catalysts

Article
Dehydrogenation of Propane to Propylene Using
Promoter-Free Hierarchical Pt/Silicalite-1 Nanosheets
Wannaruedee Wannapakdee 1 , Thittaya Yutthalekha 1 , Pannida Dugkhuntod 1 ,
Kamonlatth Rodponthukwaji 2 , Anawat Thivasasith 1 , Somkiat Nokbin 2 , Thongthai Witoon 3 ,
Sitthiphong Pengpanich 4 and Chularat Wattanakit 1, *
1 School of Energy Science and Engineering, Nanocatalysts and Nanomaterials for Sustainable Energy and
Environment Research Network of NANOTEC, Vidyasirimedhi Institute of Science and Technology,
Rayong 21210, Thailand; wannaruedee.w@vistec.ac.th (W.W.); t.yutthalekha@gmail.com (T.Y.);
s15_pannida.d@vistec.ac.th (P.D.); anawat.t@vistec.ac.th (A.T.)
2 Department of Chemistry, NANOTEC Center for Nanoscale Materials Design for Green Nanotechnology,
and Center for Advanced Studies in Nanotechnology and Its Applications in Chemical, Food and
Agricultural Industries, Faculty of Science, Kasetsart University, Bangkok 10900, Thailand;
kamonlatth@gmail.com (K.R.); fscisknb@ku.ac.th (S.N.)
3 Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering,
Faculty of Engineering, Kasetsart University, Bangkok 10900, Thailand; fengttwi@ku.ac.th
4 PTT Global Chemical Public Company Limited (PTTGC), Vibhavadi Rangsit Road, Chatuchak,
Bangkok 10900, Thailand; Sitthiphong.P@pttgcgroup.com
* Correspondence: chularat.w@vistec.ac.th; Tel.: +66-(0)33014255




Received: 14 January 2019; Accepted: 5 February 2019; Published: 13 February 2019


Abstract: Propane dehydrogenation (PDH) is the extensive pathway to produce propylene, which is
as a very important chemical building block for the chemical industry. Various catalysts have been
developed to increase the propylene yield over recent decades; however, an active site of monometallic
Pt nanoparticles prevents them from achieving this, due to the interferences of side-reactions. In this
context, we describe the use of promoter-free hierarchical Pt/silicalite-1 nanosheets in the PDH
application. The Pt dispersion on weakly acidic supports can be improved due to an increase in the
metal-support interaction of ultra-small metal nanoparticles and silanol defect sites of hierarchical
structures. This behavior leads to highly selective propylene production, with more than 95% of
propylene selectivity, due to the complete suppression of the side catalytic cracking. Moreover,
the oligomerization as a side reaction is prevented in the presence of hierarchical structures due to
the shortening of the diffusion path length.

Keywords: dehydrogenation; propane; propylene; hierarchical zeolite nanosheets; silicalite-1

1. Introduction
Propylene is one of the most important petrochemical building blocks for the production of a
diverse range of products, from solvents to plastics and other valuable intermediates, for example,
polypropylene, acrylonitrile, acrolein, and acrylic acid. In the present technology, the majority of
propylene production is obtained as a byproduct from steam cracking and fluid catalytic cracking of
hydrocarbons [1,2]. Because of an increasing demand of propylene and the depletion of petroleum
resources, on-purposed propylene production technologies from alternative substrates, such as
methanol-to-olefin (MTO), [3,4] metathesis of ethylene and butylene [5] and propane dehydrogenation
(PDH) [6] have been intensively developed. Among these technologies, propane dehydrogenation is
the most economical and shortest route for propylene production and is commercially available,
developed by several licensing processes including the Catofin process from CB&I Lummus,

Catalysts 2019, 9, 174; doi:10.3390/catal9020174 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 174 2 of 13

reference [7] and the Oleflex process from Universal Oil Products (or Honeywell UOP) [8]. Because
this reaction is a highly endothermic process and equilibrium-limited reaction, the relatively high
temperature (above 550 ◦ C) is usually required for promoting the catalytic activity. Thus, this
behavior facilitates several side-reactions, in particular, thermal/catalytic cracking and coke formation,
resulting in the low propylene selectivity and the rapid deactivation of catalysts [9]. It is, therefore,
a great challenge to develop this process, especially in terms of increasing the efficiency of catalysts
exhibiting high selectivity and stability in such severe operating conditions for the industrial production
of propylene.
A Cr-based alumina supported catalyst is considered as one of the most important catalysts
for this reaction due to their promising catalytic activity [6,8] however, the Cr is rather hazardous.
An alternative way is to replace by the Pt-based catalysts [10–12] and other non-noble metals, including
Cu, Fe, Zn and VOx [13–18]. Although the Pt-based catalysts exhibit an excellent activity, they still also
suffer from disadvantages, such as a short catalyst lifetime due to the coke formation and the sintering
of Pt clusters [19].
Several strategies have been applied to improve the catalytic performance of Pt-based catalysts,
including the addition of a second metal (e.g., Sn, Zn, Cu, Ce) as promoters [17,20–23], the development
of the synthesis method to obtain small Pt nanoclusters such as the atomic layer deposition (ALD)
technique [24] and the development of metal-support interactions to change the electron density of
Pt, which eventually leads to reducing the propylene adsorption, and then suppressing the further
catalytic cracking [22,25–28].
A zeolite is one of the most interesting materials to be widely used as a support owing to its
outstanding properties, such as a high surface area and a high thermal/hydrothermal stability [29,30].
However, it often suffers from the metal aggregation on outer surfaces after the thermal treatment,
resulting in a very low catalytic selectivity to propylene [31,32]. To prevent the metal aggregation,
the introduction of a mesoporous system into the microporous zeolite network can greatly improve
the dispersion of metal species due to a large increasing number of defect sites [33]. With the benefits
of mesoporous or hierarchical structures [34,35], an improved catalytic efficiency has been observed in
some reactions, in particular the processes involving bulky molecules, such as hydroisomerization,
aromatization and hydrodesulfurization, as compared to a conventional zeolite [36–40].
Indeed, the acidity of supports also affects the propylene selectivity because of the interferences
of the catalytic cracking and alkene oligomerization. Therefore, an alternative way is to apply the
concept of using the neutralized surface acidity with basic molecules [41] or the siliceous zeolite with a
weak acid. However, the lack of alumina in the zeolite framework results in the weak metal-support
interaction, eventually leading to the aggregation of metal species [42,43]. Thus, the development of
alternative PDH catalysts, which exhibit the interplay between minimizing the acidity and increasing
the surface interaction of support and metal species, is still a great challenge.
In the present study, we report the example of a highly selective propane dehydrogenation
over monometallic nanoparticles supported on weakly acidic siliceous MFI-type zeolite having the
hierarchical nanosheet structure. This catalyst has been chosen since it not only benefits to the
shape-selectivity of MFI structure that is preferable to propylene, but also suppresses the side catalytic
cracking on acidic surfaces and prevents the aggregation of metal species owing to the presence of
silanol defect sites, resulting in increasing the metal-support interaction. Compared to the conventional
Pt supported zeolite, another side reaction such as an oligomerization is also suppressed in the presence
of hierarchical structures due to shorten diffusion path lengths. In addition, its catalytic performance
will be discussed in terms of the roles of metal-support interaction and acidity. Finally, the degree of
propylene selectivity can be easily adjusted by changing the loading content of metal and the weight
hourly space velocity (WHSV).
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Catalysts 2019,9,9,x174
FOR ARTICLE 33ofof13
13

