An On-Demand, Selective Hydrogenation Catalysis over Pt?Fe Nanocatalysts under Ambient Condition

Article abstract of DOI:10.1002/cctc.201900232

The selective hydrogenation of organic compounds with multiple unsaturated bonds is of significant for fine chemicals, while simultaneously achieving high selectivities of different potential products is still great challenge. Herein, we have successfully designed a nanocatalysis system, which can serve as a control switch of selective α, β-unsaturated aldehydes hydrogenation towards potential products in a highly on-demand fashion. We demonstrate that the PtFe nanospheres (NSs) represent excellent selectivity (>92.8 %) to unsaturated alcohols with high conversion (>99.7 %), due to the higher electron density of the active Pt atoms. When introducing AlCl₃, the selectivity of saturated aldehydes enhances to 97.1 % at 95.8 % conversion, owing to synergy between PtFe NSs and AlCl₃. Finally, the PtFe?A NSs generated by etching away the Fe can promote the selectivity saturated alcohols (>99.7 %) with the highest activity, on account of more exposed active sites after the chemical etching. Significantly, the developed nanocatalysis system can also exhibit high activity/selectivity for other typical α, β-unsaturated aldehydes as well as excellent stability after consecutive reactions. This work provides a guideline for the rational design highly active and selective Pt-based nanocatalyst.

Full text of DOI:10.1002/cctc.201900232

Accepted Article
Title: An On-Demand, Selective Hydrogenation Catalysis over Pt-Fe
Nanocatalysts under Ambient Condition
Authors: Xiaoqing Huang, Chengyong Yang, Shuxing Bai, and
Yonggang Feng
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To be cited as: ChemCatChem 10.1002/cctc.201900232
Link to VoR: http://dx.doi.org/10.1002/cctc.201900232
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10.1002/cctc.201900232
ChemCatChem
COMMUNICATION
An On-Demand, Selective Hydrogenation Catalysis over Pt-Fe
Nanocatalysts under Ambient Condition
Chengyong Yang+, Shuxing Bai+, Yonggang Feng, and Xiaoqing Huang*
Abstract: The selective hydrogenation of organic compounds with
multiple unsaturated bonds is of significant for fine chemicals, while
simultaneously achieving high selectivities of different potential
products is still great challenge. Herein, we have successfully
designed a nanocatalysis system, which can serve as a control
switch of selective α, β-unsaturated aldehydes hydrogenation
towards potential products in a highly on-demand fashion. We
demonstrate that the PtFe nanospheres (NSs) represent excellent
selectivity (>92.8%) to unsaturated alcohols with high conversion
(>99.7%), due to the higher electron density of the active Pt atoms.
When introducing AlCl3, the selectivity of saturated aldehydes
enhances to 97.1% at 95.8% conversion, owing to synergy between
PtFe NSs and AlCl3. Finally, the PtFe-A NSs generated by etching
away the Fe can promote the selectivity saturated alcohols (>99.7%)
with the highest activity, on account of more exposed active sites
after the chemical etching. Significantly, the developed nanocatalysis
system can also exhibit high activity/selectivity for other typical α, β-
unsaturated aldehydes as well as excellent stability after consecutive
reactions. This work provides a guideline for the rational design
highly active and selective Pt-based nanocatalyst.
frameworks (MOFs),[21,22] structure,[24] etc. The presence of
organic macromolecules on the surface of metals can promote
the selectivity for unsaturated alcohols, because the steric
constraint on the α, β-unsaturated aldehydes is believed to
hinder C=C adsorption.[23] The PtCu-Cu2S hybrid nanocrystals
can improve saturated aldehydes selectivity, where the charge
transfer between PtCu and Cu2S can modify the electronic
structure, which is in favor of the production of saturated
aldehydes.[24] Although the selective hydrogenation of α, β-
unsaturated aldehydes has been achieved separately,[25,26] it is
still very difficult to simultaneously achieve high selectivities of
different potential products in a highly on-demand fashion.
