One-pot synthesis of Pd@MOF composites without the addition of stabilizing agents

Article abstract of DOI:10.1039/c4cc06568a

In this work, the first example of a facile one-pot route for the synthesis of Pd@MOF composites without additional stabilizing agents is developed. The as-synthesized MOF composite shows high activity and chemoselectivity in the hydrogenation of cinnamaldehyde even under atmosphere pressure of H₂ and at room temperature. This journal is

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One-pot synthesis of Pd@MOF composites without the
addition of stabilizing agents
Cite this: DOI: 10.1039/x0xx00000x
Liyu Chen, Huirong Chen, Yingwei Li*
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
under stabilizing agent-free conditions. In this regard, the recent
work by Tang and co-workers is noteworthy, which reports a PVP
assisted one-pot method for the preparation of core–shell Au@MOF-
5 composite that can be used as highly selective sensor for CO2 in
gas mixtures.11 To the best of knowledge, however, one-pot
synthesis of MNPs@MOF composites without the assistance of any
stabilizing agents has not been proposed to date.
In this work, the first example of a facile one-pot route for the
synthesis of Pd@MOF composite without additional
stabilizing agents is developed. The as-synthesized MOF
composite shows high activity and chemoselectivity in the
hydrogenation of cinnamaldehyde even under atmosphere
pressure of H2 and room temperature.
Herein, we report, for the first time, a facile one-pot route for the
synthesis of Pd@MOF composites without the assistance of any
stabilizing agents. The proposed methodology allows the
incorporation of highly dispersed metal nanoparticles with
surfactant-free surface on MOFs in one step, which could reduce the
production cost for ease of scale-up preparation while improve the
performance for advanced catalysts. Different from the previous
two-step procedure, this one-pot synthetic method is achieved by
directly dissolving the precursors of Pd (i.e., Pd(NO3)2) and MOF
(i.e., ZrCl4 and 2,2’-bipyridine-5,5’-dicarboxylic acid) with the
reducing agent (i.e., ammonia borane, NH3BH3) in N,N-
dimethylformamide (DMF). This protocol takes advantage of the
strong coordinating ability of 2,2’-bipyridine moieties in the organic
ligand to palladium, which could stabilize palladium NPs during the
MOF assembling process, allowing the hetero-nucleation of MOF on
the surface of Pd NPs. The as-prepared Pd@MOF composites
exhibited high chemoselectity and activity in the hydrogenation of
cinnamaldehyde, showing no reduced catalytic activity even after a
number of uses.
Metal–organic frameworks (MOFs) are emerged as a class of highly
promising porous materials, which are synthesized by assembling
metal ions with organic ligands in appropriate solvents.1 Owing to
their superior properties including diverse chemical compositions,
large surface areas, and permanent porosity, MOFs have potential
applications in a wide range of fields such as catalysis,2 gas storage,3
separation,4 and sensing.5 Over the past decades, most of the
research efforts have been focused on preparing new MOF structures
and studying their application in gas storage and separation.6 More
recently, the utilizations of MOFs as support for metal nanoparticles
have attracted tremendous attention. There have been extensive
efforts to fabricate metal nanoparticles (MNPs) on MOFs to obtain
the properties that are hardly achieved by their individual parts.7
MNPs@MOF composites can be synthesized by using MOFs as
templates to generate MNPs or by building MOF structures around
preformed MNPs.8 The latter approach9 has recently attracted
increasing attention as it could avoid the general problems facing the
former method, such as aggregation of MNPs on the external surface
and damage to the MOF structures during the post-reduction process.
Moreover, it could allow a well control of the size, composition, and
morphology of the incorporated MNPs.10 The assembling process
generally requires two steps, comprising synthesis of MNPs and then
growth of MOF around the surface of pre-synthesized MNPs.
