Preparation of Co-Pd bimetallic nanoparticles encapsulated in bamboo-like N-doped mesoporous carbon by a facile one-pot method for green Suzuki coupling

Article abstract of DOI:10.1007/s11164-019-03822-3

CoPd bimetallic nanoparticles (NPs) were successfully encapsulated in bamboo-like N-doped mesoporous carbon (bNMC) via a facile one-pot method through combination of dissolving chelation and carbonization reactions. The morphology, structure and composition of CoPd-bNMC was verified by detailed characterization including SEM, TEM, EDX, XPS, XRD, N₂ adsorption–desorption, VSM, and ICP. The as-prepared CoPd/bNMC showed excellent activity and selectivity for Suzuki coupling under mild and green condition. Though the Pd content of CoPd/bNMC was half of Pd/bNMC, the catalytic performance of CoPd/bNMC was almost the same with Pd/bNMC, which was caused by its special bimetallic alloy structure, high BET surface area and pore volume. Importantly, CoPd/bNMC with magnetic property can be separated using external magnetic field and reused for five consecutive runs in the reaction of Suzuki crossing without significant loss of activity. It was found the Pd content only showed slight loss (2.3?wt.%) after five reused reactions, which was because CoPd bimetallic NPs were inside the bamboo-like N-doped mesoporous carbon.

Full text of DOI:10.1007/s11164-019-03822-3

Research on Chemical Intermediates
https://doi.org/10.1007/s11164-019-03822-3
Preparation of Co‑Pd bimetallic nanoparticles encapsulated
in bamboo‑like N‑doped mesoporous carbon by a facile
one‑pot method for green Suzuki coupling
Li Wu1,2,3 · Yu Long3 · Jiantai Ma3 · Gongxuan Lu1
Received: 19 March 2019 / Accepted: 3 April 2019
© Springer Nature B.V. 2019
Abstract
CoPd bimetallic nanoparticles (NPs) were successfully encapsulated in bamboo-like
N-doped mesoporous carbon (bNMC) via a facile one-pot method through combina-
tion of dissolving chelation and carbonization reactions. The morphology, structure
and composition of CoPd-bNMC was verifed by detailed characterization including
SEM, TEM, EDX, XPS, XRD, N2 adsorption–desorption, VSM, and ICP. The as-
prepared CoPd/bNMC showed excellent activity and selectivity for Suzuki coupling
under mild and green condition. Though the Pd content of CoPd/bNMC was half of
Pd/bNMC, the catalytic performance of CoPd/bNMC was almost the same with Pd/
bNMC, which was caused by its special bimetallic alloy structure, high BET sur-
face area and pore volume. Importantly, CoPd/bNMC with magnetic property can
be separated using external magnetic feld and reused for fve consecutive runs in
the reaction of Suzuki crossing without signifcant loss of activity. It was found the
Pd content only showed slight loss (2.3 wt.%) after fve reused reactions, which was
because CoPd bimetallic NPs were inside the bamboo-like N-doped mesoporous
carbon.
Keywords Co-Pd · Bimetallic nanoparticles · N-doped mesoporous carbon · Suzuki
coupling
*
*
Jiantai Ma
majiantai@lzu.edu.cn
Gongxuan Lu
gxlu@lzb.ac.cn
1
2
3
Lanzhou Institute of Chemical Physics, CAS, Lanzhou 730000, People’s Republic of China
University of Chinese Academy of Sciences, Beijing 100049, People’s Republic of China
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000,
People’s Republic of China
Vol.:(0123456789)
1 3