The hydrogenation of unsaturated organic compounds is of
considerable importance for fine chemicals, fragrance and
pharmaceutical industries.[1-3] Among them, the hydrogenation of
unsaturated organic compounds with multiple unsaturated bonds
is extremely uncontrollable and challenge. For example, α, β-
unsaturated aldehydes have two competitive functional groups:
conjugated carbon-carbon double bond (C=C) and carbonyl
group (C=O).[4-7] It is generally known that the hydrogenation of
the C=C is both more thermodynamical and kinetic favour over
that of the C=O.[8-11] However, when the C=C is connected or
conjugated with other substituents[12,13] (for instance, benzene
ring, methyl, furan ring, and so on), high selectivity for C=C
hydrogenation also becomes challenging due to the steric
hindrance and electronic effect. Therefore, the design of efficient
catalysts for selective hydrogenation of α, β-unsaturated
aldehydes is highly desirable yet challenge.[14]
Numerous efforts were devoted to creating platinum (Pt)-
based catalysts for hydrogenation reactions, owing to their
outstanding hydrogenation activities.[15-17] While pure Pt can
readily hydrogenate both C=C and C=O simultaneously,[18] it is
difficult to realize the high selectivity of potential
semihydrogenation products. The conventional methods to
improve the selectivity of potential products are modifying the
metal active sites by surface ligands,[19,20] metal-organic
Scheme 1. Reaction pathways of selective hydrogenation of α, β-unsaturated
aldehydes over different Pt-Fe nanocatalysts.
Herein, we have successfully designed a highly on-demand
nanocatalysis system for the selective hydrogenation of α, β-
unsaturated aldehydes. As shown in Scheme 1, α, β-
unsaturated aldehydes have two distinct competing sites of
hydrogenation: conjugated C=O bond and C=C group, which
lead to three different hydrogenation products: unsaturated
alcohols, saturated aldehydes and saturated alcohols.
Significantly, excellent selectivity with a switchable fashion
toward all three hydrogenation products is achieved over Pt-Fe
nanocatalysts under ambient condition. Firstly, PtFe
nanospheres (NSs) can selectively hydrogenate C=O towards
unsaturated alcohols with highly selectivity (>92.8%) and
conversion (>99.7%), due to the high electron density of Pt with
donating of Fe, which can enhance the C=O adsorption and
weaken the C=C adsorption. After introducing AlCl3, the
selectivity of C=C hydrogenation to saturated aldehydes is
improved to 97.1% at high conversion (95.8%), owing to the
synergy between PtFe NSs and AlCl3, where AlCl3 can serve as
the C=O protector by Lewis acid-base interaction and boost the
activity of Pt for C=C hydrogenation via the electronic transition
between Pt and AlCl3.[27] Finally, we used HCl to etch away the
Fe from PtFe NSs and the generated PtFe-A NSs can efficiently
catalyze both the C=C and C=O hydrogenation, achieving high
selectivity of saturated alcohols (>99.7%). The high selectivity of
saturated alcohols is attributed to more exposed active sites
after the chemical etching. Significantly, these Pt-Fe
nanocatalysts can also hydrogenate other typical α, β-
unsaturated aldehydes to their corresponding potential products
[]
C. Yang,+ S. Bai,+ Y. Feng, and Prof. X. Huang
College of Chemistry, Chemical Engineering and Materials
Science, Soochow University, Suzhou 215123, Jiangsu, China
E-mail: hxq006@suda.edu.cn
These authors contributed equally to this work.
Supporting information for this article is given via a link at the end
of the document.
[+]
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10.1002/cctc.201900232
ChemCatChem
COMMUNICATION
with high conversion and selectivity. Significantly, the developed
nanocatalysis system also shows excellent stability, where both
the excellent conversion and high selectivity for potential
products have limited changes with negligible change of the
catalysts after five reaction rounds.
lattice fringes of 0.194 nm, corresponding to the (200) facet of
fcc PtFe, were observed. The alloyed structure was also
confirmed by HAADF-STEM elemental mapping analysis, where
the distribution of Pt and Fe is uniform (Figure 1e).