2. Results and Discussion

2. Results and Discussion
2.1. Structures and Properties of Catalysts
2.1. Structures and Properties of Catalysts
XRD patterns of Pt supported conventional and hierarchical siliceous zeolites represented the
XRD patterns of Pt supported conventional and hierarchical siliceous zeolites represented the
MFI structure including that the impregnation of Pt did not destroy the structural property of
MFI structure including that the impregnation of Pt did not destroy the structural property of zeolites.
zeolites. In addition, there were no detectable PtO2 characteristics in XRD patterns of all supports
In addition, there were no detectable PtO2 characteristics in XRD patterns of all supports indicating
indicating the well dispersion of Pt or the relatively low amount of Pt loading (Figure 1A). SEM
the well dispersion of Pt or the relatively low amount of Pt loading (Figure 1A). SEM images of
images of hierarchical siliceous MFI or silicalite-1 nanosheets, conventional silicalite-1 and γ-alumina
hierarchical siliceous MFI or silicalite-1 nanosheets, conventional silicalite-1 and γ-alumina exhibited
exhibited uniform particles with a narrow size distribution (see Figures 1B,D and S1) of 250.0 ± 20.0
uniform particles with a narrow size distribution (see Figure 1B,D and Figure S1) of 250.0 ± 20.0 nm,
nm, 2.5 ± 0.3 µm, and 25.0 ± 5.0 nm, respectively. The diameters of Pt particles supported on silicalite-
2.5 ± 0.3 µm, and 25.0 ± 5.0 nm, respectively. The diameters of Pt particles supported on silicalite-1
1 nanosheets, conventional silicalite-1 and γ-alumina were approximately 2.0 ± 0.5, 20.0 ± 10.0 and
nanosheets, conventional silicalite-1 and γ-alumina were approximately 2.0 ± 0.5, 20.0 ± 10.0 and
0.6 ± 0.2 nm, respectively (Figure S2) as shown in TEM images (Figures 1E–G and S2A). The Pt content
0.6 ± 0.2 nm, respectively (Figure S2) as shown in TEM images (Figure 1E–G and Figure S2A). The Pt
was confirmed after a successful impregnation of Pt on the supports by using XRF analysis as shown
content was confirmed after a successful impregnation of Pt on the supports by using XRF analysis as
in Table 1. The Pt loading content on various supports was in the same range of 1 wt.%.
shown in Table 1. The Pt loading content on various supports was in the same range of 1 wt.%.

Figure
Figure1.1.Characterizations
Characterizationsofofvarious
variousPt Ptsupported
supportedcatalysts:
catalysts:(A)
(A)XRD
XRDpatterns,
patterns,(B-D)
(B-D)SEM
SEMimages
images
ofofPt
Ptsupported
supportedon onhierarchical
hierarchicalsilicalite-1
silicalite-1nanosheets
nanosheets(1% -Si-MFI-NS), conventional
(1%PtPt-Si-MFI-NS), conventionalsilicalite-1
silicalite-1
(1%
(1%Pt -Si-MFI-CON) and alumina
Pt-Si-MFI-CON) alumina (1%
(1%Pt-Al
Pt-Al22O
O33),), respectively,
respectively,(E–G)
(E–G)TEM
TEMimages
imagesofof
1%1% Pt-Si-MFI-
Pt-Si-MFI-NS,
NS,
1% 1% Pt-Si-MFI-CON
Pt-Si-MFI-CON andand 1% Pt2-O
1% Pt-Al Al
3 ,
2 O , respectively
respectively
3 and and
(H) (H)
N 2 N sorption
sorption
2 isotherms
isotherms and and
BJHBJH
porepore
size
distributions
size (see(see
distributions inset).
inset).

Table 1. Textural properties of Pt supported catalysts, including hierarchical silicalite-1.

Table 1. Textural properties of Pt supported catalysts, including hierarchical silicalite-1.
Sample
Sample SBET aSBETSamicro b
Smicro b Sext
c
Sext c VVtotal
d
total d
Vmicro
V microe
e
Vmeso
Vmeso f %Ptg%Pt
f g

Si-MFI-NS
Si-MFI-NS 447 447 292 292 154 154 0.85
0.85 0.12
0.12 0.740.74 n.d. n.d.
1% Pt-Si-MFI-NS 399 296 104 0.56 0.12 0.45
1% Pt-Si-MFI-NS 399 296 104 0.56 0.12 0.45 1.07 1.07
Si-MFI-CON 427 334 93 0.25 0.13 0.12 n.d.
Si-MFI-CON 374 427 322 334
1% Pt-Si-MFI-CON 5293 0.25
0.22 0.13
0.13 0.120.09 n.d. 0.90
1%Pt-Al
1% Pt-Si-MFI-CON
2 O3 161 374 11 322 15052 0.22
0.96 0.13
0.005 0.090.95 0.90 1.19
a S
BET : BET1% Pt-Al
specific 2O3 area; b S161 : micropore
surface micro
11 150
surface area; 0.96
ext
0.005
c S : external surface0.95
area; d V 1.19
total : total pore
e
a volume;
S : BETVspecific
BET micro : micropore area; b Sfmicro
surface volume; Vmicro = Vtotal − surface
: micropore Vext ; All area;
surface
c Sareas and pore
ext: external volumes
surface are in
area; dV the
totalunits
: totalof
m2 .g−1 and cme3 .g−1 , respectively: g measuredf by XRF.
pore volume; Vmicro: micropore volume; Vmicro = Vtotal–Vext; All surface areas and pore volumes are
in the units of m2.g−1 and cm3.g−1, respectively: g measured by XRF.
The textural properties of all catalysts were measured using N2 sorption measurements as
presented in Figure
The textural 1H and of
properties Table
all 1. The isotherm
catalysts of γ-alumina
were measured usingexhibited an apparent
N2 sorption hysteresis
measurements as
loop at P/P range
presented in Figure
0 of 0.6 to 0.9 corresponding to the type-IV isotherm, suggesting the presence
1H and Table 1. The isotherm of γ-alumina exhibited an apparent hysteresis loop
at P/P0 range of 0.6 to 0.9 corresponding to the type-IV isotherm, suggesting the presence of
Catalysts 2019, 9, x FOR ARTICLE 4 of 13
Catalysts 2019, 9, 174 4 of 13

