Wettability-Driven Palladium Catalysis for Enhanced Dehydrogenative Coupling of Organosilanes

Article abstract of DOI:10.1021/acscatal.6b03233

Direct coupling of Si-H bonds has emerged as a promising strategy for designing chemically and biologically useful organosilicon compounds. Heterogeneous catalytic systems sufficiently active, selective, and durable for dehydrosilylation reactions under mild conditions have been lacking to date. Herein, we report that the hydrophobic characteristics of the underlying supports can be advantageously utilized to enhance the efficiency of palladium nanoparticles (Pd NPs) for the dehydrogenative coupling of organosilanes. As a result of this prominent surface wettability control, the modulated catalyst showed a significantly higher level of efficiency and durability characteristics toward the dehydrogenative condensation of organosilanes with water, alcohols, or amines in comparison to existing catalysts. In a broader context, this work illustrates a powerful approach to maximize the performance of supported metals through surface wettability modulation under catalytically relevant conditions.

Full text of DOI:10.1021/acscatal.6b03233

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Article
Wettability-Driven Palladium Catalysis for Enhanced
Dehydrogenative Coupling of Organosilanes
Jiandong Lin, Qingyuan Bi, Lei Tao, Tao Jiang, Yongmei Liu, Heyong He, Yong Cao, and Yangdong Wang
ACS Catal., Just Accepted Manuscript • DOI: 10.1021/acscatal.6b03233 • Publication Date (Web): 23 Jan 2017
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Wettability-Driven Palladium Catalysis for Enhanced
Dehydrogenative Coupling of Organosilanes
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Jian-Dong Lin,† Qing-Yuan Bi,‡ Lei Tao,† Tao Jiang,† Yong-Mei Liu,† He-Yong He,† Yong Cao,*,†
and Yang-Dong Wang*,§
† Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Department of Chemistry, Fudan
University, Shanghai 200433, People’s Republic of China
‡
State Key Laboratory of High Performance Ceramics and Superfine Microstructures, Shanghai Institute of
Ceramics, Chinese Academy of Sciences, Shanghai 200050, People’s Republic of China
§
SINOPEC Shanghai Research Institute of Petrochemical Technology, Shanghai 201208, China
ABSTRACT: Direct coupling of Si–H bond has emerged as a promising strategy for designing chemically and biologically
useful organosilicon compounds. Heterogeneous catalytic systems sufficiently active, selective, and durable for
dehydrosilylation reaction under mild conditions have been lacking to date. Herein, we report that the hydrophobic
characteristics of the underlying supports can be advantageously utilized to enhance the efficiency of palladium
nanoparticles (Pd NPs) for dehydrogenative coupling of organosilanes. As a result of this prominent surface wettability
control, the modulated catalyst showed a significantly higher level of efficiency and durability characteristics toward the
dehydrogenative condensation of organosilanes with water, alcohols, or amines as compared to existing catalysts. In a
broader context, this work illustrates a powerful approach to maximize the performance of supported metals through
surface wettability modulation under catalytically relevant conditions.
KEYWORDS: Dehydrocoupling, Organosilanes, Pd Nanoparticles, Heterogeneous Catalysis, Hydrophobicity
attractive DCC reagents to access various functionalized
organosilicon compounds serving both as highly useful
1. INTRODUCTION
The search for new robust solid catalysts for selective
building blocks or key intermediates for polymeric and
other advanced organic materials.6 To date, several effici-
chemical processes has spurred the onset of meticulous
design strategies along with ingenious synthesis of active
ent DCC strategies for silanes using hydrogen acceptors
phases (i.e., active sites).1 Alternatively, a facile and more
(i.e., oxidants) such as hydrogen peroxide and molecular
oxygen have been developed.7 From the viewpoint of
straightforward approach for catalyst tailoring lies in
modulating surface wettability such that the substrates–
catalyst interaction can be favorably manipulated in a
targeted and controlled manner.2 In this sense, one of the
most elegant examples is the enhanced activity and selec-
tivity of hydrophobic titanosilicate (TS-1) for the catalytic
oxidation of organic compounds using aqueous H2O2 as a
terminal oxidant.3 Recent progress in the understanding
of zeolite and zeotype solid acid materials with controlled
wettability has led to the successful development of a
plethora of benign acid-catalyzed processes for the produ-
ction of renewable chemicals within the biorefinery
context.4 Surprisingly, the potential offered by wettability
control in regulating the characteristics of supported
metal catalysts has remained largely unexplored,2c despite
the paramount importance of these materials in enabling
various imperative catalytic processes.
