Pd-Ni BMNPs Encapsulated in UiO-66 as an Efficient Catalyst for the Activation of “Inert” C?O Bonds

Article abstract of DOI:10.1002/cctc.201800898

A catalytic system based on Pd?Ni bimetallic nanoparticles (BMNPs) encapsulated in the nanocavities of UiO-66 was established for the activation of C?O bonds in ethers. Pd_0.25Ni₄@UiO-66 catalyst show excellent catalytic performance in the directly methylation and arylation of ethers under a mild reaction condition. High catalytic activity of the catalyst could be ascribed to the “synergistic effect” between the two metal components and strong interaction between BMNPs and the carrier (UiO-66). BMNPs encapsulated in UiO-66 also guarantee a good reusability of the catalyst, the catalyst delivered high catalytic activity for at least four cycles. Our work highlights the great potential value of ethers as powerful alternatives for aryl halides as well as the bright future of BMNPs and MOFs in the catalysis field.

Full text of DOI:10.1002/cctc.201800898

Accepted Article
Title: Pd-Ni BMNPs encapsulated in UiO-66 as an efficient catalyst for
the activation of "inert" C-O bond
Authors: Jia-wei Zhang, Dan-dan Li, Guo-ping Lu, Tao Deng, and
Chun Cai
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
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the VoR from the journal website shown below when it is published
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content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201800898
Link to VoR: http://dx.doi.org/10.1002/cctc.201800898
A Journal of
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10.1002/cctc.201800898
ChemCatChem
COMMUNICATION
Pd-Ni BMNPs encapsulated in UiO-66 as an efficient catalyst for
the activation of "inert" C-O bond
a
a
a
b
a
,
Jia-wei Zhang , Dan-dan Li , Guo-ping Lu , Tao Deng and Chun Cai *
Abstract:
A
catalytic system based on Pd-Ni bimetallic
performance.
nanoparticles (BMNPs) encapsulated in the nanocavities of UiO-66
was established for the activation of C-O bonds in ethers.
Pd0.25Ni4@UiO-66 catalyst show excellent catalytic performance in
the directly methylation and arylation of ethers under a mild reaction
conditions. High catalytic activity of the catalyst could be ascribed to
the “synergistic effect” between the two metal components and
strong interaction between BMNPs and the carrier (UiO-66). BMNPs
encapsulated in UiO-66 also guarantee a good reusability of the
catalyst, the catalyst delivered high catalytic activity for at least four
cycles. Our work highlights the great potential value of ethers as
powerful alternatives for aryl halides as well as the bright future of
BMNPs and MOFs in the catalysis field.
Based on our previous experience on design of outstanding
catalysts for green and sustainable future,[23-25] we envisage that
development of catalytic system based on bimetallic
a
nanoparticles maybe essential for C-O activation reaction.
Toward this end, herein, a Pd-Ni BMNPs catalyst was fabricated
and its catalytic performance for the coupling reactions between
ethers and Grignard reagents was evaluated. UiO-66
(Zr6O4(OH)4(BDC)6, BDC =1,4-benzenedicarboxylate) was
chosen as the matrix for the BMNPs due to its highly porous
structures and open channels, which may greatly enhance
catalytic performance due to the synergistic effect between the
nanoparticles and MOFs.[26-28] Full conversion of the substrates
was achieved in the presence of Pd0.25Ni4@UiO-66 catalyst
under a mild condition, both alkyl and aryl Grignard reagents
were applicable. Hot filtration experiments indicates that
nanoparticles were the active sites for the C-O activation
reaction, the catalyst could be reused up to 4 times without
significant loss in catalytic efficiency.
Direct use of ethers as the electrophilic coupling partner in
coupling reaction provide a more appealing synthetic method
due to their commercial availability and readily derivation from
the abundantly available natural phenolic compounds.[1-4]
A
pioneering work was reported by Wenkert et al in 1979, anisoles
were used as electrophiles to couple with aromatic Grignard
reagents.[5] Subsequent work also showcased the great potential
We started
our
investigations
by
reacting
2-
methoxynaphthalene with MeMgBr, Pd-Ni BMNPs was initially
selected as the catalyst in light of pioneering work of Chakraborti
et al[29,30] and our previous experience.[23-25] SiO2 was used as
the support at the outset of our study due to its easy availability.
