ) and Pt/MAC (571.8 h ), respectively. Clearly, the Pt/3DHPC
catalyst remarkably outperforms the Pt/MC and Pt/AMC
catalysts in selective hydrogenation of CMA towards CMO.
Meanwhile, we also compare the CMA conversion, CMO
selectivity, and TOF over the Pt/3DHPC with those over some
previously reported carbon-supported Pt catalysts at the same
reaction time of 1h. As tabulated in Table S3, our results for the
3
DHPC would be more enriching, and present more exposed
and accessible active Pt sites than those on the MC and MAC.
Evidently, the exceptionally good dispersion of Pt nanoparticles
with 3D-interconnected hierarchical pore texture in the
Pt/3DHPC can afford much more usable active sites and
expectantly give rise to superior catalytic performance.
Pt/3DHPC catalyst (92.7% CMA conversion with 91.1% CMO
o
Table 3. H
2
chemisorption uptakes and the Pt dispersions of different catalysts.
selectivity at 70 C, 1h and 2.0 MPa H
2
) apparently exceed most
of the previously-reported counterparts with varied solvents and
2
H pressures. In addition, we conduct another reference test
[
a]
[b]
Sample
H
2
chemisorption (μmol/gcat
)
D
Pt (%)
D
TEM (%)
using a catalyst denoted as “Pt/3DHPC-im” (2.8 wt.% of Pt),
which is prepared by the conventional support impregnation-
hydrogen reduction with the as-prepared 3DHPC as support, as
the Pt/MC and Pt/MAC. The corresponding sample
characterizations are showed in Figure S5 and Tables S4. It is
found that both CMA conversion (56.2%) and CMO selectivity
Pt/3DHPC
Pt/MC
41.9
14.3
23.8
75.2
24.6
38.2
72.2
20.5
34.9
Pt/MAC
[
a] DPt was calculated by H
2
chemisorption data with a stoichiometry of H/Pt =
1
/1. [b] DTEM was estimated according to DTEM = 1.133/dTEM
.
(
78.3%) over the Pt/3DHPC-im are much lower than those on
Selective hydrogenation of CMA towards CMO is a typical
the Pt/3DHPC (Table S3), which may be the result of the
mesopore blockage with low efficiency of mass diffusion (Table
S4) and relatively low Pt dispersion (42.4%) of the Pt/3DHPC-im,
further reflecting the advantages of the LPIT strategy.
reaction for the conversion of α, β-unsaturated aldehydes into
industrially important allylic alcohols. Precious metal (Au, Ir, Pt,
and Pd) nanocatalysts have been widely investigated for this
reaction and Pt has been proved to be more effective for the
formation of CMO. On the other hand, some factors that
influence the CMO selectivity, such as metal particle size, the
support nature, and the adjunction of promoters, have also been
The excellent catalytic performance of the Pt/3DHPC catalyst
in hydrogenation of CMA can be understood as the following
factors. As demonstrated in Figure 6, (i) in the macroscopical
scale, the interconnected hierarchical porous carbon framework
in the Pt/3DHPC can not only act as scaffolds to support and
stabilize Pt nanoparticles but also provide more open channels,
more accessible internal surface area, and thus more locations
for Pt dispersion; the high porosity with hierarchical mesopores
in the macroporous walls can facilitate the diffusion of reactant
molecules of CMA and product molecules of CMO whose
dimensional sizes are of ca. 0.90 nm × 0.51 nm × 0.08 nm and
0.98 nm × 0.51 nm × 0.29 nm, respectively, which is compatible
with the pore range of the Pt/3DHPC (Figure 2b). To better
understand the contribution of mass diffusion, the rate analyses
are proceeded with different initial CMA concentration. By the
fitting of linear equation, the reaction order is determined to be
about 0.92, approaching to the theoretical reaction order of “1”
for mass diffusion, and further confirming the great effect of
hierarchical porous structure of the Pt/3DHPC on mass
distribution and subsequent catalysis in our case (Figure S6). (ii)
in the nano-scale, the ultra-high dispersion of Pt nanoparticles
on the surface of 3DHPC can afford a high utilization efficiency
of Pt with rich active sites. On the other hand, the Pt/3DHPC is
[
58]
taken into consideration significantly,
however, few reports
deal with the effect of catalyst structures on the catalytic
performances. In this work, with the success in the synthesis of
Pt/C catalysts with different pore size regime, we can investigate
the effect of catalyst structures on the reactivity in selective
hydrogenation of CMA.