mesoporous structures [44]. In contrast, the isotherm of the conventional silicalite-1 exhibited only
the adsorption structures
of mesoporous at the relatively low pressure
[44]. In contrast, (P/P0 < of0.2)
the isotherm thedue to a microporous
conventional silicalite-1 structure,
exhibited
corresponding to the type-I isotherm [44]. On the other
only the adsorption at the relatively low pressure (P/P0 < 0.2) due to a microporous hand, the silicalite-1 nanosheet exhibited the
structure,
adsorption
corresponding at low pressure
to the together with
type-I isotherm [44]. theOn the hysteresis loop the
other hand, at P/P 0 in the range of 0.5 to 0.9,
silicalite-1 nanosheet exhibited
indicating
the adsorption at low pressure together with the hysteresis loop at P/P0 insizes
the combination of type-I and IV isotherms.[44] The mesopore of γ-alumina
the range of 0.5 toand0.9,
silicalite-1 nanosheets obtained by the BJH model were approximately
indicating the combination of type-I and IV isotherms [44]. The mesopore sizes of γ-alumina and 10 and 40 nm, respectively,
and no mesoporous
silicalite-1 nanosheetsstructureobtainedwas by the observed
BJH model in thewere caseapproximately
of the conventional 10 andsilicalite-1. The BET
40 nm, respectively,
surface area of γ-alumina was relatively low (161 m 2·g−1) compared to silicalite-1 (~400 m2·g−1), while
and no mesoporous structure was observed in the case of the conventional silicalite-1. The BET surface
the
areatotal pore volume
of γ-alumina waswas relatively
relatively lowhigh (161(up m2 ·tog−0.96 cm3g−1) due
1 ) compared to a high fraction
to silicalite-1 (~400 mof2 ·mesopores
g−1 ), while(S ext
the
150 m 2·g −1 ). Considering the siliceous zeolite, the silicalite-1
3
total pore volume was relatively high (up to 0.96 cm ·g ) due to a high fraction of mesopores − 1 nanosheets showed a relatively higher
total poremvolume
(Sext 150 2 ·g−1 ). (0.56 cm3·g−1) than
Considering that of the
the siliceous conventional
zeolite, one (0.25
the silicalite-1 cm3·g−1), while
nanosheets showed theamicropore
relatively
volume was in the same range (~0.12–0.13
3 − 1 cm 3·g −1 ), indicating
higher total pore volume (0.56 cm ·g ) than that of the conventional one (0.25 cm ·g ), while the presence of a large amount
3 − 1 of meso-
the
and
micropore volume was in the same range (~0.12–0.13 cm ·g ), indicating the presence oftextural
macroporosity. In addition, the silicalite-1 with Pt3 loading
− 1 slightly changed the a large
properties
amount of of meso-support. The surface areas
and macroporosity. (SBET fromthe
In addition, 447silicalite-1
to 399 m2·g −1) of Pt supported on the silicalite-
with Pt loading slightly changed the
1textural
nanosheets (1% Pt-Si-MFI-NS) and Pt supported on
properties of support. The surface areas (SBET from 447 to 399 msilicalite-1 the conventional 2 ·g−1 ) of Pt(1% Pt-Si-MFI-
supported on
CON) were decreased by a factor of 11% and 12%, respectively
the silicalite-1 nanosheets (1% Pt-Si-MFI-NS) and Pt supported on the conventional silicalite-1 (1% (Table 1).
The aluminawere
Pt-Si-MFI-CON) support is known
decreased by a factorto play of an11%important role as metal(Table
and 12%, respectively supported
1). catalysts and
provides a significant
The alumina support Pt-support
is knowninteraction,
to play an important as compared role asto metal
a conventional
supportedsilica support
catalysts [45]. To
and provides
verify the reduction behavior of metal-supported catalysts, the
a significant Pt-support interaction, as compared to a conventional silica support [45]. To verify the influences of different supports on
reduced
reductionPtbehavior
species were characterized by
of metal-supported H2-TPR.
catalysts, theThe Pt supported
influences on γ-alumina
of different supports exhibited
on reduced two
Pt
reduction peaks at a relatively higher temperature (at 385
species were characterized by H2 -TPR. The Pt supported on γ-alumina exhibited two reduction peaks°C and 460 °C) compared to siliceous
zeolites (Figure
at a relatively 2A) and
higher similar to(at
temperature what 385 has been460
◦ C and described in previous
◦ C) compared reports
to siliceous [46,47],(Figure
zeolites indicating the
2A) and
strong
similar tointeraction
what has been between
describedPt innanoparticles
previous reports and[46,47],
γ-alumina support.
indicating The interaction
the strong Pt supported betweenon
conventional silicalite-1 exhibited only one peak at 320 °C, suggesting
Pt nanoparticles and γ-alumina support. The Pt supported on conventional silicalite-1 exhibited only that Pt species on this support
were easily
one peak at reduced to metallic that
320 ◦ C, suggesting Pt compared
Pt species γ-alumina
on this support support, were confirming
easily reduced a weak interaction
to metallic Pt
between
compareda γ-alumina
Pt metal and a silica
support, support. aInterestingly,
confirming weak interaction in the case ofa Pt
between supported
Pt metal and aon silicalite-1
silica support.
nanosheets,
Interestingly,anotherin the casereduction peak at higher
of Pt supported temperature
on silicalite-1 of 500 another
nanosheets, °C was reduction
observed. peakIt is therefore
at higher
reasonable to imply ◦ that there are some Pt species having a strong
temperature of 500 C was observed. It is therefore reasonable to imply that there are some Pt species interaction with support due to
the hierarchical structure, resulting in the higher resistance towards
having a strong interaction with support due to the hierarchical structure, resulting in the higher the reduction of Pt species. All
H 2-TPR results confirmed that the different nature of supports can alter the behaviors of reduced Pt
resistance towards the reduction of Pt species. All H2 -TPR results confirmed that the different nature
species.
of supports can alter the behaviors of reduced Pt species.