Meanwhile, in order to restrict MNPs from aggregation during the
MOF assembling process, certain surfactants, capping agents or even
ions are often required for the stabilization of the pre-synthesized
MNPs. However, such stabilizing agents are difficult to be fully
eliminated from the final MNPs@MOF composites, which may have
a negative effect on the catalytic efficiencies of MNPs.
Scheme 1 One-pot synthesis of Pd@MOF1.
UiO-67 is a MOF constructed by [Zr6O4(OH)4(CO2)12] clusters
linked with biphenyldicarboxylate (bpdc).12 Recently, it was
reported that the bpdc linker could be replaced with 2,2’-bipyridine-
5,5’-dicarboxylate (bpydc), without altering the MOF structure.13
Considering that the 2,2’-bipyridine moiety on bpydc linker can
In view of the considerable time and energy consumption in
previously reported two-step synthetic procedures, and from the
viewpoint of catalysis, it is of great desire to exploit a new
methodology for one-pot synthesis of MNPs@MOF composites
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efficiently stabilize palladium NPs,14 here we chose H2bpydc as optimum Pd reducing rate that 40 mg of NH3BH3 could offer. When
ligand for the one-pot assembling of Pd@MOF1. The Pd@MOF1 the NH3BH3 amount was less than 40 mg, the concentration of the
was prepared from a mixture containing a 1:1.4 molar ratio of ZrCl4 reducing agent was not sufficient to fully reduce Pd precursors to
to H2bpydc in 30:1 v:v DMF:HCl solvent, with the simultaneous metallic Pd. However, when the reductant quantity was enhanced to
addition of palladium precursors and reducing agents (Scheme 1).
80 mg, the reduction of Pd precursors was too fast to be well
stabilized by the bpydc linkers to yield aggregated Pd NPs with a
low reactivity (Figure S1). In the absence of any reducing agent, the
obtained composite showed no catalytic activity, implying that Pd(0)
was the active site for the hydrogenation transformation under the
investigated reaction conditions.
Scheme 2 Reaction pathways in the hydrogenation of cinnamaldehyde.
The synthesis condition was modulated and the as-prepared MOF
composites were subsequently used as catalysts for the
hydrogenation of cinnamaldehyde (CAL) to evaluate the catalytic
activity, selectivity, and reusability. The hydrogenation of
cinnamaldehyde, as depicted in Scheme 2, may lead to various
products such as cinnamal alcohol (COL), hydrocinnamaldehyde
(HCAL), and hydrocinnamal alcohol (HCOL), depending on the
active metal, solvent, and promoter used in the reaction.15 Palladium
is one of the most active and selective catalysts for the
hydrogenation of CAL to HCAL in conventional organic solvents.16
Although tremendous progresses have been made in this field, the
100% selective hydrogenation of CAL to HCAL is still quite
difficult.
Fig. 2 XPS spectra of the N 1s region for (a) MOF1, and (b) 2.0% Pd@MOF1.
The synthesis process can be visibly monitored by the evolution
of the solution color. When NH3BH3 was added to the mixture, the
color of the solution quickly changed from light-yellow to dark
within a few seconds, indicating that Pd(II) was reduced to Pd(0)
NPs. It was found that when Pd NPs were formed, H2bpydc would
tend to adsorb on the surface of Pd to stabilize Pd NPs against
aggregation due to its strong affinity to Pd (see XPS characterization
as described below). Subsequently, ZrCl4 was assembled with
H2bpydc absorbed on the surface of Pd NPs to form the MOF,
achieving the encapsulation of Pd NPs in UiO-67. Fig. 1a showed
that all the Pd NPs were homogeneously distributed in the MOF
network, with a mean size of 3.2 nm. No apparent aggregation was
observed in the TEM images, indicating a high dispersion of Pd NPs.