atom efficiency and safety perspectives, an acceptor-free
approach would be ideal. Advantageously, this may also
provide a convenient route for simultaneous H2 genera-
tion and storage.6d However, with the aim to maximize
the efficiency of organosilanes as DCC reagents, the inhe-
rently sluggish kinetics for Si–H cleavage must be circum-
vented.8 While several efficient homogeneous catalysts
have been developed,9 the corresponding heterogeneous
catalysts have generally displayed significantly lower effi-
ciencies despite the large number of attempts.10 With the
aim to overcome these issues, highly robust solid cataly-
sts able to significantly improve the reaction kinetics
under moderate conditions are thus urgently required.
Metallic palladium (Pd) is commonly used as an active
component in hydrolytic oxidation of organosilanes or
dehydrogenative silylation of alcohols at low temperature
and additive-free conditions.10a-c,14a However, heterogene-
ous Pd-based catalysts are typically limited by the low
affinity interaction between organosilanes and water or
alcohols, which hinders the efficiency of the desired
Dehydrogenative cross-coupling (DCC) reactions have
emerged as a promising tool to precisely construct new
C–X and X–X (X = heteroatom) bonds via direct C–H or
X–H activation.5 In this sense, organosilanes constitute
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(a)
(b)
(c)
(e)
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336.8
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d=2.0±0.1 nm
Pdδ+: 8%
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1.4 1.6 1.8 2.0 2.2 2.4
Particle size (nm)
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Binding energy(eV)
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(f)
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Binding energy (eV)
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(g)
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Pdδ+: 10%
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Binding energy (eV)
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(d)
(h)
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d=2.4±0.1 nm
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Pdδ+: 49%
0
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Particle size (nm)
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Figure 1. Transmission electron microscopy (TEM) images, particle distribution, and Pd 3d XP spectra of: (a, e)
Pd/XC-72; (b, f) Pd/XC-72-700-Ar; (c, g) Pd/XC-72-HNO3; and (d, h) Pd/XC-72-700-Ar stored for two years.
transformation process.10a,b Engineering metal–support
interfaces displaying strong enough interactions with the
reactants while weakly interacting with the products
would offer an opportunity for enhanced catalytic effici-
encies.2c,11 Although many studies have focused on regula-
ting the electronic structure of the supported Pd or
deliberately increasing the hydrophilic properties of the
underlying supports,10a-d,f-h,j-l,n a catalyst outperforming the
state-of-the-art homogeneous systems still remains elu-
sive. We report, for the first time, that the use of highly
hydrophobic carbon black (CB) as a support material can
significantly enhance the efficiency of Pd nanoparticles
(NPs) for dehydrogenative coupling of organosilanes. As a
result of a noticeable surface wettability modulation, the
engineered catalyst showed exceedingly enhanced activity
and durability toward dehydrogenative condensation of
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the recovered Pd/XC-72-700-Ar material was reused at
organosilanes with water, alcohols, or amines as
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8
compared to existing catalysts.
least ten times while maintaining its initial activity (i.e.,
total turnover number (TON) approached 8.0 × 105,
Figure S5). To the best of our knowledge, this result is far
superior to any reported example on hydrolytic oxidation
of organosilanes (Table S8).9,10
2. RESULTS AND DISCUSSION
To begin our studies on direct coupling of Si–H bond via
hydrolytic oxidation, we selected a series of commercial
CB as a supporting material for Pd NPs, anticipating that
the inherent hydrophobic nature of these materials would
have a positive impact on the outcome of the reaction.12
In an effort to explore and evaluate the possible wettabi-
lity effects via surface engineering, we opted for a syste-
matic approach to progressively impart surface hydropho-
bicity on the modified CB materials.12b This was achieved
by subjecting the as-received commercial CB materials to
an inert gas annealing treatment at elevated temperatures
(for details, see the Supporting Information). Analysis by
water and organosilane adsorption revealed an increased
hydrophobicity in the sample exposed to temperatures
above 300 oC, in contrast to the material treated with 32%
HNO3, which was shown to be particularly effective for
generating a highly hydrophilic surface (ca. five-fold incr-
ease in water adsorption along with an eight-fold decrease
in organosilane adsorption, Table S3). Essentially, the
increased hydrophobicity was associated with a lower
number of surface oxygenated species, as revealed by
infrared and X-ray photoelectron spectroscopy (XPS) ana-
lysis (Figures S2, S3). Subsequent wet-chemical reductive
processing13 of these wettability modulated CB materials
led to the decoration with narrowly size-distributed Pd
NPs (average size ca. 2 nm) having basically similar
chemical states and metal–support interface structure
(Figures 1, S1) on the surface of the carbon supports.
