Selective Hydrogenation of Aromatic Ketone over Pt@Y Zeolite through Restricted Adsorption Conformation of Reactants by Zeolitic Micropores

Article abstract of DOI:10.1002/cctc.201902302

With thermodynamically favorable prevailing flat-lying adsorption of aromatic ketone molecules on Pt/Y catalyst via π-electron interaction, the 100 % selective hydrogenation toward aromatic alcohols is hardly achieved because of competitive hydrogenation on benzene rings. Here we developed a general method to prepare encapsulated Pt nanoparticles into Y Zeolite (Pt@Y), which provided a novel method to retard hydrogenation of benzene rings via thermodynamically unfavorable end-on adsorption conformation for almost 100 % selectivity from aromatic ketones to aromatic alcohols even at conversion close to 100 %.

Full text of DOI:10.1002/cctc.201902302

Communications
DOI: 10.1002/cctc.201902302
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Selective Hydrogenation of Aromatic Ketone over Pt@Y
Zeolite through Restricted Adsorption Conformation of
Reactants by Zeolitic Micropores
Qiang Chen,[a, b] Haozhe Kang,[b] Xuan Liu,[b] Kun Jiang,[c] Yunfei Bi,[d] Yiming Zhou,[b]
Mengyue Wang,[b] Meng Zhang,*[a] Lei Liu,*[c] and Enhui Xing*[d]
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thermodynamically favorable flat-lying conformation mode
through π-electron interactions between benzene ring and
surfaces, facilitating the hydrogenation of benzene ring group.[3]
There have been several methods to improve catalytic
activity and selectivity through controlling adsorption mode of
the reactant molecules on transition metal surfaces to prevent
undesired side reactions.[4] For example, precisely tuning the
electronic structure of transition metal through formation of
alloy nanoparticle or creation of strong metal-support inter-
actions can modify the reactants adsorption with desired
conformation to enhance catalytic selectivity.[5] However, these
regulations are mainly based on the experimental trial- and
-error methods in absence of rational guideline. Surface
modification of transition metals by ligand containing N- or S-
groups can also influence the adsorption mode via the steric
hindrance and the intermolecular interactions between the
reactant and the neighboring ligands, yet the leaching and
pollution of ligand hardly to be prevented.[6]
As inorganic aluminosilicates nanocrystalline materials with
well-defined micropore structures, Zeolites show excellent
shape selectivity in various reactions demonstrated in labs and
industry.[7] Different from classic theory on shape selectivity,
some molecules could only penetrate channels of zeolites via
constrained conformation, which provide a general method to
define adsorption mode of reactant on the surface of metal
particles encapsulated within zeolites for selectivity control
especially for competitive reactions.[8] It has been reported that
enhancement in selectivity could be achieved over metal
encapsulated within zeolites catalysts especially for aromatics
with more than one reducible groups.[9]
Based on this idea, we expect zeolite micropores can
confine reactant molecules to diffuse into, and to access, adsorb
and to be transformed over metal particles encapsulated within
pores of zeolites. Here, zeolites Y with diameter of twelve-
membered ring at 7.4 Å smaller than the molecular size of
simplest aromatic ketones acetophenone (7.5 Å), was selected
to encapsulated Pt particles within zeolite Y structure (Pt@Y).
Via shape selectivity, it could be guaranteed that the aromatic
ketones adsorbed on Pt surface via constrained the thermody-
namically unfavorable end-on adsorption mode rather than
thermodynamically favorable flat-lying mode. Catalytic results
showed that Pt@Y catalyst exhibited approaching 100%
selectivity to desired products in the hydrogenation of aromatic
ketones without formation of by-products from hydrogenation
of benzene moiety, in addition to the good reusability.
With thermodynamically favorable prevailing flat-lying adsorp-
tion of aromatic ketone molecules on Pt/Y catalyst via π-
electron interaction, the 100% selective hydrogenation toward
aromatic alcohols is hardly achieved because of competitive
hydrogenation on benzene rings. Here we developed a general
method to prepare encapsulated Pt nanoparticles into Y Zeolite
(Pt@Y), which provided a novel method to retard hydro-
genation of benzene rings via thermodynamically unfavorable
end-on adsorption conformation for almost 100% selectivity
from aromatic ketones to aromatic alcohols even at conversion
close to 100%.
