The facile approach to fabricate gold nanoparticles and their application on the hydration and dehydrogenation reactions

Article abstract of DOI:10.1016/j.jorganchem.2017.09.016

A mild and practical strategy to prepare gold nanoparticles was developed. This gold particles supported mesoporous silica was fabricated from AuPPh₃Cl under mild conditions and characterized through transmission electron microscopy, energy dispersive X-ray, X-ray power diffraction and X-ray photoelectron spectrometry. Interestingly, it was observed that this gold nanoparticle was effective to the hydration of alkynes and dehydrogenation of alcohols. The catalytic system can tolerate a variety of functional groups to afford the corresponding products in good to excellent yields.

Full text of DOI:10.1016/j.jorganchem.2017.09.016

Accepted Manuscript
The facile approach to fabricate gold nanoparticles and their application on the
hydration and dehydrogenation reactions
Ronghui Huang, Yong Fu, Wei Zeng, Liang Zhang, Dawei Wang
PII:
S0022-328X(17)30536-3
10.1016/j.jorganchem.2017.09.016
JOM 20091
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 1 August 2017
Revised Date: 2 September 2017
Accepted Date: 6 September 2017
Please cite this article as: R. Huang, Y. Fu, W. Zeng, L. Zhang, D. Wang, The facile approach to
fabricate gold nanoparticles and their application on the hydration and dehydrogenation reactions,
Journal of Organometallic Chemistry (2017), doi: 10.1016/j.jorganchem.2017.09.016.
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ACCEPTED MANUSCRIPT
Journal of Organometallic Chemistry (2017)
Contents lists available at SciVerse ScienceDirect
Journal of Organometallic Chemistry
journal homepage:www.elsevier.com/locate/jorganchem
The facile approach to fabricate gold nanoparticles and their
application on the hydration and dehydrogenation reactions
a
a,c
a,d
b
a
Ronghui Huang, Yong Fu, Wei Zeng, Liang Zhang,* and Dawei Wang*
a
Key Laboratory of Synthetic and Biological Colloid, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University,
Wuxi 214122, China.
b
National Engineering Laboratory for Cereal Fermentation Technology, Jiangnan University, Wuxi 214122, China.
Hangzhou Qingyue Pharmaceutical Technology Co. Ltd., Xixi Road Hangzhou, Zhejiang Province, China.
Dalian Wondersun Biochemical Technology Co. LTD. Double D4 street, Development zone, Dalian 116600, Liaoning Province, China.
c
d
Email: wangdw@jiangnan.edu.cn, zhangl@jiangnan.edu.cn, Tel./fax: +86 510 85917763
a r tic l e
i
n f o
a b s t r a c t
Article history:
Received
Received in revised form
Accepted
A mild and practical strategy to prepare gold nanoparticles was developed. This gold
particles supported mesoporous silica was fabricated from AuPPh Cl under mild
3
conditions and characterized through transmission electron microscopy, energy
dispersive X-ray, X-ray power diffraction and X-ray photoelectron spectrometry.
Interestingly, it was observed that this gold nanoparticle was effective to the hydration of
alkynes and dehydrogenation of alcohols. The catalytic system can tolerate a variety of
functional groups to afford the corresponding products in good to excellent yields.
Keywords:
gold
dehydrogenation
triphenylphosphine
nanoparticle
catalysis
2017 Elsevier B.V. All rights reserved.
tolerate a variety of functional groups to afford the
corresponding products.