Table 1. Study of CB-supported Pd catalysts for the
dehydrocoupling of 1a and H2O.a
Et3Si–H (1a) + H2O → H2 + Et3Si–OH (1b)
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TOF
[h-1]c
Ent
ry
Time Yield
Catalystb
[s]
[%]
1
Pd/XC-72
Pd/BP2000
Pd/M800
Pd/660R
72
>99
97
510 800
299 900
396 800
247 100
583 600
645 300
(1686000d)
623 400
-
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3
4
5
119
90
146
97
98
Pd/XC-72-300-Ar 63
Pd/XC-72-700-Ar 57
Pd/XC-72-900-Ar 59
>99
6
>99
7
>99
n.d.
n.d.
99
8
XC-72-700-Ar
720
9e
10f
11
Pd/XC-72-700-Ar 720
Pd/XC-72-700-Ar 62
-
588 700
35 260
Pd/XC-72-HNO3
980
95
Pd/XC-72-HNO3-
400-Ar
12g
470
96
75 540
a
Reaction conditions: 5 mmol 1a, 0.5 mL water, 10 mL
THF, S/C = 10000, air atmosphere, 25 oC, n.d.= not
b
c
detected. The Pd loading was 1.0 wt %. Based on
total Pd atoms. d Based on surface Pd atoms, the disper-
sion was calculated from CO chemisorption measure-
Initial experiments dealing with the hydrolysis of
triethylsilane (1a) in THF at 25 C were promising and
o
suggested that CB-supported Pd NPs could certainly perf-
orm very well (Table 1, entries 1–4). The assessment of a
number of CB structures revealed that surface-engineer-
ed Vulcan XC-72 carbons were particularly effective
support classes, with the highly hydrophobic XC-72-700-
Ar (obtained via annealing at 700 oC under Ar atmosphere)
providing an outstanding dehydrogenative silylation
efficiency with the exclusive production of triethylsilanol
(1b) as a result of the reaction (Table 1, entries 5–7). As an
illustration of the efficiency of XC-72-700-Ar as a support,
Pd/XC-72-700-Ar with a palladium content of 1.0 wt %
achieved complete hydrolysis of 1a within 1 min at a
substrate-to-catalyst (S/C, molsub./molPd) ratio of 10000,
with a turnover frequency (TOF) of 1.6 × 106 h−1 for quanti-
tative 1a hydrolysis based on surface Pd atoms (Table 1,
entry 6). This catalytic system showed fast kinetics while
maintaining its activity for an extended period of time, as
inferred by monitoring the H2 release upon sequential
injection of 1a at intervals into a THF-H2O solution
containing Pd/XC-72-700-Ar.9d This result was remark-
able, and became more relevant as the H2 gas produced
using Pd/XC-72-700-Ar was easily controlled by slowly
and continuously injecting 1a into the catalytic system
(Figure S4). Furthermore, this system also worked well
under scale-up conditions (see Supporting Information).
For example, 50 mmol of 1a were successfully transformed
into 1b in nearly quantitative yield (> 99%). In this case,
e
ments. 5 mmol 1a, 10 mL dried THF, S/C = 10000, 25
f
oC. The catalyst was stored for two years at ambient
conditions. g The catalysts was obtained after post-heat
treatment of Pd/XC-72-HNO3 under Ar atmosphere.