Selective hydrogenation of aromatic ketones to corresponding
alcohols is of great significance in the synthetic chemistry to
produce pharmaceuticals and fragrances.[1] One of the key
challenges for such reactions is the selectivity control, which is
regulated by the competitive hydrogenation on benzene ring
and carbonyl group. Recently, supported transition metal
including Pt, Pd, Ni, Ru as catalyst has been extensively
considered for its advantage in cleanness and recyclability.
However, to achieve 100% selectivity of desired alcohols at
complete conversion is still difficult.[2] The reason lies in that
aromatic ketones prefer to adsorb on metal surfaces with
[a] Dr. Q. Chen, Dr. M. Zhang
School of Chemical Engineering and Technology
Sun Yat-sen University
Zhuhai campus
Zhuhai, Guangdong 519082 (P.R. China)
E-mail: zhangm85@mail.sysu.edu.cn
[b] Dr. Q. Chen, H. Kang, X. Liu, Y. Zhou, M. Wang
School of Chemical Engineering and Technology
Xi’an Jiaotong University
Xi’an, Shaanxi 710049 (P.R. China)
[c] K. Jiang, Dr. L. Liu
Beijing Key Laboratory of Ionic Liquids Clean Process
Key Laboratory of Green Process and Engineering
State Key Laboratory of Multiphase Complex Systems
Institute of Process Engineering
Chinese Academy of Sciences
Beijing 100190 (P.R. China)
E-mail: liulei3039@gmail.com
[d] Dr. Y. Bi, Dr. E. Xing
State Key Laboratory of Catalytic Materials and Reaction Engineering
Research Institute of Petroleum Processing
Sinopec
Beijing 100083 (P.R. China)
E-mail: xingeh.ripp@sinopec.com
Supporting information for this article is available on the WWW under
https://doi.org/10.1002/cctc.201902302
ChemCatChem 2020, 12, 1–6
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The Pt@Y catalyst was synthesized through a reported
in situ hydrothermal method with [Pt(NH3)4](NO3)2 as metal
precursor.[10] Figure 1A showed the SEM image of as-synthesized
Pt@Y catalyst. Clearly, compared with parent zeolite Y sample
(Figure S1), the morphology of zeolite Y remained uniform after
encapsulation of PtNPs, unless formation of amorphous species
at small amount caused by consecutive calcination and hydro-
gen reduction step during encapsulation. Notably, the FAU
structure of Pt@Y catalyst was verified by XRD characterization
in Figure S2. HADDF-STEM image in Figure 1B indicated the
formed PtNPs with much brighter contrast for the greater
atomic weight, were distributed evenly throughout zeolite Y
crystal, with the statistical diameter of 1.9 nm. HRTEM image of
Pt@Y catalyst (Figure 1C) showed the clear lattice of zeolite Y
crystals, and PtNPs can be observed to be located within zeolite
micropore rather than residing on the surface, suggesting that
reduced PtNPS indeed within zeolite Y structure. XPS was used
to determine the valence state of encapsulated PtNPs, and
obtained result was fitted with spin-orbit split 4f7/2 and 4f5/2
components (Figure 1D). The PtNPs showed two sets of XPS
peaks, with the 4f7/2 components appearing at 71.2 and 74.8 eV
of the binding energy, respectively, attributed to the Pt0 specie,
and another set of peaks emerge with 4f7/2 appearing at 72.2
and 75.8 eV, attributed to PtII species, and the calculated ratio
of PtII to Pt0 was 2.4:1. This result is consistent with the previous
research that PtNPs with smaller size would exhibit higher
oxidation state. For PtNPs located on the surface of zeolite Y
(Pt/Y) (Figure S3) with the larger average size of 2.35 nm, XPS
peaks from PtII species disappeared, only set of peaks emerge
with 4f7/2 appearing at 74.5 and 71.0 eV, corresponding to Pt0
species (Figure S4). Significantly, a typical XPS peak assigned to
Al 2p species has also been observed in Figure 1D, indicating
the PtNPs were supported on zeolite Y samples.