1
. Introduction
During the past few decades, noble-metallic nanoparticles
Our interest in gold catalysis was initiated by triazole
ligands or NCAs (non-coordinating anions), which greatly
tuned and changed the catalytic activity of gold catalysts in
allene synthesis and borrowing hydrogenation reactions.[7]
However, it was found that it couldn’t recover these gold and
iridium catalysts. For the sake of sustainable development
and environmental friendly nature, we tuned our interest to
the recyclable gold catalysts with high catalytic activity. In
the beginning, SBA-15 was selected as the carrier to prepare
gold catalyst with classical method.[8] However, only low
yield of hydration product was achieved, when the prepared
gold nanoparticles from chloroauric acid or potassium
chloraurate were used. Interestingly, it is pleased that the gold
have drawn great interest due to their fine electronic, optical,
and catalytic properties.[1] These supported gold
nanoparticles exhibited favorable catalytic activity such as in
the classical CO oxidation, VOCs (Volatile Organic
Compounds) oxidation, PROX (Preferential Oxidation)
reaction of CO in hydrogen, and so on.[2] Traditionally,
supported gold nanoparticles were prepared from XAu(III)Cl4
(
X = H, Na, K) under reducing atmosphere condition.[3-5]
Considering the importance of the methyl ketone and
hydroxy methyl ketone functional group in organic synthesis
and medicinal chemistry,[6] we conducted an attempation to
the direct alkyne hydration to synthesis of ketones with
SBA-15 supported gold nanoparticles as the catalyst.
However, the desired product was obtained with low yield
even through a series of conditions screeningIn this paper, we
developed an easy and practical strategy to prepare SBA-15
supported gold nanoparticles, which were synthesized from
nanoparticles, fabricated from AuPPh OTf under mild
3
conditions, showed enhanced catalytic activity in the
hydration of alkynes.
2
. Results and Discussion
Au(I)PPh Cl under mild conditions. Interestingly, it was
3
observed that this phosphorus-involved gold nanoparticle was
effective to the hydration of alkynes, and the
dehydrogenation of alcohols. The catalytic system can
2
.1 Materials
All the chemicals (starting materials) were used without
further distillation or purification. De-ionized water was used
1

ACCEPTED MANUSCRIPT
in all the experiments. Boranetertbutylamine complex (97%),
Results and discussion
triphenylphosphine (98%), alkynes, alcoholes were purchased
from Energy Chemical, SBA-15 were purchased from
Nanjing JI Cang Nano Technology Co. Ltd, toluene,
chloroform, EtOH were purchased from Sinopharm Chemical
Reagent Co., Ltd (China).
3.1. Characterization of the Au@ SBA-15 catalyst
The structural characteristices of the synthesized catalyst
could be observed diametrically from the transmission
electron microscopy (TEM). As shown in Fig.1a and Fig.1b,
it was observed the gold particles supported mesoporous
silica with a few particles. In addition, Fig.1c and Fig.1d
showed a maximum number of size between 4-7 nm.
2
.2 Synthesis of AuPPh Cl
3
PPh (524 mg, 2.0 mmol) was dissolved in EtOH (8 mL) at
3
o
8
0 C and then slowly added to HAuCl ·4H O (412 mg, 1.0
4
2
mmol) in EtOH (5 mL). The mixture was stirred for 0.5 h
after the color changed from yellow to white. The crude
product was filtered under reduced pressure. Then, the white
solid was dissolved in 5 mL DCM and reprecipitated with 50
mL petroleum ether to give the pure product (Yield: 87%).
2
.3 Synthesis of Au nanoparticles
A solution of AuPPh Cl (495 mg, 1.0 mmol) was mixed
3
with dodecanethiol (0.5 mL) in toluene (100 mL) to form a
clear solution. Then, boranetertbutylamine complex (870 mg,
(a)
(b)
1
0 mmol) were added to above solution. The mixture was
12
stirred at 55 ºC for 1 hour before it was cooled to rt (room
temperature). Later, EtOH (100 mL) was added to the
mixture, and gold nanoparticles were precipitated out.. The
black gold nanoparticles were got by centrifuge and washed
with EtOH for three times. Finally, the product was dried
under vacuum condition.
120
100
80
60
40
20
0
1
0
8
6
4
2
0
3
4
5
6
7
8
3
4
5
6
7
8
2
.4 Synthesis of Au@ SBA-15
Diameter(nm)
Diameter(nm)
To a 50 mL round-bottom bottle, Au nanoparticles (10 mg),
(c)
(d)
SBA-15 (500 mg) and chloroform (30 mL) was added.The
mixture solution was stirred for 1 h at rt (room temperature).
