Porous organic cage stabilised palladium nanoparticles: Efficient heterogeneous catalysts for carbonylation reaction of aryl halides

Article abstract of DOI:10.1039/c7cc09918e

Porous organic cage stabilised palladium nanoparticles were successfully prepared using methanol as a mild reductant. The as-prepared porous composite materials show high catalytic activity for the carbonylation reaction of aryl halides under mild conditions.

Full text of DOI:10.1039/c7cc09918e

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Porous organic cage stabilised palladium nanoparticles: efficient
heterogeneous catalysts for carbonylation reaction of aryl halides
Yong Zhang†,a,b Yu Xiong†,a Jin Ge, b Rui Lin,a Chen Chen,a Qing Peng,a Dingsheng Wanga* and
Received 00th January 20xx,
Accepted 00th January 20xx
Yadong Lia
DOI: 10.1039/x0xx00000x
www.rsc.org/
Porous organic cage stabilised palladium nanoparticles were enhanced selectivities for sensing7 and separation8, and to
successfully prepared using methanol as the mild reductant. The as‐ realise even porous liquid9. Soluable organic cages can also be
prepared porous composite materials show high catalytic activity used as capping agents for the colloidal synthesis of metal
for the carbonylation reaction of aryl halides under mild condition. nanoparticles. In this contribution, Zhang’s10 and Mukherjee’s11
groups have used shape‐persistent organic cages as templates
Owing to their high surface‐to‐volume ratios with large
numbers of available active catalytic sites per unit area, metal
nanoparticles have been proved to be an important class of
heterogeneous catalysts for various chemical transformations.1
Their catalytic properties strongly depend on the size, shape
and surface characteristics of the metal nanoparticles. During
the past decade, extensive research efforts have focused on the
synthesis of monodisperse nanoparticles with well‐defined size,
shape and composition to study the structure−property
relationships of nanoparticle catalysts, and great success has
been achieved.2 Capping agents are frequently used in colloidal
synthesis to obtain monodisperse metal nanoparticles, and play
an important role in modulating the catalysis of metal
nanoparticles.3 However, limited success has been achieved in
applying porous capping agents to create porous effects that
determine the catalytic activity of heterogeneous metal
catalysts.4
for the controlled synthesis of metal nanoparticles. Both Au and
Pd were successfully encapsulated in the cavity of nonporous
amine cages (derived from the corresponding imine cages). The
cage‐embedded Pd NPs exhibit efficient catalytic performance
in Suzuki–Miyaura reaction10b and in the cyanation of aryl
halides11. Indeed, the fabrication of porous imine cages with
metal nanoparticles is a challenging task. Recently, Xu’s group4
reported the preparation of porous imine cage stablised Rh
nanoparticles using slight amounts of NaBH4 as the reductant.
Considering the unstable nature of imine bond under strongly
reductive condition12, the development of mild process to
fabricate porous imine cages with metal nanoparticles is still
highly desirable. As our continue interest in the controllable
synthesis of nanocrystals13, herein, we describe a facile method
for the synthesis of porous imine cages stabilised Pd
nanoparticles using methanol as the mild reductant.
In the past few years, Porous organic cages (POCs) have
emerged as a new class of microporous material composed of
discrete organic molecules with intrinsic, guest accessible
cavities.5 Compared to three‐dimensional porous network
systems, the most distinctive feature of POCs is their solubility
in common organic solvents.6 Therefore, POCs can be easily
processed in solution for special applications that would be
more challenging with insoluble porous solids. For examples,
POCs have been used to form composite materials with
Fig. 1 Methanol as mild reductant for the preparation of CC3‐R stabilised PdNPs.
a. Department of Chemistry, Tsinghua University, Beijing 100084, China. Email:
wangdingsheng@mail.tsinghua.edu.cn
The porous organic cage chosen for capping Pd
nanoparticles was CC3‐R, which features three‐dimensional
intrinsically porous structure, robust physicochemical stability,
and easy preparation at a large scale.5a, 14 According to the
characterisation data reported previously, the CC3‐R has
b. Key Laboratory of Organo‐pharmaceutical Chemistry, Gannan Normal University,
Ganzhou 341000, P. R. China.
† These authors contributed equally to this work.