EDS analysis confirmed the presence of Pd in the Pd@MOF1. For
comparison, biphenyldicarboxylic acid (H2bpdc) was used as ligand
instead of H2bpydc to yield Pd@MOF2 under similar preparation
conditions. However, a serious aggregation of Pd NPs was observed
on Pd@MOF2 (Fig. 1b). The comparison implied that 2,2’-bipridine
moiety on H2bpydc played an important role in the assembling
process for the stabilization and encapsulation of Pd NPs.
Fig. 1 (a) TEM image of 2.0% Pd@MOF
corresponding size distribution of Pd nanoparticles of 2.0% Pd@MOF
the EDX pattern of 2.0% Pd@MOF
1
, (b) TEM image of 2.0% Pd@MOF
2, (c)
, and (d)
1
In order to verify the interaction between Pd atoms and bpydc, we
performed X-ray photoelectron spectroscopy (XPS) analysis on
MOF1 and Pd@MOF1. The parent MOF1 exhibited one N 1s peak
1.
By finely tuning the reaction conditions, the formation rates of Pd at ca. 399.1 eV (Fig. 2a) that could be related to un-coordinated
NPs and UiO-67 in the mixed solution could be adjusted effectively. bipyridinic nitrogen. A new N 1s peak at 401.9 eV was observed for
From a screening of different kinds of palladium precursors and the Pd@MOF1 material (Fig. 2b), which was shifted by ca. 1.8 eV
reducing agents, the combination of Pd(NO3)2 with NH3BH3 was toward higher binding energies compared with that of un-
found to be the most effective, giving the MOF composite with the coordinated bipyridinic nitrogen. Such shifts reflected a decreased in
highest hydrogenation activity (Table S1). The addition of different the electron density of N, suggesting a strong coordination between
amount of NH3BH3 significantly affected the catalytic activity of the bpydc moieties and Pd atoms in the Pd@MOF1. The XPS results
Pd@MOF1. The activity of Pd@MOF1 increased gradually when confirmed that a small amount of the uncoordinated bpydc units
the quantity of NH3BH3 was increased from 5 mg to 40 mg, and a were bonded to Pd in the Pd@MOF1. In addition, as shown in Fig.
maximum activity was obtained on the MOF composite prepared S2, the Pd@MOF1 sample exhibited a Pd 3d5/2 band at ca. 335–336
with 40 mg of NH3BH3 (Table 1, entries 1-5). However, when the eV, typical of Pd metal, indicating that the Pd(II) cations were
amount of NH3BH3 was further increased to 80 mg, the resultant transformed to Pd(0) after reduction by NH3BH3.
MOF composite gave no catalytic activity. The results pointed to the
2 | J. Name., 2012, 00, 1-3
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It is noteworthy that the apparently different morphology of Pd cinnamaldehydes. The Pd@MOF1 catalyst was highly active and
NPs between the Pd@MOF1 and Pd@MOF2 composites resulted in extremely selective for the hydrogenation of the substituted
distinct activities and selectivites in the hydrogenation of CAL to cinnamaldehydes (Table S3). Cinnamaldehydes of various electronic
HCAL. As showed in Table 1, Pd@MOF1-40 showed 100% yield to characters all reacted smoothly (Table S3, entries 1–3). In general,
HCAL, however, Pd@MOF2-40 gave only 75% conversion of CAL electron-deficient cinnamaldehydes exhibited higher activity than
with 65% selectivity to the desired product under identical electron-rich ones. Notably, the sterically hindered 2-
conditions (entries 2 and 7).
methoxycimnamaldehyde also worked well and afforded the
corresponding product in 98% yield.