Table S3 lists the results for hydrogenation of CMA over the
Pt/3DHPC, Pt/MC, and Pt/MAC catalysts. In the present work,
three hydrogenation products of CMA, CMO, HCMA and HCMO
are observed. Furthermore, acetals are also detected, meaning
the occurrence of condensation of isopropanol and CMA. On the
other hand, products from cracking or decarbonylation are not
found. It is noted that the Pt/3DHPC exhibits a high CMA
conversion of 92.7% at 1h reaction time, which is far higher than
those of the Pt/MC (45.1%) and Pt/MAC (43.7%) under the
same reaction conditions. Meanwhile, the Pt/3DHPC possesses
the highest CMO selectivity (91.1%), while the selectivities
towards other products are quite low (3.9% for HCMA and 3.3%
for HCMO). In contrast, CMO selectivity over the Pt/MAC is
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ChemCatChem
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supported Ir and Pt-Sn catalysts for some selective
[
64]
hydrogenation reactions, such as, CMA towards CMO,
[
65]
crotonaldehyde towards crotyl alcohol,
and 4-nitrostyrolene
[
66]
towards 4-vinylaniline. With the similar particle size and metal
loading, they attributed the pronounced enhancements on both
hydrogenation activity and selectivity of catalysts to the strong
metal-support interaction, during which the reported novel
2
supports (H-MoOx and Mo C) could donate (or gain) electrons to
(
or from) the active metal, and thereby giving rise to superior
catalytic performance.In our case, the formation of Pt
nanoparticles also originates from the thermal reduction with the
carbon itself as the reducing agent, together with the formation
of three-dimensionally hierarchical porous structure. Moreover,
2 6 2
the Pt precursor (H PtCl ·6H O) have been mixed uniformly with
the carbon precursor (RF resol) before they are infiltrated into
the interstices of the PMMA template arrays and then subjected
to pyrolysis. Such one-pot formed Pt nanoparticles are mainly
imbedded in or anchored on the 3DHPC walls, which would
inevitably create intimate interfacial contact and strong
interaction between the Pt nanoparticles and the carbon scaffold,
i.e., substantial metal-support active centres and strong metal-
support interaction. This can provide a similar microcosmic
scenario in particle size and electron transfer as the reported
catalysts. We can therefore infer that the smaller particle size of
Pt (1.57 nm) with stronger ability of electron transfer in the
Pt/3DHPC would contribute the higher CMO selectivity.In
addition to the aforementioned factors, there might be other
potential reasons for the high catalytic activity and selectivity of
the Pt/3DHPC. Indeed, multistep reaction in heterogeneous
catalysis is always a very complicated process, and the degree
Figure 6. The proposed diagram for synthesis and selective CMA
hydrogenation of the Pt/3DHPC catalyst.
o
synthesized by N
2
-pyrolysis at 700 C, which can eliminate most
of the oxygen-containing functional groups on the formed
3
DHPC surfaces (Tables 2), and subsequently produce
[
60]
outstanding electronic conductivity.
Vu et al. suggested that
the conductivity of CNT was improved by removing
electronegative oxygen atoms from the CNT surface, which
enhanced the electron transfer from CNT to active Pt sites and
reduced the probability of C=C bond coordinated to Pt active
sites due to the electronic repulsion, thereby increased the CMO
[
61]
selectivity.
Yang et al. found that removal of oxygen-
containing functional groups from CNT surfaces could elevate
both CMA conversion and CMO selectivity, due to the
suppressed side reactions catalyzed by acid and enhanced
of the rate control of the elementary step might experience some
[
8]
[67, 68]
electron transfer from CNT to Pt nanoparticles. According to
these reports, we can infer that the Pt/3DHPC would have
stronger ability in electron transfer between active Pt and carbon
scaffold than the Pt/MC and Pt/MAC due to its less oxygen-
containing functional groups (Tables 2 and S2). Furthermore,
the Pt/3DHPC is monolithic with a relatively continuous network,
which possesses smoother electronic conductivity than the
irregularly cracked and loose-aggregated Pt/MC or Pt/MAC
changes over different catalyst formulations.
therefore deserves to be further explored.
