Precise regulation of the selectivity of supported nano-Pd catalysts using polysiloxane coatings with tunable surface wettability

Article abstract of DOI:10.1039/c9cc03800k

A facile method was developed for surface modification of supported nano-Pd catalysts with tailorable wettability. The obtained Pd/TiO₂@POS catalytic materials could be used in the controllable synthesis of styrene and ethylbenzene obtained from hydrogenation of phenylacetylene and the selective synthesis of imine and N-methylanilines via a reductive amination reaction. The precise modification of the hydrophilicity/hydrophobicity of the catalyst surface is crucial to realize this targeted transformation.

Full text of DOI:10.1039/c9cc03800k

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DOI: 10.1039/C9CC03800K
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Precise regulation of selectivity of supported nano-Pd catalysts
using polysiloxane coatings with tunable surface wettability
Hongli Wang, ‡a Ziqian Gao, ‡a Xinzhi Wang, a,b Ruiping Wei, a,b Junping Zhang* and Feng Shi *
a
a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A facile method was developed for surface modification of selectively poisoning the active centers.24 Although above nice
supported nano-Pd with tailorable wettability. The obtained methods have been established, there is still room for the
Pd/TiO
2
@POS catalytic materials could be used in controllable development of facile, cost-effective procedures for improving
synthesis of styrene and ethylbenzene from hydrogenation of the selectivity of heterogeneous catalytic reaction.
phenylacetylene, and the selective synthesis of imine and N-
methylanilines in reductive amination reaction. The precise for enhancing selectivity in heterogeneous catalysis.
Recently, surface modification has become a powerful tool
2
5-34
Owing
modification of the hydrophilicity/hydrophobicity of the catalyst to their flexibility and versatility, hydrophobic–hydrophilic
surface is the crucial operation to realize this targeted surface modification represents an important set for the surface
3
5-41
transformation.
modification of heterogeneous catalysts.
the product could be improved by influencing the
adsorption/desorption of reaction intermediate on
The selectivity of
Heterogeneous catalysts are extensively used in industrial
manufacture of bulk and fine chemicals due to their easy
a
hydrophobic–hydrophilic properties of a catalyst. Because
hydrophobic surface could promote desorption of the
hydrophilic molecules, modification of hydrophobic surface for
enhancing the selectivity has been applied in a series of
reactions, such as reduction of aromatic ketones to alcohols,
oxidation of aliphatic alcohols to acids, oxidation of sulfide to
1
, 2
recoverability, and reusability. From the view of economical,
energy-saving, and environmentally benign, development of
highly selective heterogeneous catalytic processes is highly
demanded.3 However, it is difficult to control the selectivity
toward the desired products in heterogeneous catalysis when
products can be further reacted to afford undesired by-
products or more than one reactive group is present in the
substrates. For example, the selective hydrogenation of alkynes
to generate alkenes is a key industrial process to manufacture
polymer-grade alkenes and to synthesize new chemicals,
, 4
35
38
39
sulfoxide. Compared with modification of hydrophobic
surface, the influence of hydrophilic surface on the product
selectivity is rarely studied. Recently, Xiao and co-workers
presented the selective hydrogenation of furfural to furan using
Pd@S-1-OH catalyst with appropriate hydrophilicity.
Moreover, it is still challenging to extend this strategy to other
heterogeneous catalytic reactions.
41
a
5
pharmaceuticals, and materials. Nevertheless, the highly
selective synthesis of alkenes from alkynes remains
tremendous challenge because alkenes are prone to further
hydrogenation to produce the alkanes.
reaction selectivity over the heterogeneous catalysts, a number
of strategies have been developed, such as adjusting the metal
nanoparticle sizes and shapes,
nanoparticles with additional metals,
metal−support interactions,
a
Here, we report a facile method for the preparation of
6, 7
To improve the
polysiloxane (POS)-modified Pd/TiO
Pd/TiO @POS catalysts can be precisely tailored from
hydrophilic to hydrophobic (Fig. 1). The obtained Pd/TiO @POS
2
materials. The
2
2
8
-13
constructing multimetallic
catalysts feature good selectivity in controllable synthesis of
styrene and ethylbenzene, which is the first example of
application of surface wettability in selective hydrogenation of
phenylacetylene. Meanwhile, controllable synthesis of N-
methyleneaniline and N-methylamines can be achieved by
adjusting the hydrophilicity/hydrophobicity of the catalyst, too.