Notably, this hydrolytic oxidation proceeded very
efficiently even under sub-ambient temperatures, albeit
the reaction rate significantly increased with temperature
(Table S1). The apparent activation energy (Ea) was
estimated to be 38.9 kJ mol-1 (Figure S6), which is lower as
compared to most of the previously reported systems.9f-h
The control experiments showed no reaction at all in the
absence of Pd species or in dried THF under identical
conditions (Table 1, entries 8 and 9), thereby confirming
that the Pd species serve as the active sites for this
reaction and the H2 gas is formed from 1a and water (i.e.,
water provides one H atom). With the aim to gain a
better understanding of the nature of the catalytic active
sites, a Pd/XC-72-700-Ar sample stored under air for a
two-year period was evaluated. Interestingly, the catalytic
activity remained nearly unchanged (Table 1, entry 10 and
Figure S7), although the relative fraction of surface PdO
in the air-stored sample, as confirmed by XPS, was signi-
ficantly larger as compared to its freshly prepared coun-
terpart (Figure 1h). This result excludes the possibility of
the particular surface chemical state of Pd NPs markedly
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influencing the activity, in contrast to recent studies when the surface of the catalyst is hydrophilic in nature.
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8
underlining the positive role of surface oxygenated Pd
species on the efficiency of the anaerobic hydrolytic
oxidation of organosilane.10b,c
Therefore, it seems that the favorable interaction between
the organosilane molecules and the underlying hydro-
phobic support can provide a unique driving force to sign-
ificantly decrease the activation barriers associated with
silane activation during the 1a transformation.
Apart from CB, various other carbon nanostructures
were also evaluated as supporting materials for the
hydrolysis of 1a. As shown in Table S2, Pd deposited on
carbon nanotubes (CNTs), activated carbon (AC), and
reduced graphene oxide (GO) nanosheets showed very
poor performance under identical reaction conditions,
although the content, shape, and size of the Pd species in
these samples were similar to those of Pd/XC-72-700-Ar
(Figure S1). It should be mentioned that Pd loaded on the
hydrophilic surface of modified XC-72-HNO3 also showed
very low activity toward hydrolysis of 1a (Table 1, entry 11).
All these observations indicate that the hydrophobicity of
the underlying support plays a key role in achieving high
dehydrocoupling capability in this process. With the aim
to clarify the role of the support wettability, the rate
dependence on the substrate concentration was studied.
The reaction orders with respect to 1a were 0.0 and +0.51
for Pd/XC-72-700-Ar and Pd/XC-72-HNO3 (Figure S8),
respectively, thereby indicating that the substrate was
more strongly adsorbed on the surface of Pd/XC-72-700-
Ar, and this tendency was also supported by comparing
the amount of adsorbed 1a for all the catalysts examined
(Table S3).
On a Pd-decorated hydrophobic surface, an excess of
surface metal coverage may disfavor the adsorption of
silanes at the microenvironment surrounding the Pd NPs,
thereby resulting in lower catalytic activities. In this sense,
a Pd loading of 1.0 wt % on XC-72-700-Ar was beneficial
to a cooperative metal-support interaction, as shown in
Figure S12. It was also noticed that a polar solvent (i.e.,
THF) played an important role in ensuring good miscibi-
lity of the organosilanes with water (Figure S13). When
compared with Pt, Ru, Rh, and Ir NPs supported on
XC-72-700-Ar as reference catalysts, Pd on hydrophobic
CB showed a unique activity for silane hydrolysis (Table
S6), thereby stressing the indispensable role of metallic
Pd in facilitating the crucial Si–H activation at conditions
relevant to dehydrogenative silylation. Meanwhile, Pd
catalysts supported on conventional solid oxides showed
very poor performance under identical conditions (Table
S6, entries 5–8), thereby showing that the coupling of
XC-72-700-Ar with Pd is essential for achieving a high
dehydrocoupling activity. Note that the use of hydropho-
bically-modified TiO2 (P25) and Al2O3 as supports resulted
in markedly enhanced dehydrocoupling activities (Table
S6, entries 9 and 10), further confirming that surface
hydrophobicity is imperative for this reaction system.
Nevertheless, in view of the significantly lower perform-
ance levels associated with the hydrophobically modified
mineral oxide supported systems, it is likely that the
modification of the electronic properties of surface ancho-
red Pd by the underlying support might also contribute to
the enhanced silane activation observed in the Pd-
decorated CB materials.
