Highly Chemoselective Reduction of Nitroarenes Using a Titania-Supported Platinum-Nanoparticle Catalyst under a CO Atmosphere

Article abstract of DOI:10.1002/cjoc.201600715

The discovery that supported gold catalysts can promote CO/H₂O-mediated reduction at ambient temperatures is important to chemoselective synthesis and has gained significant attention in recent years. Whether the alternative Pt group metal (PGM) catalysts can exhibit such exceptional performance is thus an interesting research issue. So far, no PGM catalyst shows activity for CO/H₂O-mediated reduction at ambient temperatures. Here, we demonstrate that it is possible to transform nonactive into highly active and selective catalysts for CO/H₂O-mediated reduction by modulating the interfacial structure and electronic properties at the metal-support interfaces. Thus, highly active and chemoselective hydrogenation Pt, Ir, Rh and Pd catalysts can be prepared by decorating the exposed metal faces with partially reduced support species by means of a simple catalyst activation procedure. In this way, it has been possible to dramatically facilitate the previously unappreciated PGM-catalyzed activation of CO molecules under mild conditions, which can make a significant contribution not only to reveal the intrinsic catalytic potential of supported PGMs but also to establish a more sustainable and industrially-relevant process.

Full text of DOI:10.1002/cjoc.201600715

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DOI: 10.1002/cjoc.201600715
Highly Chemoselective Reduction of Nitroarenes Using a
Titania-Supported Platinum-Nanoparticle Catalyst under a
CO Atmosphere
Shushuang Li, Fuzerong Wang, Yongmei Liu, and Yong Cao*
Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry,
Fudan University, Shanghai 200433, China
The discovery that supported gold catalysts can promote CO/H2O-mediated reduction at ambient temperatures
is important to chemoselective synthesis and has gained significant attention in recent years. Whether the alternative
Pt group metal (PGM) catalysts can exhibit such exceptional performance is thus an interesting research issue. So
far, no PGM catalyst shows activity for CO/H2O-mediated reduction at ambient temperatures. Here, we demonstrate
that it is possible to transform nonactive into highly active and selective catalysts for CO/H2O-mediated reduction
by modulating the interfacial structure and electronic properties at the metal-support interfaces. Thus, highly active
and chemoselective hydrogenation Pt, Ir, Rh and Pd catalysts can be prepared by decorating the exposed metal faces
with partially reduced support species by means of a simple catalyst activation procedure. In this way, it has been
possible to dramatically facilitate the previously unappreciated PGM-catalyzed activation of CO molecules under
mild conditions, which can make a significant contribution not only to reveal the intrinsic catalytic potential of
supported PGMs but also to establish a more sustainable and industrially-relevant process.
Keywords nitroarenes, reduction, carbon monoxide, PGM catalysts, strong metal-support interactions
Introduction
ditions as well as the perceived problems of the CO-
poisoning effect on the traditional PGM catalysts.[7]
In recent years, there has been tremendous interest in
developing more benign chemical synthesis facilitated
by supported gold nanoparticles (NPs), in part due to the
unique capability of this class of catalytic materials to
subtly activate a range of industrially important small
molecules under mild and clean conditions.[8] As part of
our continued efforts to develop innovative catalysis for
green synthesis, we recently discovered the outstanding
catalytic ability of supported Au NPs for the deoxygen-
ation of nitroaromatics to their corresponding anilines
using CO/H2O as a reducing reagent.[5a] In such
CO-mediated reductions, an Au-hydride species was
generated in situ from the reaction of H2O with CO,
which led to the highly chemoselective reduction. In
short, this provides an efficient alternative that can cir-
cumvent the limited hydrogen delivery rate associated
with previous Au-catalyzed hydrogenation processes.