The hydrophilic/hydrophobic polysiloxane (POS)-modified
catalysts were firstly prepared by deposition–precipitation
1
4-19
generating strong
doping the supports23 and
2
0-22
a. State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute
of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou730000, China.
b.
University of Chinese Academy of Sciences, No. 19A, Yuquanlu, Beijing 100049,
P.R. China.
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
2
method to afford Pd/TiO followed by hydrolytic condensation
of n-hexadecyltrimethoxysilane (HDTMS) and TEOS onto the
‡
These authors contributed equally.
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pristine Pd/TiO
2 2
to generate the Pd/TiO @POS catalysts (Fig. 1). TEM image, as they were covered by the POSViewcoAartticilnegO.nliInne
In order to control the hydrophilicity/hydrophobicity of the addition, the TEM images also revealedDOtIh: 1a0t.1a03ll9/tCh9eCCP0d3/8T0iO0K
2
catalyst samples, the volume of HDTMS was adjusted from 0.12 precursors were completely coated with the POS coatings after
to 2.06 mL whilst keeping the other synthesis parameters subjected to ammonia-assisted sol-gel process.
constant.
Fig. 1 Schematic illustration for the controllable preparation of hydrophilic/hydrophobic
Pd/TiO @POS catalysts.
2
In order to investigate the wettability nature of the modified
nano-Pd samples, water contact angles (CAwater) of the catalyst
samples were measured. The influence of the amounts of
HDTMS on wettability of the Pd/TiO
Table S1. The pristine Pd/TiO sample showed a CAwater of 22.9°
in air. When the volume of HDTMS was low (0.12 mL), the water
miscibility of Pd/TiO @POS-1 catalyst was apparently
2
@POS coatings is shown in Fig. 2 SEM images of samples. (a) Pd/TiO @POS-1, (c) Pd/TiO
2
, (b) Pd/TiO
2
2
2
@POS-
2
, (d) Pd/TiO @POS-3, (e) Pd/TiO @POS-4, (f) Pd/TiO @POS-5.
2
2
2
Moreover, the XRD patterns of the samples are shown in Fig.
S2. The Pd/TiO sample showed mixed phases of anatase and
rutile TiO . Neither a palladium oxide nor a metallic palladium
diffraction pattern was detectable in Pd/TiO catalyst, which
might be ascribed to that the Pd species in these catalysts were
amorphous or well dispersed on the surface of TiO . Compared
with Pd/TiO , the Pd/TiO @POS sample exhibited a new
diffraction peak located at 20.7°. This peak is the typical
diffraction peak of silica (PDF#76–0931), which strongly proves
successful modification of POS coatings on the surface of
2
o
2
o
emaciated to circa 44.5 . The CAwater increased from 44.5 to
2
o
1
0
44.3 step by step with increasing the volume of HDTMS from
.12 to 1.21 mL. Further increasing of HDTMS volume to 2.06
2
o
mL increased the CAwater to 154.5 , which indicates that the
modified catalyst became superhydrophobic. The above results
clearly suggested that the POS coating could transform the
surface character of the nanocomposite from hydrophilic to
hydrophobic and even superhydrophobic.
2
2
2
The Pd/TiO
by scanning electron microscopy (SEM), transmission electron
microscopy (TEM), XRD, XPS and N adsorption–desorption
2 2
and Pd/TiO @POS samples were characterized
2
Pd/TiO .
Next, the XPS studies of the catalysts were performed to
determine the chemical state of Pd species. As shown in Fig. S3,
2
studies to reveal their structures. Firstly, the morphologies of
the materials were measured by SEM and TEM. The SEM images
of the samples are shown in Fig. 2. As is shown in Fig. 2a, the
Pd/TiO sample had a spherical shape with a relatively smooth
2
surface and a diameter of approximately 30-70 nm. After
modification by POS, the original spherical morphology of
2
the Pd 3d5/2 signal of Pd/TiO appeared at 335.1 eV, which
suggested that metallic Pd was mainly formed on the surface of
Pd/TiO
2
.
