Effect of Alkyl Structures on the Anti-stacking and Anchoring of Pd/Diamine-Functionalized Graphene Nanoparticles in Application in Suzuki Reaction

Article abstract of DOI:10.1002/cjoc.202100265

Three diamines (1,8-diaminooctane/p-phenylenediamine/biphenylenediamine) with different alkyl groups were used to synthesize the functionalized graphene networks. Pd as the common metal catalyst was used to explore the effects of alkyl types of diamines on anti-stacking, metal anchoring ability of functional graphene and hence the catalytic performance. The results were discussed by characterization of the material and its catalytic properties. All catalysts showed excellent catalytic performance on the Suzuki cross-coupling reaction with a high yield of up to 100%. The p-phenylenediamine and biphenylenediamine functionalized graphene with larger specific surface area was beneficial to improve the stability of the graphene catalyst and maintain good catalytic activity after 5 cycles. The Pd nanoparticles in 1,8-octanediamine materials have smaller size and a smaller loading with the same or even better catalytic performance than p-phenylenediamine, biphenylenediamine materials, due to the stronger electron donating ability of N of octanediamine than that of p-phenylenediamine.

Full text of DOI:10.1002/cjoc.202100265

Chinese Journal
of Chemistry
CJC 中 国 化 学 - An International Journal
Accepted Article
Title: Effect of alkyl structures on the anti-stacking and anchoring of Pd/diamine -
functionalized graphene nanoparticles in application in Suzuki reaction
Authors: Yinbing Tian, Zijie Tang, Yu Ru, Yuanyuan Wang*, and Liyi Dai*
This manuscript has been accepted and appears as an Accepted Article online.
This work may now be cited as: Chin. J. Chem. 2021, 39, 10.1002/cjoc.202100265.
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published online in Early View: http://dx.doi.org/10.1002/cjoc.202100265.
ISSN 1001-604X • CN 31-1547/O6
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Tian Yinbing (Orcid ID: 0000-0002-3916-6687)
Wang Yuanyuan (Orcid ID: 0000-0002-9705-4050)
Dai Li Yi (Orcid ID: 0000-0002-7111-6268)
Cite this paper: Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Effect of alkyl structures on the anti-stacking and anchoring of Pd/diamine -
functionalized graphene nanoparticles in application in Suzuki reaction
&
&
Yinbing Tian , Zijie Tang , Yu Ru, Yuanyuan Wang*, and Liyi Dai*
College of Chemistry and Molecular Engineering, East China Normal University, 500 Dongchuan Road, Shanghai 200241, China
&
These authors contributed equally to this work and should be considered co-first authors
Keywords
Diamine | Graphene | Anti-stacking | Anchoring | Alkyl Types
Main observation and conclusion
Three diamines (1,8-diaminooctane/p-phenylenediamine/biphenylenediamine) with different alkyl
groups were used to synthesize the functionalized graphene networks, Pd as the common metal catalyst
was used to explore the effects of alkyl types of diamines on anti-stacking, metal anchoring ability of
functional graphene and hence the catalytic performance, the results were discussed by characterization
of the material and its catalytic properties. All catalysts showed excellent catalytic performance on the
Suzuki cross-coupling reaction with a yield of high up to 100%, the p-phenylenediamine and bi-
phenylenediamine functionalized graphene with larger specific surface area was beneficial to improve
the stability of the graphene catalyst and maintain good catalytic activity after 5 cycles. the Pd nanopar-
ticles in 1,8-octanediamine materials have smaller size and a smaller loading with same even batter cat-
alytic performance than p-phenylenediamine, biphenylenediamine materials, which due to the stronger
electron donating ability of N of octanediamine than that of p-phenylenediamine.
Comprehensive Graphic Content
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Chin. J. Chem. 2018, XX, 1－X

Running title
Chin. J. Chem.
sheets were stabilizing the Pd nanoparticles and also supplying ad-
equate electron density to the anchored Pd(0) species to facilitate
the catalyst activity. The use of different types of diamines results
Background and Originality Content
Graphene is a monolayer of sp2 bonded carbon atoms arranged
in a two dimensional (2D) honeycomb-like lattice and the interest
in graphene has been significant over the past 20 years owing to
their high surface area, well developed porosity, outstanding elec-
[23]
in different material properties. Jia et al.
used a series of dia-
mines (including aliphatic and aromatic diamines) as cross-linkers
to explore the effect of diamines molecular structure on the elastic
modulus, contact angle, swelling degree and ion dialysis separation
of GO membranes which provides a deep understanding on tuning
the properties of GO membranes by varying the structures of cross-
linkers. The diamine can be functionalized by reaction with an
epoxy group or a carboxyl group of graphene oxide which acts as a
[
1-
tronic properties and promising mechanical and thermal stability,
3
]
However, the major challenge still remains, these include poor
solubility, low reactivity and the availability of well-defined pristine
graphene in large quantity have hampered the rapid development
[4-6 ]
of graphene-based functional devices.