The PtFe-A NSs were obtained by etching PtFe NSs with HCl
(see Supporting Information for details). Typical TEM image
(Figure S1a) shows that the PtFe-A NSs remain the original
morphology of the PtFe NSs after etching with HCl. The Pt/Fe
composition is around 92.5/7.5, as confirmed by SEM-EDX
(Figure S2a). SEM-EDX and XPS (Figure S2) were used to
confirm the removal of Cl-, where the Cl- was not found,
indicating that the surface of PtFe-A was cleaned. The PXRD
pattern of PtFe-A NSs (Figure S1c) shows that the main pattern
peaks are transferred from the PtFe phase towards the pure Pt
phase. The HRTEM image (Figure S1d) identifies the lattice
spacing of PtFe-A NSs to be 0.196 nm, which is assigned to the
(200) plane of pure Pt. The PtFe-A NSs are further confirmed by
the HAADF-STEM elemental mapping (Figure S1e), where the
Pt distributes throughout the whole NS with very low
concentration of Fe.
Figure 1. (a) HAADF-STEM image, (b) PXRD pattern, (c) SEM-EDX, (d) TEM
image (insert is HRTEM image) and (e) HAADF-STEM image and elemental
mappings of PtFe NSs.
We proposed
a simple route to synthesize the Pt-Fe
nanocatalysts to control the selective hydrogenation of α, β-
unsaturated aldehydes. Firstly, the uniform PtFe NSs were
produced
by
simultaneous
reduction
of
platinum(II)
Figure 2. (a) Reaction pathways of selective hydrogenationof CAL.
Conversion and selectivity of hydrogenation of CAL catalyzed by (b) PtFe NSs,
(c) PtFe NSs + AlCl3, and (d) PtFe-A NSs. Reaction condition: CAL, 0.8 mmol;
catalyst, 0.25 mgPt for Pt-Fe NSs; temperature,60 °C; H2 pressure, 0.24 MPa;
solvent, 4 mL ethanol.
acetylacetonate (Pt(acac)2) and diiron nonacarbonyl (Fe2(CO)9),
by the use of oleylamine as solvent and surfactant, and phenol
as the reducing agent (see Supporting Information for details).
The morphology and structure of the PtFe NSs were
characterized by high-angle annular dark-field scanning
transmission electron microscopy (HAADF-STEM) (Figure 1a),
where the products consist of uniform nanocrystals with a nearly
spherical profile, and the nanostructures are highly
monodisperse with an average diameter of ~ 50 nm, showing
the high-yield preparation of the PtFe NSs. Importantly, each
nanostructure is of a porous nature with highly branched
subunits, which is beneficial for improving the utilization of noble
metals.[28] The powder X-ray diffraction pattern (PXRD, Figure
1b) was conducted to determine the phase of the PtFe NSs,
where the positions of diffraction peaks were in good agreement
with PtFe phase (JCPDS no. 29-0717). The scanning electron
microscopy energy-dispersive X-ray spectroscopy (SEM-EDX,
Figure 1c) reveals that PtFe NSs are composed of Pt and Fe,
where the atomic ratio of Pt/Fe is 61.5:38.5. To further figure out
the detailed structure of the PtFe NSs, high-resolution TEM
(HRTEM) image for PtFe NSs is collected (Figure 1d). The
To explore the selectivity of Pt-Fe nanocatalysts for the
hydrogenation of α, β-unsaturated aldehydes, we first used
cinnamaldehyde (CAL) as a model molecule. As shown in
Figure 2a, highly selective hydrogenation of CAL into cinnamyl
alcohol
(COL),
hydrocinnamaldehyde
(HCAL)
and
hydrocinnamyl alcohol (HCOL) should be achieved under
ambient condition. As shown in Figure 2b, by using PtFe NSs
as catalysts the conversions of CAL have a linear relationship
with time, and finally reach 99.7% after 3.5 h at 60 °C and 0.24
MPa H2. Importantly, the high selectivity to COL (>82.8%) of
PtFe NSs can be largely maintained even prolonging the
reaction time, indicating that PtFe NSs have high selectivity for
C=O hydrogenation in
a specific time. Interesting, after
introducing AlCl3 (Figure 2c), the excellent selectivity of HCAL
(>97.1%) can be easily achieved at 0.5 h. Moreover, the
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10.1002/cctc.201900232
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COMMUNICATION
conversion of CAL on PtFe NSs is only 69.6% after 2 h, where
the CAL conversion (93.6%) of PtFe NSs + AlCl3 after 2 h is 1.3
folds higher than PtFe NSs, indicating that the addition of AlCl3
can also enhance the reaction rate. As shown in Figure 2d,
when using PtFe-A NSs to catalyze CAL hydrogenation, the
conversion of CAL is 92.3% at 0.5 h with the selectivity of HCOL
is 82.3%. With the prolongation of time, the selectivity of HCOL
is increasing gradually and finally in 99.8% at 3 h. For
comparison, the CAL conversion on the conventional Pt
nanoparticle (NPs) (Figure S3-4) is 26.2% after 2 h with
selectivity for COL/HCAL/HCOL of 53.9%/7.7%/38.4%, showing
the enhanced activity of PtFe-A NSs. For PtFe NSs + AlCl3, Fe
is inactive, and the AlCl3 is introduced to the reaction solution as
a homogeneous Lewis acid to protect the C=O (Lewis basic).