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The important role of support wettability in facilitating
the above Pd-mediated catalysis is further highlighted by
the fact that dramatic enhancement of catalytic activity
can be achieved by subjecting the hydrophilic Pd/XC-72-
HNO3 sample to a post-heat treatment in an inert atmo-
sphere (Table 1, entry 12). In line with the pristine CB
material case, annealing the Pd/XC-72-HNO3 smaple at
elevated temperatures also leads to an effective removal
of oxygen-containing surface functional groups, as verifi-
ed by the IR analysis as well as the organosilane and water
adsorption data (Figure S2 and Table S3). Additioal TEM
measurements shown in Figure S1 revealed an essentially
Pd/XC-72-700-Ar also showed high activity for hydroly-
tic oxidation of various organosilanes (Table 2). In this
sense, trialkylsilanes and aromatic silanes were effectively
o
equivalent Pd size (ca. 2.5 nm) for the 400 C-treated Pd/
XC-72-HNO3 samples. These facts, together with the evi-
dently enhanced activity registered for the similarly post-
heat treated Pd catalysts loaded on other carbon nanostr-
uctures (Table S2), strongly favor the suggestion that the
hydrophobicity of the underlying support is one of the
key factors in contributing the observed high activity.
Table 2. Dehydrocoupling of various silanes and H2O
over 1.0 wt % Pd/XC-72-700-Ar.a
R(4-n)Si–Hn + n H2O → R(4-n)Si–(OH)n + n H2
TOF
[h-1]b
Time
[min]
Yield
[%]
Entry
Silane
Having demonstrated the superiority of the surface mo-
dulation approach, we sought to further elucidate the
fundamental aspects underlying the wettability-driven
phenomenon. Considering that water is also involved in
1b formation, an additional set of experiments focused on
examining the dependence of 1a conversion on H2O con-
centration was undertaken. As opposed to the trends
observed with 1a concentration, the reaction rate was
found to be H2O insensative for both Pd/XC-72-700-Ar
and Pd/XC-72-HNO3 samples (Figure S9). Coupled with
the inherently low kinetic isotope kH/kD value of only ca.
1.1-1.2 observed for the reaction of 1a with H2O and D2O at
1
Et3SiH
1
>99
90
98
98
99
98
99
99
645 300
97 700
7164
2
Et2SiH2
6
3c
4
5
(i-Pr)3SiH
(n-Bu)3SiH
PhMe2SiH
Ph2MeSiH
Ph3SiH
21
2.4
3
263 500
213 200
27 500
2482
6
7c
8d
23
60
15
Et3SiH
628 400
a
Reaction conditions: 5 mmol silane, 0.5 mL water, 10
mL THF, S/C = 10000, air atmosphere, 25 oC. b Based on
o
total Pd atoms. S/C = 2500. d 50 mmol 1a, 5 mL water,
c
25 C (Table S4), these results indicate that the activa-
100 mL THF, S/C = 80000, air atmosphere, 25 oC.
tion of H2O is extremely facile, whereas the Si-H cleav-
age could be relatively slow.10b This is especially the case
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biomass,17 were also suitable substrates for this etherifi-
oxidized to their corresponding silanols without the
1
2
3
4
5
6
7
8
formation of any disiloxane products. It was noted that
the reactions involving less sterically hindered trialkylsi-
lanes proceeded significantly faster as compared to their
bulky counterparts (Table 2, entries 1 and 4). The same
reactivity trend was also observed upon increasing the
number of phenyl substituents on the organosilanes
(Table 2, entries 5–7). Remarkably, we attempted the
oxidation of sterically hindered triisopropylsilane which is
well known to be problematic (i.e., it requires either an
extensive reaction time of 24 h10d or low S/C ratio of 3310e).
In our case, a significantly shorter time of 20 min with a
high S/C ratio of 2500 was sufficient for the reaction until
completion. In addition, considerably higher organosilan-
ol yields were also obtained (via conversion of triphenylsi-
lane into triphenylsilanol) for Pd/XC-72-700-Ar (99%, 60
min) as compared to the previously reported supported-
gold catalyst (28%, 24 h).10d
cation (entries 6, 7), thereby further substantiating the
utility of this approach for Si–O–C bond construction
together with on-demand H2 generation.