No peak of Pd 3d5/2 was observable in the
@POS samples, which might be attributed to the POS
. In the XPS survey spectra of
@POS catalysts, intensive Si 2p (103.0 eV) and Si 2s
153.7 eV) peaks appeared as well as Ti 2p peak disappeared
Pd/TiO
2
coating on the surface of Pd/TiO
the Pd/TiO
(
2
2
2
Pd/TiO was almost preserved, but the modified samples
showed a rough surface and an enlarged thickness of the
spherical shape. This phenomenon was observed clearly when
changing the volume of HDTMS. When the volume increased
from 0.12 to 2.06 mL, the resultant materials increased in
particle size gradually. The results implied that the assembly of
POS coatings took place controllably on the surface of Pd/TiO .
2
The TEM images of samples are shown in Fig. S1. As illustrated
in Fig. S1a, the mean particle diameter of Pd nanoparticles in
simultaneously (Fig. S4). The results clearly demonstrated
successful modification of the POS coating on the surface of the
pristine Pd/TiO
The N adsorption–desorption tests showed that the BET
surface areas of the Pd/TiO , Pd/TiO @POS-1, Pd/TiO @POS-2,
Pd/TiO @POS-3, Pd/TiO @POS-4, and Pd/TiO @POS-5 were
5.325, 37.548, 24.116, 25.587, 27.182, and 11.932 m g ,
respectively (Table S1). The BET surface areas of the modified
materials present a slight decrease with respect to Pd/TiO . In
addition, the Pd/TiO @POS samples give similar average pore
2
, which is consistent with the XRD results.
2
2
2
2
2
2
2
2
-1
5
pristine Pd/TiO
homogeneously dispersed on the TiO
with a POS layer, the Pd nanoparticles were not visible in the
2
was 2.1±0.5 nm, and these nanoparticles were
2
2
surface. After coated
2
radius(Table S1). By the use of ICP-AES, the Pd loadings of the
2
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Pd/TiO
2
@POS catalysts were measured as 0.22, 0.07, 0.03, 0.04, conclusion that modification by hydrophilic/hydrophobic POS
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DOI: 10.1039/C9CC03800K
and 0.07 wt%, respectively (Table S1).
coatings on the nano-Pd surface could indeed regulate the
selectivity of hydrogenation of phenylacetylene. The
Pd/TiO
good selectivity for the formation of styrene while the
Pd/TiO @POS catalyst with appropriate hydrophobicity displays
2
@POS catalyst with appropriate hydrophilicity exhibits
2
good selectivity toward ethylbenzene. The Pd contents in the
solution were tested by ICP-AES but it was out of the test limit
(0.05 ppm). So the influence of leached palladium on the
reaction can be neglected.
2
Fig. 3 Catalytic hydrogenation of phenylacetylene over various Pd/TiO @POS
2
catalysts. Reaction conditions: phenylacetylene (1.0 mmol), H (1.0 atm), EtOH
o
(
4.0 mL), 50 C, 2 h.
We have further checked whether the surface
hydrophilization/hydrophobization of Pd/TiO @POS catalysts
2
could really regulate the catalytic performance in catalytic
reactions. The first model reaction is the catalytic
hydrogenation of phenylacetylene as the tuning of the
selectivity to styrene and ethylbenzene is quite difficult (Fig. 3 Fig. 4 Reductive amination of aniline with paraformaldehyde over various
Pd/TiO
2
@POS catalysts. Reaction conditions: aniline
1
(1.0 mmol),
C, 4 h.