Graphene oxide (GO),
"
spacer" for preventing the accumulation of graphene nanosheet.
which is obtained by deep oxidation of graphite and subsequent
exfoliation of the resulting graphite oxide, may contain different
functional groups, mainly epoxides, hydroxyls, and a little amount
of carboxylic acids and has been shown to be actually amphiphilic
with hydrophilic edges and hydrophobic basic planes. In addition,
GO is easy to be reduced (rGO) with chemical agents such as hydro-
gen, metal ion borohydride, and hydrazine agents. Due to the char-
acteristics of GO, it is often regarded as an effective platform for
At the same time, the amino group at the other end can be used to
anchor the metal, effectively enhancing the bonding force between
the carrier and the nanoparticles. However, up to now, most re-
search about the diamine-functionalized graphene are focused on
applications electrochemical, membrane separation and superca-
pacitors. Although recent progress has been made regarding dia-
mines in the preparation of graphene-based metal catalysts, the ef-
fect of diamine structures on properties of metal/ rGO nanocom-
posites has been rarely resported.
[7]
[8-
obtaining functionalized or modified graphene based materials.
10]
In this paper, the graphene oxide was functionalized with the
diamine with different type alkyl groups (aliphatic and aromatic di-
amines) through the nucleophilic ring-open reaction and palladium
nanoparticles were introduced by in-situ reduction to synthesize
the Pd/functionalized graphene nanocomposites of 1,8-diaminooc-
tane/p-phenylenediamine/biphenylenediamine. Palladium-cata-
lyzed carbon-carbon (C-C) coupling reaction which have proven to
be valuable tools for constructing biaryl units in organic synthesis
and corresponding catalysts own many potential advantages, such
as, simplified recovery and reusability,24, 25 which was used as
model reaction to explore the effect of functionalization of gra-
phene on catalytic activity of catalyst.22, 24, 26-30 All catalysts
show excellent catalytic performance in the Suzuki cross-coupling
reaction. The effects of graphene stacking and anchoring metal
ability on catalytic activity were discussed by characterization of
the material and its catalytic properties.
It is a consensus that the formation of van der Waals interac-
tions between nanosheets aggregates them and turns back into
graphite structure, reducing the surface area of the rGO materials.
In addition, when it is used as carrier, few number of functional
groups on the rGO will lead to that the interaction between gra-
phene and metal nanoparticles is not strong, which limits their de-
11-13
velopment in the field of catalysis.
In order to solve the above
problems and meet the needs of the application, adding other com-
ponents and modifying different structures on the base of gra-
phene oxide to form a new class of functionalized reduced gra-
phene oxide which is much more adaptable for a number of appli-
[6, 9, 10, 14-16]
cations.
In recent years, diamine-based chemicals have been reported
[
7, 17, 18]
to be good materials for graphene functionalization.
Various
diamines are successfully grafted onto graphene sheets, the multi-
ple amine groups of a crosslinker can react with epoxy groups
within one GO sheet or between two GO sheets. the roles of pri-
mary amine or secondary amine groups in the formation of gra-
Scheme 1 Known knowledge and conceptual advance of this contribution
(a) Known knowledge (Effect of amines on structure, performance of
[
19-21]
phene-based materials.
The diamines with two amino groups
graphene materials
20, 22
in its opposite position can react with functional group of GO.[
]
As a results, the graphene sheets can be crosslinked by the bifunc-
tional molecules, which are embedded in graphene sheets so as to
prevent restacking and aggregation of graphene materials.
23]
Tong’s[ group reported structure-tunable three-dimensional (3D)
network of graphene hydrogel by using 1,8-diaminooctane as the
linker, which resulting in high specific capacitance and good rate
capability. Song et al.2 used three phenylenediamine (PD) mono-
mers to prepare functionalized graphene (PD/rGO) networks and
investigate the effect of different molecular geometries on gra-
phene’ s structural, electrochemical features, the results suggest
PPD and MPD molecules could efficiently enlarge graphene inter-
layer spacing while OPD molecules showed disorderly bonded or
noncovalently bonded structures, resulting in small and variable in-
terlayer distances, PPD/rGO exhibited the largest specific capaci-
tance of 422 F/g with excellent cycling stability and low charge
4
[
24 ]
transfer resistance. Lu’s group synthesized PPD (p-phe nylenedi-
amine) functionalized GO/rGO by a facile solution processing to in-
vestage the mechanism of graphene modification by PPD. They
found that PPD functionalizd GO/rGO composite materials can pre-
vent the stacking of graphene sheet and were used as the elec-
trodes materials of supercapacitors, exhibiting excellent electro-
chemical performance. Pillared diamine molecules chemically an-
chor at one end and are capable of undergoing a different reaction
on the other end, resulting in three different conformations of gra-
(
b) This work (Effect of alkyl structures on the anti-stacking and
anchoring of Pd/diamine -functionalized graphene nanoparti-
cles)
[25, 26]
phene derivatives.
In addition, the amine functionalized GO
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and 67.5°, corresponding to (111), (200), and (220) planes of Pd
crystal (PDF#46-1043), respectively. In the diamine functionalized
graphene, only broad metal peaks appeared at 40°, indicating that
the diamine functionalized graphene has an anchoring effect to
more uniformly disperse the Pd nanoparticles.