While the morphology of PtFe-A shows little changes, the total
number of Pt atoms does not increase. Based the above the
result, turnover frequency (TOF) of Pt was calculated. The TOF
of PtFe-A NSs (405 h-1) is 2.34- and 1.33-fold higher than those
of the PtFe NSs (173.4 h-1) and PtFe NSs + AlCl3 (303.1 h-1)
(Table S1).
AlCl3 (0.088). In contrast, the ranking of COL hydrogenation is
as follows: PtFe-A NSs (9.72) > PtFe NSs + AlCl3 (0.426) > PtFe
NSs (0.028) (Figure 3c), indicating that PtFe NSs exhibit low
C=C hydrogenation activity and high C=O hydrogenation activity.
By using PtFe NSs + AlCl3 as catalysts, the conversion of COL
is 96.6%, which is far higher than that of the PtFe NSs (15.4%),
indicating that AlCl3 can be used as a protective agent for C=O,
as well as an accelerant for C=C hydrogenation. For PtFe-A NSs
generated by etching away the Fe from PtFe NSs, they exhibit
the best activity among the three catalysts, due to more exposed
active sites after the chemical etching. When electrons transfers
from Fe to Pt, the surface Fe of PtFe NSs exhibits the oxidation
state, which benefits to the adsorption of C=C. However, due to
the the electronic transition, the surface Pt of PtFe NSs has
electron density, which is favor of the adsorption of C=O, thus
increasing the selectivity of C=O hydrogenation. The above data
indicates that the Pt-Fe nanocatalysts have on-demand
selectivity for specific unsaturated bonds, achieving the excellent
control of the high selectivity of α, β-unsaturated aldehydes
hydrogenation.
Table 1. Selective hydrogenation of α, β-unsaturated aldehydes over different
Pt-Fe NSs catalysts.a
Selectivity /%
Catalyst
Substrate
Con. /%
C=C
C=O
C=C
C=O
3-Methyl-2-butenal
Crotonaldehydeb
Furfuralc
CALd
CALe
93.6
97.8
96.2
97.3
99.8
99.3
99.9
99.0
99.3
99.1
98.4
99.9
99.9
98.7
99.3
0.3
0.3
-
7.9
17.7
0.1
91.8
82.0
99.9
94.8
89.0
10.0
0.1
0.4
-
PtFe NSs
2.2
0.8
87.0
99.8
95.6
99.8
99.3
1.8
2.1
2.1
1.1
0.4
3.0
10.2
3.0
3-Methyl-2-butenal
Crotonaldehydeb
Furfural
CALd
CALe
0.1
PtFe NSs
+ AlCl3
4.0
0.2
0.6
0.1
0.2
-
3-Methyl-2-butenal
Crotonaldehydeb
Furfural
CALd
CALe
98.0
97.9
95.4
98.3
99.6
Figure 3. (a) HCAL and (b) COL hydrogenations of PtFe NSs, PtFe NSs +
AlCl3 and PtFe-A NSs. The rate constant k values of (c) HCAL and COL
hydrogenation by PtFe NSs, PtFe-A NSs and PtFe NSs + AlCl3. (d) Pt 4f XPS
curves of PtFe NSs, PtFe NSs + AlCl3, PtFe-A NSs and Pt NPs.