Figure 2. (A) H -TPR profiles of Pt supported on different supports, including hierarchical silicalite-1
Figure 2. (A) H2-2TPR profiles of Pt supported on different supports, including hierarchical silicalite-1
nanosheets (1% Pt-Si-MFI-NS) (blue), conventional silicalite-1 (1% Pt-Si-MFI-CON) (red) and alumina
nanosheets (1% Pt-Si-MFI-NS) (blue), conventional silicalite-1 (1% Pt-Si-MFI-CON) (red) and
(1% Pt-Al2 O3 ) (black), and (B) 29 Si NMR spectra of (a) hierarchical silicalite-1 nanosheets (Si-MFI-NS)
alumina (1% Pt-Al2O3) (black), and (B) 29Si NMR spectra of (a) hierarchical silicalite-1 nanosheets (Si-
and (b) conventional silicalite-1 (Si-MFI-CON).
MFI-NS) and (b) conventional silicalite-1 (Si-MFI-CON).
One reason for the strong interaction between Pt and silicalite-1 nanosheets is that the hierarchical
One reason for the strong interaction between Pt and silicalite-1 nanosheets is that the
siliceous zeolite can provide a large number of defect sites, and therefore improve the interaction
hierarchical siliceous zeolite can provide a large number of defect sites, 29and therefore improve the
with metals. To confirm this hypothesis, the NH3 -TPD profiles and Si MAS NMR spectra of
interaction with metals. To confirm this hypothesis, the NH3-TPD profiles and 29Si MAS NMR spectra
silicalite-1 nanosheets were also observed, as shown in Figure S3 and Figure 2B. Compared to the
of silicalite-1 nanosheets were also observed, as shown in Figures S3 and 2B. Compared to the
Catalysts 2019, 9, 174 5 of 13

conventional silicalite-1, the large number of weak acid sites of Pt supported silicalite-1 nanosheets
remarkably increased (1.17 and 0.03 mmol·g−1 , for silicalite-1 nanosheets and the conventional
silicalite-1, respectively), implying an increase in the surface silanol density due to the hierarchical
structures. To further verify the presence of surface silanols of MFI zeolite, the 29 Si MAS NMR
revealed the environment of Si framework representing as Qn -groups in which n is 1 to 4 according
to the number of tetrahedral Si unit as the next-nearest neighbors [48]. Interestingly, the hierarchical
silicalite-1 exhibited the higher ratio of Q3 to Q4 (2.90) and the presence of Q2 species, which was the
characteristic of silanol surfaces due to a Si atom linked with two O–H groups. In strong contrast to
this, the conventional silicalite-1 showed the significantly lower ratio of Q3 to Q4 (1.14) in the absence
of Q2 characteristic (see Figure 2B). This relates to the fact that the hierarchical nanosheets can enhance
the surface silanol density located on external surfaces.
The electronic properties of Pt species were characterized by XPS analysis. The Pt4f XPS spectra
of all catalysts exhibited doublet peaks corresponding to a spin-orbit splitting of Pt4f7/2 and Pt4f5/2
states (Figure S4) [49]. Unfortunately, the binding energy (B.E.) of Pt 4f5/2 was very close to that of Al
2p in case of γ-alumina support [50]. The decomposition of such Pt 4f7/2 and 4f5/2 XPS peaks were
used to analyze the predominant species in catalysts (Figure S4 and Table S1). Accordingly, the B.E.s at
71.1–74.4, 72.8–76.1 and 74.3–77.6 eV were assigned to metallic Pt (Pt0 ), PtII O and PtIV O2 , respectively.
The Pt 4f7/2 B.E.s of the Pt supported on hierarchical silicalite-1 nanosheets obviously shifted to a lower
binding energy compared with the conventional silicalite-1, indicating that defect sites in hierarchical
structures can change the electron density of Pt to be an electron richer due to the strong interaction of
metal and support, and thus, this material exhibited the improved metal-support interaction.
To clarify these behaviors, the theoretical study by a computational chemistry approach was used
to investigate the electronic properties of catalysts. The interaction of Pt cluster supported on different
silicon species (Q4 , Q3 , and Q2 ) was investigated as shown in Figure S5 and Table S3. The binding
energy of Pt4 cluster supported on the Q3 species (Pt4 /Q3 -MFI) was approximately −7.0 kcal·mol−1 ,
whereas the binding energy of Pt4 cluster supported on the Q4 species (Pt4 /Q4 -MFI) was significantly
lower (approximately −4.0 kcal·mol−1 ). Moreover, the Natural Population Analysis (NPA) charge
(Table S4) revealed that the electron transfer from a support to Pt4 cluster in the Pt4 /Q3 -MFI model
was more predominant compared to the Pt4 /Q4 -MFI model. The partial atomic charges of Pt4 cluster
were reduced from 0.000 e (bare Pt4 cluster) to −0.290 e and −0.252 e for Pt4 /Q3 -MFI and Pt4 /Q4 -MFI
models, respectively. The reason of this higher negatively charge over the Pt4 /Q3 -MFI compared to the
Pt4 /Q4 -MFI related to the improved charge-transfer from defects or silanol surfaces of zeolites to the
Pt4 cluster. These observations confirmed the improved interaction of metal-support in the presence
of defects or silanol surfaces of the Pt supported on silicalite-1 nanosheet. In addition, the lower
adsorption energy of propylene on the Pt4 /Q3 -MFI model (−29.5 kcal·mol−1 ) compared to that of
the Pt4 /Q4 -MFI model (−36.1 kcal·mol−1 ) indicated to a weaken adsorption strength of propylene
from active site. It is therefore reasonable to assume that the propylene product is easily desorbed over
defects or silanol surfaces, resulting in the suppression of further side reactions. This eventually leads
to an increase in overall propylene selectivity over Pt supported silicalite-1 nanosheets.

2.2. Dehydrogenation of Propane over Pt Nanoparticles Supported on Different Supports

The above-mentioned acidity and metal-support interaction makes it clear that the hierarchical
silicalite-1 not only improves the metal-support interaction compared to the conventional silicalite-1,
but also reduces the acidity of supports with respect to γ-alumina. Therefore, this material is expected
to benefit to the catalytic activity and selectivity of propane dehydrogenation.
To illustrate the benefits of Pt supported hierarchical silicalite-1 nanosheets (Pt/MFI-NS) on
the propane dehydrogenation (PDH), it clearly demonstrates that the modified catalyst exhibits a
relatively high activity with the Turnover Frequency (or TOF) value of 1112.2 h−1 and an improved
catalytic stability even after time on stream (TOS) of 12 h (Figure 3A). Interestingly, the high selectivity
of propylene above 95% was observed, indicating that the side reactions were diminished on this
Catalysts 2019, 9, x FOR ARTICLE 6 of 13
Catalysts 2019, 9, 174 6 of 13
on this catalyst. In strong contrast to this, the conventional silicalite-1 (Pt/Si-MFI-con) showed a much
lower activity of the propane conversion with the TOF of 157.6 h−1 with the propylene selectivity of
catalyst. In strong contrast to this, the conventional silicalite-1 (Pt/Si-MFI-con) showed a much lower
50%. Although the high activity (TOF = 278.4 h−1) was observed over the fresh alumina-based catalyst
−1 with the propylene selectivity of 50%.
activity of the propane conversion with the
(Pt/Al2O3), the deactivation rate was also very TOF of 157.6 h
fast with the 20-fold increase in the deactivation rate
Although the high activity −1 ) was observed over the fresh alumina-based catalyst
constant compared to those(TOF = 278.4
of over the Pthsupported hierarchical silicalite-1 nanosheets (Pt/Si-MFI-
(Pt/Al 2 O3 ), S6).
NS) (Figure the deactivation
As expected,rate
the was also very
selectivity fast with the
of propylene also20-fold increase
decreased fromin80the
to deactivation
55% after 12 rate
h of
constant
TOS. compared to those of over the Pt supported hierarchical silicalite-1 nanosheets (Pt/Si-MFI-NS)
(Figure S6). As expected, the selectivity of propylene also decreased from 80 to 55% after 12 h of TOS.