This issue
The reusability is a fundamental parameter for precious metal
catalysts from an economic point of view. Recently, Mao et al.
synthesized a Pd@C catalyst via in situ entrapment of Pd
nanoparticles in mesoporous carbon. The Pd nanoparticles with
an average diameter of 3 ± 0.8 nm were largely encapsulated
inside the mesoporous carbon channels without any serious
aggregation. This catalyst exhibited excellent cycling stability
without any significant loss of activity for 10 recycles in various
heterogeneous hydrogenation reactions. They attributed the
superior performance to the large surface area (SBET of 327.85
(
Figure S7). Therefore, the electron is more easily transferred
from the 3DHPC to the Pt centre, which favors the back-bonding
interactions with πC=O to a larger extent than πC=C, and thereby
[2, 6]
increasing the CMO selectivity.
In addition, Su et al. reported
2
-1
that a series of Ru/C catalysts prepared by a thermal reduction
method displayed a remarkably high catalytic activity and
stability in benzene hydrogenation compared with Ru/C catalysts
prepared by traditional impregnation-hydrogen reduction method. resistance.
m g ), high exposure of active Pd nanoparticles to the reactant,
and the mesoporous pores allowing the reactants to easily
access the catalyst without suffering large mass transportation
[
69]
Compared with the reported Pd@C catalyst, the
[
62]
They attributed such a high activity to the intimate interfacial
Pt/3DHPC in our case possesses not only an ultra-high
dispersion of active Pt, but also more open three-dimensionally
hierarchical structure with a uniform Pt-carbon constitution, a
contact between Ru particles and the carbon support. Szöllösi et
al. applied ultrasonic irradiation to prepare a series of Pt-based
catalysts for the hydrogenation of CMA to CMO, and found that
the selectivity towards CMO with the smaller particle size of Pt
2
-1
richer porosity (SBET of 668 m g ), and a smoother mass
transportation path, which would properly deserve a stronger
reusability. Figure 7a indicates the cycle durability of the
Pt/3DHPC catalyst under identical reaction conditions. To our
delight, the catalyst can be easily recovered and shows no
distinct decays in both CMA conversion and CMO selectivity
even after fifteen cycles. These values begin to present a
[
63]
was higher than the one with the larger particle size of Pt. This
difference in the selectivity was explained in terms of the
formation of effective metal-support active centres, which
provided strong acceptor sites for C=O adsorption. Gao et al.
2
fabricated a series of hydrogenated MoOx (H-MoOx) and Mo C
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ChemCatChem
10.1002/cctc.201701301
FULL PAPER
decreased trend when the catalyst is subjected to the sixteenth
use. This is likely stemmed either from the post-treatment
Because of the successful application of the Pt/3DHPC in
hydrogenation of CMA reaction, it is therefore reasonable to
conjecture that it would exhibit the versatility for hydrogenation
of other α, β-unsaturated aldehydes to unsaturated alcohol. As
listed in Table 4, these reactions proceeds extraordinarily well in
a wide range of α, β-unsaturated aldehydes with various
molecular configurations. For example, crotonaldehyde and leaf
aldehyde appear to be very easy for hydrogenation with
extremely high selectivities towards crotyl alcohol and trans-2-
hexenol, respectively. As the molecular configuration of
substrate becomes more complicated with longer carbon chain
and larger substituents (citral and α-methylcinnamaldehyde), the
increasing steric hindrance leads to relatively low conversion
into the desired product.
(
separation, ethanol wash, and drying out) for the used catalyst
from the reaction system, which causes the gradual powdering
of catalyst, or from the active Pt leaching during the recyclings.
The ICP analysis of the catalyst after the fifteenth cycles reveals
that only a trace amount of Pt leaching (<0.03 ppm) in solution is
found, further reinforcing the strong interaction between the Pt
nanoparticles and the carbon scaffold. The TEM image, XRD
pattern, and XPS analysis (Figure S8-S10) also verify that the
dispersion and crystalline state of Pt nanoparticles in the
recovered Pt/3DHPC do not change significantly after fifteen
cycles. In addition, the three-dimensionally hierarchical structure
of the Pt/3DHPC is still maintained with partial pore distortion
and damage to some extent, and the whole structural integrity
remains considerably, as shown in Figure 7b. All of these results
suggest that the Pt/3DHPC is economically suitable for
repeating utilization.