PtFe-A
NSs
2.5
0.6
-
aReaction conditions: 0.8 mmol of reactant, 0.25 mgPt for Pt-Fe NSs in 4 ml
ethanol, 100 °C, 0.24 MPa H2. bReaction performed at 60 °C. cReaction
performed at 0.5 mgPt for PtFe NSs + AlCl3. dSelective hydrogenation of the
first reaction round. eSelective hydrogenation of the fifth reaction round.
To further understand the distinct performance of catalysts for
CAL hydrogenation, the conversion of HCAL and COL was also
studied by using these three catalysts. The conversion of HCAL
after 3.5 h is in the order of PtFe-A NSs (99.5%) > PtFe NSs
(98.1%) > PtFe NSs + AlCl3 (23.2%) (Figure 3a). In contrast, the
conversion of COL is as low as 26.4% after 3.5 h by using PtFe
NSs as catalysts (Figure 3b). Additionally, the rate constant k
was calculated from the rate equation ln(C/C0) = kt. The plot of
ln(C/C0, HCAL) or ln(C/C0, COL) versus reaction time at various
HCAL or COL concentrations is also shown in Figure S5. A
linear evolution is observed between reaction time and ln(C/C0,
HCAL) or ln(C/C0, COL), indicating that HCAL or COL hydrogenation
reaction catalyzed by Pt-Fe nanocatalysts is a typical first-order
reaction for the HCAL or COL concentration. The ranking for k
values of HCAL hydrogenation on Pt-Fe nanocatalysts is as
follows: PtFe-A NSs (10.26) > PtFe NSs (0.486) > PtFe NSs +
To explore the versatility of Pt-Fe nanocatalysts system for the
selective hydrogenation of other typical α, β-unsaturated
aldehydes, we also used these three catalysts to hydrogenate
other typical α, β-unsaturated aldehydes (Table 1& Figure S6-8).
Obviously, PtFe NSs, PtFe NSs + AlCl3 and PtFe-A NSs can
readily achieve high selectivities for the hydrogenation of other α,
β-unsaturated aldehydes. For example, for the selective
hydrogenation of furfural (Figure S6b), PtFe NSs exhibit high
selectivity (>99.9%) of C=O at 96.2% conversion, and the
excellent selectivity (>95.6%) of C=C is achieved at 99.0%
conversion by using PtFe NSs + AlCl3 (Figure S6c). The PtFe-A
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NSs have high selectivity (>95.4%) and activity (>99.9%) for the
hydrogenation of both C=C and C=O (Figure S6d). Similar
results appear in the hydrogenation of 3-methyl-2-butenal and
crotonaldehyde (Figure S7-8). Moreover, we also investigated
the recyclability of Pt-Fe nanocatalysts for up to five cycles
under the same condition. The catalytic performances did not
show detectable loss in both activity and selectivity in the
following four cycles after the initial run (Table1 & Figure S9),
suggesting the excellent stability of those catalysts. After the
reaction, we also conducted TEM, XRD, SEM-EDX (Figure S10-
11) for the used catalyst. It is shown that there is no obvious
morphology change for the PtFe NSs after fifth cycles (Figure
S10c-d) with the XRD pattern being assigned to fcc PtFe
(Figure S11a) and the Pt/Fe composition of 62.2%/37.8% being
limited element loss (Figure S11b).
remarkable selectivity of PtFe NSs is attributable to the high
electron density of Pt owing to electronic interaction between Fe
and Pt. With the addition of AlCl3, the selectivity for saturated
aldehydes of PtFe NSs is as high as 97.1%, because AlCl3 can
be performed as a protective agent for C=O as well as an
accelerant for C=C hydrogenation. While PtFe-A NSs can
enhance the selectivity of saturated alcohols to >99.8%, it could
be due to the increased exposure of active sites after chemical
etching, making the simultaneous hydrogenation of both C=C
and C=O. Significantly, the Pt-Fe nanocatalysts can also be
applied to the selective hydrogenation of other typical α, β-
unsaturated aldehydes to corresponding potential products, and
show limited decays in catalytic activity and selectivity after
consecutive reactions. We expect that the present work can
inspire rational design of efficient Pt-based nanocatalyst with
excellent activity and selectivity for hydrogenation reactions and
beyond.
