A route for direct transformation of aryl halides to benzyl alcohols: Via carbon dioxide fixation reaction catalyzed by a (Pd@N-GMC) palladium nanoparticle encapsulated nitrogen doped mesoporous carbon material

Article abstract of DOI:10.1039/c6gc01038e

A nitrogen doped mesoporous carbon material was synthesized from glucose and melamine under hydrothermal treatment. A soft template, Brij-35 was used as a template. A nitrogen containing high surface area and porous channels makes this material an important support for palladium nanoparticles as well as a carbon dioxide capturing agent. Ethylene glycol was used as a reducing agent for the palladium nanoparticle synthesis. The palladium nanoparticle embedded porous nitrogen doped carbon material (Pd@N-GMC) was used for the synthesis of benzyl alcohols from aryl iodides via carbon dioxide fixation reaction. The catalyst was highly stable and reusable without any significance loss of its activity.

Full text of DOI:10.1039/c6gc01038e

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A Route for Direct Transformation of Aryl Halides to Benzyl
Alcohols via Carbon Dioxide Fixation Reaction Catalyzed By
(Pd@N-GMC) Palladium Nanoparticles Encapsulated Nitrogen
Doped Mesoporous Carbon Material
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx0
www.rsc.org/
Rostam Ali Molla,a Md. Asif Iqubal,b,‡, Kajari Ghosh,a,‡, S. M. Islam*a
Abstract
A nitrogen doped mesoporous carbon material was synthesized from glucose and melamine under hydrothermal
treatment. Soft template, brij-35 was used as a template. Nitrogen containing high surface area and porous channels make
this material an important support for palladium nanoparticles as well as carbon dioxide capturing agent. Ethylene glycol
was used as a reducing agent for the palladium nanoparticles synthesis. The palladium nanoparticles embedded porous
nitrogen doped carbon material (Pd@N-GMC) was used for the synthesis of benzyl alcohols from aryl iodides via carbon
dioxide fixation reaction. The catalyst was highly stable and reusable without any significance loss of its activity.
conversion of carbon dioxide to alcohol synthesis is limited to
methanol only. Synthesis of higher carbon chain alcohol via C-C
coupling between substrate and CO2 is highly desirable. In this
context literature study revealed that Yasushi Tsuji et al reported a
methodology for the synthesis of homoallylic alcohols from allenes
using CO2 and hydrosilanes as a hydroxymethyl (CH2OH) source and
homogeneous CuCl was used as a catalyst.4c
1. Introduction
In recent years, synthesis of value-added products from carbon
dioxide (CO2) has attracted much interest.1 CO2 is a more green and
economical C1 source than carbon monoxide (CO) because CO2 is
non toxic, cheap, easy to handle, renewable and environmental
friendly.2 Activation of CO2 and consequently CO2 transformation of
activated form of CO2 to chemicals is highly challenging due to high
stability of CO2.3 Up till now, several works have been reported on
CO2 involved chemical conversion. So far carbon dioxide was used
for the synthesis of cyclic carbonate, aldehyde, carboxylic acid,
alcohols and many others important value added chemicals.4
Previously benzyl alcohols were prepared from benzaldehyde or
benzoic acid via hydrogenation.9 Several medicinally important
compounds can be prepared from benzyl alcohols such as aliskiren
and gastrodin.10 To the best of our knowledge there is no report on
direct transformation of aryl halides to benzyl alcohols via CO2
fixation reaction. Thus, we are first to report
a new green
methodology for addition of hydroxymethyl (CH2OH) group onto
aryl halides using CO2 and hydrosilane as a hydroxymethyl (CH2OH)
source, catalyzed by newly prepared Pd nanoparticles embedded
nitrogen doped carbon material.