Table 4. Hydrogenation of other α, β-unsaturated aldehydes to unsaturated
alcohol over the Pt/3DHPC catalyst.
a
Conclusions
In this work, we have successfully synthesized a monolithic
Pt/3DHPC nanocomposite using an effective LPIT strategy with
hydrochloroplatinic acid and resorcinol-formaldehyde resol as
precursors and polymethyl methacrylate opal microspheres as
b
template.
Compared
with
the
conventional
support
impregnation-hydrogen reduction, the direct integration of Pt and
carbon in the three-dimensionally hierarchical porous
nanoarchitecture enables such a nanocomposite to possess an
ultra-high dispersion of Pt nanoparticles and strong interaction
between the two components. For selective CMA hydrogenation
towards CMO, the resulting Pt/3DHPC shows a high TOF up to
-1
1
553.7 h , 1.3 and 2.7-fold activity of single-sized MC and MAC
supported counterparts, respectively, and affords excellent
reusability to fifteen time run. More importantly, our strategy
opens up a meaningful platform for designing robust precious
metal-based catalysts with an ultra-high dispersion for a broad
range of applications in catalysis.
Figure 7. Reusability of the Pt/3DHPC catalyst for the hydrogenation of CMA
towards CMO. Reaction conditions: 0.2 g of catalyst, 5 ml of CMA in 100 ml of
isopropanol (reaction solvent), 2 MPa of H
2
pressure, 70 °C, and 2 h (a). SEM
image of the Pt/3DHPC catalyst after completing 15 reuse (b).
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Catalytic activity measurements: The CMA hydrogenation was carried
out in a 150 mL custom-designed stainless autoclave with a Teflon inner
layer. After the addition of 0.2 g catalyst, 5 ml CMA and 100 ml
isopropanol (reaction solvent) were used. The selection of isopropanol
was determined by advanced screening of reaction solvent (Table S1).
Then the autoclave was sealed, and the air residue was expelled by
pressurizing and releasing hydrogen several times. The reaction mixture
was stirred with a magnetic stirrer at a rate of 900 rpm with a pre-
optimization (Figure S1). The reaction was started when the required
temperature was achieved, and was monitored by taking around 1.0 mL
samples from the reaction mixture periodically to determine the
conversion and selectivity. The reaction products were analyzed by a gas
chromatography (Agilent 6890) equipped with a flame ionization detector
and a 0.25 mm x 30 m FFAP capillary column (Figure S2). For
comparison, commercial mesoporous carbon (MC) and microporous
activated carbon (MAC) were used as supports for preparing Pt/MC and
Pt/MAC catalysts by the conventional support impregnation-hydrogen
reduction (see Supporting information for details). The exact Pt contents
of the two catalysts were also determined by ICP.
Experimental Section
Chemical agents: Pluronic F127 (EO106PO70EO106) was supplied by
Sigma-Aldrich and has an average molecular weight of 12,600. Methyl
methacrylate (MMA), potassium persulfate (K
2 2 8
S O ), hydrochloroplatinic
acid (H PtCl ·6H O, >37.5% Pt basis) and sodium hydroxide (NaOH)
2
6
2
were purchased from Tianjin Kermel Chemical Reagent Co. Ltd.
Resorcinol, formaldehyde (37 wt.%), hydrochloric acid (37 wt.%) (HCl),
and ethanol were purchased from Shenyang Chemical Preparation Corp.
All the chemicals were used as received without further purification.
Deionized water was used in all experiments.
Synthesis of Pt/3DHPC: The polymethyl methacrylate (PMMA) colloidal
crystal templates with an average diameter of ~270 nm were synthesized
via a soap-free-emulsion polymerization based on Ref. 70. In a typical
synthesis of Pt/3DHPC, 1.2 g of resorcinol (R) was dissolved in a solution
containing 1.0 g of F127 and 7 g of ethanol/water (1:1 vol.%) under
stirring until
formaldehyde (F) was added dropwise to the above solution followed by
an extra of stirring. Then, desired amount of solution of
PtCl ·6H O was added to the R/F127/F solution. The acid, formed
a brown solution was formed. Afterwards, 0.9 g of
3
h
a
Calculation of turnover frequencies (TOFs): The TOF, reflecting the
conventional calculation of turnover frequency based on the metal
dispersion, was calculated in order to compare the intrinsic activity of the
Pt/3DHPC catalyst with others Pt-based catalysts in the previously
reported literature in hydrogenation of CMA. The TOF is defined as the
H
2
6
2
from the ionization in the solution, was just utilized as the catalyst for RF
polymerization. Next, the resulting solution composed of RF resol and
H PtCl ·6H O was added to a beaker containing the PMMA templates.