In this work, graphene is modified by different methods to syn-
Figure 2 The XRD pattern of (a) GO, 1,8D-GO, BIP-GO and PPD-GO, (b)
Pd/rGO, Pd/1,8D-rGO, Pd/BIP-rGO and Pd/PPD-rGO
thesize a series of functional graphene-loaded palladium-based
metal composite materials. Three kinds of diamine materials (1,8-
octanediamine, p-phenylenediamine, biphenylenediamine) to
functionally modify graphene oxide, and prepare diamine cova-
lently functionalized graphene composite materials through epoxy
The proposed mechanism of functionalization has been further
supported by Raman spectroscopy through the analysis of the D
[
20, 27 ]
ring-opening reaction.
Noble metal Pd was introduced using
-
1
-1
and G peaks characteristics around 1350 cm and 1600 cm . The
chloropalladium acid as the metal source, and diamine-functional-
ized graphene-supported palladium catalysts (Pd/1, 8D-rGO,
Pd/BIP-rGO, and Pd/PPD-rGO) were prepared. By complexing with
the amine or amide group of the carrier, the strong electrostatic ad-
sorption between the cationic Pd precursor and GO can be en-
hanced, thereby improving the dispersibility of Pd nanoparticles
3
former directly correlates with the amount of sp bonding present
in graphene as well as the defects in the sp carbons caused by the
2
lattice motion of the center of the Brillouin zone that is usually used
to indicate defects in a graphene material sample. While the latter
gives insight into the chemical state of the carbon through the scat-
2
[13]
2+
2
tering of the E G phonon of the sp carbon bond. The intensity
formed after Pd ion reduction. The irreversible agglomerate of
graphene nanosheets driven by the strong π-π interactions can also
be averted with the assistance of those active diamine “spacers”
materials, thus increases the availability of graphene materials
D G
ratio I /I is commonly used to quantify the degree of graphitization
and the size of any structural defects or graphitic clusters existing in
disordered carbon. In Figure 2a, PPD-GO, BIP-GO ,1,8D-GO show
higher intensity ratios as 1.13, 1.01 and 0.98. The results show that
functionalization makes graphene move toward more disorder and
more defects. And as the Pd metal is loaded on the functionalized
graphene, the degree of defect is also enhanced, and the order of
the original disorder remains unchanged: Pd/PPD-GO>Pd/BIP-
GO>Pd/1,8D-GO>Pd/GO.
(
Scheme 1).
Results and Discussion
Characterization of DFGO and Pd/DF-rGO
Figure 1 The XRD pattern of (a) GO, 1,8D-GO, BIP-GO and PPD-GO, (b)
Pd/rGO, Pd/1,8D-rGO, Pd/BIP-rGO and Pd/PPD-rGO
Figure 3 The TGA curves of (a) GO, 1,8D-GO, BIP-GO and PPD-GO, (b)
Pd/rGO, Pd/1,8D-rGO, Pd/BIP-rGO and Pd/PPD-rGO
An intercalated layered structure of DFGO and the load of Pd men-
tal was identified based on XRD patterns. In Fig. 1a, GO showed a
single diffraction peak at 2θ of 10.4°, corresponding to the (0 0 1)
plane with the d-spacing of 7.8 Å. When GO is reacted with organic
amines, a significant shift in the peak was observed. The diffraction
peak of the 1,8D-GO shifted to 8.5°, providing an enlarged spacing
of 10.8 Å. The offset peak of PPD-GO, BIP-GO moves to 7°, 7.3° with
the spacing of 12.9 Å, 12.0 Å. The expansion was consistent with
the previous literatures and arose from the intercalation with dia-
mine covalently attached with GO sheets.13 It is worth noting that
the layer spacings of PPD-GO, BIP-GO are greater than 1,8D-GO.
This may be because the PPD, BIP are aromatic rigid structures,
while the 1,8D may be curved and obliquely embedded. The for-
mation of palladium nanoparticles was confirmed from Figure 1b.