L. Wu et al.
Introduction
Noble-metal-based heterogeneous catalysts have been widely applied for selective
hydrogenation [1–8], oxidation [9–16], carbon–carbon coupling reactions [17–19] and
electrocatalysis [20–23]. Although noble-metal catalysts are acknowledged to be fne
option due to superior catalytic properties, the simple noble metal NPs are prone to
merge and agglomerate because of their high surface energy and high reactivity. More-
over, they are expensive, low atomic utilization rate and easy to lose, poisoning their
autologous activity greatly, which is a major limitation of their practical applications.
Many strategies have been developed to improve stability and reduce cost of noble
metal catalysts [24–31]. As an efective method, transition metals, such as Fe, Co, Ni
were introduced to prepare noble-metal–M (M=Fe, Co, Ni) bimetallic alloy catalyst.
Noble-metal-M alloy catalyst can not only reduce the loading dosage of noble-metal,
but also can be benefcial for increase catalytic efciency and selectivity [32–35]. For
this kind of alloy catalysts containing noble and non-noble metals, it is crucial to opti-
mize the interaction and proportion of noble and non-noble metals [36]. In order to
achieve high catalytic activity and selectivity, Co-based bimetallic alloy catalysts have
attracted extensive attention [37–44].
To avoid nanocatalyst losses in separation processes or difusion factors, carbon
nanotubes are a better choice than conventional carriers [45, 46]. Metal NPs loaded in
carbon nanotubes or inside carriers can greatly inhibit metal loss. Thereinto, N-doped
mesoporous carbon materials have been identifed as the most promising catalyst sup-
ports for the development of robust and efcient catalytic systems, due to its unique
chemical, electrical and functional properties [47–51]. It is widely accepted that N-dop-
ing can enhance the interaction between metal and support and provide high electron
mobility, thus greatly improving its catalytic performance and stability [52, 53]. In
addition, the unique porosity and nanostructure of N-doped mesoporous carbon coated
metal catalyst endowed the catalysts other advantages, such as high shape-selectivity
for various heterogeneous catalytic reaction. Therefore, N-doped mesoporous carbon
coated bimetallic alloy catalyst may efectively increase both catalytic efciency and
selectivity, as well as improve stability.
Nowadays, many eforts have been devoted to design a simple and efective method
to easily prepare N-doped mesoporous carbon coated metal catalyst. As well known,
one-pot synthetic process is the ideal method for preparing multicomponent cata-
lyst. Herein, we report a facile, efcient and large-scale approach to prepare N-doped
mesoporous carbon coated CoPd bimetallic alloy catalysts. A simple one-pot prepa-
ration method was used to prepare bimetallic cobalt palladium NPs/bamboo-like
N-doped mesoporous carbon (CoPd/bNMC) composite by combination of dissolving
chelation and carbonization reactions. The as-prepared CoPd/bNMC composite was
applied for the Suzuki coupling reaction and showed excellent activity and selectivity
for Suzuki coupling under mild and green condition.
1 3

Preparation of Co-Pd bimetallic nanoparticles encapsulated…
Experimental
Materials
Co(NO3)2·6H2O, Pd(Ac)2, NaBH4, methanol, Melamine (MA), polyacrylonitrile
(PA) and were purchased from Kelong Chemical Reagents Company (Chengdu,
China). N, N-dimethylformamide (DMF) and ethanol were obtained from Sinop-
harm Chemical Reagent Co. Ltd. (China). All chemicals used in this study were of
analytical grade and used without further purifcation.
Synthesis of the CoPd/bNMC catalysts
The CoPd/bMNC catalyst was prepared via one-pot pyrolysis of a homogeneous
mixture of Co(NO3)2·6H2O, Pd(Ac)2, PA, and MA at high temperature (≥700 °C)
under a N2 atmosphere. In a typical synthesis procedure: 1.06 g of PA and 500 mg
of Co(NO3)2·6H2O were frst dissolved in 100 mL of DMF in a 250-mL round-bot-
tom fask-2-neck and stirred for 1 h at 100 °C (oil bath), until a homogeneous solu-
tion was formed. Second, 20 g of melamine were slowly added to the as-prepared
homogeneous solution followed by mechanical stirring for 2 h to obtain a thick
slurry, and corresponding molar quantity palladium acetate were added to the fask
and stirred for 1 h at room temperature, which was evaporated on a rotary evapora-
tor and ground into powder. The as-obtained powder was subsequently pyrolysis at
800 °C for 1 h via programmed heating at 10 °C/min under N2 atmosphere, to obtain
the CoPd/bMNC nanocatalyst. In addition, a Co-free material (bMNC) and Pd-free
material (bMNC) were prepared by a similar one-pot pyrolysis method without add-
ing Co(NO3)2·6H2O or Pd(Ac)2.
CoPd/bMNC catalyst for Suzuki reaction
A mixture of aryl halide (1 mmol), arylboronic acid (1.5 mmol), PdCo/bNMC (for
aryl bromide 1 mol %, for aryl chloride 2 mol %), and K2CO3 (2 mmol) was stirred
in EtOH-H2O at suitable temperature for indicated time in air. After completion of
the reaction, the mixture was cooled to room temperature, separated by magnetic
decantation, and extracted by Et2O (10 mL) for three times. And then the organic
phase was combined and evaporated under reduced pressure. Finally, the reaction
yields were obtained by GC. the concrete calculation method of the yields is gas
chromatography area normalization method.
Characterizations
Transmission electron microscopy (TEM, FEI Tecnai G2 F30,200 kV) was used
to observe the morphology and elemental mapping of the prepared catalysts. Pow-
der X-ray difraction (PXRD, Rigaku D/max-2400) was performed in the 2θ range
of 10–90 degree using Cu-Ka radiation (k=1.542 Å) as the X-ray source operat-
ing at 50 kV and 300 mA. X-ray photoelectron spectroscopy (XPS, Perkin-Elmer
1 3