Reduction of carbon dioxide to lower oxidation level using green
methodology is a current challenge. Several metal based catalysts
have been reported for the reduction of CO2 where hydrogen was
used as reducing agent.5 Handling of high pressure of H2 and CO2
gases are very tough. Thus researchers have found another way to
reduce CO2 using ZnEt2, AlEt3, and hydrosilanes as a reducing
agent.6 Very recently hydrosilanes were used for the formylation of
amines and aryl halide via reduction of CO2. In these reports, CO2
was converted to the aldehyde oxidation level.7 Baba et al. and
other groups reported the methodology of conversion of CO2 to
formic acid using hydrosilanes.6e On the other hand, CO2 was
successfully converted to methanol (alcohol) using various
homogeneous and heterogeneous based catalyst.8 Uptill now,
On the other hand, the material that has been used as a catalyst
(Pd@N-GMC) is also the first report where nitrogen doped porous
material is used as novel support produced from biomass derived
glucose as a carbon source and melamine as a nitrogen source and
brij-35 was used as a soft template.
Nitrogen doped porous material attracted massive attention as a
support of various nanoparticles and has also been used in the field
of sensing, drug delivery, adsorption and CO2 sequestration.11
Introduction of nitrogen atoms in the carbon material increased the
basicity of the material. Simultaneously, presence of nitrogen atom
in the carbon materials improved the coordinating property which
increased the stability of nanoparicles present in nitrogen doped
carbon materials. Furthermore a well-planned nitrogen doped
carbon material for the carbon dioxide capture and conversion
should have certain necessary characteristics, such as appropriate
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CHO
specific surface area and surface high stability, as well as a handy
porosity. These properties of nitrogen doped carbon materials
improved the catalytic activity. Till now numerous nitrogen doped
carbon materials were reported using hard, soft template or
without template.12 Nitrogen doped carbon from biomass
derivatives as a carbon source is highly desirable from point view of
economical and green prospective. The amount of nitrogen present
in the material leads the performance of these materials. When
moderate amount of nitrogen is present in the nitrogen doped
carbon material, it increases the interaction with carbon dioxide.
NH2
Brij-35
H
HO
H
OH
H
(Template)
N
N
+
OH
H2SO4
H2N
N
NH2
H
OH
CH2OH
Melamine
Nitrogen Source
Glucose
Carbon source
Calcined
Keeping all these factors in mind we have synthesized a novel
nitrogen doped carbon material (N-GMC) from glucose and
melamine using soft template (brij-35) under hydrothermal
treatment. Palladium nanoparticles are doped into porous nitrogen
doped carbon material and as the prepared material is porous in
nature and contained nitrogen atoms in its porous channel, small
sized nanoparticles are well distributed and highly stabilized. The
material (Pd@N-GMC) is used as catalyst for the direct synthesis of
benzyl alcohols from aryl halides using carbon dioxide and
hydrosilane as -CH2OH source.
PdCl2
Ethylene glycol
Pd NPs
Nitrogen doped Carbon N-GMC
Pd@N-GMC
2. Experimental Section
Scheme 1 Schematic illustration of the synthesis process of Pd@N-
2.1 Synthesis of nitrogen doped mesoporous carbon (N-GMC):
GMC
3. Results and discussion
In a typical synthesis, 2 gm of Brij-35 (a polyether and aliphatic
hydrocarbon chain surfactant) was dissolved in 0.2M H2SO4 aqueous
solution (20 mL) and 700 mg melamine was added under stirring for
15h to get a milky suspension. After that 3 gm D-glucose was added
3.1. Characterization of the Pd@N-GMC
Wide angle XRD analysis of the Pd@N-GMC material is shown in
Fig.1a. A broad peak appearing at 260 indicate that the nitrogen
doped carbon material (N-GMC) that has been used as support for
palladium nanoparticles is a graphitic stacking peak. This peak may
be assigned to be the reflections from the (002) plane of the N-GMC
material. Four other diffraction peaks also appeared at 39.90,
46.60, 68.00 and 81.70 degree corresponding to (111), (200), (220)
and (311) reflections planes from crystalline palladium
nanoparticles present in the mesoporous N-GMC.13 Oxidation state
of palladium nanoparticle is further determined by XPS analysis (Fig.
1B). Figure 1B shows two Pd 3d peaks at different binding energies.