The peaks of Pd/GO emerged in XRD patterns at 2θ=40.0°, 46.1°,
TGA measurements were undertaken in order to explore the
changes in the thermal behavior of GO samples after diamine
function,as well as to estimate an approximate degree of chemical
functionalization. The TGA curves obtained for amine-treated GOP
samplesexhibit considerable differences as compared to the one of
pristine GO. The thermogram for DFGO (Fig. 3a) has three main
weight losses The First step is associated with the elimination of
adsorbed water; the second step is related to the oxidation of
covalently bonded diamine molecules; and the final step is due
to the decomposition of graphene backbone. Thus, all diamine-
modied GO samples exhibit a higher thermal stability than the one
found for pristine GO, the highest content of amine species is
observed in 1,8D-GO, then the second is PPD-GO. The result is con-
sistent with Fig. 3b
[
28]
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Figure 4 showed the TEM images and the particle size
distribution of Pd/rGO 5a, Pd/BIP-rGO 5b, Pd/PPD-rGO 5c and
Pd/1,8D-rGO 5d. As shown in Figure 5a , the dispersion of the Pd
NPs in the Pd/rGO was extremely non-uniform, and obvious
agglomeration occurred. The average particle size was 6.8 nm. The
spherical palladium particles with uniform size were
homogeneously dispersed on BIP-rGO, PPD-rGO and 1,8D-
rGO.(Figure 5b-d) The particle range of BIP-rGO, PPD-rGO is mainly
concentrated between 3 nm and 4 nm. Their average particle size is
not much different, and the range is mainly concentrated between
3
-4 nm, indicating that simply increasing the chain length of the
modifier has little effect on the loaded metal particles. The metal
particles of Pd/1,8D-rGO material are significantly smaller, with an
average particle size of 1.9 nm. The order of Pd particle size is:
Pd/1,8D-rGO<Pd/BIP-rGO≈Pd/PPD-rGO. It may be because the
end group of the chain structure diamine anchors the Pd metal
nanoparticles better than the conjugated structure containing
benzene ring. The result suggested that the surface of graphene
oxide is modified using the amine functional groups can not only
help stabilization and distribution of Pd NPs but also reduce the
particle size of the metal nanoparticles, which is beneficial to
increase the catalytic activity. The lattice fringe with the d-spacing
of 0.22 nm can be readily indexed to the (1 1 1) lattice planes of Pd.
Figure 4 The XPS N 1s spectrum of (a) Pd/1.8D-rGO, Pd/PPD-rGO and
Pd/BIP-rGO, respectively; The XPS Pd 3d spectrum of (b) Pd/1.8D-rGO,
Pd/PPD-rGOand Pd/BIP-rGO, respectively.
XPS can not only analyze the elemental composition of the
catalyst and the valence state of the metal, but also reveal the
interaction between the electrons of each component of the
catalyst to some extent. The XPS survey scan reveals the presence
of C and O and N ( Figure S1). The XPS narrow scan of N in Figure 4a
showed two peaks which can be attributed to primary amine and a
secondary amine. This indicated the presence of the diamine: one
end is grafted onto the surface of the graphene oxide in the form of
2
ring-opening of the epoxy group, and the exposed NH at the other
end is used to anchor the metal. T compared with the standard N1s
and Pd 3d binding energy, the binding energy of the functionalized
catalysts have been shifted to different degrees, explaining the
different interaction strength between metal and functionalized
graphene materials. The degree of deviation of 1, 8-octanediamine
materials is greater than that of p-phenylenediamine and benzidine
materials, indicating that the role of aliphatic diamine anchoring
metals is stronger than that of p-phenylenediamine and benzidine.
Moreover, the existence of small nanoparticles requires a suitable
electronic structure environment, the Pd nanoparticles in 1,8-
octanediamine materials have smaller size and a smaller loading
with same even batter catalytic performance, which means the
Figure 6 The SEM images and the particle size distribution of (a) Pd/rGO,
(b) Pd/BIP-rGO, (c) Pd/PPD-rGO and (d) Pd/1,8D-rGO. The EDX images of (e)
Pd/PPD-rGO..
[28]
The morphology of materials was shown in Figure 6, graphene
influence of the material on the atomic structure of Pd. The small
shift in Pd 3d binding energy between Pd/1.8D-GO and Pd / PPD-
nanosheets are randomly stacked, Among them, Pd/PPD-rGO is
stacked more orderly and can form larger bulks which contain more
pores and is more conducive to contact with reactants, This effect
still exists Pd/1,8D-rGO and Pd/PPD-rGO, which is consistent with
the results of Figure 6 and Table 1. The EDX spectrum of the
Pd/graphene nanocomposite synthesized through functionalization
0
GO is consistent with this result. The Pd state of the Pd metal was
further confirmed by the peak of Pd 3d5/2 and Pd 3d3/2.
(
Fig 6e, Figure. S4b, c) shows relatively higher amount of Pd on
comparing the Pd : C ratio with that of Pd : C obtained from the Pd
nanocomposite (Fig. S4a), synthesized without functionalization.
Figure 5 The TEM images and the particle size distribution of (a) Pd/rGO,
(
(
b) Pd/BIP-rGO, (c) Pd/PPD-rGO and (d) Pd/1,8D-rGO. The HRTEM images of
e)Pd/BIP-rGO, (f) Pd/PPD-rGO and (g) Pd/1,8D-rGO.
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reach 100%, which is significantly higher than other bases. To
determine the best solvent, the Suzuki coupling reaction was
carried out in N,N-dimethylformamide(DMF), MeOH, EtOH and H O.
2
According to the results shown in Figure 7b, when the reactions are
proceed in polar aprotic solvents, DMF, the product is detected in
lower yield than conducted in polar protic solvents. (MeOH, EtOH
2
and H O). The result is consistent with the solvent polarity effects
reported in other literature. In addition, we found an interesting
phenomenon: when ethanol and water are mixed, the reaction
yield is higher than that of water alone. Next, we adjusted the ratio
of ethanol to water and found that when the ratio of ethanol to
water is 5:1, the yield of the product can reach 100%. Based on the
screening of the above reaction conditions, the following Suzuki
coupling reactions are carried out using K
O (5 : 1) as solvents.