Electronic Supplementary Information (ESI) available: Synthetic Procedures and
Supplementary Figures (Fig. S1‐S5). See DOI: 10.1039/x0xx00000x
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Fig. 2 (a) TEM, (b) HRTEM images of Pd@CC3‐R‐MeOH (insert is enlarged HRTEM
image of Pd@CC3‐R‐MeOH). (c) HAADF‐STEM image and corresponding EDX
mapping of Pd@CC3‐R‐MeOH, C (blue), N (green) and Pd (red) (d) Size histograms
of Pd NPs base on over 100 NPs.
tetrahedral symmetry: each cage has an internal cavity with a
diameter of 0.72 nm and four windows with a diameter of 0.58
nm. Porous organic cage CC3‐R stabilised Pd nanoparticle was
prepared by a solution process using methanol as a mild
reductant (Fig. 1). Briefly, CC3‐R (20 mg) and Pd(OAc)2 (22.5 mg)
were stirred vigorously in MeOH (50 mL) for 6 h at room
temperature. Although the solubility of CC3‐R in MeOH is quite
low, the CC3‐R was completely dissolved in MeOH in the
presence of Pd(OAc)2. The resulting solution was then stirred at
o
80 C for 1 h. After completion of the reaction (the solution
colour changes from yellow to black), solvent was removed
under vacuum, and the obtained solid was washed several
times with ethanol‐acetone mixture via centrifugation,
followed by drying under vacuum overnight to obtain Pd@CC3‐
R‐MeOH as a black solid.
The palladium loading was estimated by inductively coupled
plasma optical emission spectrometry (ICP‐OES) to be ∼36 wt%.
Despite a very high loading of palladium nanoparticles,
transmission electron microscopy (TEM) and high resolution
TEM (HRTEM) images of the as‐obtained Pd@CC3‐R‐MeOH
nanoparticles showed that they were well‐dispersed particles
with a narrow size distribution (average diameter around 2.6
nm) (Fig. 2). Considering the internal cavity size of CC3‐R (0.72
Fig. 3 Nitrogen adsorption (filled symbols) and desorption (empty symbols)
isotherms of Pd@CC3‐R‐MeOH (blue) and CC3‐R (black).
nm) is much small than the as‐obtained Pd nanoparticles (2.6

0.6 nm), we believed that most of NPs are stabilised outside of
the cage. The enlarged HRTEM image of such nanoparticles
shows the d‐spacing of adjacent fringes is 2.36 Å, which is close
to that of (111) planes of fcc‐Pd (Fig. 2b). High‐angle annular
dark‐field scanning transmission electron microscope (HAADF‐
STEM) image and the corresponding Energy‐dispersive X‐ray
(EDX) mapping analysis of Pd@CC3‐R‐MeOH (Fig. 2c) reveal that
C and N are homogeneously distributed around the Pd
nanoparticles. In addition, X‐ray photoelectron spectroscopy
(XPS) analysis identifies the formation of PdNPs with binding
energies at 335.1 and 340.5 eV (Fig. S1), which could be ascribed
respectively to Pd0 3d5/2 and Pd0 3d3/2.
Fig. 4 Nitrogen adsorption (filled symbols) and desorption (empty symbols)
isotherms of Pd@CC3‐R‐‐NaBH4‐1 (black) and Pd@CC3‐R‐‐NaBH4‐2 (black).
Fig. 5 PXRD patterns of CC3‐R, Pd@CC3‐R‐MeOH and Pd@CC3‐R‐NaBH4‐1.
The permanent porosity of PdNP‐Cage composites was
confirmed by N2 adsorption/desorption experiments at 77 K.