Essentially, the distinct capability of Au to enable
CO/H2O-activation lies in the much lower adsorption
strength of CO on Au than on PGM.[8d] Considering that
the adsorption affinity of CO might be tuned in favor of
a weaker condition by a rational regulation of the metal-
support interaction (MSI) in the PGM catalyst sys-
Selectivity is one of the key issues in chemical
transformations especially when molecules present two
or more reacting groups and only one of them has to be
transformed.[1] This is, for instance, the case for chemo-
selective hydrogenations, for which Pt group metal
(PGM) is frequently used as catalysts.[2] Nevertheless, it
is difficult to control the chemoselectivity of PGM cat-
alysts due to their inherently high hydrogenation activi-
ty.[3] An alternative approach that can achieve a higher
degree of selectivity control is via transfer hydrogena-
tion (TH) in the presence of various hydrogen donors.[4]
In this regard, abundantly available CO/H2O couple has
emerged as a promising hydrogen source particularly
suitable for controlled reduction of polar unsaturated
bonds.[5] Even more appealing is the fact that using CO
directly as a reductant offers distinct advantages as the
current practice of multistep high-temperature H2 gas
production process would potentially be simplified into
an energy-efficient single step.[6] Despite of these envi-
sioned benefits, the implementation of such a conven-
ient approach for selective reductions remains chal-
lenging, largely due to the lack of effective catalyst ca-
pable of activating the CO/H2O couple under mild con-
*
E-mail: yongcao@fudan.edu.cn; Tel.: 0086-021-55665287; Fax: 0086-021-65643774
Received October 25, 2016; accepted December 15, 2016; published online XXXX, 2017.
In Memory of Professor Enze Min.
Chin. J. Chem. 2017, XX, 1—5
© 2017 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Li et al.
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tem,[9,10] we were motivated to explore Pt NPs deposited
on titania bearing tailored MSIs as a possible catalyst
for chemoselective reduction of nitro compounds.
tion, the conversion and product selectivity were peri-
odically determined by GC analysis (Agilent GC-6820
gas chromatograph equipped with a capillary column
DB-Wax (30 m×0.25 mm) and FID detector) using
n-decane as an internal standard. The identification of
the products was performed by using a GC-MS spec-
trometer.
Experimental
Catalyst preparation
Pt/SiO2, Pt/Al2O3, Pt/TiO2, Rh/TiO2, Ir/TiO2 and
Pd/TiO2 samples were prepared by incipient wetness
technique at the desired metal contents. Chloroplatinic
acid hexahydrate (H2PtCl6•6H2O, Pt≥37.5 wt%), palla-
dium chloride (PdCl2, Pd≥60.0 wt%), rhodium chloride
hydrate (RhCl3•xH2O, Rh≥38.5 wt%), and iridium
chloride (H2IrCl6, Ir≥35.0 wt%) precursors were used
to impregnate the Al2O3 (Evonik, Aluminum oxide C),
SiO2 (Evonik, Aerosil 380), and TiO2 (Evonik, P25)
supports. As an example, 1.0 g TiO2 was added to 10
mL of an aqueous solution containing 5.3 mg
H2PtCl6•6H2O. After a perfect mixing of the slurries,
samples were dried at 80 ℃ overnight and then re-
duced under 5 vol% H2/Ar flow at 300 or 600 ℃ for 2
h to give the corresponding 0.2% Pt/TiO2-300 and 0.2%
Pt/TiO2-600 catalysts.
Results and Discussion
To begin our studies on the effect of MSI on Pt cata-
lysts for CO-mediated reduction, a series of Pt/TiO2
catalysts have been prepared containing different
amounts of Pt that reduced under different temperature
in 5 vol% H2/Ar atmosphere. As determined by TEM
measurements, the average particle size of Pt NPs in-
creases from 2.1 to 3.5 nm when the Pt content is in-
creased from 0.2 to 2 wt%. Notably, in the case of 0.2
wt% Pt/TiO2, small size distributions of Pt NPs were
kept when the reduction temperature increased from 300
to 600 ℃, while a significant aggregation of Pt NPs to
7 nm was observed for 2 wt% Pt/TiO2 under elevated
reduction temperature. The electron microscopic results
have been complemented with a structural characteriza-
tion of the Pt metal surface by CO adsorption combined
with DRIFTS measurements. This was done in order to
gain information about the available CO adsorption sites
on these different Pt/TiO2 samples (Figure 1). A signifi-
cant coverage of CO on Pt is indicated by linear CO
species with peaks at 2088 and 2034 cm1 and bridged
CO species of a broad band around 1840 cm1 was ob-
served in the 2 wt% Pt/TiO2-300 catalyst.[11] The domi-
nant IR band at 2088 cm1 is related to extended Pt
crystal faces while IR band at 2034 cm1 corresponds to
Characterization
Transmission electron microscopy (TEM) observa-
tions were carried out using a JEOL 2011 electron mi-
croscope operating at 200 kV. High-resolution transmis-
sion electron microscopic (HRTEM) images were car-
ried out using Tecnai G2 F20 S-Twin at 200 kV. The
size distribution of the metal clusters was determined by
measuring about 200 random particles on the images.