The Pd 3d peaks at 336.1 eV and 341.4 eV corresponding to Pd 3d5/2
and Pd 3d3/2 respectively, reveals that in this case, palladium is in
zero state.14
0
to the above emulsion. After being stirred for 30 min at 90 C, the
mixture was transferred into an autoclave at 403 k for 72h. The
brown colored solid product was filtered, washed with water and
dried for 24 h at room temperature. The solid product was further
calcined at 450 0C for 2 h in a N2 atmosphere and final product
denoted as N-GMC (Scheme 1).
2.2 Synthesis of nitrogen doped mesoporous carbon embedded
palladium NPs (Pd@N-GMC):
500 mg of N-GMC was taken in 50 ml round bottom flask containing
10 ml water. 30 mg PdCl2 was dissolved in 5 ml water and it was
added drop wise and stirred for 30 mints. After that water was
completely evaporated. Then 20 ml ethylene glycol was added to it
0
and heated at 170 C for 6h under stirring condition. After that it
was cooled to room temperature then washed with water followed
by methanol and dried for 10 h at 80 0C and denoted as Pd@N-
GMC.
2.3 Synthesis of benzyl alcohol from aryl halide:
In a typical reaction, 50 ml high pressure reactor was charged with
aryl halide (2 mmol), acetonitrile (5 ml), H2O (0.4 mL) catalyst (50
mg) and diphenylmethylsilane (6 mmol). Reactor was then charged
0
with CO2 (1MPa) and heated at 80 C for 9 h. After the completion
of reaction it was cooled down and gas was released. After that, the
organic part of the reaction mixture was separated by extraction
with ethyl acetate and water. Reaction mixture was then analyzed
by GC equipped with a flame-ionized detector and a capillary
column.
Fig. 1 Wide angle XRD pattern (A) and XPS analysis (B) for PdNPs of
the Pd@N-GMC.
FE-SEM image of the material is shown in Fig. 2 which suggests that
spherical sized material is connected with each other to form a
polymeric nature. The palladium doped carbonized material
exhibited approximately the same morphology throughout the
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specimen. The energy dispersive X-ray spectroscopy (EDX) mapping palladium nanoparticles embedded material suggests that Pd
of the material (Pd@N-GMC) shows that carbon, nitrogen, oxygen nanoparticles are crystalline in nature.
and palladium elements are present in this carbon matrix (Fig. 3).
From EDX analysis it has been found that C: N: Pd (wt.%) ratio is
54:23:9 = 6.0:2.5:1.
Fig.2 FESEM analysis of the Pd@N-GMC material
Fig: 4 HRTEM images of the Pd@N-GMC material
N2-absorption desorption isotherms of Pd@N-GMC material show
type-IV curve which indicates the mesoporous nature of the
material.15 As shown in Fig. 5 the BET surface area possess about
337 m2 g-1 and BJH pore size distribution of Pd@N-GMC is centered
at 4-5 nm (Fig.S1). On the other hand, the Raman spectroscopy of
the material (Pd@N-GMC) is shown in Fig. 6. We have got valuable
information about the material from peak position and intensity of
the D and G bands. In this analysis mainly two band i.e D and G
band are situated at 1375 and 1591 cm-1 respectively. The ratio
between the D and G (ID/IG) is ≈ 0.94. Low intensity ratio indicates
the disordered nature of the carbon material due to nitrogen
doping.16
350
Absorption isotherm
Desorption isotherm
(a)
300
250
200
150
100
Fig.3 Energy dispersive X-ray spectroscopy (EDX) mapping of the
material (Pd@N-GMC)
(b)
The morphology of the Pd@N-GMC was analyzed by scanning
electron microscope (SEM) and high resolution transmission
electron microscopy (HRTEM) analysis. As shown in Fig. 4 spherical
natured material is interconnected with each other and average
size of the sphere is 80-90 nm. Similar type of observation is also
made from TEM images which indicate that spherical natured
material contained several pores in its framework (Fig. 4d). During
the polymerization, solvent was trapped and this might be the
reason behind the creation of void space inside the specimen.