Table 1. Results of hydrogenation of cinnamaldehyde (CAL).a
Pd@MOF1 could be easily recovered by centrifugation after
removing the supernatant and washing with THF. The recovered
catalyst was subsequently reused for a next run under identical
conditions with fresh reagents. The catalyst showed no appreciable
reduction of activity even after five runs (Table 1, entry 11). PXRD
patterns of the used catalyst suggest that the structural integrity of
the MOF composite was mostly maintained after the catalytic
reactions (Fig. S3). The heterogeneous nature of the Pd@MOF1 was
verified by hot filtration experiment at approximately 19%
conversion, which showed that the isolated solution did not exhibit
any further reactivity. These findings were consistent with AAS
experiments for which no Pd traces (below the detection limit) were
found in the reaction solution. Moreover, the Pd loading of the
reused material was almost the same as the fresh one. These results
indicated that the loss of palladium species was negligible and a
truly heterogeneous hydrogenation reaction was taken place on the
catalyst surface.
Selectivity (%)
HCAL HCOL COL
Conversion
(%)
Entry
Catalysts b
1
2
3
4
5
6
7
8
9
2.0% Pd@MOF1-80
2.0% Pd@MOF1-40
2.0% Pd@MOF1-20
2.0% Pd@MOF1-10
2.0% Pd@MOF1-5
2.0% Pd@MOF1-0
2.0% Pd@MOF2-40
0.5% Pd@MOF1-40
1.0% Pd@MOF1-40
4.0% Pd@MOF1-40
Reused 2.0%
<1
100
75
85
8
99
100
79
67
99
0
65
92
>99
99
1
0
21
33
1
0
35
8
0
0
0
0
0
0
0
0
0
0
0
75
72
97
90
<1
1
10
11
Pd@MOF1-40 (five
uses)
99
100
0
0
a
Reaction conditions: cinnamaldehyde (0.1 mmol), catalyst (Pd 1 mol%),
b
Moreover, the one-pot synthesis method developed in this work is
likely a general technique for the preparation of other catalytically
active metal@MOF1 composites, for example, Au@MOF1 and
Pt@MOF1 (Fig. S7 and Table S4).
THF (2 mL), 1 atm H2, 25 C, 6 h. The prepared Pd@MOF composite is
denoted as Pd@MOF-x, where x indicates the amount of NH3BH3 (mg)
added in the solution.
As measured by atomic absorption spectroscopy (AAS), we could
achieve different Pd loadings (e.g., 0.5, 1.0, 2.0, and 4.0 wt%) by
adding different amount of Pd precursor to the starting materials for
the MOF composites. It is interesting to note that the actual loadings
were identical to the calculated values. Thus, the proposed strategy
could facilitate the accurate control of Pd loading on the MOF.
The powder X-ray diffraction (PXRD) patterns of the samples
with different Pd loadings matched well with that simulated from the
single-crystal structure, confirming the formation of UiO-67 type
structures (Figs. S3 and S4). The absence of a Pd diffraction pattern
could be related to the low Pd contents in the materials. All of the
obtained Pd@MOF1 samples were characterized by N2 adsorption at
77 K, and the results are summarized in Fig. S5 and Table S2. As the
loading of Pd increased, the corresponding surface area of
Pd@MOF1 decreased, probably due to the pore filling by the doped
Pd NPs in the composites. The thermogravimetric analysis (TGA)
curve of 2.0% Pd@MOF1 revealed that the structure of Pd@MOF1
was thermally stable up to 450 C under N2 atmosphere (Fig. S6).
All the Pd@MOF1-40 samples with different Pd loadings were
also applied in the hydrogenation of CAL, and the results are showed
in Table 1 (entries 2, 8-10). Results of the hydrogenation of CAL
pointed to an optimized performance of 2.0% Pd@MOF1-40, which
provided a quantitative conversion of CAL to HCAL at 25 C within
6 h (entry 2). It should be noted that our catalytic system represents a
rare example for the selective hydrogenation of CAL with 100%
selectivity for HCAL under atmosphere pressure of H2 and room
temperature. Considering the adsorption of substrate on the catalyst
will significantly influence the catalytic reaction, we speculate that
In summary, we have developed, for the first time, a novel, facile,
and effective methodology for one-pot synthesis of Pd@MOF
composites. This strategy features the utilization of MOF ligand for
the stabilization of Pd NPs during the encapsulation of Pd NPs
within MOF. No additional stabilizing agent was needed here thus
could allow the incorporation of metal nanoparticles with surfactant-
free surface (a property important for catalysis applications). The as-
synthesized Pd@MOF composite was highly active in the selective
hydrogenation of cinnamaldehyde, achieving 100% yield to
hydrocinnamaldehyde under atmosphere pressure of H2 and room
temperature. Moreover, the catalyst was stable and reusable,
showing no reduced catalytic activity even after a number of uses.