The diffuse reflectance infrared Fourier transform spec-
troscopy (DRIFTS) characterization was performed
with a ThermoFisher Nicolet 6700 FT-IR spectrometer
equipped with a DRIFTS cell. The catalyst (20 mg) was
pretreated with He at 250 ℃ for 1h before being
cooled down to 25 ℃ to collect the background spectra.
Subsequently, the sample was exposed to a flow (20
mL•min1) of 1 vol% CO/He for 1 h followed by purg-
ing with pure He for 30 min to remove the gas phase
CO. Water-gas shift temperature programmed surface
reaction (WGS-TPSR) was run in a Micromeritics Au-
toChem HP 2950 instrument equipped with a mass
spectrometer. For each experiment, the catalyst was sta-
bilized in 1 vol%CO-3 vol%H2O-He for 20 min at
40 ℃ before being heated up to 300 ℃ at 10 ℃•
min1.
General procedure for the reduction of nitroarenes
with CO/H2O
A 25-mL Hastelloy-C high pressure Parr reactor was
used to carry out the liquid phase reduction reaction. A
mixture of 4-nitrostyrene (0.5 mmol), supported metal
catalysts (metal 0.5 mol%), organic solvent (2 mL), wa-
ter (1 mL) was loaded into the reactor. The reactor was
stirred at a rate of 800 r•min1 under 1 MPa CO for a
specific reaction time at a given temperature. After reac-
Figure 1
DRIFT spectra of CO desorption of (a) 2%
Pt/TiO2-300, (b) 2% Pt/TiO2-600, (c) 0.2% Pt/TiO2-300, (d) 0.2%
Pt/TiO2-600.
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Chin. J. Chem. 2017, XX, 1—5

Chemoselective Reduction of Nitroarenes Using a Titania-Supported Platinum-Nanoparticle Catalyst
Pt sites of low surface coordination. A very weak band
is detected at higher frequency of 2181 cm1 indicating
the presence of oxidized Pt species in such low-tem-
perature reduced catalyst. Similar IR bands are also ob-
served in 2% Pt/TiO2-600 inspite of a sharp decrease of
the intensity of CO adsorption due to the observable
growth of Pt particles after high temperature (HT) re-
duction. In the case of 0.2% Pt/TiO2-300, the intense
linear CO adsorption at low-coordinated Pt sites (2034
cm1) reflects the smaller particle size at a low Pt con-
tent. Dramatically, with the HT-reduced 0.2% Pt/TiO2-
600 catalyst, only one band at 2046 cm1 related to Pt-Ti
interface sites is observed without the observation of
linear or bridged CO adsorption on Pt aggregates.[12a]
Table 1 Reduction of 4-nitrostyrene under a CO atmosphere in
the presence of H2Oa
Select./%
EntryCatalyst
Temp./℃CO/MPaConv./%
2a 3a azo
－
－
－
－
－
－
－
－
－
－
＞99
－
－
－
－
－
－
－
－
－
1
2
3
4
5
6
7
8
9
0.2%Pt/TiO2-300 100
0.2%Pt/TiO2-600 100
1
1
1
1
1
1
1
1
1
1
－
1
12
＞99
＞99
－
66
2%Pt/TiO2-300
2%Pt/TiO2-600
100
100
Trace
Trace
Trace
Trace
Trace
Trace
11
－
－
0.2%Pt/SiO2-300 100
0.2%Pt/SiO2-600 100
0.2%Pt/Al2O3-300 100
0.2%Pt/Al2O3-600 100
0.2%Pt/CeO2-300 100
－
－
－
69
31
18
－
－
10 0.2%Pt/CeO2-600 100
11b 0.2%Pt/TiO2-600 100
12 0.2%Pt/TiO2-600 150
42
82
＞99
97
－
＞99
－
－
－
－
－
－
13 0.2%Pt/TiO2-600 80
14 0.2%Pt/TiO2-600 100
15 0.2%Pt/TiO2-600 100
1
15
53
40
＞99
＞99
＞99
2
Figure 2 HRTEM images of (a) 0.2% Pt/TiO2-300 and (b) 0.2%
Pt/TiO2-600.