In line with our expectations, Pd1Ni4/SiO2 could catalyze the C-O
activation reaction in the absence of the ligand although the
reaction yield was moderate (Table 1, entry 1). Only traces of
the product, if any, was detected using the monometallic
nanoparticles as the catalyst (entries 2~3), which emphasizes
the vital role of the unique electronic structure of BMNPs for this
reaction. Better catalytic performance of BMNPs may originate
from the accelerated electron flow on the catalyst surface, which
was caused by the charge heterogeneity exists on the BMNPs
surface.[23-25] To optimize the reaction condition, solvent effects
on this reaction were evaluated, as illustrated in Table S1
(Supporting information), much lower yields were obtained when
the reactions were proceed in other solvents compared with
toluene, indicating that choice of the solvent played a vital role in
the efficiency of this reaction.
4, 6-8]
of ethers as electrophiles in the coupling reactions.[3,
However, due to the robust nature of C-O bonds, catalysts for C-
O activation reactions are often carefully designed.[9] Catalysts
reported up to date are mainly homogeneous Ni complex,[10-13]
which always suffer from catalyst recyclability and products
purification. Since heterogeneous catalytic system for activation
of C-O bonds is rare, it’s reasonable to propose that an excellent
heterogeneous catalyst with high efficiency and stability may
greatly broaden the application field of the C-O activation
reaction using ethers as electrophiles.[8]
Nano-catalyst has long been regarded as the bridge
between homogeneous and heterogeneous catalysis,[14]
decreasing the size of a particle results in a larger share of the
atoms located on the surface, which can increase the utilization
efficiency of metal elements.[15] Since some C-O activation
reaction involve the utilization of Grignard reagents like MeMgBr,
which can reduce the Ni complex into nanoparticles,[16] it’s
reasonable to propose that Ni nanoparticles maybe the real
active site for this reaction. BMNPs, emerging as a new platform
for design of highly efficient catalysts, often show superior
catalytic performance to corresponding single metal catalyst due
to a phenomenon collectively referred as “synergistic effects”.[17-
Furthermore, much higher yield was obtained while 1 mol%
dcype was introduced as a ligand (Table 1, entry 4). After
several phosphine ligands had been surveyed (entries 4~11),
PCy3 was emerged to be the optimal ligand for this reaction. In
the presence of PCy3 (an electron-rich ligand), oxidative addition
of C-O to Ni(0) could proceed through the pathway with
relatively low energy barrier, which may greatly speed up the
reaction process.[31] Subsequently, initial attempt to perform the
reaction at relatively low temperature reveals that 2-
methoxynaphthalene could also be completely transformed into
2-methylnaphthalene at 40 oC (entry 12). However, reducing the
22]
Doping metal nanoparticle with another metal could greatly
change its electronic states and structural conformations, which
were regarded as the origin of the enhanced catalytic
J. Zhang, D. Li, Prof. G. Lu, T. Deng and Prof. C. Cai
a Chemical Engineering College, Nanjing University of Science &
Technology Xiaolingwei 200, Nanjing 210094, P. R. China
b Institute of Tropical Medicine, Guangzhou University of Chinese Medicine,
Guangzhou 510405, China
o
reaction temperature to 30 C caused obvious lose in catalytic
o
performance (entry 13), so 40 C was selected as the reaction
*E-mail: c.cai@njust.edu.cn
temperature in the further conditions optimization process (14-
20). MOFs have attracted great interest due to their outstanding
Supporting information for this article is given via a link at the end of the
document.
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10.1002/cctc.201800898
ChemCatChem
COMMUNICATION
Table 1. Optimization of the reaction conditions.a
of nitrogen atoms in UiO-66(NH2), which could compete with
PCy3 for metal binding.[36]
Entry
1
Catalyst
Pd1Ni4/SiO2
Pd/SiO2
T(oC)
80
80
80
80
80
80
80
80
80
80
80
40
30
40
Ligand
--
Yield (%)b
57
2c
3d
4
--
NR
NR
98
Ni/SiO2
--
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd1Ni4/SiO2
Pd0.25Ni4@UiO-66
dcype
dppf
5
<5
6
dppe
dppb
PPh3
PCy3
Xantphos
Xphos
PCy3
PCy3
PCy3
18
7
<5
8
7
9
100
20
10
11
12
13
14
Fig.1 TEM imagines of Pd0.25Ni4@UiO-66
60
Composition of the BMNPs was reported to be vital for its
catalytic performance,[17,18,20,37] changing Ni in the BMNPs into
Co results in obvious loss in catalytic performance, only minor
product was detected after reaction (entry 16). What’s more,
replacing Pd with other metal elements such as Fe, Co and Cu
also caused significant decrease in catalytic efficiency (entries
17-19). No reaction transpired in the absence of the catalyst
(entry 20). Those results clearly indicated that both Pd and Ni
are essential for the high catalytic efficiency.