Figure 3. Catalytic
Catalytic performance
performance of propane
propane dehydrogenation over 1 wt.% of Pt supported on different
supports, including
including hierarchical
hierarchicalsilicalite-1
silicalite-1nanosheets
nanosheets(Pt/Si-MFI-NS)
(Pt/Si-MFI-NS)(blue),
(blue),conventional
conventionalsilicalite-1
silicalite-
(Pt/Si-MFI-CON)
1 (Pt/Si-MFI-CON)(red), (red),and
andaluminum
aluminumoxide oxide(Pt/Al
(Pt/Al22O33) (black) in terms of (A) TOF of propane
propylene (open
conversion (solid symbol) and selectivity to propylene (open symbol)
symbol) as
as aa function
function of
oftime-on-stream
time-on-stream
(TOS) and (B) Product
Product selectivity
selectivityat
at10
10hhofofTOS
TOSobtained
obtainedatatweight
weight hourly
hourly space
space velocity
velocity (WHSV)
(WHSV) of
2of.82 h-1.h−1 .
2.82

The distribution
The distribution of of products
products after
after 10
10 hh of
of TOS
TOS is is shown
shownin inFigure
Figure3B. 3B.Unfortunately,
Unfortunately,the thePt/Al
Pt/Al22OO33
noticeably exhibited a high selectivity to cracked products (methane and
noticeably exhibited a high selectivity to cracked products (methane and ethane) (~40%). The ethane) (~40%). The relatively
high selectivity
relatively of crackedof
high selectivity products
crackedwas also observed
products was alsoover the conventional
observed zeolite (Pt/Si-MFI-CON)
over the conventional zeolite (Pt/Si-
(~50%). These results indicated that the nature of supports plays
MFI-CON) (~50%). These results indicated that the nature of supports plays an important an important role in therole
selective
in the
production of light cracked
selective production of lighthydrocarbons. The reason
cracked hydrocarbons. forreason
The this increase
for thisinincrease
cracked in product
cracked selectivity
product
relates to the
selectivity fact to
relates that
thethe Althat
fact 2 O3 support
the Al2Ocomposes of the highofamount
3 support composes the highofamount
acid sitesof as shown
acid in
sites as
NH
shown -TPD results (see Figure S3), resulting in the promotion of cracking reaction.
3 in NH3-TPD results (see Figure S3), resulting in the promotion of cracking reaction. Compared Compared to the
hierarchical
to silicalite-1
the hierarchical nanosheets,
silicalite-1 the cracked
nanosheets, product
the cracked selectivity
productover the conventional
selectivity over thesilicalite-1
conventionalwas
also remarkably increased. This is most likely due to the fact that the formation
silicalite-1 was also remarkably increased. This is most likely due to the fact that the formation of of lighter hydrocarbons
via C–Chydrocarbons
lighter bond cleavage viaisC–C
inevitably excludedisusing
bond cleavage Pt-based
inevitably catalysts
excluded [49].
using It is well
Pt-based known[49].
catalysts thatItthe
is
side reactions, such as catalytic cracking of hydrocarbons over Pt-based catalysts
well known that the side reactions, such as catalytic cracking of hydrocarbons over Pt-based catalysts are structure-sensitive
reactions
are and they can reactions
structure-sensitive be accelerated overcan
and they largebePt clusters [10].
accelerated overThis behavior
large eventually
Pt clusters leads
[10]. This to the
behavior
formation ofleads
eventually a lightto C–C bond cracking
the formation of a over
lighttheC–Cconventional
bond cracking silicalite-1,
over the containing large silicalite-1,
conventional Pt clusters.
containing large Pt clusters.
2.3. Effects of WHSV and Pt Loading on the Propylene Selectivity
2.3. Effects of WHSV
The degree and Pt Loading
of propylene on the Propylene
selectivity Selectivity
can be simply tuned by changing the loading content of
metalTheanddegree
the weight hourly selectivity
of propylene space velocity
can be(WHSV).
simply Figure
tuned by 4A,B demonstrates
changing the conversion,
the loading content of
TOF and selectivity of propylene over the hierarchical silicalite-1 nanosheets
metal and the weight hourly space velocity (WHSV). Figure 4A,B demonstrates the conversion, obtained at different
TOF
TOS and WHSV. The conversion of propane was in the range of 30–35% and it
and selectivity of propylene over the hierarchical silicalite-1 nanosheets obtained at different TOSagreed well with
the theoretical
and WHSV. The equilibrium
conversionvalue at 550 ◦ Cwas
of propane is ~37%,
in the[8,15]
range(Figure 4A). Obviously,
of 30–35% and it agreed at the lowwith
well WHSV,
the
the selectivity of propylene was decreased to 89% and the selectivity of cracked
theoretical equilibrium value at 550 °C is ~37%, [8,15] (Figure 4A). Obviously, at the low WHSV,products was rather
the
high (~11%, Figure 4B). Such an observation suggested that at low WHSV, the side catalytic
selectivity of propylene was decreased to 89% and the selectivity of cracked products was rather high cracking
was
(~11%,preferentially
Figure 4B). occurred due to a long
Such an observation time of reaction
suggested mixtures
that at low WHSV, being
the in contact
side withcracking
catalytic the catalyst.
was
In contrast, it was also found that the highly selective production of propylene (>95%)
preferentially occurred due to a long time of reaction mixtures being in contact with the catalyst. was observedIn
when the WHSV was greater than 2.8 h −1 , indicating that the short contact time suppressed side
contrast, it was also found that the highly selective production of propylene (>95%) was observed
when the WHSV was greater than 2.8 h−1, indicating that the short contact time suppressed side
Catalysts 2019, 9, 174 7 of 13
Catalysts 2019, 9, x FOR ARTICLE 7 of 13

reactions.
reactions. In
In addition,
addition,the
theTOF
TOFincreased asas
increased a function of WHSV;
a function however,
of WHSV; at too
however, at high WHSV
too high the TOF
WHSV the
becomes smaller (Figure 4B).
TOF becomes smaller (Figure 4B).