2 | J. Name., 2012, 00, 1‐3
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The Brunauer‐Emmett‐Teller (BET) surface areas of CC3‐R and Pd@CC3‐R‐MeOH, Pd@CC3‐R‐NaBH4‐1, Pd@CC3‐R‐NaBH4‐2
Pd@CC3‐R‐MeOH were calculated respectively to be 438 m2 g‐1 and commercial Pd/C. As we can see, Pd@CC3‐R‐MeOH and
and 256 m2 g‐1 (Fig. 3). Considering a high catalyst loading and Pd@CC3‐R‐NaBH4‐1 with high specific surface area exhibited
the nonporous nature of palladium nanoparticles, we believed significantly higher activity than Pd@CC3‐R‐NaBH4‐2 and
that the pore structure of CC3‐R was maintained during the commonly used Pd/C19. The reason for the enhanced catalytic
reduction process using methanol as the reductant. As a activity of Pd@CC3‐R‐MeOH may be ascribed to the unique
comparison, we used NaBH4 as the reductant for the structure and gas adsorption property of Pd@CC3‐R‐MeOH. The
preparation of PdNP‐Cage composites. Although appreciable reusability of Pd@CC3‐R‐MeOH catalyst is examined by using
porosity (SBET = 240 m2 g‐1) in the composites was maintained in the model chemical transformation (iodobenzene to ethyl
a short reaction time (5 min for Pd@CC3‐R‐NaBH4‐1), a prolong benzoate), and no significant loss in activity is observed over
reaction time (12 h for Pd@CC3‐R‐NaBH4‐2) resulted in a five cycles. After catalytic tests, TEM images of the recovered
significant decrease of surface area (SBET = 35 m2 g‐1) (Fig. 4), materials suggest no obvious change for the size and
which could be ascribed to the slow reduction of CC3‐R to the morphology of Pd NPs (Fig. S3).
corresponding amine cage in the presence of NaBH4.12b Powder
X‐ray diffraction (PXRD) analysis indicates the formation of
PdNP‐Cage composite materials for both Pd@cage‐MeOH and
Pd@cage‐NaBH4 (Fig. 5). Compared to Pd@cage‐NaBH4, the
crystallinity of cage was well maintained in Pd@cage‐MeOH.
The observed PXRD patterns of Pd@cage‐MeOH showed a
reflex peak at a 2θ of 39.8o, which correspond to metallic Pd
(JCPDS no. 46‐1043). However, another shoulder peak at a 2θ
of 39.1o was observed for Pd@cage‐NaBH4, which could be
attributed to Palladium hydride (JCPDS no. 18‐0951). In addition,
1H NMR spectroscopy of Pd@CC3‐R‐MeOH dispersed in CDCl3
also demonstrates that the structure of porous organic cage
CC3‐R was well maintained in this composite material (Fig. S5).
According to the results of comparison experiment, we found
that methanol displays a great advantage as reductant for the
formation of PdNPs in the presence of porous imine cage CC3‐
R.
Palladium catalysed alkoxycarbonylation of aryl halides
represents a valuable tool for fine chemical synthesis.15 Various
homogeneous palladium catalysts have been explored for such
a transformation with high selectivity, activity and low catalyst
loading.16 However, the recovery and recycling of the
Fig. 6 (a) Alkoxycarbonylation reaction of aryl iodides. Reaction conditions:
1 (1.0
mmol), Pd@CC3‐R‐MeOH (2 mol%), NEt3 (3.0 equiv) in ethanol (2.0 mL) at 80 oC,
GC yields. (b) Conversion (%) as a function of time in the alkoxycarbonylation
reaction of iodobenzene over Pd@CC3‐R‐MeOH (A), Pd@CC3‐R‐NaBH4‐1 (B),
commercial Pd/C (10 wt. %) (C), and Pd@CC3‐R‐NaBH4‐2 (D). (c) Products and
yields of isolated products from the alkoxycarbonylation of aryl iodides catalyzed
by Pd@CC3‐R‐MeOH. (d) Recyclability of the Pd@CC3‐R‐MeOH catalysts.
homogeneous palladium catalyst is a challenging task. In order
to address this problem, heterogeneous palladium catalysis is a
promising choice.17 In this context, palladium complexes or
nanoparticles have been immobilised on solid supports such as
silica18, activated carbon (charcoal)19, organic polymers20 and
MOF21. However, most of these methods suffer from some
drawbacks such as the use of expensive phosphine ligands and
additives, harsh reaction conditions and short‐term stability.
Hence, it is still necessary to develop highly active and stable
heterogeneous catalysts for this important chemical
transformation.
To evaluate the catalytic activity of the porous organic cage
stabilised Pd nanoparticles, the alkoxycarbonylation of aryl
halides was selected as the model reaction (Fig. 6). Pd@CC3‐R‐
MeOH proved to be an effective catalyst for such a reaction
even under mild reaction condition (CO balloon, 80oC and NEt3
as the base). Aryl iodides with both electron‐donating and ‐
withdrawing groups performed equally well and the desired
products were obtained in high to excellent yields. Different
alcohols such as 2‐propanol and n‐propanol were also
applicable to give the corresponding products. Fig. 6b displays
the kinetic curves for the alkoxycarbonylation reactions of
In summary, a solvent process that uses porous organic cage
as capping reagent for the synthesis of PdNPs is developed.