100
67
100
Pd0.25Ni4@UiO-
66(NH2)
15
40
PCy3
0
16
17
18
19
20
Pd0.25Co4@UiO-66
Co1Ni1@UiO-66
Cu1Ni1@UiO-66
Fe1Ni1@UiO-66
--
40
40
40
40
40
PCy3
PCy3
PCy3
PCy3
PCy3
<5
70
63
58
NR
a
Reaction condition: 2-methoxynaphthalene (0.1 mmol),
MeMgBr (0.2 mmol), 4 mol% Catalyst (based on Ni), ligand (1
mol%), Toluene (1 mL) was used as the solvent, the reaction
was proceed under argon atmosphere at corresponding
temperature for 2h. b Yields were determined by GC. c 1 mol%
Pd/SiO2 was used as the catalyst. d 4 mol% Ni/SiO2 was used
as the catalyst.
Fig.2 TEM-EDS mapping images of Pd0.25Ni4@UiO-66
After the optimization of the reaction conditions, the
morphological character and microstructure of the as-prepared
catalyst were investigated using the transmission electron
microscopy (TEM) measurements. As can be seen from Fig. 1,
some dispersed nanoparticles were encapsulated in UiO-66
frameworks, indicating the successful synthesis of the Pd-
Ni@UiO-66 composites. Average diameter of the NPs was
measured to be 4.5 nm, ultrafine nanoparticles provide more
active unsaturated metal atoms and more contact opportunities
between the active sites and substrates, resulting in higher
catalytic efficiency. High-resolution TEM (HRTEM) analysis was
used to verify the formation of BMNPs, as shown in the inset of
Fig. 1c, the nanoparticles have clear crystalline fringe patterns
and the lattice distance is measured to be 0.21 nm, which could
be assigned to the d-spacing of the (111) plane of the Pd–Ni
alloy.[25] TEM-EDS mapping of the Pd0.25Ni4@UiO-66 catalyst
was also carried out (Fig. 2), which indicates a uniform
distribution of Ni and Pd elements in UiO-66. ICP-MS result
showed that the Pd and Ni loading of the as prepared
properties. Combination of the host-guest cooperation and
bimetallic synergy in catalysis may greatly boost the catalytic
efficiency, so we hope to apply MOFs as catalyst carrier to
improve the catalytic efficiency.[26, 32-34] As a ‘‘star’’ MOF, UiO-66
was chosen as the catalyst matrix. Gratifying, a satisfactory
catalytic efficiency of the BMNPs was still remained while
reducing the Pd amount (entry 14), which may greatly decrease
the cost of the catalyst. Outstanding catalytic performance of
Pd0.25Ni4@UiO-66 could be ascribed to porous structure of UiO-
66, nanocavities of UiO-66 can act as nanoreactors to facilitate
diffusion of the reactants, ensuring a good interaction between
reactants and the active sites.[35] However, when UiO-66(NH2)
was applied as the support, no product was detected (entry 15),
ineffectiveness of this catalyst could be ascribed to the presence
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Pd0.25Ni4@UiO-66 was 0.14wt% and 1.25wt% respectively (ESI,
Table S2), which confirmed that the Pd/Ni ratio was almost
consistent with the designed composition of the Pd0.25Ni4
BMNPs. Powder X-ray diffraction pattern of the prepared
catalysts were also performed, as shown in Figure S2 (ESI),
crystallinity and structure of UiO-66 were retained after metal
loading. But diffraction peaks for Pd or Ni were not observed,
and we think this maybe due to low metal content and small size
of nanoparticles in the catalyst.[26]
oxygen components of the carboxylate groups due to the
unreactive ligand.[40]
Fig.
4 Comparison of Pd 3d scan of the as prepared
Pd0.25Ni4@UiO-66 catalyst and unsupported Pd0.25Ni4 BMNPs.