Dehydrogenative condensation of organosilanes and
amines also represents one of the most attractive and
atom-economic synthetic approach to access silylamines,
an important class of silicon compounds that have been
widely used as silylation agents, ligands for organo-
metallic compounds, and precursors for Si and N
polymeric materials.18 Both homogeneous and heteroge-
neous catalysts have been reported for this reaction,19
although the control of the selectivity for Si–N coupling
has been proved to be challenging as the reaction can lead
to several products with different Si/N ratios (e.g.,
polysilazanes) as a result of multiple dehydrocoupling
steps. Remarkably, we found that Pd/XC-72-700-Ar can
robustly and selectively furnish the desired silylamines
(Scheme 1), with activities (TOF) being orders of
magnitude higher as compared to previously employed
catalysts for this transformation.19b,c,j As in the case of
hydrolytic and alcoholic oxidations of organosilanes (see
Tables 1 and 3), the hydrophobic Pd/XC-72-700-Ar
catalyst persistently showed a boosted efficiency as
compared to its hydrophilic counterpart (Table S7). To
the best of our knowledge, this hydrophobic-driven
catalysis represents the most efficient, simple, and eco-
friendly catalytic system to date achieving convenient and
controlled organosilane aminolysis (Table S10).
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Table 3. Production of various silyl ethers via dehy-
drocoupling of 1a and alcohol.a
n Et3Si–H (1a) + R(OH)n → (Et3Si-O)nR + n H2
TOF
[h-1]b
Time
[min]
Yield
[%]
Entry Alcohol
1
MeOH
1
>99
>99
>99
>99
99
619 300
230 400
24 930
208 100
346 500
48 230
4101
2
EtOH
2.7
25
3
3
i-PrOH
4
n-BuOH
benzyl alcohol
ethylene glycol
glycerol
5
1.8
3
6c
7d
8e
96
35
94
MeOH
53
99
11 570
a Reaction conditions: 20 mmol 1a, 30 mmol alcohol, 1.0
wt % Pd/XC-72-700-Ar, S/C = 10000, air atmosphere, 25
b
c
oC. Based on total Pd atoms. 10 mmol alcohol, S/C =
d
2500. Yield refers to the bis-silylation product. 6.7
o
mmol alcohol, S/C = 2500, 60 C. Yield refers to the
tri-silylation product. e 1.0 wt % Pd/XC-72-HNO3.
Given the superb reactivity observed for Pd/XC-72-700-
Ar toward silane hydrolysis, we were curious to check
whether this hydrophobic-driven Pd catalysis would be
also allow for the dehydrogenative condensation of organ-
osilanes with alcohols. As an alternative method for the
synthesis of valuable silyl ethers, this transformation has
recently attracted considerable attention9d,14 because of its
critical advantage over the conventional etherification
method, which suffers from several drawbacks associated
with the use of chlorosilanes15 or disilazanes.16 The results
presented in Table 3 indicate that it is possible to achieve
direct dehydrogenative alcoholysis of the organosilanes in
pure alcohols, with the efficiency of this process being
essentially comparable to that of silane hydrolysis. For
example, at a S/C ratio of 10000, the silyl ether produced
from 1a and MeOH was exclusively obtained over a period
of 1 min at 25 oC (corresponding to a TOF of 6 × 105 h−1 for
alcohol silylation, entry 1). Note that polyalcohols such as
ethylene glycol and glycerol, which can be derived from
Scheme 1. Production of various silylamines via dehydro-
coupling of 1a and amines over 1.0 wt % Pd/XC-72-700-Ar.
Reaction conditions: 5 mmol 1a, 5 mmol amine, 5 mL
dried THF, S/C=2500, Ar atmosphere, 60 oC.
3. CONCLUSIONS
In summary, the hydrophobic characteristics of the
underlying supports were favorably utilized for boosting
the efficiency of Pd NPs-catalyzed dehydrogenative coup-
ling of organosilanes. The catalytic activities obtained for
these dehydrogenative silylation reactions were, to our
knowledge, the highest reported to date. Our results
revealed the key role of the surface wettability modu-
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o
lation in maximizing the performance of supported noble
metals under catalytically relevant conditions. While the
reported system holds promise for the development of a
practical dehydrogenative silylation technology based on
Si–H activation, we believe that careful tuning of the
support wettability to meet reaction requirements will
open a new avenue for heterogeneous catalysis processes
mediated by supported metals.