L. Wu et al.
PHI-5702) was employed to analyze the surface electronic states of the prepared
catalysts. Brunauer–Emmett–Teller (BET, Micromeritics ASAP 2010) measure-
ments were employed to measure the pore size distribution, surface area and the
pore volume. Inductively coupled plasma atomic emission spectroscopy (ICP-AES)
was employed to analyze the Co and Pd content in the obtained CoPd/bMCN sam-
ples. The magnetic properties of the prepared catalysts were measured by a vibrating
sample magnetometer (VSM) at room temperature by varying the applied magnetic
feld from 0 to 20 kOe. GC–MS (Agilent 5977E) was employed for monitoring the
reaction conversion and selectivity. Agilent Technologies 7820 A is used for analy-
sis, the column length is 30 m and the diameter is 0.250 nm.
The general preparation strategy of CoPd/bMCN is displayed in Scheme 1.
Results and discussion
Characterization of catalysts
The nanotube mesoporous structure CoPd/bMNC samples were prepared by pyrol-
ysis a mixture of melamine, Co(NO3)2·6H2O and PA, and Scheme 1 displays the
simple synthetic pathway of the CoPd/bMNC. In this experiment, melamine acts as
not only a carbon source, but a nitrogen source, which chelates positively charged
melamine and cobalt ions, thus forming a homogeneous chelate precipitate in aque-
ous solution by the protonated carboxyl group. Meanwhile, melamine can be easy
to decompose when the temperature beyond 200 °C, and form layered graphitic car-
bon nitride when the temperature is 550 °C through a slow heating rate. Moreo-
ver, when the temperature is up to 600 °C, the layered graphitic carbon nitride will
decompose immediately. In the pyrolysis process, carbonized polyacrylonitrile (PA)
is condensed to the carbon skeleton. Because of forming better porous materials, the
calcination temperature setup of catalysts is 800 °C.
Figure 1 shows SEM image of and TEM images of CoPd/bMCN nanocata-
lyst. As shown in Fig. 1a, SEM image of as-prepared CoPd/bMCN was tubular
structures similar to carbon nanotubes. From the TEM image in Fig. 1b, it could
be easily observed CoPd/bMCN was bamboo-like nanotubes structure. And the
CoPd bimetallic NPs were encapsulated in bMCN. As evidenced in Fig. 1c, the
average diameters of CoPd NPs were approximately 8 and 6 nm. The high-angle
Scheme 1 Total synthetic strategy for the CoPd/bMCN catalysts
1 3

Preparation of Co-Pd bimetallic nanoparticles encapsulated…
Fig. 1 a, b The TEM images of CoPd/bMNC, c The SEM images of CoPd/bMNC, d EDX mapping of
CoPd/bMNC
annular dark-feld scanning transmission electron microscopy (HAADF-STEM)
was also applied to examine the component and structure of CoPd/bMCN, which
are displayed in Fig. 1d. From the results of HAADF-STEM, we can easily fnd
out CoPd NPs show good dispersion, and the doped N was successfully inserted
into carbon material. Element distribution mappings of selected area revealed the
really existence of CoPd bimetallic NPs encapsulated in bMCN.
The chemical compositions of the as-prepared CoPd/bMCN catalyst were
measured by XPS measurements. The wide-range XPS spectrum of CoPd/bMNC
(shown in Fig. 2a) demonstrates the presence of elemental C, N, O, Co and Pd
in the as –prepared CoPd/bMNC sample. To further explore the valence state of
Co and Pd, the Pd 3d and Co 2p XPS spectra of the sample were also acquired.
The peak at around 780 eV is assigned to the Co0 (shown in Fig. 2b), indicating
the appearance of cobalt nanoparticles in the pyrolysis process, and the peak at
around 787 eV is attributed to the cobalt oxide, which may be caused by the oxi-
dization of cobalt nanoparticles in the XPS sampling process. From these results
we can conclude that the Co–O was indeed formed, followed by the replacement
of N by O in CoNx, and fnally Co0 was formed through the decomposition of
CoNx or reduction with carbon at high-temperature under inert atmosphere.
In the Pd 3d XPS spectrum (Fig. 2c), two characteristic peaks attributed to Pd
3d3/2 and Pd 3d5/2 at around 338.7 and 333.5 eV indicate that the existence of
Pd nanoparticles in the CoPd/bMCN catalyst. In addition, the chemical composi-
tions of diferent elementals of the as-prepared samples are exhibited in Table 1,
and the Co and N contents the CoPd/bMCN catalyst are 11.95 and 14.1 wt.%,
respectively.
1 3