Table 2. Methylation and arylation of different ethers.a
Entry
1
2
3
Yield (%)b
1
2
3
4
MeMgBr
MeMgBr
MeMgBr
MeMgBr
100
87
76
71
5
MeMgBr
MeMgBr
93
74
6c
7
8c
9
MeMgBr
MeMgBr
MeMgBr
81
68
87
10c
11c
12c
13c
PhMgBr
PhMgBr
PhMgBr
PhMgBr
100
81
Fig. 3 XPS spectrum of the as-prepared Pd0.25Ni4@UiO-66
catalyst
To determine the chemical compositions and the valence
state of the metal elements on the catalyst surface, X-ray
photoelectron spectroscopy (XPS) measurements were
performed and the corresponding results were shown in Fig. 3.
Fig. 3(a) presents overall surveys of the as-synthesized
Pd0.25Ni4@UiO-66 nano-composites, which clearly reveal Zr, O,
C, Ni and Pd element signals. The XPS data points out that the
ratio of the surface concentration between Pd and Ni is 0.15,
which indicates that the BMNPs is in a random alloy form and
Pd tends to distribute on the surface of the BMNPs. High-
resolution XPS spectrum of C 1s was shown in Fig. 3(b), which
could be fitted by three peaks at binding energies of around
284.6, 288.7 and 285.0 eV. Peaks at 284.6 and 288.7 eV could
be assigned to phenyl and carboxyl signals, while peak at about
285.0 eV may be due to the carbon on the surface of the
sample.[38] Peaks for Zr 3d5/2 and Zr 3d3/2 could be found at
around 182.5 and 184.9 eV, indicating that Zr exists as ZrO2 in
the tetragonal phase (Fig. 3(c)).[39] Fig. 3 (d) shows the O 1s
XPS spectrum of Pd-Ni@UiO-66, which could be deconvoluted
into three peaks. The peak located at 530.4 eV could be
ascribed to lattice oxygen due to Zr-O bonds, peak around 531.7
eV could be attributed to oxygen absorbed on the catalyst
surface, and peak located at 532.6 eV could be assigned to
71
70
14c
15c
PhMgBr
PhMgBr
72
77
16c
17c
PhMgBr
PhMgBr
92
62
a All the reactions were carried out on the scale of 0.1 mmol of
1, MeMgBr (0.2 mmol), PCy3 (1 mol%), 4 mol% Catalyst
(based on Ni), Toluene (1 mL) was used as the solvent. The
reaction was proceed under argon atmosphere at 40 oC for 2h.
b GC yields. c The reaction temperature was 80 oC.
Doublet peaks appeared at 334.5 (Pd 3d5/2) and 340.1 eV
(Pd 3d3/2) (Fig. 3e) indicates that most of the Pd species in the
catalyst were in the metallic form (Pd0).[41] While Ni 2p XPS (Fig.
3f) displays two spin−orbit doublets at 855.8 and 873.5 eV and
two shakeup satellites at 861.7 and 880.3 eV, which are
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10.1002/cctc.201800898
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COMMUNICATION
consistent with Ni oxide and Ni hydroxide.[42] Oxidation of the
surface nickel can easily occur when exposed to air, the
prepared catalyst exposed in air for several hours was proved to
be non effective for this reaction, which indicates that metallic
Pd-Ni was the effective site of this catalyst. Therefore, to
guarantee high catalytic efficiency, the catalyst must kept under
dry and inert atmosphere. Furthermore, XPS spectrum of the
unsupported Pd0.25Ni4 BMNPs was also performed (Fig 4). As
shown in Fig. 4, an obvious shift of Pd 3d peaks to lower binding
energy in Pd0.25Ni4@UiO-66 catalyst was observed when
compared with unsupported Pd-Ni BMNPs, indicating a strong
electronic interaction between the UiO-66 and BMNPs, which
may contribute for the activation of C-O bonds.
Table 3. Reusability of the Pd0.25Ni4@UiO-66 catalyst.
Cycles
1st
2nd
3rd
4th
Yield (%)
100
94
87
81
Cycles
1st
2nd
3rd
4th
Yield (%)
92
87
83
84
After the promising initial results, subsequent efforts were
devoted to examine the applicability of this protocol (Table 2).