and Table S3). In view of the elementary steps in catalysis, paraformaldehyde 2 (1.0 mmol), H (1.0 atm), toluene (4.0 mL), 80
o
2
desorption of styrene from the catalyst surface has a significant
effect on the selectivity of reaction. Specifically, if hydrophobic
These surface-modified nano-Pd catalysts can also be applied
styrene could rapidly desorb from hydrophilic catalyst surface, to the reductive amination of aniline with paraformaldehyde for
it would avoid the further hydrogenation of styrene to controllable synthesis of imine and N-methylanilines (Fig. 4 and
ethylbenzene and thus increase the selectivity of alkene. On the Table S4). By applying Pd/TiO
other hand, hydrogenation of phenylacetylene to ethylbenzene aniline with 60.7% N-methyleneaniline selectivity were
would be realized when hydrophobic styrene still adsorbs on obtained. With the hydrophilic Pd/TiO @POS-1 as a catalyst, 84%
2
as catalyst, 86% conversion of
2
hydrophobic catalyst surface. The reactions were performed by conversion of aniline with 90.1% N-methyleneaniline selectivity
using the same dosage of nano-Pd catalyst and 1.0 mmol of and 9.9% N-methyl aniline selectivity were obtained. The
o
phenylacetylene in EtOH at 50 C under 1 atm of H
2
for 2 h. The selectivity of N-methylanilines increased to 21.1% if
@POS-2 was used as catalyst. As expected, high
reaction over Pd/TiO
2
@POS-1 was sluggish and only 20% Pd/TiO
2
conversion of phenylacetylene was obtained, although the selectivity toward N-methylanilines was achieved by increasing
good styrene selectivity of 91.7% was observed. Given that the the CAwater of catalyst, i.e., 94.0% selectivity was achieved in the
o
CAwater of Pd/TiO
2
@POS-1 is 44.5 , the low conversion should be presence of Pd/TiO
2
@POS-4. The enhanced selectivity to N-
attributed to difficult adsorption of phenylacetylene on a methylanilines can be explained by the high hydrophobicity of
hydrophilic surface. When Pd/TiO @POS-2 was used as catalyst, the POS coatings, in which hydrophobic imine was easily
2
the conversion of phenylacetylene increased to 87% and accommodated into the shell of the catalyst followed by
selectivity to styrene remained high (91.7%). As expected, hydrogenation. The results clearly demonstrated that the
ethylbenzene product was generated with further increasing selectivity of imine and N-methyl aniline could be regulated by
2
the CAwater of the catalyst. For example, the Pd/TiO @POS-3, changing the hydrophilic/hydrophobic of catalyst surface. The
Pd/TiO @POS-4, and Pd/TiO @POS-5 catalysts led to 99% reductive amination of aniline with paraformaldehyde involved
2
2
conversion of phenylacetylene with 99% ethylbenzene three main steps, i.e., the addition of aniline to formaldehyde,
selectivity, probably because styrene could not rapidly desorb imine formation via dehydration and imine hydrogenation to
from hydrophobic catalyst surface and was further reduced to generate N-methylaniline. The hydrophilic surface of
generate ethylbenzene. By applying Pd/TiO
conversion of phenylacetylene with 67.9% selectivity to styrene intermediate to selective afford imine product, while the
were obtained. Clearly, these results were similar to those hydrophobic surface of Pd/TiO @POS-4 favors accumulation of
2 2
as catalyst, >99% Pd/TiO @POS-1 benefits desorption of hydrophobic
2
obtained by hydrophilic Pd/TiO
Pd/TiO
2
, i.e., Pd/TiO
2
@POS-1 and hydrophobic N-methyleneaniline intermediate followed by
2
@POS-2. From the above results, we could draw a hydrogenation to form N-methylanilines.
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As the selectivity of these two reactions is time-dependent, 13. H. J. Liang, B. Zhang, H. B. Ge, X. M. Gu, S. F. ZhaVnigewaAnrtdiclYe.OQnliinne,
ACS Catal. , 2017, 7, 6567-6572.
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DOI: 10.1039/C9CC03800K
typical catalysts with hydrophilic and hydrophobic properties,
i.e., Pd/TiO @POS-2 and Pd/TiO @POS-4, were compared with
varied reaction times (Fig. S6 and 7). Clearly, higher selectivity
to styrene and N-methyleneaniline were achieved over
1
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aniline were obtained over hydrophobic Pd/TiO
2
@POS-2 while ethylbenzene and N-methyl
@POS-4. So the
2
selectivities were mainly tuned by the surface properties of
catalysts but not reaction time.
In summary, we have developed a convenient method for 18. H. R. Zhou, X. F. Yang, L. Li, X. Y. Liu, Y. Q. Huang, X. L. Pan, A. Q.
surface modification of nano-Pd using POS coatings with
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resultant Pd/TiO @POS catalysts exhibit good selectivity in the
2
2
2
2
hydrogenation of phenylacetylene to styrene and
ethylbenzene. Furthermore, controllable formation of imine
and N-methylanilines in reductive amination reaction can also
be realized by regulating the hydrophilicity/hydrophobicity of
the catalysts, too. This work may promote the development of
controllable preparation of heterogeneous catalysts via precise
modification of the catalyst surface.
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