Round shaped black spots indicate the palladium nanoparticles
which are embedded homogeneously throughout the material (Fig.
4b). The average size of the Pd NPs is close to 8 nm which is clearly
observed from HRTEM image (Fig. 4c). The SAED pattern of the
0.2
0.4
0.6
0.8
1.0
Relative Pressure (P/P )
0
Fig. 5 N2 absorption and desorption isotherm (a) and BJH pore size
distribution (b) of Pd@N-GMC
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We have designed and synthesized Pd@N-GMC for the above
mentioned carbon dioxide fixation reaction. Thus, our initial focus
was on feasibility of the reaction i.e transformation of aromatic
halide to benzyl alcohol using carbon dioxide and
diphenylmethylsilane as a source of hydroxymethyl (CH2OH) group
(Scheme 2). We have taken transformation of iodobenzene to
benzyl alcohol as a model reaction under 1 atm CO2 pressure at 80
0C in aqueous acetonitrile solvent medium and we have got small
amount yield of benzyl alcohol as a product after workup (Scheme
3). To optimize the reaction condition for better conversion of
iodobenzene we have screened carbon dioxide pressure, solvent,
reaction temperature, reaction time and catalyst amount one by
one.
G
D
18000
15000
12000
9000
6000
3000
I
800
1200
1600
2000
2400
CO
2, Pd@N-GMC
OH
-1
Raman shift (cm
)
Ph
CH3
Si
H
Fig. 6 Raman spectra of Pd@N-GMC material
Ph
The thermal stability of Pd@N-GMC in dynamic nitrogen
atmosphere was analyzed up to 450 0C. In Fig. 7 TGA curve shows
that material is well stable upto 250 0C, after that decomposition
rate increases and at 400 0C temperature it undergoes complete
decomposition.
Acetonitrile-H2O
Scheme 3: direct transformation of iodobenzene to benzyl alcohol
In this reaction carbon dioxide plays a crucial role and a vital
reaction parameter, thus we have tested the effect of CO2 pressure
by variation of CO2 pressure upto 1.5 MPa under reaction condition
mentioned at Fig. 8. Even at low pressure region of 0.5 MPa CO2
pressure, we have got interesting results where the yield of benzyl
alcohol was almost 60%. But maximum yield of benzyl alcohol (86%)
was obtained at 1MPa CO2 pressure. Beyond this pressure, yield of
benzyl alcohol remained same. Similarly, other parameters such as
solvent and reaction temperature are also important for this
transformation.
100
80
60
40
20
90
80
70
60
50
100
200
300
0
400
Temperature ( C)
Fig.7 TGA plot of the Pd@N-GMC material
3.2 Catalytic Activity
route a
COOH
Carboxylation
40
X
CO2
CO2
OH
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
Previous report
Formylation
Reducing
agent
Reducing
Agent
CO pressure (MPa
)
2
This work
CHO
X= I
Fig. 8 effect of CO2 pressure on the reaction
route
b
Reaction conditions: iodobenzene (2 mmol), methyldiphenylsilane
(6 mmol), catalyst (50 mg), acetonitrile (5 ml), H2O (0.4 ml),
temperature (80 0C) and 9h.
Scheme 2: Pd catalyzed aryl halide to various transformations
Effects of solvent and temperature on the reaction are summarized
in Table 1 which indicates that acetonitrile and THF gave the higher
yield than other polar solvents like DMF and less polar solvent like
toluene. In this case trace amount of byproduct such
benzyloxymethyldiphenylsilane was obtained but maximum yield of
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benzyl alcohol and lowest byproduct were obtained in acetonitrile responding well and produced corresponding benzyl alcohol. No
medium (ACN) at 80 0C temperature. At 90 0C temperature aldehyde product was detected after the completion of reaction
formation of benzyl alcohol remained same, thus all other under the optimized reaction conditions. But aryl bromide or
experiment was done at 80 0C temperature (Table 1).
chloride was not responding in this reaction. Thus, we have varied
some electron donating aryl iodides and some electron withdrawing
aryl iodides. Both the groups produced moderate to excellent yield
of benzyl alcohols. But, in most of the cases it was found that
electron donating groups were most effectively converted to benzyl
alcohols compared to electron withdrawing groups. Detailed results
are given in Table 3.