Figure 4.4.Catalytic
Figure Catalyticperformances
performances of propane dehydrogenation
of propane over Pt over
dehydrogenation supported hierarchical
Pt supported silicalite-1
hierarchical
nanosheets with different effects: (A) The conversion of propane as a function of TOS over
silicalite-1 nanosheets with different effects: (A) The conversion of propane as a function of TOS over hierarchical
silicalite-1
hierarchicalnanosheets
silicalite-1 (1% Pt-Si-MFI-NS)
nanosheets (blue), -conventional
(1% Pt-Si-MFI silicalite-1 (1%
NS) (blue), conventional Pt-Si-MFI-CON)
silicalite-1 (red)
(1% Pt-Si-MFI-
and alumina (1%
CON) (red) and aluminaPt-Al O
2 (1%
3 ) (black). (B) TOF as a function of WHSV on 1% Pt-Silicalite-1 nanosheets
Pt-Al2O3) (black). (B) TOF as a function of WHSV on 1% Pt-Silicalite-1
obtained
nanosheets at TOS of 1 h.
obtained at (C)
TOSEffect of(C)
of 1 h. Pt loading
Effect ofon
Pthierarchical Silicalite-1 nanosheets
loading on hierarchical Silicalite-1was taken atwas
nanosheets 3h
of TOSatand − 1
taken 3 hWHSV
of TOS of and2.82 h . of 2.82 h−1.
WHSV
The conversion of propane and propylene selectivity as a function of Pt loading over the Pt
The conversion of propane and propylene selectivity as a function of Pt loading over the Pt
supported hierarchical silicalite-1 nanosheets at WHSV of 2.8 h−1 is presented in Figure 4C. As expected,
supported hierarchical silicalite-1 nanosheets at WHSV of 2.8 h−1 is presented in Figure 4C. As
the silicalite-1 nanosheets without Pt loading, there was no activity and the selectivity of propylene was
expected, the silicalite-1 nanosheets without Pt loading, there was no activity and the selectivity of
in a very low level of 45%, demonstrating that the support itself could not serve as the dehydrogenated
propylene was in a very low level of 45%, demonstrating that the support itself could not serve as the
active site. It was also found that a small amount of methane and ethane derived from catalytic
dehydrogenated active site. It was also found that a small amount of methane and ethane derived
cracking was observed. In strong contrast to this, the Pt supported catalyst exhibited the selectivity
from catalytic cracking was observed. In strong contrast to this, the Pt supported catalyst exhibited
of propylene about 95.2%, although the low Pt loading of 0.5 wt.% was used. The different loading
the selectivity of propylene about 95.2%, although the low Pt loading of 0.5 wt.% was used. The
of Pt showed a significant influence on the TOF of propane conversion. When the loading of Pt was
different loading of Pt showed a significant influence on the TOF of propane conversion. When the
relatively low (0.5 wt.%), the low TOF (734.3 h−1 ) of propane conversion was observed. With a further
loading of Pt was relatively low (0.5 wt.%), the low TOF (734.3 h−1) of propane conversion was
increase in Pt loading to 1 wt.%, the TOF increased and reached the highest value of 1112.2 h−1 ,
observed. With a further increase in Pt loading to 1 wt.%, the TOF increased and reached the highest
while the high propylene selectivity was still observed (95%). At the relatively high Pt loading level of
value of 1112.2 h−1, while the high propylene selectivity was still observed (95%). At the relatively
1.5 wt.%, the TOF becomes smaller (741.2 h−1 ). This may be explained by the fact that the excessive
high Pt loading level of 1.5 wt.%, the TOF becomes smaller (741.2 h−1). This may be explained by the
loading of Pt leads to the aggregation of Pt particles, and consequently the lower catalytic activity.
fact that the excessive loading of Pt leads to the aggregation of Pt particles, and consequently the
Such an observation suggested that the Pt supported on silicalite-1 nanosheets containing 1 wt.% of Pt
lower catalytic activity. Such an observation suggested that the Pt supported on silicalite-1
exhibited the superior performance in terms of propane activity and propylene selectivity.
nanosheets containing 1 wt.% of Pt exhibited the superior performance in terms of propane activity
In summary, the obtained results indicate that the superior catalytic performance of Pt supported
and propylene selectivity.
on hierarchical silicalite-1 nanosheets for propane dehydrogenation (PDH) can be achieved to
In summary, the obtained results indicate that the superior catalytic performance of Pt
selectively convert propane to propylene without the catalyst deactivation even after the time on
supported on hierarchical silicalite-1 nanosheets for propane dehydrogenation (PDH) can be
stream (TOS) of 12 h. TEM, H2 -TPR, 29 Si NMR, XPS measurements and DFT calculations confirmed the
achieved to selectively convert propane to propylene without the catalyst deactivation even after the
presence of small active Pt particles supported on29silanol or defect surfaces of the hierarchical silicalite-1
time on stream (TOS) of 12 h. TEM, H2-TPR, Si NMR, XPS measurements and DFT calculations
nanosheet catalyst. This relates to the fact that the silanol surfaces or defect sites of hierarchical zeolite
confirmed the presence of small active Pt particles supported on silanol or defect surfaces of the
nanosheets can be greatly enhanced compared to the conventional silicalite-1, eventually resulting
hierarchical silicalite-1 nanosheet catalyst. This relates to the fact that the silanol surfaces or defect
sites of hierarchical zeolite nanosheets can be greatly enhanced compared to the conventional
Catalysts 2019, 9, 174 8 of 13
Catalysts 2019, 9, x FOR ARTICLE 8 of 13

insilicalite-1,
enhancingeventually resulting
the interaction in enhancing
of metal the interaction
and support, of metalthe
thus preventing and support, thus
aggregation preventing
of Pt clusters
the aggregation
(Scheme 1). of Pt clusters (Scheme 1).

Scheme1.1.Illustration
Scheme Illustrationofofthe
theproposed
proposedconcept
conceptofofthe
themetal-support
metal-supportinteraction
interactioneffect
effectofofPt
Ptsupported
supported
on silicalite-1 zeolite; the stabilized Pt nanoparticles promoting the selective propane
on silicalite-1 zeolite; the stabilized Pt nanoparticles promoting the selective propane dehydrogenation
dehydrogenation
to propylene. to propylene.