2 3
CO as base and EtOH-
Figure 7
and Pd/1,8D-rGO.
N adsorption-desorption isotherms of Pd/BIP-rGO, Pd/PPD-rGO
2
H
2
Table 1 BET pore volume, surface area and average pore size of Pd/BIP-rGO
Pd/PPD-rGO and Pd/1,8D-rGO.
SBET
Pore volume Average pore
Entry
Catalysts
2
3
(m /g)
（cm /g） diameter (nm)
1
2
3
Pd/PPD-rGO
Pd/1,8D-rGO
Pd/BIP-rGO
324
210
306
1.31
1.23
1.32
3.84
3.72
3.95
Figure
9
Suzuki coupling reaction effect of iodobenzene and
phenylboronic acid under (a) different loadings and (b) different times.
The nitrogen adsorption-desorption isotherm was collected in or-
der to examine the effect of different diamine function on the
structure of catalyst. (Figure 7) All isotherms were type IV hystere-
a
reaction conditions: K2CO3 (2 mmol), catalyst 10 mg (Pd / PPD-rGO, Pd / 1,
o
8
D-rGO, Pd / BIP-rGO) and EtOH-H
2
O (v/v = 5 : 1, 24 mL) at 80 C, 60 min
3
b
under air. reaction conditions: K
rGO 8 wt%, Pd / 1, 8D-rGO 6 wt%, Pd / BIP-rGO 8 wt%) and EtOH-H
5
2
CO (2 mmol), catalyst 10 mg (Pd / PPD-
3
sis with an H -type hysteresis loop, proving the presence of meso-
27
2
O (v/v =
porous and macroporous structures. The BET surface areas, pore
size and pore volumes of catalysts are summarized in Table 1. The
test results show that the surface area of Pd/PPD-GO is as high as
o
: 1, 24 mL) at 80 C, under air.
2
The catalytic activity of Pd/rGOPd/1,8D-GO, Pd/PPD-GO with
3
24 m /g, whereas the surface area of Pd/1,8D-GO is just 220 m2/g.
The pore volume of Pd/PPD-GO and Pd/1,8D-GO are measured to
different Pd loading and Pd NPs towards the Suzuki coupling
reaction was evaluated, and the result was shown in Figure 9. Under
the same reaction conditions, when the theoretical loading amount
of Pd on 1,8D-rGO was increased from 2 wt% to 6 wt%, the yield of
product increased from 62% to 100%. While it remained almost
unchanged after improved the dosage of Pd loading. In the term of
Pd/PPD-GO, when the Pd loading enhanced to 8wt%, the yield was
up to 100%. These results imply that Pd/1,8D-GO and Pd/PPD-GO
with less palladium exhibited excellent catalytic activity towards
Suzuki reaction and the optimal Pd loading for Pd/1,8D-GO and
Pd/PPD-GO was 6 wt% and 8 wt%, respectively.The catalytic
performance of Pd/1,8D-rGO and Pd/PPD-rGO with different time
was summarized in Figure 9b. When the reaction time is 2 hours, all
three catalysts can increase the reaction yield to 100%. However,
when the reaction time is shortened to one hour, the catalytic
performance of Pd/GO is reduced to 50%. When the time is set at
3
3
be 1.31 cm /g and 1.23 cm /g, respectively. It turns out that the
immobilization of PPD to graphene sheets can effectively prevent
the aggregation which obviously superior to those of 1,8D
Figure
8
Suzuki coupling reaction effect of iodobenzene and
phenylboronic acid under (a) different bases and (b) different solvents
3
0 min, Pd/PPD-GO still maintained the superior performance,
a
while obvious deterioration in the yield with Pd/PPD-GO was
observed. This significantly different catalyst performance may be
due to the better anti-stacking capabilities of PPD.
reaction conditions: different bases (2 m mmol mol), Pd/PPD-rGO (Pd 8
2
wt%, 10 mg), Pd/1,8D-rGO(Pd 8 wt%, 10 mg) and EtOH-H O (v/v = 5 : 1, 24
o
mL)
at
80
C,
60
min
under
air.
b
Several coupling reactions of various aryl halides with phenyl
boronic acid were evaluated under the optimized conditions and
the results presented in Table 2. For both catalysts, aryl halides with
electron-withdrawing or releasing groups reacted with
phenylboronic acid to afford the corresponding products in high
yields. It has been reported that an electron-rich carrier promotes
oxidative addition, which is a key step in increasing the catalytic
reaction conditions: K
2
CO (2), Pd/PPD-rGO (Pd 8 wt%, 10 mg), Pd/1,8D-
3
rGO(Pd 8 wt%, 10 mg) and different solvents at 80 oC, 60 min under air.
The catalyst was tested in the Suzuki cross-coupling reaction of
iodobenzene with phenylboronic acid. The choice of base and
solvent play an important role in the Suzuki reaction. On the current
study, the use of inorganic bases are more common. Therefore,
various inorganic bases were examined in the Suzuki coupling
reaction using Pd/1,8D-GO and Pd/PPD-GO as catalysts. From
[27, 29-32]
activity of a palladium catalyst in a Suzuki coupling reaction.