With different alkoxy groups, the methylation was took place with
moderate to excellent yield (entries 1-4, Table 2). Steric
hindrance have an obvious impact on the efficiency of the
reaction, larger alkoxy groups caused obvious decrease on the
Yield. Methylation of 1-methoxynaphthalene also proceed
smoothly under the established reaction condition (entry 5), but
only moderate yield was obtained when 6-methoxy-1,2,3,4-
tetrahydronaphthalene was used as the substrate (entry 6).
What’s more, sterically hindered trimethylsilyl (TMS) ether
(entries 7, 8) also afforded good yields of the desired products
under the optimized condition. Moreover, ester was also
compatible with this protocol, excellent yield was obtained when
naphthalen-2-yl pivalate was applied as the substrate (entry 9).
Furthermore, arylation of 2-methoxynap-hthalene was attempted
in our established catalytic system, and full conversion was
achieved while increase the reaction temperature to 80oC (entry
10). Functional group tolerance of the arylation reaction was
also explored, the reaction performed well under optimized
conditions affording biaryl compound with satisfactory yields
(entries 11-17).
and reused in the next cycle. As shown Table 3, Pd0.25Ni4@UiO-
66 catalyst delivered high catalytic activity for at least four cycles
in the methylation of ether and arylation of ester. The unaltered
morphology of used Pd0.25Ni4@UiO-66 illustrates their structural
stability (Figure S1), no obvious increase in the size of the
recovered catalyst was observed when compared with the fresh
prepared catalyst. Based on these results, we could propose
that the drop of catalytic activity may be due to oxidation of the
catalyst during the recycle process.
In summary, we have designed a catalytic system based on
Pd-Ni BMNPs encapsused in UiO-66 for the C-O bond activation
reaction. Directly methylation and arylation of ethers could be
achieved under a mild reaction condition in the presence of
Pd0.25Ni4@UiO-66 catalyst, which highlights the potential value
of ethers as powerful alternatives for aryl halides. Besides,
“synergistic effect” between the two metal components and the
strong interaction between BMNPs and UiO-66 contribute a lot
for the activation of reactants. These results could serve as
inspiration for the further exploitation of the MOFs supported
BMNPs at mild conditions for the chemical reactions that happen
under previously restricted conditions.
Conflicts of interest
The authors declare no conflict of interest.
Acknowledgements
We gratefully acknowledge Chinese Postdoctoral Science
Foundation (2015M571761, 2016T90465) for financial support.
This work was a project funded by the Priority Academic
Program development of Jiangsu Higher Education Institution.
We also thank Wan-ying Tang at Analysis and Test Center
Nanjing University & Technology for the help in obtaining the
ICP-MS data.
Fig 5. Hot filtration test results. Red line, time=0.5 h, and blue
line, time=1 h
Furthermore, to clarify the heterogeneous nature of
Pd0.25Ni4@UiO-66 catalyst, a hot filtration test was performed
(Fig. 5). The catalyst was filtered in the middle of the reaction,
no reaction was proceeded in the filtrate after remove of catalyst
at two different times. No obvious metal leaching was observed
by ICP analysis of the filtrate, which further confirmed that active
specie in the catalytic system is the heterogeneous metallic
nanoparticles.
Long-term stability and reusability are the most important
features of heterogeneous catalysts. After the reaction, the
Pd0.25Ni4@UiO-66 catalyst was recovered from the reaction
solution via centrifugation, washed with toluene for three times
Keywords: Bimetallic nanoparticles • MOFs • C-O activation •
Methylation • Arylation
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This article is protected by copyright. All rights reserved.

10.1002/cctc.201800898
ChemCatChem
COMMUNICATION
COMMUNICATION
Jia-wei Zhang, Dan-dan Li, Guo-ping Lu,
Tao Deng and Chun Cai*
Page 1. – Page 5.
Pd-Ni BMNPs encapsulated in UiO-66
as an efficient catalyst for the
activation of "inert" C-O bond
A recyclable Pd-Ni bimetallic nanoparticles encapsulated in UiO-66 is fabricated
and applied in the C-O activation reaction of ethers, which highlights the great
potential value of ethers as electrophiles. “Synergistic effect” between the two metal
components and strong interaction between BMNPs and the carrier (UiO-66) all
contribute to outstanding catalytc performance of Pd0.25Ni4@UiO-66 catalyst.
This article is protected by copyright. All rights reserved.