0.5
a Reaction conditions: 4-nitrostyrene (0.5 mmol), catalyst (Pt: 0.5
mol%), ethanol (2 mL), water (1 mL), 2 h. b H2 (1 MPa).
It has been reported that high reduction temperatures
of Pt/TiO2 catalysts produce a decoration of Pt NPs with
TiOx species that increases the interface between Pt and
TiO2,[12,13] which is consistent with the CO adsorption
results given above. This was further confirmed by HR-
TEM measurement. According to the HRTEM image of
0.2% Pt/TiO2-600 (Figure 2b), Pt NPs were partially
covered by a thin layer of TiOx while the encapsulation
was not observed in 0.2% Pt/TiO2-300. From all these
evidences, we can infer that a strong metal-support in-
teraction (SMSI) occurs between Pt NPs and TiO2 sup-
port. The formation of SMSI has been proved to signif-
icantly alter the geometrical arrangement[10h] and elec-
tronic property[9] of metal NPs. In our case, the SMSI
between Pt and TiO2 effectively stabilizes Pt NPs from
sintering under relatively high reduction temperature.
Such geometrical encapsulation and the electronic mod-
ification of Pt NPs by reduced TiOx nanolayers lead to a
significant suppression of CO chemisorption on active
Pt sites, which might help Pt tolerate CO thus promoting
the Pt catalyzed CO-mediated reduction.
Scheme 1 Intermolecular competitive reaction of nitrobenzene
and styrene using 0.2 Pt/TiO2-600 in the presence of CO/H2O.
NO2
NH2
0.2% Pt/TiO2-600
(Pt: 0.5 mol%)
(0.5 mmol)
>99% Yield
+
+
Ethanol (2 mL), H2O (1 mL)
CO (1 MPa), 100 oC, 3 h
not detected
(0.5 mmol)
tively high temperature of 600 ℃, shows the best per-
formance (Table 1, Entry 2). On the contrary, 0.2%
Pt/TiO2-300 has only very limited activity (Entry 1)
while the reduction hardly occurs and no trace of 2a
could be detected using 2% Pt/TiO2 catalysts (Entries 3,
4) as the strong adsorption of CO on Pt sites inhibited
the further activation of substrate molecules. To further
confirm the participation of SMSI in this CO/H2O-me-
diated reduction, 0.2% Pt/CeO2, 0.2 Pt/Al2O3, 0.2%
Pt/SiO2 catalysts were prepared and reduced at 300 ℃
and 600 ℃, respectively. For non-reducible oxides like
SiO2 and Al2O3 supported Pt NPs, there are no SMSI
between Pt sites and support, which are consistently
To check this hypothesis, we choose the selective
reduction of 4-nitrostyrene (1a) to 4-aminostyrene (2a)
as the reaction model. For these initial assays the condi-
tions studied were 100 ℃, 1 MPa CO, and a catalyst
loading of 0.5 mol% (the amount of the active metal
species relative to the substrate). Notably, 0.2% Pt/TiO2-
600, in which a favorable SMSI formed under a rela-
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Li et al.
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inactive in such CO-mediated process (Entries 5－8).
On the other hand, partially reducible CeO2 shows sim-
ilar behavior with TiO2 that the high reduction tempera-
ture enhanced the activity of Pt/CeO2 catalyst, although
the selectivity decreases due to the formation of azo
compounds (Entries 9, 10). These results confirm that
the combination of small-size Pt NPs with a suitable
TiO2 support treated at high reduction temperature of
600 ℃ could achieve the best activity and selectivity.
Raising the reaction temperature to 150 ℃ observably
decreasing the reaction time while under a lower tem-
perature of 80 ℃ the reaction can still occur at a mod-
erate rate (Entries 12, 13). The effect of CO pressure
shows a volcanic curve indicating that CO adsorption on
catalyst surface is the key factor in this reaction (Entries
14, 15).
It is noteworthy that complete chemoselectivity for
nitro groups in the presence of olefinic functionalities
was achieved in such SMSI-induced Pt-CO/H2O reduc-
tion system. In sharp contrast, by using H2 as reducing
agent instead of CO/H2O, we observed substantial for-
mation of the over-reduced product of 4-ethylaniline (3a)
(Table 1, Entry 11). This result is consistent with other
reported Pt-H2 reduction systems as the homolytic
cleavage of H2 often leads to unselective hydrogenation
of polar and nonpolar unsaturated groups.[3] The high
chemoselectivity of 0.2% Pt/TiO2-600 for nitro func-
tionalities was further investigated in the intermolecular
competitive reaction of nitrobenzene and styrene. Inter-
estingly, nitrobenzene was completely reduced to ani-
line while styrene remained unreacted (Scheme 1).