Table 1: effects of solvent and temperature on the reaction
Entry
Solvent
Temp.
(0C)
Yielda (%)
1
2
3
5
6
7
8
ACN
THF
80
80
80
60
70
90
80
86
75
59
67
73
84
28
Table 3: Synthesis of various benzyl alcohols from aryl halides
I
DMF
ACN
CO2,
Pd@N-GMC
OH
methyldiphenylsilane
R
Acetonitrile
H2O
R
ACN
ACN
Entry
1
Aryl halide
product
Yield
(%)a
Toluene
I
Reaction conditions: iodobenzene (2 mmol), methyldiphenylsilane
(6 mmol), catalyst (50 mg), solvent (5 ml), H2O (0.4 ml), 9h, and CO2
(1MPa). aGC yield of alcohol.
86
OH
We also tested the effect of various supported catalyst and their
amount (Table 2) on the reaction. In the absence of catalyst,
reaction did not proceed and yield was nil (Table 2, entry 1) which
indicates that catalyst is necessary for this transformation.
Maximum yield was obtained when catalyst (Pd@N-GMC) amount
was 50 mg. In the presence of excess Pd@N-GMC selectivity of
benzyl alcohol slightly decreased where small amount byproduct
such as C-C coupled product (biphenyl) was formed. Other two
catalysts such as Pd@mPMF and Pd@SiO2 were less effective
compared to Pd@N-GMC. Similarly, we have varied the reaction
time from 6 h to 10 h but at 9 h maximum yield was obtained (Table
2, entry 4).
I
2
90
OH
Me
Me
I
3
4
92
64
OH
MeO
MeO
Table 2: effects of catalysts and reaction time on the reaction
I
Yield (%)a
OH
Entry
Catalyst (mg)
Reaction
time (h)
OMe
OMe
1
2
nil
9
9
0
Pd@N-GMC (30)
53
3
Pd@N-GMC (40)
9
67
I
5
6
80
77
OH
4
5
Pd@N-GMC (50)
Pd@N-GMC (60)
9
9
86
82
F
F
6
7
Pd@N-GMC (50)
Pd@N-GMC (50)
6
8
58
77
I
OH
OH
8
9a
Pd@N-GMC (50)
Pd@mPMF (50)
10
9
86
65
Cl
Cl
10
Pd@SiO2 (50)
9
37
I
7
37
Reaction conditions: iodobenzene (2 mmol), diphenylmethylsilane
(6 mmol), Temp. 80 0C, ACN (5 ml), H2O (0.4mL) and CO2 (1MPa).
aGC yield of alcohol. amPMF is mesoporous paraformadehyde
melamine polymer.
O2N
O2N
Under optimized condition several aryl halides were tested in this
reaction. Surprisingly, we have found that aryl iodides were
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mixture to confirm that there is no significant metal leaching during
the reaction.
OH
45
57
NC
NC
I
OH
9
N
N
Reaction conditions: Aryl halide (2 mmol), methyldiphenylsilane (6
mmol), Catalyst (50 mg), ACN (5 ml), H2O (0.4ml), Temperature (80
0C), 9h, and CO2 (1MPa). aGC yield of alcohol.