The achieved success in the one-pot synthesis of Pd@MOF
composites may pave the way to practical application of metal-
loaded MOF materials due to its facile handling, reduced production
cost, and ease of up-scaling.
We thank the National Natural Science Foundation of China
(21322606 and 21436005), the Fundamental Research Funds for the
Central Universities (2013ZG0001), and Guangdong Natural
Science Foundation (S2011020002397 and 10351064101000000)
for financial support.
Notes and references
a School of Chemistry and Chemical Engineering, South China University
of Technology, Guangzhou 510640 (China), E-mail: liyw@scut.edu.cn
†
Electronic Supplementary Information (ESI) available: [experimental
details, catalysts characterization, and additional reaction results]. See
aromatic ligands of MOF1 would strengthen the adsorption of DOI: 10.1039/c000000x/
aromatic rings of CAL via π,π-stacking interaction. So CAL would
be likely to diffuse into the pore of Pd@MOF1 in the direction of
1
(a) H. Furukawa, K. E. Cordova, M. O’Keeffe and O. M. Yaghi,
aromatic ring. This will benefit the adsorption of the C=C bond on
the doped Pd surface due to its close distance to the aromatic ring of
CAL, thus promote the preferential hydrogenation of C=C bond over
C=O bond.
Science, 2013, 341, 1230444; (b) M. Li, D. Li, M. O’Keeffe and O.
M. Yaghi, Chem. Rev., 2014, 114, 1343; (c) O. K. Farha, I. Eryazici,
N. C. Jeong, B. G. Hauser, C. E. Wilmer, A. A. Sarjeant, R. Q. Snurr,
We further investigated the hydrogenation of different
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S. T. Nguyen, A. O
̈
2014, 26, 1119; (c) W. Zhang, G. Lu ,C. Cui, Y. Liu, S. Li, W. Yan,
C. Xing, Y. Robin Chi, Y. Yang and F. Huo, Adv. Mater., 2014, 26
2012, 134, 15016.
,
2
3
4
(a) T. Zhang and W. Lin, Chem. Soc. Rev., 2014, 43, 5982; (b) A.
4056; (d) K. Khaletskaya, J. Reboul, M. Meilikhov, M. Nakahama, S.
Diring, M. Tsujimoto, S. Isoda, F. Kim, K. Kamei, R. A. Fischer, S.
Kitagawa and S. Furukawa, J. Am. Chem. Soc., 2013, 135, 10998; (e)
T. Tsuruoka, H. Kawasaki, H. Nawafune and K. Akamatsu, ACS
Dhakshinamoorthy and H. Garcia, Chem. Soc. Rev., 2014, 43, 5750;
(c) J. Gascon, A. Corma, F. Kapteijn and F. X. Llabrés i Xamena,
ACS Catal., 2014, 4, 361.
(a) Y. W. Li and R. T. Yang, J. Am. Chem. Soc., 2006, 128, 726; (b)
M. P. Suh, H. J. Park, T. K. Prasad and D.-W. Lim, Chem. Rev., 2012,
Appl. Mater. Interfaces, 2011,
3, 378; (f) P. Wang, J. Zhao, X. Li, Y.
Yang, Q. Yang and C. Li, Chem. Commun., 2013, 49, 3330.
112, 782; (c) T. A. Makal, J. R. Li, W. Lu and H. C. Zhou, Chem. Soc. 10 (a) M. Zhao, K. Deng, L. He, Y. Liu, G. Li, H. Zhao and Z. Tang, J.