Then the solvent was removed by centrifugation and the
product was washed several times. Finally, the solid was
dried in Freeze-dryer for 12 h to give Au@SBA-15 (2 wt.%).
Au@SBA-15 (8 wt.%) was also synthesized with Au
nanoparticles (30 mg), SBA-15 (500 mg) and chloroform (50
mL) in a 100 mL round-bottom bottle.
Fig. 1. TEM images of (a) Au@SBA-15 (0.8 wt.%), (b) Au@
SBA-15 (6 wt.%), (c) particles size distribution as figure out from (a)
of Au@SBA-15 (0.8 wt.%), (d) particles size distribution as figure
out from (b) of Au@SBA-15 (6 wt.%).
Fig. 2 showed the X-ray power diffraction (XRD) pattern
of Au@SBA-15, the peak in the 2θ region of 15°-30° was
attributed to mesoporous silica and exhibited diffraction lines
at 77.6°, 64.6°, 44.4° and 38.2° assigned to the (311), (220),
2
.5 Dehydrogenation of alcohols
(
200) and (111) crystal faces of Au nanoparticles.
Benzyl alcohol (108 mg, 1.0 mmol), Au@SBA-15 (6 wt.%,
0 mg) and K CO (829 mg, 6.0 mmol) was dissoveled in
No other impurity diffraction peak has been observed.
2
2
3
toluene (6.0 mL), the reaction mixture was stirred for 12 h at
In addition, X-ray photoelectron spectrometry (XPS) was
measured to characterize the chemical elements on the
surface of Au@SBA-15. As shown in the Fig. 3, XPS
full-scan spectrum for the synthesized catalyst revealed the
presence of elements such as Au, O, C and Si, which provides
an efficient proof for the Au nanoparticles supported by
mesoporous silica. Furthermore, the spectral peak at binding
energy 87.68 and 83.98 eV for the Au4f5/2 and Au4f7/2
o
110 C. It was monitored by TLC. After the reaction was
completed, the solvent was removed under reduced pressure
and purified of the crude product by column chromatography
on silica-gel afforded the title compound.
2
.6 Hydration of alkynes
To a 25 mL Schlenk tube, Au@SBA-15 (6 wt.%, 20 mg),
AgOTf (0.05 mmol) was added to
a
solution of
1+
levels in the Fig. 4, indicated most of the Au ions were
reduced by boranetertbutylamine complex.
phenylacetylene (1.0 mmol) in HOAc/H O (3.0 mL, 15:1)
2
under ambient air, the resulting mixture was stirred for 6 h at
o
1
10 C. It was monitored by TLC. After the reaction was
completed, the solvent was removed under reduced pressure
and purified of the crude product by column chromatography
on silica-gel afforded the desired compound.
2

ACCEPTED MANUSCRIPT
With these Au@SBA-15 catalysts in hand, the standard
oxidation reaction of alcohols was first explored to examine
this catalyst. To our pleasure, the aldehyde product was
smoothly achieved in 72% yield (Table 1, entry 1). For a
better yield, the reaction conditions screening was conducted
and the results were concluded in Table 1. First, the bases
such as Cs CO , NaOH, tBuOK, NEt were tested and the
Au@SBA-15(0.8 wt.%)
Au@SBA-15(6 wt.%)
(
111)
2
3
3
results showed the yields ranged from 34 to 92% (Table 1,
entries 1-5). Next, solvent screening indicated that toluene is
the best solvent, while other solvents like DCM, MeOH,
EtOH, dioxane, THF and MeCN gave the yields from 11 to
(200)
(311)
(220)
4
2% (Table 1, entries 6-11). Additionally, the control
1
0
20
30
40
50
60
70
80
90
experiments were conducted without catalyst or base,
however, no desired product was detected (Table 1, entries
2θ(degree)
1
2-13).