L. Wu et al.
Fig. 2 a the wide-range XPS spectrum of CoPd/bMNC; b the Pd 3d and c C1s d Co 2p region of CoPd/
bMNC
Table 1 Texture parameters and the element content of the prepared catalysts
Catalyst
Surface area Pore size (nm)
Pore volume Pd (wt.%)
Co (wt.%)
N (wt.%)
(m2 g−1
)
(cm3 g−1
)
Co/bMCN
Pd/bMNC
CoPd/bMCN
251.89
269.96
281.69
6.56
4.47
3.75
0.41
0.41
0.26
0
3.05
1.72
3.98
0
2.95
15.90
14.80
14.10
XRD analysis was used to examine the structures of Co/bMNC, Pd/bMNC
and CoPd/bMNC samples, the results are displayed in Fig. 3. The peak at around
25° is assigned to the carbon (002) plane of CNT difraction of amorphous car-
bon. For the XRD pattern of CoPd/bMNC, the peaks at 40°, 46°, 68°, and 83°
are attributed to the Pd (111), (200), (220) and (311) crystal planes respectively
(JCPDS NO.05-0681), for bimetallic NPs, the Pd species also show strong dif-
fraction peaks, further demonstrating that the Pd species of CoPd/bMNC show
a face-centered cubic structure phase, corresponding to the standard Pd card
(JCPDS NO.05-0681). Moreover, the difraction peaks attributed to Pd in CoPd/
bMNC shift slightly to higher 2θ values compared with the standard Pd card
(JCPDS NO.05-0681), proving the lattice contraction caused by the incorporation
1 3

Preparation of Co-Pd bimetallic nanoparticles encapsulated…
Fig. 3 XRD patterns of the prepared catalysts a CoPd/bMNC, b Co/bMNC, and c Co/bMNC
of Co species into the Pd face-centered cubic structure. This is an evidence of
Pd-Co alloy formation.
The N2 adsorption–desorption profles and pore size distribution for Co/bMNC,
Pd/bMNC and CoPd/bMNC catalysts are displayed in Fig. 4. According to the
IUPAC classifcation, the isotherms with a large hysteresis loop in the relative pres-
sure (P/P0) range of 0.4–1.0 show a type IV curve, corresponding to the charac-
teristics of mesoporous materials with micro- and mesoporous pore size distribu-
tion. The large hysteresis loop suggests that a capillary condensation phenomenon
has occurred in the mesoporous structure. However, Pd/bMCN has a very small
hysteresis loop, which should be due to the formation of dense graphitic carbon
nitride. CoPd/bMNC shows a higher specifc surface area, originating from the
Fig. 4 a Nitrogen adsorption–desorption isotherm plots of the prepared CoPd/bMCN materials that car-
bonized at diferent temperatures. b Pore size distributions of the prepared CoPd/bMCN materials
1 3