To study why Pt-Fe nanocatalysts can selectively hydrogenate
α, β-unsaturated aldehydes, X-ray photoelectron spectroscopic
(XPS) was carried out to reveal the electronic interaction
between the Pt and Fe of Pt-Fe nanocatalysts (Figure 3d &
Figure S12). In general, Pt 4f XPS spectra of Pt-Fe nanocrystals
show two peaks that can be assigned to Pt 4f7/2 and Pt 4f5/2 and
can be further split into two doublets, associated with Pt0 and
Pt2+. Compared with the binding energy (BE) of Pt0 in Pt NPs
(71.6 eV), the lower BE in PtFe NSs (70.7 eV) indicates higher
electron density of Pt [29,30], mainly caused by the electronic
transition from Fe to Pt. The Fe 2p spectrum of PtFe NSs is
summarized in Figure S12. It is clear that the Fe 2p spectra of
the sample can be deconvoluted into eight peaks. The major
peaks are assigned to Fe2+ and Fe3+, indicating that the surface
Fe of PtFe NSs exhibits the oxidation state and no Fe0 exist on
the surface, which is consistent with the results of Pt 4f XPS. It is
well-known that the C=O and C=C in CAL has electrophilicity
and nucleophilicity, indicating that the higher electron density of
surface Pt in PtFe NSs benefits to the adsorption of C=O and
hamper the adsorption of C=C, thus to increase the selectivity of
C=O hydrogenation (Figure S13a). When introducing AlCl3, the
excellent selectivity of C=C can be easily achieved. It is
indicated that AlCl3 as Lewis acid can be used as protective
agent for C=O (Lewis basic) to suppress C=O hydrogenation by
Lewis acid-base interaction (Figure S13b), where the adsorption
of C=O on the surface of the catalyst is inhibited [27]. Compared
with the BE of Pt0 in PtFe NSs (70.7 eV), after introducing AlCl3
the BE of Pt0 shifts to 71.0 eV, which are higher than the PtFe
NSs. The higher BE in PtFe NSs + AlCl3 indicates lower electron
density of Pt, which is beneficial for enhancing the C=C
hydrogenation (Figure S13b). It is indicated that AlCl3 not only
acts as the protective agent for C=O, but also adsorbs on the
surface of PtFe catalyst to adjust the Pt electronic structure and
enhance the reactivity for C=C hydrogenation. In addition, the
BE of Pt0 in PtFe-A NSs is very similar to that of the PtFe NSs +
AlCl3, where PtFe-A NSs can achieve high selectivity of both
C=C hydrogenation and C=O hydrogenation in the absence of
C=O protector of AlCl3.
Acknowledgements
This work was financially supported by the Ministry of Science
and Technology (2016YFA0204100, 2017YFA0208200), the
National Natural Science Foundation of China (21571135),
Young Thousand Talented Program, Jiangsu Province Natural
Science Fund for Distinguished Young Scholars (BK20170003),
the Priority Academic Program Development of Jiangsu Higher
Education Institutions (PAPD), and the start-up supports from
Soochow University.
Keywords: Hydrogenation • Pt • Selectivity • On-demand • α, β-
Unsaturated aldehyde
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10.1002/cctc.201900232
ChemCatChem
COMMUNICATION
Entry for the Table of Contents
Chengyong Yang+, Shuxing Bai+, Yonggang Feng,
and Xiaoqing Huang*
An On-Demand, Selective Hydrogenation
Catalysis over Pt-Fe Nanocatalysts under
Ambient Condition
Pt-Fe nanocatalysts can be adopted as selectivity
controllers for
α, β-unsaturated aldehydes
hydrogenation, where the PtFe NSs, PtFe NSs +
AlCl3 and PtFe-A NSs exhibit excellent selectivities
for unsaturated alcohols, saturated aldehydes and
saturated alcohols, respectively.
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