These results clearly demonstrated that the Pt-CO/H2O
catalytic system showed complete chemoselectivity for
nitro functionalities in the presence of inter- and intra-
molecular olefinic functionalities. Together with the fact
that no H2 was detected in the gas phase after the
CO/H2O-mediated reduction, the Pt-CO/H2O reduction
system is supposed to proceed through active polar hy-
drogen species generated by CO induced H2O activation
on the interface between Pt NPs and TiO2, facilitating
the desired reduction of the polar nitro groups.
catalyst for CO/H2O-mediated reduction by modulating
the metal-support interaction in the Pt/TiO2 system, we
were curious to find if the concept could be extended to
other metals. Results from Figure 3 show that Ir, Rh and
Pd, which are almost inactive for the CO/H2O-mediated
reduction of 1a, can now be converted into active and
selective catalysts by supporting them on TiO2 and re-
ducing at 600 ℃. To explain the strong effect of the
catalyst activation conditions on Pt/TiO2, as well as on
the other PGM catalysts, we can assume that the SMSI
occurred between metals and TiO2 support can be man-
ifested by modifying the electron density of small clus-
ters by charge transfer from partially reducible supports,
through the unique properties of metal-support border-
line sites, and/or by decoration of the metal by mobile
support.[9,10] To gain insight into the origin of the
SMSI-enhanced CO/H2O-mediated reduction activity of
PGM catalysts, WGS-TPSR was performed for the typ-
ical 0.2% Pt/TiO2-300 and 0.2% Pt/TiO2-600. As shown
in Figure 4, 0.2% Pt/TiO2-300 is almost inactive below
200 ℃ in this TPSR mode, while the H2 formation
over 0.2% Pt/TiO2-600 occurs at a lower temperature
and a much higher rate. These results demonstrated that
the CO-induced H2O activation is the first and most
important step in this CO/H2O-mediated reduction. To-
gether with HRTEM and DRIFTS results, the formation
of SMSI between PGM and TiO2 at high reduction
temperature significantly changes the CO adsorption
characteristics on active PGM sites, promoting the WGS
pathway and sequential reduction process.
Figure 4 WGS-TPSR (1%CO-3%H2O-He, 20 mL•min1; 100
mg sample) data for the H2 produced.
Conclusions
In summary, we have demonstrated an efficient and
chemoselective 0.2% Pt/TiO2-600 catalyst for reduction
of nitroarenes in the presence of other reducible func-
tional groups to give the corresponding anilines in high
yields using CO/H2O as hydrogen source. The unusual
performance of this catalyst can be attributed to the
SMSI formed between small-size Pt NPs and TiO2 un-
der relatively high reduction temperature, which geo-
metrically and electronically enhances the tolerance of
Figure 3 Results of CO/H2O-mediated reduction of 1a on PGM
catalysts (conditions: 1a 0.5 mmol, metal 0.5 mol%, ethanol 2
mL, H2O 1 mL, 100 ℃, 2 h).
Given the encouraging results obtained in converting
the “nonactive” Pt into a highly active and selective Pt
4
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Chin. J. Chem. 2017, XX, 1—5

Chemoselective Reduction of Nitroarenes Using a Titania-Supported Platinum-Nanoparticle Catalyst
D. Chin. J. Catal. 2016, 37, 1669.
[6] Rostrup-Nielsen, J.; Christiansen, L. J. Concepts in Syngas Manu-
Pt to CO poisoning. We anticipate this conception po-
tentially provides a general and simple design of PGM
catalysts that can be applied to varied CO-mediated cat-
alytic processes.
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Acknowledgement
This work was supported by the National Natural
Science Foundation of China (Nos. 21273044,
21473035, 91545108), the Science & Technology
Commission
of
Shanghai
Municipality
(No.
16ZR1440400), SINOPEC (No. X514005) and the
Open Project of State Key Laboratory of Chemical En-
gineering (No. SKL-ChE-15C02).
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