Toobtain
To obtainthe the high
high yield
yield of propylene,
of propylene, the effects
the effects of metal
of metal loading loading
content content
and weightand weight
hourly hourly
space
space velocity
velocity (WHSV) (WHSV) were systematically
were systematically studiedstudied to fine-tune
to fine-tune the optimalthe optimal experimental
experimental conditions. conditions.
It was
It wasthat
found found that the silicalite-1
the silicalite-1 nanosheetsnanosheets
containing containing
1 wt.% of Pt1with wt.%theofWHSVPt with of the h−1 exhibited
5.64 WHSV of 5.64the h−1
exhibited
highest the highestwith
performance performance
the TOF ofwith 1394.2 − 1
theh TOF andof propylene
1394.2 h selectivity
−1 and propylene of 96%.selectivity
In strongofcontrast
96%. In
tostrong contrast
this, the to this, the
Pt supported Pt supported
conventional conventional
silicalite-1 silicalite-1Pt/Al
and commercial and 2commercial
O3 catalystsPt/Al 2O3 catalysts
exhibited a very
exhibited
low activity,a propylene
very low selectivity
activity, propylene
and short selectivity and short
catalyst lifetime. catalyst they
In particular, lifetime. In particular,
preferentially they
facilitate
preferentially
the side-reactions, facilitate
such asthe side-reactions,
catalytic cracking suchdue toasthecatalytic
presence cracking
of largedue to the presence
Pt clusters and high of largeof
acidity Pt
clusters and
supports for thehigh Pt acidity
supported of supports
conventional for the Pt supported
silicalite-1 conventional
and commercial Pt/Alsilicalite-1
O
2 3 , and
respectively.commercial
Pt/Al 2O3, respectively.
Scheme 1 illustrates the proposed concept of the improved metal-support interaction in
Scheme 1onillustrates
Pt supported the proposed
hierarchical silicalite-1 concept
to promoteof thetheimproved
selective metal-support interaction in to
propane dehydrogenation Pt
supported This
propylene. on hierarchical
is consistent silicalite-1
with the view to promote the selective
that the modified propane
hierarchical dehydrogenation
structure enhances theto
propylene.
PDH This is consistent
performances by changing with thethe view that
structure the The
of Pt. modified hierarchical
high dispersion structure
degree of smallenhances the PDH
Pt particles is
performances
responsible by changing
for the enhancement the structure
of the propane of Pt.dehydrogenation
The high dispersion degree of The
performances. small Pt particles
smallest size ofis
Ptresponsible
particles can forbetheobtained
enhancementin the of casetheofpropane dehydrogenation
hierarchical performances.
silicalite-1 nanosheets due toThe thesmallest size of
high external
Pt particles
surface can be obtained
area together with thein the case of silanol
increasing hierarchical silicalite-1
or defect surfacesnanosheets
which can due enhanceto the thehigh external
interaction
surface
with areaIntogether
Pt [51]. addition,withthe Pt the increasing
metal of silanol
nanoparticles or defect
supported surfaces
on zeolite which can
nanosheets have enhance
remained the
interaction
the with Ptwith
well-dispersion [51].the
In addition,
similar size theofPt2.1
metal
± 0.7nanoparticles
nm. To confirm supported on zeolite
this hypothesis, thenanosheets
computational have
remainedwas
approach theperformed
well-dispersion with the
to understand thesimilar
surfacesize of 2.1 ±
interaction and 0.7electron
nm (Figure
transfer S7). To confirm
in different this
silanol
hypothesis, the computational approach was performed to understand
network systems. It was found that silanol surfaces can greatly enhance the binding energy with Pt the surface interaction and
electronimplying
clusters, transfer in different
that silanol network
Pt is strongly bound tosystems. It was found
the hierarchical that silanol
nanosheet surfaces surfaces
compared can greatly
to the
enhance the binding
conventional energy it
one. Therefore, with Pt clusters,toimplying
is reasonable suppose that the Pt isimproved
strongly bound
interaction to the of hierarchical
Pt clusters
nanosheet
and surfaces
the silanol groups compared
eventually to leads
the conventional
to preventingone. theTherefore,
aggregation it of
is reasonable to suppose
Pt over hierarchical that the
silicalite-1
improved interaction
nanosheets. In addition,ofthe Pt electronic
clusters and the silanol
properties of Pt groups eventually
over different leadswere
supports to preventing
also changed. the
aggregation of Pt over hierarchical 3
silicalite-1 nanosheets. In addition,
The negative charge of Pt over the Pt4 /Q -MFI model is relatively larger than that of the Pt4 /Q -MFIthe electronic properties 4 of Pt
over different
model, suggesting supports were
that the also changed.
silanol groups can Thepromote
negativethe charge
electronof Pttransfer
over the Pt4/Q
from the-MFI
3 modeltois
supports
Ptrelatively largeristhan
cluster. This that ofwith
consistent the Pt 4/Q
the view that the Q3 species are
4-MFI model, suggesting thatpredominant
the silanol groups can promote
in the hierarchical
the electron transfer from the supports to Pt cluster. This is consistent with the view that the Q3 species
are predominant in the hierarchical silicalite-1 nanosheets, then facilitating the strong interaction
Catalysts 2019, 9, 174 9 of 13

silicalite-1 nanosheets, then facilitating the strong interaction between metal and support. The change
of electronic properties of Pt on different supports also affects the desorption of propylene as a product.
As expected, the silanol surfaces can directly weaken the adsorption of propylene on Pt sites. This leads
to an increase in propylene selectivity due to the suppression of further side-reaction. In addition,
the hierarchical structure provided a good benefit for promoting the propylene production, resulting in
the suppression of the further oligomerization as a side reaction due to the shortening of the diffusion
path length of catalysts. These observations may have the benefit of an increase in metal dispersion
and it is complementary to the development of the well-dispersed metallic nanoparticles on solid
supports in PDH reaction [52].

3. Materials and Methods

3.1. Synthesis of Silicalite-1 Zeolites

Hierarchical silicalite-1 nanosheets (Si-MFI-NS) and conventional silicalite-1 (Si-MFI-CON) were
synthesized by using tetra-(n-butyl)phosphonium hydroxide (TBPOH) and tetrapropylammonium
hydroxide (TPAOH) as structure directing agents (SDAs), respectively. The hierarchical silicalite-1
nanosheets were crystallized from a gel precursor in the absence of aluminum source by following the
modified literature procedures [53]. The molar composition of the precursor was 60SiO2 18TBPOH:
0.75NaOH: 240EtOH: 600H2 O. The resultant gel was stirred at room temperature for 12 h and then
heated at 130 ◦ C for 2 days. The conventional silicalite-1 was synthesized from a gel precursor with the
composition of 10SiO2 : 1TPAOH: 1.03NaOH: 240EtOH: 400H2 O and crystallized at 180 ◦ C for 3 days.
The synthesized products were collected and washed with distilled water until the pH of filtrate less
than 9. Finally, the products were calcined in air at 550 ◦ C for 8 h to remove the SDAs.

3.2. Preparation of Pt Supported Silicalite-1 Zeolites

The Pt was loaded on silicalite-1 zeolites by a wet impregnation method. Typically, a 1.2 g of a
calcined zeolite catalyst was added to a 10 mL of an aqueous solution of tetraammineplatinum
nitrate (Pt (NH3 )4 (NO3 )2 ) with various Pt loading contents (0.5, 1 and 1.5 wt.%). The slurry
was stirred overnight at room temperature. Afterward, the water was carefully removed by the
freeze-drying method.