Therefore, the high catalytic activity of Pd/DF-rGO can be attributed
to the promotion of their electron-rich support. The coupling
2 3
Figure 7a, it can be seen that the yield in the system of K CO can
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Running title
Chin. J. Chem.
reaction between the aryl chloride and the phenylboronic acid
requires an extended reaction time than the aryl iodide and
bromide, but only a lower yield is obtained. It can be well explained
by the theory of ionization energy. The products could be purified
by column chromatography and characterized by NMR
spectroscopy after reaction according to the corresponding
literature.
The stability is also an important character of an advanced
catalyst. As for the heterogeneous catalyst, it can be easily recycled.
In order to study the stability of the catalyst, we repeated the three
catalysts functionalized with diamine in the same Suzuki coupling
reaction for 5 times. The results are shown in Figure 10 Pd/PPD-rGO
and Pd/BIP-rGO can be reused at least five times, and their catalytic
activity will not be significantly reduced compared with Pd NPs and
Pd/-rGO, which shows that Pd/PPD-rGO and Pd/BIP-rGO have high
stability and recyclability. However, in the Pd/1,8D-rGO catalytic
cycle, there was a significant decrease in the second time, the yield
was reduced to 72%, and after five cycles, the product yield was
Recyclability of Pd/DF-rGO.
5
8%. The above results indicate that the rigid conjugated diamine-
modified graphene composite catalysts (Pd/PPD-rGO and Pd/BIP-
rGO) are superior to the flexible diamine-modified graphene
composite catalysts (Pd/1,8D-rGO). It is proved once again that PPD
and BIP with better anti-stacking capabilities contribute to the
stability of the catalyst.
Hot filtration test has been conducted to verify that catalyst are
truly heterogeneous(Figure S5)
Figure 10 The cycle effect of Pd/BIP-rGO, Pd/PPD-rGO and Pd/1,8D-rGO.
Table 2 The Suzuki coupling reactions of aryl halides and arylboronic acids catalyzed with Pd/PPD-rGO(Pd 8 wt%), Pd/1,8D-rGO(Pd 6 wt%) and Pd/BIP-
rGO(Pd 8 wt%).
Entry
Reactant
Product
Time（h）
Yield
%)
(
1
/2
100a
1
I
100b
1
1
1
1
1
8
8
8
100c
75a
2
3
4
5
6
Br
Cl
68b
64c
32a
37b
31c
1
/2
81a
79b
H C
I
I
I
CH3
NO2
CN
1
3
1
74c
1
/2
97a
O N
2
1
96b
1
95c
1
/2
92a
89b
NC
1
1
88c
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1
/2
94a
7
8
9
HO
I
OH
NH2
94b
1
1
93c
1
/2
90a
91b
H N
2
I
1
1
89c
1
/2
95a
H CO
I
OCH3
1
97b
3
1
94c
Reaction conditions: aryl halides (1 mmol), phenylboronic acid (1.3 mmol), K
under air. a: Pd/PPD-rGO (Pd 8 wt%) b: Pd/1,8D-rGO(Pd 6 wt%) c :Pd/BIP-rGO(Pd 8 wt%).
The adsorption of diamine on the surface of graphene based
2
CO
3
(2 mmol) and EtOH-H
2
O (v/v = 5 : 1, 24 mL) at 80 oC,
[33]
materials was initially confirmed using UV–Vis spectroscopy . The
BIP as an example was used to confirm the change of functionalized
materials before and after cycling. The characteristic absorption
bands of BIP appear at ~ꢀ300 nm (red line Fig 12, whereas, the HRG
has a typical absorption band at ~ꢀ270 nm (black line, Fig 12). this is
also confirmed by the absence of these peaks in the UV spectrum
of Pd/BIP-rGO, and Pd/BIP-rGO after cycling.
Table 3 The loading of Pd/PPD-rGO(Pd 8 wt%), Pd/1,8D-rGO(Pd 6 wt%) and
Pd/BIP-rGO(Pd 8 wt%) before and after cycling.
Theoretical
Entry
Catalysts
Actual loading After cycling
loading
8%
1
2
3
4
Pd/rGO
7.32%
5.85%
7.92%
7.53%
7.05%
5.79%
7.82%
7.31%
Figure 11 The XRD spectrum of Pd/rGO, Pd/1,8D-rGO, Pd/BIP-rGO, and
Pd/PPD-rGO after 5 cycles.
Pd/1,8D-rGO
Pd/PPD-rGO
Pd/BIP-rGO
6%
8%
8%
The crystallinity and phase purity of graphene nanocomposites
after cycling was confirmed by XRD analysis. As shown in Figure 12,
The peaks of Pd/rGO emerged in XRD patterns at 2θ=40.0°, 46.1°,
and 67.5°, corresponding to (111), (200), and (220) planes of Pd
crystal (PDF#46-1043), respectively, which becomes more sharper
after cycling. The peaks of Pd/1,8D-rGO, Pd/BIP-rGO, and Pd/PPD-
rGO only broad metal peaks appeared at 40° and become a little
sharper,It shows that the morphology and crystallinity of the metal
do not change significantly after the cycle, which proves the
stability of the functionized material.