at 25 C for 30 min under ambient atmosphere of air. The
adsorption amounts were determined by changes of 1a
concentrations monitored by GC using ethylbenzene as
an internal standard according to the previous report.20
1
2
3
4
5
6
7
8
4.5. Alcoholysis of organosilanes in an open system.
1a (20 mmol) and alcohol were mixed in a reaction vessel
under steady magnetic stirring (800 rpm) at given tempe-
rature under air atmosphere, which is connected to an
automatic gas burette. The reaction was started by the
addition of a certain amount of catalyst. In addition, the
evolved gas was qualitatively and quantitatively analyzed
by Agilent 6820 GC equipped with a TDX-01 column
connected to a TCD. Catalyst was centrifuged and the
yield of corresponding silyl ether was analyzed by Agilent
7820A GC equipped with a HP-5 column connected to a
FID using bibenzyl as an internal standard. Identification
of the products was performed by NMR analyses. The
initial TOF was calculated on the organosilanes conver-
sion at 15%.
9
4. EXPERIMENTAL SECTION
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4.1. Hydrolysis of organosilanes in an open system.
All catalytic experiments were carried out under ambient
atmosphere of air, unless otherwise stated, the reactions
were performed in a double-walled thermostatically
controlled reaction vessel with a reflux condenser, which
is connected to an automatic gas burette, where the gases
are collected. Silane and H2O (or D2O) were mixed with 10
mL THF in a reaction vessel under steady magnetic stirr-
ing (800 rpm) at given temperature (17–33 oC). The
reaction was started by the addition of a certain amount
of catalyst. In addition, evolved gas was qualitatively and
quantitatively analyzed by Agilent 6820 GC equipped
with a TDX-01 column connected to a TCD. Catalyst was
centrifuged and the yield of corresponding organosilanol
was analyzed by Agilent 7820A GC equipped with a HP-5
column connected to a FID using ethyl-benzene as an
internal standard. Identification of the products was perf-
ormed by using a GC-MS spectrometer. The initial TOF
was calculated on the organosilanes conversion at 15%.
4.6. Aminolysis of organosilanes in an open system.
1a (5 mmol), amine (5 mmol), dried THF (5 mL) and a
certain amount of catalyst were mixed in a reaction vessel
o
under steady magnetic stirring (800 rpm) at 60 C under
Argon atmosphere with a reflux condenser, which is
connected to a drying tube and an automatic gas burette.
In addition, the evolved gas was qualitatively and
quantitatively analyzed by Agilent 6820 GC equipped
with a TDX-01 column connected to a TCD. Catalyst was
centrifuged and the yield of corresponding silylamine was
analyzed by Agilent 7820A GC equipped with a HP-5
column connected to a FID using naphthalene as an
internal standard. The product was isolated by distillation
and identified by NMR analyses. The initial TOF was
calculated on the organosilanes conversion at 15%.
4.2. Generation of hydrogen on-demand using 1
wt % Pd/XC-72-700-Ar as catalyst. H2O (2.5 mL) and
Pd/XC-72-700-Ar (S/C = 2500) were mixed with 50 mL
THF in a two-neck flask under steady magnetic stirring
o
(800 rpm) at 25 C, which is connected to an automatic
gas burette. The flask was sealed with an injector connec-
ted to an injection pump. For the stepwise hydrolysis
process, 1a (25 mmol) was sequentially injected into the
flask at intervals until the 1a was fully consumed. For the
continuously controllable hydrolysis process, 1a (25
mmol) was continuously injected into within 27 min until
the 1a was fully consumed. In addition, the evolved gas
was qualitatively and quantitatively analyzed by Agilent
6820 GC equipped with a TDX-01 column connected to a
TCD.
4.7. Characterization. The metal loading was meas-
ured by inductively coupled plasma atomic emission
spectroscopy (ICP-AES) using a Thermo Electron IRIS
Intrepid II XSP spectrometer. The BET specific surface
areas of the prepared catalysts were determined by
adsorption–desorption of nitrogen at liquid nitrogen
temperature, using a Micromeritics TriStar 3000 equip-
ment. Sample degassing was carried out at 300 oC prior to
acquiring the adsorption isotherm. The crystal structures
were characterized with X-ray diffraction (XRD) on a
Bruker D8 Advance X-ray diffractometer using the
Ni-filtered Cu Kα radiation source at 40 kV and 40 mA.