3.3. Characterizations
X-ray diffraction (XRD) patterns of all catalysts were recorded on Bruker (Massachusetts,
United States) D8 ADVANCE instrument with CuKα radiation (40 kV, 40 mA). Scanning electron
microscopy (SEM) and transmission electron microscopy (TEM) images were obtained from
JEOL-JSM-7600F (at 2 kV) (Tokyo, Japan) and JEOL-JEM-2100 (at 200 kV) (Tokyo, Japan) microscopes,
respectively. The average particle size of Pt and zeolite was estimated from at least 200 particles.
N2 sorption techniques were used to examine the textural properties of catalysts. The measurements
were carried out on Belmax (MicrotracBEL Corp., Tokyo, Japan) apparatus, and all the prepared
samples were degassed at 300 ◦ C for 24 h before the measurement. The specific surface area (SBET ) was
determined by using the BET theory. The micropore volume (Vmicro ), the micropore area (Smicro ) and
the external surface area (Sext ) were calculated from the t-plot method. The total pore volume (Vtotal )
was estimated at P/P0 = 0.98. The composition and Pt loading content of prepared catalysts were
measured by X-ray fluorescence (XRF) spectrometry performed on a Bruker (Massachusetts, United
States) AXS S4 Pioneer instrument. The temperature-programmed reduction of H2 (H2 -TPR) and H2
pulse chemisorption were performed on the Belcat II (Tokyo, Japan) chemisorption analyzer equipped
with thermal conductivity detectors (TCD). In H2 -TPR experiments, the sample was pretreated in
Ar (50 mL·min−1 ) at 300 ◦ C for 1 h and then the temperature was ramped from 50 ◦ C to 700 ◦ C at
5 ◦ C·min−1 under the flow of 2% H2 /Ar (50 mL·min−1 ). For the H2 pulse chemisorption, all samples
were heated to 300 ◦ C under the Ar flow (50 mL·min−1 ). Subsequently, the consecutive pretreatment by
Catalysts 2019, 9, 174 10 of 13

O2 and H2 was introduced. Finally, samples were cooled down to 50 ◦ C and the H2 pulse measurement
was operated under the flow of 2% (v/v) H2 in Ar with the flow rate of 50 mL·min−1 . XPS spectra
were obtained using JEOL JPS-9010 (Tokyo, Japan). Non-monochromatic Mg Ka X-rays (1486.6 eV)
were used as primary excitation. The C 1s was selected as the reference, which value was accepted
equal to 284.7 eV.

3.4. Catalytic Testing

The dehydrogenation of propane to propylene was carried out in a continuous-flow fixed-bed
reactor. Prior to the reaction testing, the similar particles size of a catalyst was controlled in the range
of 425–850 µm. A 0.2 g of catalyst was placed into the reactor and activated at 550 ◦ C under the flow
of H2 (2.4 mL·min−1 ) for 2 h. Then, the propane in N2 with the molar volume ratio of 1:1 was fed
with various flow rates to study the effect of weight hourly space velocity (WHSV). The WHSV was
varied from 1.4 to 11.3 h−1 by changing the flow rate of the reactant mixture at constant reactor volume.
The turnover frequency (TOF) was calculated according to the following Equation:

mole o f converted reactant A

TOF (h−1 ) =
(mole o f total metal ) x ( Dm ) x (unit time)

where the number of active sites was calculated based on the total number of active metal sites derived
from the H2 chemisorption measurement [54]. Dm is the dispersivity of metal. All reactions were
carried out at 550 ◦ C, and atmospheric pressure. The analysis of the reaction mixtures was performed
by an online gas chromatograph (GC) (Agilent 7820A) equipped with a flame ionization detector (FID)
and a GS-GASPRO capillary column (60 m × 0.32 mm) at an interval time of 1 h. To validate the
performance of catalysts in the kinetic regime, the experimental criteria due to heat and mass transfer
limitation are also discussed as shown in the Supplementary Materials.

4. Conclusions
In conclusion, the results demonstrate the first example, describing the improved metal-support
interaction of hierarchical nanosheet structures. A promoter-free Pt on hierarchical silicalite-1
nanosheets exhibited the highly selective production of propylene from propane dehydrogenation
above 95% at the propane conversion level of 30%. The observations from TEM, H2 -TPR, 29 Si NMR,
XPS measurements and DFT calculations confirmed that the hierarchical silicalite-1 nanosheet catalyst
promoting the presence of small active Pt particles supported on silanol or defect surfaces of the
hierarchical silicalite-1 nanosheet catalyst. Therefore, a novel design of supported catalysts with
hierarchical structures can promote active species for the highly selective propane dehydrogenation,
which has a great potential to be utilized in the important petrochemical catalytic reactions.

Supplementary Materials: The following are available online at http://www.mdpi.com/2073-4344/9/2/174/s1,

Figure S1: Particle size distribution of various supports, Figure S2: (A) TEM images and (B) Particle size
distribution of Pt supported on various supports, Figure S3: NH3 -TPD profiles of various supports, Figure S4:
XPS spectra of Pt supported on different supports, Figure S5: Computational modeling study, Figure S6:
Deactivation rate of various catalysts, Table S1: Summary of the contribution of Pt species, Table S2: Summary of
metal size and the percentage of metal distribution of Pt supported catalysts obtained by H2 chemisorption
technique, Table S3: Selected geometrical parameters of Pt4 /Q3-MFI and Pt4 /Q4-MFI zeolites and the
corresponding adsorption complexes including isolated Pt4 , propane and propylene, Table S4: Summarized
partial charges determined by the natural atomic orbital (NAO).
Author Contributions: Conceptualization, C.W.; Methodology, W.W., T.Y., P.D., K.R., A.T.; Formal Analysis, T.Y.,
S.N., T.W.; Investigation, S.P.; Writing—Original Draft Preparation, W.W., T.Y., A.T.; Writing—Review & Editing,
W.W., C.W.
Catalysts 2019, 9, 174 11 of 13

Funding: This work was supported in part by grants from Vidyasirimedhi Institute of Science and Technology
(VISTEC), Thailand Research Fund (TRF) (MRG6180099), the Office of Higher Education Commission (OHEC),
TTSF research project supported by Thailand Toray Science Foundation. In addition, this work has been partially
supported by the National Nanotechnology Center (NANOTEC), NSTDA, Ministry of Science and Technology,
Thailand, through its program of Research Network NANOTEC (RNN). Furthermore, the authors would like to
acknowledge the Frontier Research Center, VISTEC for technical support.
Conflicts of Interest: The authors declare no conflict of interest.

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