L. Wu et al.
porous and multi-channel bamboo-like structure in the rod solids as evidenced in
Fig. 2. Table 1 summarizes the BET surface area, pore volume, and average pore
size of the prepared catalysts (i.e., Co/bMCN, CoPd/bMCN, Pd/bMCN). As shown
in Table 1, CoPd/bMCN exhibited the highest BET surface area and pore volume
(281.69 m2 g−1, and 0.26 cm3 g−1 respectively), with an average pore size of 3.7 nm.
The more developed mesoporous of those materials pyrolyzed at high temperatures
was thought to enhance the exposure of the Co active sites, thereby increasing its
catalytic activity. The elemental compositions of the prepared catalysts are also
demonstrated in Table 1, the CoPd/bMCN catalyst showed N and Co contents of
14.1 and 2.95 wt.%, respectively.
The magnetic property of CoPd/bMCN was also tested (displayed in Fig. 5).
According ro the magnetic measurement, the magnetization saturation value of
CoPd/bMCN is 9.55 emu g−1. Owing to its magnetite content, CoPd/bMCN could
be rapidly separated from the reaction mixture with the external magnetic feld. This
characteristic property can provide a more portable and efcient way to separate the
CoPd/bMCN catalyst from the after reaction system for recycle under the external
magnetic feld.
Catalytic activity, generality and recyclability for Suzuki coupling reaction
by CoPd/bMNC
We have chosen Suzuki coupling reaction as the model reaction, the optimal reac-
tion conditions, the catalysts composition, the general applicability, and recyclability
of CoPd/bMNC were investigated.
The optimized reaction condition for Suzuki coupling reaction by CoPd/bMNC
was examined (Table 2). All reactions were tested under N2 atmosphere. As shown
in Table 2, entries 1-5, under the reaction conditions of 0.5 mmol of iodobenzene,
0.75 mmol of phenylboronic acid, 5.0 mol % of CoPd/MNC catalyst and 2.0 mmol
Fig. 5 Room-temperature magnetization curves of the CoPd/bMCN catalyst
1 3

Preparation of Co-Pd bimetallic nanoparticles encapsulated…
Table 2 Optimization of conditions for the Suzuki reaction of iodobenzene with phenylboronic
acid
Entry
Solvent
Catalyst
Base
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
DMF
Toluene
H2O
EtOH
EtOH-H2O
EtOH-H2O
EtOH-H2O
EtOH-H2O
EtOH-H2O
EtOH-H2O
EtOH-H2O
CoPd/bMNC
CoPd/bMNC
CoPd/bMNC
CoPd/bMNC
CoPd/MNC
CoPd/bMNC
CoPd/MNC
CoPd/bMNC
CoPd/bMNC
Pd/bMNC
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
NaHCO3
NaOAc
KOH
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
60.6
43.3
68.2
97.9
95.8
78.1
11.4
45.1
Trace
97.5
8.3
9
10
11
No base
K2CO3
K2CO3
Co/bMNC
Reaction conditions: iodobenzene (0.5 mmol), phenylboronic acid (0.75 mmol), H2O (2.5 mL), EtOH
(2.5 mL), CoPd/MNC (5.0 mol %), 80 °C
aDetermined by using GC
base at 80 °C in a 5 mL solvent, the solvent efect on this reaction was frstly stud-
ied, the screening of many solvents exhibites that EtOH/H2O is the most suitable
solvent. Further, diferent bases were investigated on this Suzuki coupling reac-
tion, because diferent bases have diferent infuences on catalytic performance. As
shown in Table 2, entries 6-9, we can know that the reaction gave no product in the
absence of base, and K2CO3 showed the best catalytic performance in various bases.
Under the optimal reaction condition, the catalytic activities of Co/bMNC and Pd/
bMNC for the Suzuki C–C coupling reaction were tested (Table 2, entries 10, 11).
It is found Co/bMNC exhibited a very low catalytic performance for this Suzuki
C–C coupling reaction (8.3% yield), while, Pd/bMNC showed a high yield of tar-
get product. Though the catalytic performance of Pd/bNMC (97.5% yield) was a
little higher than CoPd/bNMC (95.8% yield), the Pd content of Pd/bNMC was more
than twice the Pd content of CoPd/bNMC, which was caused by its special bimetal-
lic structure. Notably, the Mott-Schottky-based CoPd/bMNC heterogeneous catalyst
can greatly enhance the catalytic activity through designing the Mott-Schottky inter-
face in metal (CoPd) and bMNC. Besides, introducing cobalt to form the bimetallic
alloy catalytic system can efectively prevent the noble nanoparticles agglomeration
as well activating the Pd center through electron charge transfer between Pd and Co.
The generality of this Suzuki coupling reaction was also studied, difer-
ent substituted phenylboronic acid with diferent halides (I, Br, Cl) were tested
under the optimized conditions. CoPd/bMNC showed high yield of targat prod-
ucts when reacting phenyl iodides, bromides and chlorides with phenylboronic
acid (Table 3, entries 1–9). Aryl halides could bear both electron-withdrawing
1 3