To understand the mechanism behind this reaction and role of
nitrogen doped carbon (N-GMC) support and palladium
nanoparticles we have studied some literatures and proposed a
probable mechanism, although the exact reaction sequence was
not determined. As we have used nitrogen doped carbon material
where basic nitrogen(s) are present, these nitrogen are able to
capture the carbon dioxide and activate it to a formoxysilane
intermediate.4i On the other side aryl halide undergoes oxidative
addition step on PdNPs present in Pd@N-GMC to produce
arylpalladium halide which reacts with formoxysilane intermediate
and may produce aldehyde product which immediately reacts with
diphenylmethylsilane and water to produce direct benzylalcohol as
the major product. The product of hydrosilylation of benzyldehyde
Fig.9 Recycling test of Pd@ N-GMC catalyst
Conclusion
In this work, we report the synthesis of novel palladium
nanoparticles embedded nitrogen doped porous carbon material
where we have used Brij-35 as a soft template, glucose as a carbon
source and melamine as nitrogen source. Palladium nanoparticles
incorporated into the surfaces of the material and basic nitrogen
present in the material play dual role; one is as stabilizing agent of
the palladium nanoparticles and other one is carbon dioxide
fixation reaction. The material has been used in the synthesis of
benzyl alcohols from aryl halides using carbon dioxide as C1 source.
The present catalyst is highly stable. As the starting materials are
easily commercially available and inexpensive, it makes the whole
process cost effective. On the other hand, the catalyst can be
reused for five consecutive cycles with consistent catalytic activity.
Further work is in progress to broaden the scope of this catalytic
system for other organic transformation.
0
was detected when reaction temperature was low (< 60 C). But at
high temperature i.e under the optimized condition no
hydrosilylation product was obtained. This proposed mechanism is
well supported by some previous reports.17
I
CHO
Acknowledgements
Ref. 4i
SMI acknowledges DST-SERB, UGC (Project Sanction F.No.-43-
180/2014 (SR) and DST-W.B., Project No 811(Sanc)/ST/P/S&T/4G-
8/2014 for financial support. RAM acknowledges UGC, New Delhi,
India for his Maulana Azad National Fellowship (F1-17.1/2012-
13/MANF-2012-13-MUS-WES-9628/SA-III). SK acknowledges CSIR,
New Delhi for his senior research fellowship. AB thanks DST, New
Delhi for DST-SERB and DST-UKIERI project grants. We also
acknowledge DST and UGC for providing funds to the University of
Kalyani under FIST, PURSE and SAP programs.
CHO
OH
Ref. 17a
I
OH
This work
Notes and references
* Author to whom correspondence should be addressed.
Dr. Sk. Manirul Islam, Department of Chemistry, University of
Kalyani, Kalyani, Nadia, 741235, W.B., India. Phone: + 91- 33-2582-
8750, Fax: 91-33-2582-8282, E-mail: manir65@rediffmail.com
Scheme 4: Iodobenzene to benzaldehyde and benzaldehyde to
benzylalcohol stepwise and direct transformation
Recycling Test
1
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In case of supported catalyst, reusability of the catalyst is highly
desirable. Thus we have checked the reusability of the reported
catalyst, N-MGC. After completion of the model reaction (Table 3,
entry 1), the catalyst was removed by simple filtration and washed
0
with methanol and dried at 60 C and the same reaction was again
performed under similar condition. The conversion and selectivity
remained almost same. In this way we have reused the catalyst
upto five times with no significant loss of activity (Fig. 9). We have
also carried out AAS analysis of the filtrate part of the reaction
2
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Green Chemistry
Page 8 of 8
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DOI: 10.1039/C6GC01038E
A Route for Direct Transformation of Aryl Halides to Benzyl Alcohols via Carbon
Dioxide Fixation Reaction Catalyzed By (Pd@N-GMC) Palladium Nanoparticles
Encapsulated Nitrogen Doped Mesoporous Carbon Material
Rostam Ali Molla,a, Md. Asif Iqubal,b, ‡, Kajari Ghosh,a, ‡ S. M. Islam *a
aDepartment of Chemistry, University of Kalyani, Kalyani, Nadia 741235, W.B., India
bDepartment of Chemistry, IIT Roorkee, Roorkee 247667, Uttarakhand, India
A nitrogen doped mesoporous carbon material was synthesized from glucose and melamine under hydrothermal treatment.
Soft template, brij-35 was used as a template. The palladium nanoparticles embedded porous nitrogen doped carbon material
(Pd@N-GMC) was used for the synthesis of benzyl alcohols from aryl iodides via carbon dioxide fixation reaction. The catalyst
was highly stable and reusable without any significance loss of its activity.