It can be seen from the Table 3 that the difference between the
actual load and the theoretical load is very small, indicating that the
metal can be effectively loaded on the carrier modified by the dia-
mine functionalization. Moreover, although there is metal loss after
the cycle, the metal loading on the functionalized graphene mate-
rial does not change more compared with Pd/rGO, which also
proves the anchoring effect of the diamine on the metal and the
stability of catalysts.
Figure 13 The SEM of (a, d) Pd/1,8-D/rGO, (b, e) Pd/BIP-rGO,and (c, f)
Pd/PPD-rGO after 5 cycles.
Figure 12 The UV-Vis specium of Pd/rGO, BIP, Pd/BIP-rGO, and Pd/BIP-
rGO after cycling.
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Running title
Chin. J. Chem.
mosphere with high yields. The synthesis of amine functional gra-
phene supported Pd nanoparticles may open up a new way to pre-
pare new catalyst for the practical application of organic coupling
reactions.
As Figure 13 shows , the graphene sheets of Pd/BIP-rGO and Pd/PPD-rGO
have hardly agglomeration and can still maintain the original morphology.
According to the EDX images (Figure S3, 4) , it can be seen that the main
element types of the material have not changed after the cycle. The
graphene sheets of Pd/BIP-rGO were shown a little stacked which means
the inferior cycle performance.
Experimental
General procedures
All chemicals are commercially available and used as purchased
without any further purification. All chemicals were purchased
from Aladdin Reagent Co., Ltd. and Sinopharm Chemical Reagent
Co., Ltd. The rest of the materials were obtained from local suppli-
ers. Deionized water was used throughout the experiments.
Figure 14 The TEM images of (a) Pd/rGO, (b) Pd/1,8D-rGO, (c) Pd/BIP-rGO
and (d) Pd/PPD-rGO after cycling.
Synthesis of Graphene Oxide
The TEM characterization of catalyst Pd/rGO, Pd/1,8D-rGO,
Pd/BIP-rGO and Pd/PPD-rGO after 5 cycles of use is shown in Figure
Graphene Oxide (GO) was prepared from natural graphite
flakes (1200 mesh) according to the modified Hummers’ method.
The detailed preparation method is described in our previous work.
1
3. The Pd nanoparticles of Pd/BIP-rGO and Pd/PPD-rGO was
evenly distributed on the graphene sheets without any
agglomeration and theparticle size was hardly changed. It indicated
that the Pd/BIP-rGO and Pd/PPD-rGO are very stable in th ecatalytic
reaction. The Pd nanoparticles of Pd/rGO, Pd/1,8D-rGO has mildly
agglomerated which corresponding the slightly poor performance.
[
34, 35]
Synthesis of diamine-functionalized graphene ox-
ide(DFGO)
Table 5 Catalytic performances of different Pd-based catalysts
in the coupling of iodobenzene and phenylboronic acid.
The diamine--functionalized graphene oxide was prepared by
epoxy ring opening reaction. In a typical procedure for the synthesis
of P-Phenylenediamine-functionalized graphene oxide (PPD-GO),
4
0 mg of GO was dissolved in 20 ml deionized water and sonicated
for 30 min, This yielded a GO dispersion with the concentration of
2
−
1
mg·mL . Next, 40 mg KOH (0.2 g/mL, 200 μL) and 40 mg P-Phe-
nylenediamine (0.04 g/mL, 1 mL) were added. The mixture was re-
fluxed with mechanical stirring at 90 °C for 3 h. Subsequently, the
solution was filtered and washed with ethanol and ultrapure water.
The rinsing-filtration process was repeated for a few times to re-
move the physically adsorbed PPD. Finally, the filtrate cake was
freeze-dried. The methods for synthesizing 1,8-octanediamine
functionalized graphene oxide, biphenyldiamine functionalized
graphene oxide are the same as the above method, except that the
functionally modified amine is changed, the samples are recorded
as PPD-GO, 1,8D-GO, BIP -GO, respectively.
Figure 14 The TEM images of (a) Pd/rGO, (b) Pd/1,8D-rGO, (c) Pd/BIP-rGO
and (d) Pd/PPD-rGO after cycling.
For the sake of comprehensive comparison, the GO sample was
treated using the same condition without the addition of diamine:
2
The as-synthesized GO powder was solvothermally treated in H O
at 90 °C for 3 h, and similarly washed and recovered. Thus treated
GO sample was used for characterization and for the synthesis of a
Pd/GO catalyst.
Synthesis of Pd anchoring on diamine--functionalized
graphene(Pd/DF-rGO)
Conclusions
Pd/DFGO was prepared by using a universal impregnation-re-
duction system. Typically, about 20 mg of DFGO (PPD-GO, 1,8D-GO
or BIP-GO) was dispersed under ultrasound in 5 mL of deionized
water. Then, the required amount of PdCl2 aqueous solution (0.01
g/mL) was added to the bottle. Then, the mixture was kept soni-
In summary, the amine functional graphene have been pre-
pared successfully, Pd nanoparticles as model catalyst were effi-
ciently loaded on functional graphene presenting different struc-
ture and then applied for Suzuki coupling reaction. Pd/PPD-GO,
Pd/BIP-rGO and Pd/1,8D-GO have difference both in structures and
catalytic properties. Pd/PPD-GO and Pd/BIP-rGO showed larger
specific surface area and good sustainability performance, which
can be reused at least five times without loss of catalytic activity.