L. Wu et al.
Table 3 Heterogeneous Suzuki–
Miyaura reaction of aryl halides
(R1C6H4X) with phenylboronic
acid (R2C6H4B(OH)2) catalysed
by CoPd/MNCa
Entry
R1
X
R2
Time (h)
Yield (%)b
1
2
3
4
5
6
7
8
H
H
I
I
I
I
I
I
I
I
H
0.5
1
99.9
90.2
88.9
91.5
93.2
94.8
93.1
73.0
71.3
83.6
89.7
23.9
CH3
CH3
H
H
H
4-CH3
4-COCH3
4-CH3
4-OH
4-NO2
4-OH
4-NO2
4-OCH3
H
2 h
2 h
2 h
2 h
2 h
2 h
2 h
2 h
2 h
2 h
H
Cl
Cl
Cl
H
9
I
10
11
12
Br
Br
Cl
H
H
aReaction conditions: iodobenzene (0.5 mmol), phenylboronic
acid (0.75 mmol), H2O (2.5 mL), EtOH (2.5 mL), CoPd/MNC
(5.0 mol%)
bDetermined by using GC. Our chromatographic model is Agilent
Technologies 7820A, the column length is 30 m and the diameter
is 0.250 nm, the TIC image integral used to compute the percentage
and electron-releasing groups reacting with phenylboronic acid to acquire high
yield of products. It is noteworthy that 2-bromothiophene and 2-iodothiophene
reacting with phenylboronic acid give 99.9 and 94.8% product yields, respec-
tively (shown in Table 3, entries 1 and 6).
In view of both industrial production and green chemistry, the recyclability
of the catalyst is also an important index to evaluate the comprehensive perfor-
mance of catalyst. So the recyclability of CoPd/bMNC was estimated. In this
recycle experiment, the CoPd/bMNC catalyst was separpted from reaction mix-
ture by using a magnet after each cycle run, and and exhaustively washed with
deionized water and ethanol. Finally, the catalyst was dried at 80 °C for 24 h
and reused for the next cycle reaction experiment. It can be seen that the CoPd/
bMNC catalyst could be applied for fve times and still maintain high production
yields (Fig. 6). The good catalytic perfomance could be due to the strong cataly-
sis synergistic efect of Co nanoparticles and Pd nanoparticles with active sites
of N-doped carbon materials. Moreover, the morphology and structure of the
reused catalyst was also investgated. As shown in Fig. 6, the TEM image of the
reused CoPd/bMNC indicates that the catalyst shows no change in morphology
after fve times reaction. The contents of Pd of CoPd/bMNC before and after
fve times reaction were also measured by applying ICP-AES analysis, which is
2.65 and 2.59 wt.% respectively. This result indicates that Palladium is stably
supported on the BMNC and there is almost no leaching during the reaction.
1 3

Preparation of Co-Pd bimetallic nanoparticles encapsulated…
Fig. 6 a, b The TEM images of CoPd/MNC after fve runs. c Recycle of the CoPd/MCN catalyst
Conclusions
In summary, we synthesized highly active bimetallic CoPd/bMNC nanoparticle cat-
alysts, and showed good activity towards Suzuki coupling reaction in water–ethanol
solution for various substrates. Though the Pd content of CoPd/bNMC was half of
Pd/bNMC, the catalytic performance of CoPd/bNMC was almost the same with Pd/
bNMC. Notably, the Mott-Schottky-based CoPd/bMNC heterogeneous catalyst can
greatly enhance the catalytic activity through designing the Mott-Schottky interface
in metal (CoPd) and bMNC. Besides, introducing cobalt to form the bimetallic alloy
catalytic system can efectively prevent the noble nanoparticles agglomeration as
well activating the Pd center through electron charge transfer between Pd and Co.
Moreover, the CoPd/bMNC catalyst has the advantages of low-price, easy to recycle
from the reaction mixture through the magnetic feld and the CoPd/bMNC catalyst
can be prepared in large-scale, we think our catalyst could be applied more widely
in various felds. Overall, such a low-cost and high-performance nanocatalyst may
bring new design opportunities for C–C coupling catalysis on an industrial scale in
the future.
Acknowledgements This research was supported by the National Natural Science Foundation of China
(China, 21433007, 21872066).
References
1. F. Meemken, A. Baiker, Chem. Rev. 117, 11522 (2017)
1 3