Utilising methanol as mild reductant, the structure of porous
imine cage is well maintained during the formation of PdNPs.
The as‐prepared porous organic cage stabilised PdNPs show
high catalytic activity for the carbonylation reaction of aryl
halides under mild condition. Considering imine bonds existed
widely in porous organic cages, this strategy provides a
powerful entry into metal NPs with porous surface properties
to achieve enhanced performance.
This work was supported by the National Natural Science
Foundation of China (No. 21502021, 21521091, 21390393,
U1463202, 21471089, 21671117), the China Ministry of Science
and Technology under Contract of 2016YFA (0202801), and 111
Project (B16028).
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A. I. Cooper, Chem. Mater., 2015, 27, 3207; (d) J.‐H. Zhang, S.‐
M. Xie, L. Chen, B.‐J. Wang, P.‐G. He and L.‐M. Yuan, Anal.
Chem., 2015, 87, 7817; (e) S. Jiang, L. Chen, M. E. Briggs, T.
Hasell and A. I. Cooper, Chem. Commun., 2016, 52, 6895; (f)
Q. L. Song, S. Jiang, T. Hasell, M. Liu, S. J. Sun, A. K. Cheetham,
E. Sivaniah and A. I. Cooper, Adv. Mater., 2016, 28, 2629.
Conflicts of interest
There are no conflicts to declare.
Notes and references
9
(a) N. Giri, C. E. Davidson, G. Melaugh, M. G. Del P
A. Jones, T. Hasell, A. I. Cooper, P. N. Horton, M. B. Hursthouse
and S. L. James, Chem. Sci., 2012, , 2153; (b) G. Melaugh, N.
Giri, C. E. Davidson, S. L. James and M. G. Del P polo, Phys.
Chem. Chem. Phys., 2014, 16, 9422; (c) N. Giri, M. G. Del
polo, G. Melaugh, R. L. Greenaway, K. R etzke, T. Koschine,
ópolo, J. T.
1
(a) E. Gross and G. A. Somorjai, Top. Catal., 2014, 57, 812; (b)
L. L. Chng, N. Erathodiyil and J. Y. Ying, Acc. Chem. Res., 2013,
46, 1825; (c) F. Zaera, Chem. Soc. Rev., 2013, 42, 2746; (d) W.
J. Stark, P. R. Stoessel, W. Wohlleben and A. Hafner, Chem.
Soc. Rev., 2015, 44, 5793.
3
ó
P
ó
ä
L. Pison, M. F. C. Gomes, A. I. Cooper and S. L. James, Nature,
2
(a) K. M. Bratlie, H. Lee, K. Komvopoulos, P. Yang and G. A.
2015, 527, 216.
Somorjai, Nano Lett., 2007, 7, 3097; (b) S. H. Joo, J. Y. Park, J. 10 (a) R. McCaffrey, H. Long, Y. Jin, A. Sanders, W. Park and W.
R. Renzas, D. R. Butcher, W. Huang and G. A. Somorjai, Nano
Lett., 2010, 10, 2709; (c) D. Wang and Y. Li, Adv. Mater., 2011,
23, 1044; (d) B. Wu and N. Zheng, Nano Today, 2013,
Zhang, J. Am. Chem. Soc., 2014, 136, 1782; (b) L. Qiu, R.
McCaffrey, Y. Jin, Y. Gong, Y. Hu, H. Sun, W. Park and W. Zhang,
8
, 168;
Chem. Sci., 2018, 9, 676.
(e) H. Zhang, M. Jin, Y. Xiong, B. Lim and Y. Xia, Acc. Chem. 11 B. Mondal, K. Acharyya, P. Howlader and P. S. Mukherjee, J.
Res., 2013, 46, 1783; (f) M. Chen, S. Chen, C. He, S. Mo, X.
Wang, G. Liu and N. Zheng, Nano Res. 2017, 10, 1234.
Am. Chem. Soc., 2016, 138, 1709.
12 (a) Y. Jin, Y. Zhu and W. Zhang, CrystEngComm, 2013, 15
,
3
(a) Z. Niu and Y. Li, Chem. Mater., 2014, 26, 72; (b) P. Liu, R.
Qin, G. Fu and N. Zheng, J. Am. Chem. Soc., 2017, 139, 2122;
(c) I. Schrader, J. Warneke, J. Backenköhler and S. Kunz, J. Am.