Rev., 2012, 41, 7761.
Am. Chem. Soc., 2014, 136, 1738; (b) C.-H. Kuo, Y. Tang, L.-Y.
Chou, B. T. Sneed, C. N. Brodsky, Z. Zhao and C.-K. Tsung, J. Am.
Chem. Soc., 2012, 134, 14345.
(a) A. L. Dzubak, L. C. Lin, J. Kim, J. A. Swisher, R. Poloni, S. N.
Maximoff and L. Gagliardi, Nat. Chem., 2012, 4, 810; (b) S. Xiang,
Y. He, Z. Zhang, H. Wu, W. Zhou, R. Krishna and B. Chen, Nat. 11 L. He, Y. Liu, J. Liu, Y. Xiong, J. Zheng, Y. Liu and Z. Tang, Angew.
Commun., 2012, , 954; (c) S. Chaemchuen, N. A. Kabir, K. Zhou Chem. Int. Ed., 2013, 52, 3741.
and F. Verpoort, Chem. Soc. Rev., 2013, 42, 9304; (d) Z. R. Herm, B. 12 J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S.
M. Wiers, J. A. Mason, J. M. van Baten, M. R. Hudson, P. Zajdel, C. Bordiga and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130, 13850.
M. Brown, N. Masciocchi, R. Krishna and J. R. Long, Science, 2013, 13 (a) J. B. DeCoste, G. W. Peterson, H. Jasuja, T. G. Glover, Y. Huang
3
340, 960.
and K. S. Walton, J. Mater. Chem. A, 2013, 1, 5642; (b) M. J. Katz, Z.
5
6
(a) Z. Hu, B. J. Deiberta, J. Li, Chem. Soc. Rev., 2014, 43, 5815; (b)
L. E. Kreno, K. Leong, O. K. Farha, M. Allendorf, R. P. Van Duyne
and J. T. Hupp, Chem. Rev., 2012, 112, 1105.
J. Brown, Y. J. Colón, P. W. Siu, K. A. Scheidt, R. Q. Snurr, J. T.
Hupp and O. K. Farha, Chem. Commun., 2013, 49, 9449; (c) L. Li, S.
Tang, C. Wang, X. Lv, M. Jiang, H. Wu and X. Zhao, Chem.
(a) F. Vermoortele, M. Maes, P. Z. Moghadam, M. J. Lennox, F.
Commun., 2014, 50, 2304.
Ragon, M. Boulhout, S. Biswas, K. G. M. Laurier, I. Beurroies, R. 14 (a) G. Petruccia, W. Oberhauserb, M. Bartolia, G. Giachia, M.
Denoyel, M. Roeffaers, N. Stock, T. Du
̈
Frediania, E. Passagliac, L. Capozzolid and L. Rosi, Appl. Catal. A-
Gen., 2014, 469, 132; (b) M. Crespo-Quesada, R. R. Dykeman, G.
Laurenczy, P. J. Dyson and L. Kiwi-Minsker, J Catal., 2011, 279, 66.
Vos, J. Am. Chem. Soc., 2011, 133, 18526; (b) B. Li, Z. Zhang, Y. Li,
K. Yao, Y. Zhu, Z. Deng, F. Yang, X. Zhou, G. Li, H. Wu, N. Nijem,
Y. J. Chabal, Z. Lai, Yu Han, Z. Shi, S. Feng and J. Li, Angew. Chem. 15 (a) X. Yang, D. Chen, S. Liao, H. Song, Y. Li, Z. Fu and Y. Su, J
Int. Ed., 2012, 51, 1412.
Catal., 2012, 291, 36; (b) K. Sun, Y. Hong, G. Zhang and B. Xu,
ACS Catal., 2011, , 1336; (c) B. Wu, H. Huang, J. Yang, N. Zheng
7
8
(a) J. Juan-Alcañiz, J. Gascon and F. Kapteijn, J. Mater. Chem., 2012,
22, 10102; (b) H. R. Moon, D.W. Limb and M. P. Suh, Chem. Soc.