L. Wu et al.
2. Y. Long, Y. Liu, Z. Zhao, S. Luo, W. Wu, L. Wu, H. Wen, R.-Q. Wang, J. Ma, J. Colloid Interf. Sci.
496, 465 (2017)
3. H.N. Chai, B. Liu, A.Q. Liu, K. Yu, J. Mol. Catal. (China) 32, 481 (2018)
4. H. Cao, X. Chen, Y. Du, C.H. Liang, J. Mol. Catal. (China) 32, 501 (2018)
5. G.X. Li, Q. Li, X.L. Zeng, J. Bian, H.W. Li, H.F. Mu, J. Mol. Catal. (China) 31, 316 (2017)
6. L.G. Chen, X.H. Zhang, Q.Y. Liu, Q. Zhang, T.J. Wang, C.G. Wang, L.L. Ma, J. Mol. Catal. (China)
31, 267 (2017)
7. Y. Long, B. Yuan, J. Niu, X. Tong, J. Ma, New J. Chem. 39, 1179 (2015)
8. C. Huang, X. Wang, F. Yu, B. Yuan, C. Xie, S. Yu, Res. Chem. Intermed. 44, 13 (2018)
9. Y. Long, Z. Zhao, L. Wu, S. Luo, H. Wen, W. Wu, H. Zhang, J. Ma, Mol. Catal. 433, 291 (2017)
10. J.H. Guo, C.X. Lin, C.J. Jiang, P.Y. Zhang, Appl. Surf. Sci. 475, 237 (2019)
11. Q. Zhang, Q. Liu, P. Ning, X. Liu, L. Xu, Z. Song, Y. Duan, T. Zhang, Res. Chem. Intermed. 43,
2017 (2017)
12. L.L. Chen, Z.X. Wang, B.X. Dou, K. Han, J. Y. Xin 32, 574 (2018)
13. H.X. Guo, R.X. Yan, X.H. Xi, J. Mol. Catal. (China) 32, 471 (2018)
14. S.C. Chen, F. Han, J.H. Liu, C.G. Xia, J.X. Ma, J. Mol. Catal. (China) 32, 382 (2018)
15. H.P. Yan, Y.C. Zhang, H.Y. Zhang, J.Q. Zhao, J Mol Catal (China) 32, 117 (2018)
16. L. Liu, C.H. Zheng, X. Gao, J. Mol. Catal. (China) 32, 54 (2018)
17. J. Xia, Y. Fu, G. He, X. Sun, X. Wang, Appl. Catal. B.-Environ. 200, 39 (2017)
18. Y. Long, K. Liang, J. Niu, X. Tong, B. Yuan, J. Ma, New J. Chem. 39, 2988 (2015)
19. M.M. Khodaei, A. Alizadeh, M. Haghipour, Res. Chem. Intermed. (2019)
20. J. Wang, F. Xu, H.Y. Jin, Y.Q. Chen, Y. Wang, Adv. Mater. 29, 35 (2017)
21. S. Gao, M.X. Yang, S.M. Li, J. Mei, S. Xie, H. Liu, J. Mol. Catal. (China) 32, 261 (2018)
22. Z.K. Xie, X.Y. Chen, W.B. Hu, X.G. Shu, X.H. Zhou, W.W. Chen, J. Mol. Catal. (China) 32, 520
(2018)
23. Y. Ren, D.R. Liu, Y. Pan, J. Feng, W. Xiong, D.H. Qiu, J. Mol. Catal. (China) 32, 8 (2018)
24. J. Tang, R.R. Salunkhe, J. Liu, N.L. Torad, M. Imura, S. Furukawa, Y. Yamauchi, J. Am. Chem.
Soc. 137, 1572 (2015)
25. K. Shen, X. Chen, J. Chen, Y. Li, ACS Catal. 6, 5887 (2016)
26. W. Xia, R. Zou, L. An, D. Xia, S. Guo, Energy Environ. Sci. 8, 568 (2015)
27. X. Li, Y. Fang, X. Lin, M. Tian, X. An, Y. Fu, R. Li, J. Jin, J. Ma, J. Mater. Chem. A. 3, 17392
(2015)
28. A. Aijaz, Q. Xu, J. Phys. Chem. Lett. 5, 1400 (2014)
29. C. Bai, X. Yao, Y. Li, ACS Catal. 5, 884 (2015)
30. R.V. Jagadeesh, A.-E. Surkus, H. Junge, M.-M. Pohl, J. Radnik, J. Rabeah, H. Huan, V. Schüne-
mann, A. Brückner, M. Beller, Science 342, 1073 (2013)
31. Z. Wei, J. Wang, S. Mao, D. Su, H. Jin, Y. Wang, F. Xu, H. Li, Y. Wang, ACS Catal. 5, 4783 (2015)
32. Z.P. Dong, X.D. Le, C.X. Dong, W. Zhang, X.L. Li, J.T. Ma, Appl. Catal. B-Environ. 162, 372
(2015)
33. J. Yang, W.D. Wang, Z.P. Dong, J. Colloid Interface Sci. 524, 84 (2018)
34. X.L. Cui, Y. Long, X. Zhou, G.Q. Yu, J. Yang, M. Yuan, J.T. Ma, Z.P. Dong, Green Chem. 20, 1121
(2018)
35. S. Komeili, M.T. Ravanchi, A. Taeb, Res. Chem. Intermed. 44, 1335 (2018)
36. H. Fang, J.H. Yang, M. Wen, Q.S. Wu, Adv. Mater. 30, 10 (2018)
37. H. Ma, H. Wang, T. Wu, C. Na, Appl. Catal. B-Environ. 180, 471 (2016)
38. R.V. Jagadeesh, D. Banerjee, P.B. Arockiam, H. Junge, K. Junge, M.-M. Pohl, J. Radnik, A. Brück-
ner, M. Beller, Green Chem. 17, 898 (2015)
39. P. Hu, M. Long, Appl. Catal. B-Environ. 181, 103 (2016)
40. R.V. Jagadeesh, K. Murugesan, A.S. Alshammari, H. Neumann, M.-M. Pohl, J. Radnik, M. Beller,
Science 358, 326 (2017)
41. X.L. Cui, H. Li, G.Q. Yu, M. Yuan, J. Yang, D. Xu, Y.M. Hou, Z.P. Dong, Int. J. Hydrogen Energy
42, 27055 (2017)
42. P. Zhou, Z. Zhang, L. Jiang, C. Yu, K. Lv, J. Sun, S. Wang, Appl. Catal. B-Environ. 210, 522 (2017)
43. X. Cui, K. Liang, M. Tian, Y. Zhu, J. Ma, Z. Dong, J. Colloids Interface Sci. 501, 231 (2017)
44. T.A. Revathy, T. Sivaranjani, A.A. Boopathi, S. Sampath, V. Narayanan, A. Stephen, Res. Chem.
Intermed. 45, 815 (2019)
45. Y.B. Yan, J.W. Miao, Z.H. Yang, F.X. Xiao, H.B. Yang, B. Liu, Y.H. Yang, Chem. Soc. Rev. 44,
3295 (2015)
1 3