2 6 2
Care was taken to keep the solution level below the top of the PMMA
templates. Complete infiltration of the solution into PMMA templates
occurred at about 12 h. After excess solution was wiped off the templates,
[
18]
following equation:
o
these obtained pieces were heated in an oven at 100 C overnight to
induce thermal polymerization. Finally, the resultant was pyrolyzed under
o
flowing N
2
at 400 C for 3 h to remove the PMMA templates and then at
o
7
00 C for another 2 h for RF resol carbonization with a heating rate of 1
o
-1
C min . The as-synthesized sample was denoted as the Pt/3DHPC
catalyst and the exact Pt content was determined by inductively coupled
plasma (ICP) measurement.
where CMOyielded is the mole of obtained CMO, t is the reaction time (h),
cat is the amount of catalyst (g), X is the Pt content in the catalyst (wt.%),
D is the Pt dispersion (%) calculated from H -chemisorption data or
m
2
-
average particle size of Pt, and M is the molar weight of Pt (195.1 g mol
1
Sample characterizations: The morphology and microstructure of
).
samples were observed by
microscope (SEM) and
microscopy (TEM), respectively. Textural properties were measured by
a
JSM 6360-LV scanning electron
a
JEOL 2000EX transmission electron
o
Acknowledgements
2
N -sorption at -196 C on a Micromeritics ASAP 2010 apparatus. Before
o
measurement, the samples were degassed firstly at 110 C for 2 h and
o
then at 300 C for 3 h under vacuum. The specific surface areas (SBET) of
Financial support by the National Natural Science Foundation of
China (No. U1662125), the Postdoctoral Science Foundation of
China (No. 2016M590418), the Natural Science Foundation of
Liaoning Province (No. 201602457), the Foundation of Liaoning
Province Educational Committee (No. L201683672), and the
Key Laboratory of Functional Materials Physics and Chemistry
samples were calculated by the Brunauer-Emmett-Teller equation. The
pore size distributions (PSD) and the mesopore volumes (Vmeso) were
derived from the desorption branches of the isotherms using the Barrett-
Joyner-Halenda method. The total pore volumes (V
from the adsorption branches at a relative pressure (P/P
micropore volumes (Vmic) were determined by the t-plot method. Powder
X-ray diffraction (XRD) patterns were collected with D/Max-βb
P
) were estimated
0
) of 0.998. The
(
Jilin Normal University, No. 2015007), Ministry of Education of
a
diffractometer using Cu Kα radiation source (λ= 0.15432 nm). The exact
Pt contents in samples were determined by an IRIS Intrepid II XSP
instrument. X-ray photoelectron spectroscopy (XPS) was conducted on
PHI Quantum 2000 equipped with an Al Kα radiation source. All binding
energies (BE) were calibrated with graphitic carbon C1s peak at BE of
China, are gratefully acknowledged.
Keywords: hierarchical pore • cinnamaldehyde hydrogenation •
Pt nanoparticles • nanocomposites • heterogeneous catalysis
2
284.5 eV as a reference. H -Chemisorptions were performed using a
Micromeritics AutoChem II 2920 instrument with a pulse chemisorption
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ChemCatChem
10.1002/cctc.201701301
FULL PAPER
FULL PAPER
Duo Hu, Wenqian Fan, Zhi Liu*, and
Ling Li*
Page No. – Page No.
Three-dimensionally hierarchical
porous Pt/C nanocompsite with ultra-
high dispersion of Pt nanoparticles
as a highly efficient catalyst for
chemoselective cinnamaldehyde
hydrogenation
Ultra-high dispersion of Pt nanoparticles synthesis: A three-dimensionally
hierarchical porous Pt/C nanocompsite with ultra-high dispersion of Pt nanoparticles
is synthesized by means of an effective multi-component infiltration of polymethyl
methacrylate templates. Pt nanoparticles are ultra-highly dispersed in the wall of the
carbon scaffold and give rise to sufficient active sites for the cinnamaldehyde
hydrogenation. The interconnected hierarchical porous carbon framework facilitates
the diffusion of reactant molecules of cinnamaldehyde and product molecules of
cinnamyl alcohol.
This article is protected by copyright. All rights reserved.