Furthermore, the porosity of zeolite Y before and after
supporting of the PtNPs has been characterized by N2
adsorption/desorption. As shown in the table 1, in contrast to
the pure zeolite Y with the surface area of 616.0 m2 gÀ 1, the
incorporation of PtNPs into zeolite Y led to the surface area
decreases to 535.0 m2 gÀ 1 and 486.0 m2 gÀ 1 for the Pt@Y and the
Pt/Y catalysts respectively owing to the blockage of zeolite
micropore by inclusion of Pt species. Particularly, for Pt/Y
catalyst, locating of PtNPs on external surface of zeolite Y
resulted in the higher reduction of surface area than that of
Pt@Y catalyst, which could be attributed to the more of the
micropore mouths of zeolite being blocked by external Pt
nanoparticles. Pt@Y and Pt/Y catalysts also showed lower
micropore volume than that of pure zeolite Y for the loading of
PtNPs. It should be pointed out that encapsulation of PtNPs
into zeolite Y resulted in the slightly increase in total volumes
of mesopore plus macropore, which could reflect the local
disruption of supercage structure in zeolite Y near the location
of encapsulated PtNPs for the larger size of reduced PtNPs than
the diameter size of supercage.[11] Presumably, as a result of
smaller size, the dispersion of platinum nanoparticle encapsu-
lated into zeolite was better than that of Pt/Y catalyst.
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Figure 2 showed catalytic property of Pt@Y and Pt/Y
catalysts in hydrogenation of acetophenone (1a) to phenyl-
ethanol (2a). Clearly, Pt@Y catalyst gave the desired 2a
Table 1. The porosity of synthesized samples
[a]
[b]
Sample
SBET
Vp
Vmeso+macro
Pt loading Pt dispersion[c]
[m2 gÀ 1
]
[cm3 gÀ 1
]
[cm3 gÀ 1
]
[%]
[%]
Zeolite Y 616.0
0.262
0.223
0.245
0.03
0.08
0.03
–
1.23
1.30
–
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Pt@Y
Pt/Y
535.1
486.1
[a] Micropore volume (Vp) was determined by the t-plot manners. [b] Total
volume of mesopore plus macropore (Vmeso+macro) was estimated with the
amount of adsorbed N2 at P/P0 =0.990. [c] Platinum dispersion was
calculated by the formula of D (dispersion)=1.13/d (diameter, unit: nm).
Figure 1. A) Scanning electron microscopy (SEM) image of synthesized Pt@Y
catalyst. B) High-angle annular dark-field imaging scanning transmission
electron microscopy (HAADF-STEM) image of Pt@Y catalyst, and the inset
picture showed the size distribution of platinum NPs in Pt@Y. C) high-
resolution (HR) TEM images of the Pt@Y catalyst. Typical encapsulated
platinum NPs are highlighted by red circles. D) X-ray photoelectron
spectroscopy (XPS) characterization of Pt@Y catalyst.
Figure 2. A) Time-dependent catalytic properties of the hydrogenation of 1a
with Pt@Y as catalyst. B) TOF (per surface Pt atom) and catalytic selectivity to
2a (at the conversion of 10% 1a) of Pt@Y and Pt/Y catalyst in the
hydrogenation of 1a. Reaction conditions: 1a (0.1 mmol), platinum-based
°
catalysts (0.001 mmol), ethanol (3 mL), H2O (0.5 ml), 120 C, 3 MPa H2. The
results were determined by GC-MS analysis.
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approaching 99% yield during the reaction, without obvious
observation of any by-products 3a and 4a throughout the
reaction (Figure 2A). In contrast, Pt/Y catalyst (Figure S3)
exhibited lower catalytic selectivity to 2a (76%) even at the
conversion of 10%, and over-hydrogenation products 3a and
4a were unavoidably formed at the initial of the reaction,
although it showed comparable catalytic activity with Pt@Y
catalyst in view of the similar size of Pt nanoparticle (Figure 2B).
As deduced, the over-hydrogenation products were observed
during the reaction in 240 min with Pt/Y as catalyst as well.
(Figure S5). Pt@Y catalyst also exhibited good reusability for this
reaction. As shown in Figure S6, Pt@Y catalyst could show
outstanding catalytic property after used 4 times, and no
decrease of catalytic selectivity was observed. Additionally, in
contrast to Pt/Y, the excellent catalytic selectivity of Pt@Y can
be extended to other aromatic ketones including substituted
acetophenone and benzophenone (Figure S7).