Rev., 2013, 42, 1807; (c) Q. Zhu and Q. Xu, Chem. Soc. Rev. 2014,
43, 5468; (d) L. Chen, H. Chen, R. Luque and Y. Li, Chem. Sci.,
2014, DOI: 10.1039/c4sc01847h.
1
and G. Fu, Angew. Chem. Int. Ed., 2012, 51, 3440; (d) K. R. Kahsar,
D. K. Schwartz and J. W. Medlin, J. Am. Chem. Soc., 2014, 136, 520;
(e) G. Kennedy, L. R. Baker and Gabor A. Somorjai, Angew. Chem.
Int. Ed., 2014, 53, 3405.
(a) A. Dhakshinamoorthy and H. Garcia, Chem. Soc. Rev., 2012, 41
,
16 (a) H. Mao, H. Yu, J. Chen and X. Liao, Sci. Rep., 2013,
3, 2226; (b)
5262; (b) Y. Liu and Z. Tang, Adv. Mater., 2013, 25, 5819; (c) M.
Meilikhov, K. Yusenko, D. Esken, S. Turner, G. Van Tendeloo and R.
A. Fischer, Eur. J. Inorg. Chem., 2010, 3701; (d) D.-W. Lim, J. W.
G. Kong, S. Ou, C. Zou and C. Wu, J. Am. Chem. Soc., 2012, 134
,
19851; (c) H. Kochkar, M. Aouine, A. Ghorbel and G. Berhault, J.
Phys. Chem. C, 2011, 115, 11364.
Yoon, K. Y. Ryu and M. P. Suh, Angew. Chem. Int. Ed., 2012, 51
,
9814; (e) J. Hermannsdörfer, M. Friedrich, N. Miyajima, R. Q.
Albuquerque, S. Kümmel and R. Kempe, Angew. Chem. Int. Ed.,
2012, 51, 11473; (f) B. Yuan, Y. Pan, Y. Li, B. Yin and H. Jiang,
Angew. Chem. Int. Ed., 2010, 49, 4054; g) H. Liu, G. Chen, H. Jiang,
Y. Li and R. Luque, ChemSusChem., 2013,
Akita, N. Tsumori and Q. Xu, J. Am. Chem. Soc., 2013, 135, 16356;
(i) A. Aijaz, A. Karkamkar, Y. J. Choi, N. Tsumori, E. Ronnebro, T.
Autrey, H. Shioyama and Q. Xu, J. Am. Chem. Soc., 2012, 134
5, 1892; (h) A. Aijaz, T.
̈
,
13926; (j) C. Zlotea, R. Campesi, F. Cuevas, E. Leroy, P. Dibandjo,
C. Volkringer, T. Loiseau, G. Férey and M. Latroche, J. Am. Chem.
Soc., 2010, 132, 2991; (k) B. W. Jacobs, R. J. T. Houk, M. R. Anstey,
S. D. House, I. M. Robertson, A. A. Talinc and M. D. Allendorf,
Chem. Sci., 2011, 2, 411.
9
(a) G. Lu, S. Z. Li, Z. Guo, O. K. Farha, B. G. Hauser, X. Y. Qi, Y.
Wang, X. Wang, S. Y. Han, X. G. Liu, J. S. DuChene, H. Zhang, Q.
C. Zhang, X. D. Chen, J. Ma, S. C. J. Loo, W. D. Wei, Y. H. Yang, J.
T. Hupp and F. W. Huo, Nat. Chem., 2012,
4, 310; (b) Y. Liu, W.
Zhang, S. Li, C. Cui, J. Wu, H. Chen and F. Huo, Chem. Mater.,
4 | J. Name., 2012, 00, 1-3
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