Fig. 2. XRD pattern of Au@SBA-15.
a,b
Table 1. Optimization of reaction conditions
O1s
b
Entry
Catalyst
Base
Solvent
Yield[%]
1
2
3
4
5
6
7
8
9
Au@SBA-15
Au@SBA-15
Au@SBA-15
Au@SBA-15
Au@SBA-15
Au@SBA-15
Au@SBA-15
Au@SBA-15
Au@SBA-15
Au@SBA-15
Au@SBA-15
-
Cs CO3
toluene
toluene
toluene
toluene
toluene
DCM
MeOH
EtOH
Dioxane
THF
72
63
65
34
92
21
17
11
42
14
27
<5
<5
2
NaOH
tBuOK
NEt3
K CO3
2
K CO3
2
K CO3
2
Si2p
K CO
2 3
Si2s
Au4f
O2s
K CO3
C1s
2
1
1
0
1
K CO3
2
1
000
800
600
400
200
0
K CO3
MeCN
toluene
toluene
2
Binding energy(eV)
1
1
2
3
-
-
K CO3
2
a
Reagents and conditions: 1a (1.0 mmol), catalyst (6 wt.%, 20 mg),
K CO (6.0 mmol), toluene (6.0 mL), air, 12 h, reflux. Based on
GC.
b
2
3
Fig. 3. XPS wide-scan spectrum of Au@SBA-15.
Next, other alcohols were investigated under the best
reaction conditions, the results were shown in Table 2. Most
of the alcohols were transformed into the corresponding
aldehydes in good to high yields. Meanwhile, it is worth
noting that the substrates with electron-donating and
electron-withdrawing groups had light effect for this reaction.
When (2-nitrophenyl)methanol was tested, only moderate
yield was achieved. Interestingly, good result could be
obtained with 2-thiophenemethanol as the substrate.
Au 4f7/2
Au 4f5/2
Table 2. Substrate expansion of dehydrogenation of alcohols
a,b
100
98
96
94
92
90
88
86
84
82
80
Binding energy(eV)
Fig. 4. High-resolution spectrum of Au4f.
3

ACCEPTED MANUSCRIPT
CHO
OH
Au@SBA-15
R
R
K2CO3, Toluene, Air
The functionalized ketones represent an important
1
2
class of organic materials and intermediates.[9] In order
to demonstrate the importance of Au nanoparticles
supported on mesoporous silica, the hydration reaction of
phenylacetylene was explored. As shown in Table 3, this
reaction could be performed smoothly in presence of
gold nanoparticles and the corresponding products were
isolated in good to high yields. It should be noted
non-coordinating anion could slightly enhance the yields
of hydration of alkynes (see Table S1 in Supporting
Information for details), which was supported by
CHO
CHO
CHO
NO2
CHO
I
2
a: 92%
2b: 87%
2c: 89%
2d: 61%
CHO
CHO
CHO
OMe
CHO
Cl
O2N
2
e: 88%
2f: 87%
CHO
2g: 64%
CHO
2h: 90%
CHO
S
CHO
previous
results
[10].
The
alkynes
with
Cl
MeO
t-Bu
electro-withdrawing or electron-donating on the aromatic
ring almost produced the same results.
2
i: 86%
2j: 91%
2k: 89%
2l: 85%
CHO
CHO
CHO
CHO
Recycling
Br
F
Br
To a 25 mL Schlenk tube, Au@SBA-15 (6 wt.%, 40 mg),
2m: 84%
2n: 83%
2o: 87%
2p: 90%
AgOTf (0.05 mmol) was added to
a
solution of
a
Conditions: 1 (1.0 mmol, 1.0 equiv.), Au@SBA-15 (6 wt.%, 20
phenylacetylene (2.0 mmol) in HOAc/H O (6.0 mL, 15:1)
2
b
mg), K CO (6.0 mmol, 6.0 equiv.), toluene (6.0 mL), air, 12 h.