The above experimental results clearly indicated that
encapsulation of PtNPs within zeolite Y structure enhanced
catalytic selectivity. Treatment of Pt@Y catalyst with concen-
trated NaOH solution to destroy the zeolite Y structure leading
to the decreased catalytic selectivity further confirmed the
significance of encapsulation in enhancement of catalytic
selectivity. Notably, the synthesized Pt À 1.2 nm catalyst
composed of Pt0 and PtII species (Figure S8) showing relatively
low catalytic selectivity (83%) to desired product 2a in the
hydrogenation of 1a at the conversion of 80% well excluded
the effect of chemical valence state of PtNPs on the catalytic
selectivity for this reaction (Scheme S1).
reaction rate. As shown in Figure 3, with the Pt/Y catalyst, 9,10-
dihydroanthracene could be converted into hydrogenation
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products at 120, 130 and 140 C (Figure 3A), and the calculated
reaction rate was ~0.027, ~0.038 and ~0.046 mol reactant
consumed per mol of surface platinum per second, respectively.
In contrast, 9,10-dihydroanthracene cannot be catalyzed by
°
Pt@Y catalyst at all at the range of 120 to 140 C (Figure 3B).
This control experimental result suggested that flat-lying
adsorption mode of benzene moiety would facilitate the
hydrogenation process, which has been extensively verified in
literatures and industrial units.[3] However, there is few reports
on the inhibition effects of constrained end-on adsorption
mode of benzene group on hydrogenation rate of benzene
rings over Pt surface. Here for the first time, we verified the fact
that thermodynamically unfavorable end-on conformation
could significantly decrease hydrogenation of benzene rings,
which is completely different from general facts on the
enhancement of thermodynamically favorable flat-lying mode.
Returning to the concerned substrate 1a, DFT calculation
indicated that 1a preferred to be chemisorbed on the Pt (111)
surface with the benzene moiety parallel to the catalyst surface
via π-electron interactions (Figure S9). Accordingly, as shown in
Figure 3C, thermodynamic favorable adsorption mode made
the benzene and ketone groups can be simultaneously hydro-
genated to their corresponding products with comparable
reaction energy barriers (0.9438 eV Vs 1.0179 eV). On the basis
of control experiment and DFT calculations, it can be presumed
that 1a would adsorb on Pt surface of Pt/Y catalyst with flat-
lying geometry, leading to the hydrogenation of benzene ring
and the carbonyl groups at the same time, thus observing the
appearance of by-products 3a and 4a during the reaction.
In the case of Pt@Y catalyst, due to the confinement of the
micropore of zeolite Y, substrate 1a should be confined to
adsorb on encapsulated Pt surface through either the benzene
group or the ketone group in the end-on conformation. As
indicated by control experiment of hydrogenation of 9,10-
dihydroanthracene, when 1a was adsorbed on encapsulated Pt
surface via the end of benzene moiety, the hydrogenation of
this specific adsorbed benzene ring group would be hardly to
be happened. In such a way, the hydrogenation reaction rate
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It seemed that the rate of hydrogenation on benzene ring is
significantly decreased via the end-on conformation of aceto-
phenone, which provided experimental evidence to support
inhabitation of hydrogenation through such thermodynamically
unfavorable conformation. Then the control experiments
combined with DFT calculations were conducted to study the
role of encapsulation in this enhanced catalytic selectivity.
Initially, 9,10-dihydroanthracene with its molecular size larger
than zeolite Y micropore was chosen as model substrate to
investigate the effect of adsorption conformation of benzene
moiety over Pt surface on the corresponding hydrogenation
°
Figure 3. Conversion of 9,10-dihydroanthracene as a function of reaction time over the Pt/Y (A) and Pt@Y catalyst at the 120, 130 and 140 C (1 MPa H2). DFT
calculation of reaction pathway of hydrogenation of benzene group and carbonyl group respectively in 1a on Pt (111) surface.