XPS data were recorded with a Perkin Elmer PHI 5000C
system equipped with a hemispherical electron energy
analyzer. The spectrometer was operated at 15 kV and 20
mA, and a magnesium anode (Mg Kα, hν = 1253.6 eV) was
used. The C 1s line (284.6 eV) was used as the reference to
calibrate the binding energies (BE). The Fourier transform
infrared spectroscopy (FT-IR) spectra were recorded by a
Nicolet iS10 FT-IR spectrometer equipped with a DTGS
detector, in the range 400 – 4000 cm-1, by applying an
optical resolution of 0.4 cm-1. The samples were investi-
gated by using the KBr pellet technique. A JEOL 2011
microscope operating at 200 kV equipped with an EDX
unit (Si(Li) detector) was used for the TEM investigations.
The samples for electron microscopy were prepared by
grinding and subsequent dispersing the powder in
4.3. Large-scale durability of 1 wt % Pd/XC-72-700-
Ar catalyst for hydrolysis of 1a. 1a (50 mmol) and water
(5 mL) were mixed with 100 mL THF in a reaction vessel
(250 mL) under steady magnetic stirring (800 rpm) at 25
oC, which is connected to an automatic gas burette. The
reaction was started by the addition of Pd/XC-72-700-Ar
(S/C = 80000). After the reaction completed, the centr-
ifuged catalysts from parallel activity tests were collected
and washed with distilled water, followed by drying in air
at 100 oC for 12 h. All catalytic activity tests were
repeatedly carried out by following the same procedure as
described above.
4.4. Triethylsilane adsorption ability of various
supports. Various supports (0.5 g) were placed in a
o
Schlenk tube and pretreated at 150 C under outgassing
for 30 min, followed by the addition of 1a (5 mmol), H2O
(0.5 mL) and THF (10 mL). Then the mixtures were stirred
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(5) (a) Li, C.-J. Acc. Chem. Res. 2009, 42, 335-344. (b) Scheue-
ethanol and applying a drop of very dilute suspension on
1
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8
rmann, C. J. Chem. Asian J. 2010, 5, 436-451.
carbon-coated grids. The size distribution of the metal
nanoparticles was determined by measuring about 200
random particles on the images. n-hexane or H2O
adsorption experiment was performed at 25 C on a BEL
SORP-max adsorption instrument. The adsorption
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o
amount of n-hexane or H2O was recorded at the saturated
o
vapor pressure of n-hexane (25 C, 20.16 KPa) or H2O (25
oC, 3.169 KPa). Pd surface area was measured by CO
chemisorptions using AutoChem HP 2950 apparatus with
quantitative loop from Micromeritics. The sample was
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first pretreated with 5 vol % H2/Ar at 200 C for 2 h, and
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o
then pure CO was pulsed over the sample at 25 C for
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several times to saturated adsorption. The total amount of
CO adsorbed was measured by assuming a chemisorption
stoichiometry of CO/Pd=1 and a Pd surface atomic density
of 1.27×1019 m−2.21 The dispersion (D) was calculated
according to the formula of D = (surface number of Pd
atoms)/(total number of Pd atoms).
ASSOCIATED CONTENT
The Supporting Information is available free of charge on the
ACS Publication website at DOI: xx.xxxx/acscatalxxxxxxx
Experimental details of the catalyst preparation, TEM
data, FT-IR data, adsorption capacity study, XPS data,
optimization of reaction conditions, kinetic experiments,
spectral parameters, and NMR data of products (PDF)
AUTHOR INFORMATION
Corresponding Author
* Email: yongcao@fudan.edu.cn
* Email: wangyd.sshy@sinopec.com
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was supported by National Natural Science
Foundation of China (21273044, 21473035, 91545108), Science
&
Technology Commission of Shanghai Municipality
(16ZR1440-400), SINOPEC (X514005) and the Open project of
State Key Laboratory of Chemical Engineering
(SKL-ChE-15C02).
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139x125mm (150 x 150 DPI)
ACS Paragon Plus Environment

ACS Catalysis
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167x141mm (300 x 300 DPI)
ACS Paragon Plus Environment