Chem. Soc., 2015, 137, 905; (d) G. Chen, C. Xu, X. Huang, J. Ye,
L. Gu, G. Li, Z. Tang, B. Wu, H. Yang, Z. Zhao, Z. Zhou, G. Fu and
N. Zheng, Nat Mater, 2016, 15, 564; (e) Y. Wang, X.‐K. Wan, L.
Ren, H. Su, G. Li, S. Malola, S. Lin, Z. Tang, H. Häkkinen, B. K.
1484; (b) S. I. Swamy, J. Bacsa, J. T. A. Jones, K. C. Stylianou, A.
Steiner, L. K. Ritchie, T. Hasell, J. A. Gould, A. Laybourn, Y. Z.
Khimyak, D. J. Adams, M. J. Rosseinsky and A. I. Cooper, J. Am.
Chem. Soc., 2010, 132, 12773; (c) J. L. Culshaw, G. Cheng, M.
Schmidtmann, T. Hasell, M. Liu, D. J. Adams and A. I. Cooper,
J. Am. Chem. Soc., 2013, 135, 10007; (d) M. Liu, M. A. Little, K.
E. Jelfs, J. T. A. Jones, M. Schmidtmann, S. Y. Chong, T. Hasell
and A. I. Cooper, J. Am. Chem. Soc., 2014, 136, 7583.
Teo, Q.‐M. Wang and N. Zheng, J. Am. Chem. Soc., 2016, 138
,
3278; (f) L. Ren, P. Yuan, H. Su, S. Malola, S. Lin, Z. Tang, B. K. 13 (a) X. Wang, J. Zhuang, Q. Peng and Y. Li, Nature, 2005, 437
,
Teo, H. Häkkinen, L. Zheng and N. Zheng, J. Am. Chem. Soc.,
2017, 139, 13288.
121; (b) D. Wang, T. Xie and Y. Li, Nano Res., 2009,
2, 30; (c) Y.
Wu, D. Wang and Y. Li, Chem. Soc. Rev., 2014, 43, 2112.
4
5
J. K. Sun, W. W. Zhan, T. Akita and Q. Xu, J. Am. Chem. Soc., 14 T. Hasell, M. Schmidtmann, C. A. Stone, M. W. Smith and A. I.
2015, 137, 7063.
Cooper, Chem. Commun., 2012, 48, 4689.
(a) T. Tozawa, J. T. A. Jones, S. I. Swamy, S. Jiang, D. J. Adams, 15 M. Beller, X.‐F. Wu, Transition Metal Catalyzed Carbonylation
S. Shakespeare, R. Clowes, D. Bradshaw, T. Hasell, S. Y. Chong,
C. Tang, S. Thompson, J. Parker, A. Trewin, J. Bacsa, A. M. Z.
Slawin, A. Steiner and A. I. Cooper, Nat. Mater., 2009,
(b) J. R. Holst, A. Trewin and A. I. Cooper, Nat. Chem., 2010,
915; (c) G. Zhang and M. Mastalerz, Chem. Soc. Rev., 2014, 43
1934; (d) T. Hasell and A. I. Cooper, Nat. Rev. Mater., 2016,
Reactions: Carbonylative Activation of C–X Bonds, Springer,
Heidelberg, 2013.
8, 973; 16 (a) X. F. Wu, H. Neumann and M. Beller, Chem. Soc. Rev., 2011,
2
,
,
,
40, 4986; (b) Y. Hu, J. Liu, Z. Lü, X. Luo, H. Zhang, Y. Lan and A.
Lei, J. Am. Chem. Soc., 2010, 132, 3153; (c) W. Fang, Q. Deng,
M. Xu, T. Tu, Org. Lett., 2013, 15, 3678.
1
1; (e) A. Avellaneda, P. Valente, A. Burgun, J. D. Evans, A. W. 17 (a) H. Gruber‐Woelfler, P. F. Radaschitz, P. W. Feenstra, W.
Markwell‐Heys, D. Rankine, D. J. Nielsen, M. R. Hill, C. J. Sumby
and C. J. Doonan, Angew. Chem. Int. Ed., 2013, 52, 3746; (f) L.