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Figure 4. Conversion of 9,10-dihydroanthracene (A) and 1-cyclohexylethan-1-one (B) as a function of reaction time over the Pt@Y catalyst at the 110, 120 and
°
130 C (1 MPa H2). Adsorption of 1a on Pt(111) surface with end-on conformation through benzene ring group (C) and through carbonyl group (D). The
numbers below each image indicate the calculated adsorption energies of molecules on the platinum surface.
would be much slower (Figure 4A). While, for the hydro-
genation of end-on adsorbed carbonyl group, taking hydro-
genation of 1-cyclohexylethan-1-one as model reaction, it can
be observed that this hydrogenation process over Pt@Y catalyst
can proceed smoothly, giving the reaction rate was ~0.035,
~0.042 and ~0.070 mol reactant consumed per mol of surface
largely decreased hydrogenation rate for this benzene group
for the very weak adsorption energy on Pt surface with this
specific conformation. On the one hand, the encapsulation
defined substrate to adsorb on encapsulated metal surface with
thermodynamically unfavorable end-on conformation to well
differentiate the hydrogenation reaction rate of sole adsorbed
functional group. On the other hand, the encapsulation can
effectively avoid the competitive hydrogenation on two func-
tional groups presented in one molecule adsorbing on metal
surface, which provide a perfect strategy to regulate catalytic
selectivity through discriminating adsorption mode of sole
adsorbed functional group on metal surface.
°
platinum per second at the 110, 120 and 130 C, respectively
(Figure 4B). Therefore, the unique end-on adsorption conforma-
tion caused by zeolite encapsulation can well discriminate the
hydrogenation reaction rate between the sole adsorbed
benzene ring group and carbonyl group, thus resulting in the
excellent catalytic selectivity of Pt@Y catalyst in this trans-
formation.
The reaction process of Pt@Y-catalyzed hydrogenation of
1a was further investigated with H2-D2 exchange experiment Acknowledgements
and DFT calculations. As shown in figure S10, secondary isotope
effect was observed with the ratio of hydrogenation reaction
rates (kH/kD) being 0.93, indicating that both of hydrogen
dissociation step and dissociated H atom did not involve into
the rate-determination step. Thus, the rate-determination step
can be presumed to be derived from the adsorption step of
substrate 1a. The calculated adsorption energy of 1a on Pt
surface with end-on adsorption geometry through benzene
ring group was 45.48 kJ/mol versus the 86.65 kJ/mol for end-on
adsorption of carbonyl group (Figure 4C and D), suggesting the
thermodynamically preferred adsorption of carbonyl group
than that of benzene ring group. Therefore, the origin of nearly
100% catalytic selectivity of Pt@Y catalyst in the reaction can
be attributed to selective adsorption of end-on adsorbed
carbonyl group on encapsulated Pt surface and the largely
retarded hydrogenation reaction rate of end-on adsorbed
benzene ring group.
In conclusion, compared with Pt/Y catalyst, synthesized
Pt@Y catalyst exhibited remarkable catalytic selectivity in the
hydrogenation of aromatic ketones throughout the reaction.
Through kinetic studies and DFT investigations, the excellent
catalytic selectivity over Pt@Y catalyst can be attributed to the
controlled end-on adsorption behavior of benzene moiety
presented in aromatic ketone molecules, then leading to the
This work was supported by the National Natural Science
Foundation of China (No.21706204), China Petroleum & Chemical
Corporation (No.119004-2), and CAS Pioneer Hundred Talents
Program (L. L.).
Keywords: catalytic selectivity · hydrogenation · adsorption
conformation · Pt nanoparticle · zeolite encapsulation
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Manuscript received: December 10, 2019
Revised manuscript received: January 19, 2020
Version of record online: ■■■, ■■■■
ChemCatChem 2020, 12, 1–6
www.chemcatchem.org
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These are not the final page numbers!

Communications
COMMUNICATIONS
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All works out in the end: Zeolite Y
encapsulated Pt nanoparticles (Pt@Y)
catalyst provided a novel method to
retard hydrogenation of benzene
rings via thermodynamically unfavor-
able end-on adsorption conforma-
tion for almost 100% selectivity from
aromatic ketones to aromatic
alcohols even at conversion close to
100%.
Dr. Q. Chen, H. Kang, X. Liu, K. Jiang,
Dr. Y. Bi, Y. Zhou, M. Wang, Dr. M.
Zhang*, Dr. L. Liu*, Dr. E. Xing*
1 – 6
Selective Hydrogenation of
Aromatic Ketone over Pt@Y Zeolite
through Restricted Adsorption Con-
formation of Reactants by Zeolitic
Micropores
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