Based on GC.
2
3
under ambient air, the resulting mixture was stirred for 6 h at
o
1
10 C. After centrifugation, the recovered catalyst was dried
in Freeze-dryer. The hydration of alkynes reaction was
carried out for next time with the recovered catalyst from the
frontal reaction. Generally, it was pleased to find that the
reaction could perform even five times, although a slightly
reduced yield was achieved (Fig. 5). To better illustrate this
catalyst, XRD experiment was investigated to test the
recovered gold catalyst and the result revealed that almost no
loss of gold in the supporters were observed (Fig. 6).
a,b
Table 3. Substrate expansion of hydration of alkynes
O
Au@SBA-15, AgOTf
HOAc/H2O, 110 o
R
C
R
3
4
O
O
O
O
O2N
4a: 90%
4b: 93%
4c: 88%
4d: 91%
100
O
O
O
O
MeO
80
S
MeO
6
4
2
0
0
0
0
4
e: 90%
4g: 90%
4h: 92%
4
f: 94%
O
O
O
O
OMe
i: 92%
F
NO2
4l: 87%
4
4j: 90%
4k: 91%
O
O
O
O
1
2
3
4
5
Runs
Cl
Cl
Br
O2N
4
m: 85%
4n: 88%
4o: 86%
4p: 90%
Fig. 5. Recyclability of Au@SBA-15 in the dehydrogenation of
O
O
alcohols reaction.
F
4q: 87%
4r: 89%
a
Conditions: 3 (1.0 mmol, 1.0 equiv.), Au@SBA-15 (6 wt.%, 20
b
mg), AgOTf (5.0 mol%.), HOAc/H O (3.0 mL, 15:1), 6 h. Isolated
2
yields based on 3.
4

ACCEPTED MANUSCRIPT
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fabricated from AuPPh Cl under mild conditions. It is worth
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hydration of alkynes and dehydrogenation of alcohols.
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Acknowledgements
We gratefully acknowledge financial support of this
work by the National Natural Science Foundation of
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Graphical abstract
The facile approach to fabricate gold nanoparticles and their
application on the hydration and dehydrogenation reactions
a
a,c
a,d
b
a
Ronghui Huang, Yong Fu, Wei Zeng, Liang Zhang,* and Dawei Wang*
a
Key Laboratory of Synthetic and Biological Colloid, Ministry of Education, School of Chemical and Material
b
Engineering, Jiangnan University, Wuxi 214122, China. National Engineering Laboratory for Cereal
c
Fermentation Technology, Jiangnan University, Wuxi 214122, China. The Research Academy of Jiangsu Hansoh
Pharmaceutical Group Co., Ltd., Dongjin Road, Huaguoshan Avenue, Lianyungang 222069, Jiangsu Province,
d
China. Dalian Wondersun Biochemical Technology Co. LTD. Double D4 street, Development zone, Dalian
116600, Liaoning Province, China.
Email
：wangdw@jiangnan.edu.cn, zhangl@jiangnan.edu.cn, Tel./fax: +86 510 85917763
ABSTRACT: A mild and practical strategy to prepare gold nanoparticles was developed. This
mesoporous silica-coated gold nanoparticle was fabricated from AuPPh Cl under mild conditions
3
without high temperature and characterized through transmission electron microscopy (TEM), energy
dispersive X-ray (EDX), X-ray power diffraction (XRD) and X-ray photoelectron spectrometry (XPS).
Interestingly, it was observed that this gold nanoparticle was effective to the hydration of alkynes and
dehydrogenation of alcohols. The catalytic system can tolerate a variety of functional groups to afford
the corresponding products in good to excellent yields.
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ACCEPTED MANUSCRIPT
•
•
•
A mild and practical strategy to prepare gold nanoparticles
Gold particles supported silica was fabricated from AuPPh
3
Cl
This gold nanoparticle was effective to hydration and dehydrogenation