While Pd/1,8D-GO displayed excellent catalytic performance with
less Pd loading due to an electron-rich in 1,8D-GO. By the catalysis
of Pd/PPD-GO, Pd/BIP-rGO and Pd/1,8D-GO, a variety of aryl io-
dides were successfully coupled to phenylboronic acid in an air at-
4
cated for 30 minutes, and a freshly prepared aqueous NaBH solu-
tion (0.5 mol/L) was slowly added. Then, the reaction mixture was
stirred for 30 minutes. The resulting reaction mixture was filtered
and the black powder product was washed several times and then
carried out under vacuum by using deionized water and EtOH. The
resulting reaction mixture was then lyophilized overnight in a ly-
ophilizer.
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Typical Suzuki coupling reaction
6179-6212.
Xu, H.; Shang, H.; Wang, C.; Du, Y., Recent Progress of Ultrathin 2D
Pd-Based Nanomaterials for Fuel Cell Electrocatalysis. Small 2021, 17
In a typical procedure, aryl halide (1 mmol), arylboronic acid
(
1.3 mmol), base (1.0 mmol) and catalyst (10 mg Pd/1,8D-GO, con-
taining 6 wt% Pd or 10 mg Pd/PPD-GO, containing 8wt% Pd) were
added into a 25 mL pressure tube. The solvent (2mL) was added to
disperse the reactants well and the resulting mixture was stirred
under air atmosphere. Upon the completion of the reaction, the fil-
tered filtrate is dehydrated with MgSO4 and the product is quanti-
tatively analyzed by the gas chromatography (GC-2014, Shimadzu).
Hot filtration test for the Suzuki cross-coupling reactions at
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8
0ꢁ°C; After 5ꢁmin at 80ꢁ°C, the reaction between aryl halide and
phenylboronic acid was completed with full conversion. The cata-
lyst (0.5ꢁmg and 10ꢁmg in parallel reactions) was filtered from the
reaction mixture. New reactants with undecane as an internal
standard were added to the filtrate and stirred at 80ꢁ°C for 10ꢁmin.
The conversions were analysed with GC after each period of time
the gas chromatography (GC2014, Shimadzu).
2
80.
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Characterization of materials
X-ray diffraction (XRD) patterns were obtained using the Bruker
AXS D8 diffractometer with a scanning speed 15o min-1. Raman
spectroscopy was conducted using Thermo DXR with a 532 nm laser
excitation. X-ray photoelectron spectroscopy (XPS) results were ob-
tained using the PHI-5500 spectrometer with Al Ka X-ray radiation
as the X-ray excitation source. Transmission electron microscopy
(
TEM) was conducted using JEM-2100F, and infrared spectra results
were obtained using the NEXUS 670 Fourier transform infrared
FTIR) spectrometer. The N adsorption–desorption isotherms were
(
2
acquired using the Micromeritics Tristar 3000 analyzer. The specific
surface areas and pore size distributions of the catalysts were cal-
culated by the Brunauer–Emmett–Teller (BET) and Barrett–Joyner–
Halenda (BJH) methods, respectively.
Thermogravimetric analysis(TGA) curves were acquired by us-
ing a SDT-Q600 analyzer from TA Instruments, under air flow of 100
-1
-1
mL·min and with a heating ramp of 10 ℃·min .
2
018, 47, 2165-2216.
Song, B.; Choi, J. I.; Zhu, Y.; Geng, Z.; Zhang, L.; Lin, Z.; Tuan,
C.-c.; Moon, K.-s.; Wong, C.-p., Molecular Level Study of Graphene
Networks Functionalized with Phenylenediamine Monomers for Su-
percapacitor Electrodes. Chem. Mater. 2016, 28, 9110-9121.
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Supporting Information
The supporting information for this article is available on the
WWW under https://doi.org/10.1002/cjoc.2021xxxxx.
Acknowledgement
This work was finally supported by the National Key R&D Pro-
gram of China（No. 2021YFE0104900, 2020YFA0710200), the Na-
tional Natural Science Foundation of China (No. 22078103).
Kandjou, V.; Perez-Mas, A. M.; Acevedo, B.; Hernaez, M.;
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Manuscript revised: XXXX, 2021
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Manuscript accepted: XXXX, 2021
Accepted manuscript online: XXXX, 2021
Version of record online: XXXX, 2021
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Entry for the Table of Contents
Effect of alkyl structures on the anti-stacking and anchoring of Pd/diamine -functionalized graphene nanoparticles in application in Suzuki reac-
tion
&
&
Yinbing Tian , Zijie Tang , Yu Ru, Yuanyuan Wang*, and Liyi Dai*
Chin. J. Chem. 2021, 39, XXX—XXX. DOI: 10.1002/cjoc.202100XXX
Text for Table of Contents.
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