Haas, J. G. Khinas, J. Catal., 2012, 286, 30; (b) S. T. Gadge and
B. M. Bhanage, RSC Adv., 2014, , 10367.
4
Chen, P. S. Reiss, S. Y. Chong, D. Holden, K. E. Jelfs, T. Hasell, 18 (a) M. Opanasenko, P. Štěpnička and J. Čejka, RSC Adv., 2014,
M. A. Little, A. Kewley, M. E. Briggs, A. Stephenson, K. M.
Thomas, J. A. Armstrong, J. Bell, J. Busto, R. Noel, J. Liu, D. M.
Strachan, P. K. Thallapally and A. I. Cooper, Nat. Mater., 2014,
4
, 65137; (b) M. V. Khedkar, T. Sasaki, B. M. Bhanage, ACS
Catal., 2013, , 287; (c) M. Genelot, V. Dufaudm and L.
Djakovitch, Adv. Synth. Catal., 2013, 355, 2616.
3
13, 954; (h) G. Zhang, O. Presly, F. White, I. M. Oppel and M. 19 (a) J. Liu, J. Chen and C. Xia, J. Catal., 2008, 253, 50; (b) J.
Mastalerz, Angew. Chem. Int. Ed., 2014, 53, 1516; (i) K. Ono,
K. Johmoto, N. Yasuda, H. Uekusa, S. Fujii, M. Kiguchi and N.
Iwasawa, J. Am. Chem. Soc., 2015, 137, 7015; (j) T. Hasell, M.
Miklitz, A. Stephenson, M. A. Little, S. Y. Chong, R. Clowes, L.
Salvadori, E. Balducci, S. Zaza, E. Petricci and M. Taddei, J. Org.
Chem., 2010, 75, 1841. (c) R. S. Mane, B. M. Bhanage, RSC
Adv., 2015,
5, 76122; (d) R. S. Mane, B. M. Bhanage, J. Org.
Chem., 2016, 81, 1223.
J. Chen, D. Holden, G. A. Tribello, K. E. Jelfs and A. I. Cooper, J. 20 (a) R. A. Molla, M. A. Iqubal, K. Ghosh, A. S. Roy, S. M. Islam,
Am. Chem. Soc., 2016, 138, 1653; (k) A. G. Slater, M. A. Little,
A. Pulido, S. Y. Chong, D. Holden, L. Chen, C. Morgan, X. Wu,
RSC Adv., 2014,
4, 48177; (b) Y. Lei, L. Wu, X. Zhang, H. Mei, Y.
Y. Gu, G. Li, J. Mol. Catal. A: Chem., 2015, 398, 164.
G. Cheng, R. Clowes, M. E. Briggs, T. Hasell, K. E. Jelfs, G. M. 21 (a) T. T. Dang, Y. Zhu, J. S. Y. Ngiam, S. C. Ghosh, A. Chen, A.
Day and A. I. Cooper, Nat. Chem., 2017,
9
, 17.
M. Seayad, ACS Catal., 2013, 3, 1406; (b) T. T. Dang, Y. Zhu, S.
6
7
A. G. Slater and A. I. Cooper, Science, 2015, 348, 988.
(a) M. Brutschy, M. W. Schneider, M. Mastalerz and S. R.
Waldvogel, Adv. Mater., 2012, 24, 6049; (b) M. Brutschy, M.
W. Schneider, M. Mastalerz and S. R. Waldvogel, Chem.
Commun., 2013, 49, 8398.
C. Ghosh, A. Chen, C. L. L. Chai, A. M. Seayad, Chem. Commun.,
2012, 48, 1805; (c) Z. Zhang, Y. Chen, S. He, J. Zhang, X. Xu, Y.
Yang, F. Nosheen, F. Saleem, W. He and X. Wang, Angew.
Chem. Int. Ed., 2014, 53, 12517.
8
(a) T. Hasell, H. Zhang and A. I. Cooper, Adv. Mater., 2012, 24,
5732; (b) A. F. Bushell, P. M. Budd, M. P. Attfield, J. T. A. Jones,
T. Hasell, A. I. Cooper, P. Bernardo, F. Bazzarelli, G. Clarizia and
J. C. Jansen, Angew. Chem. Int. Ed., 2013, 52, 1253; (c) A.
Kewley, A. Stephenson, L. J. Chen, M. E. Briggs, T. Hasell and
4 | J. Name., 2012, 00, 1‐3
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Graphical Abstract
Porous organic cage stabilised palladium nanoparticles were prepared using methanol as the mild reductant, and
displayed high catalytic activity for the carbonylation reaction of aryl halides under mild condition
.
5