Preparation of Co-Pd bimetallic nanoparticles encapsulated…
46. B.T. Liu, Y.L. Xu, S.Y. Zhang, X.M. Lv, Y.Q. Ling, Z.J. Zhou, J. Liu, Mater. Lett. 239, 124 (2019)
47. B. Chen, L. Wang, W. Dai, S. Shang, Y. Lv, S. Gao, ACS Catal. 5, 2788 (2015)
48. A. Aijaz, J. Masa, C. Rösler, W. Xia, P. Weide, A.J.R. Botz, R.A. Fischer, W. Schuhmann, M. Muh-
ler, Angew. Chem. Int. Ed. 55, 4087 (2016)
49. J. Wei, Y. Hu, Y. Liang, B. Kong, J. Zhang, J. Song, Q. Bao, G.P. Simon, S.P. Jiang, H. Wang, Adv.
Funct. Mater. 25, 5768 (2015)
50. M.Y. Fan, Y. Long, Y.Y. Zhu, X.W. Hu, Z.P. Dong, Appl. Catal. a-Gen. 568, 130 (2018)
51. D. Li, Y. Liu, H. Liu, Z. Li, L. Lu, J. Liang, Z. Huang, W. Li, Res. Chem. Intermed. (2018)
52. H. Su, K.-X. Zhang, B. Zhang, H.-H. Wang, Q.-Y. Yu, X.-H. Li, M. Antonietti, J.-S. Chen, J. Am.
Chem. Soc. 139, 811 (2017)
53. S. Cheng, X. Meng, N. Shang, S. Gao, C. Feng, C. Wang, Z. Wang, New J. Chem. 42, 1771 (2018)
Publisher’s Note Springer Nature remains neutral with regard to jurisdictional claims in published
maps and institutional afliations.
1 3