Page 7 of 17
Journal of the American Chemical Society
ported as part of the Hydrogen and Fuel Cell Program under Award
that the catalytic reaction occurred exclusively in MOF cavity,
1
2
3
4
5
6
7
8
Number DEꢀEEꢀ0007049. S. Yuan also acknowledges the Texas A&M
Energy Institute Graduate Fellowship funded by ConocoPhillips and
Dow Chemical Graduate Fellowship. We thank Mr. Mathieu Bosch for
his proofreading and feedback.
whereas the external surface of the MOF crystal was only responsiꢀ
ble for very limited conversion of alcohols. Based on the experiꢀ
mental result and literature, a simplified mechanism is proposed for
the aerobic alcohol oxidation reaction catalyzed by PCNꢀ700ꢀ
BPYDC(Cu), which is shown in Scheme S2. To evaluate the recyꢀ
clability, PCNꢀ700ꢀBPYDC(Cu) catalyst was simply separated
from the mixture at the end of the reaction by centrifuge and reused
for the next reaction. The catalytic activity was wellꢀmaintained
after three cycles (Table S5). PCNꢀ700 can be functionalized with
various catalysts by judicious selection of chelating linkers and
metal precursor, allowing the development of heterogeneous cataꢀ
lysts with unprecedented degree of control. PCNꢀ700 system also
serves as an inherent crystalline platform, possibly facilitating the
observation of catalytic center and reaction intermediates by singleꢀ
crystal Xꢀray diffraction to gather fundamental insight into metalꢀ
catalyzed reactions.
REFERENCES
(1) (a)Zhou, H. C.; Long, J. R.; Yaghi, O. M. Chem. Rev. 2012, 112
,
673; (b)Li, H.; Eddaoudi, M.; O'Keeffe, M.; Yaghi, O. M. Nature 1999,
402, 276; (c)Furukawa, H.; Cordova, K. E.; O'Keeffe, M.; Yaghi, O. M.
Science 2013, 341, 1230444.
(2) (a)Yaghi, O. M.; O'Keeffe, M.; Ockwig, N. W.; Chae, H. K.;
Eddaoudi, M.; Kim, J. Nature 2003, 423, 705; (b)Li, M.; Li, D.;
O’Keeffe, M.; Yaghi, O. M. Chem. Rev. 2014, 114, 1343; (c)Furukawa,
H.; Ko, N.; Go, Y. B.; Aratani, N.; Choi, S. B.; Choi, E.; Yazaydin, A.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
O.; Snurr, R. Q.; O'Keeffe, M.; Kim, J.; Yaghi, O. M. Science 2010, 329
424; (d)Fukushima, T.; Horike, S.; Inubushi, Y.; Nakagawa, K.;
Kubota, Y.; Takata, M.; Kitagawa, S. Angew. Chem. Int. Ed. 2010, 49
,
,
4820; (e)Doonan, C. J.; Morris, W.; Furukawa, H.; Yaghi, O. M. J. Am.
Chem. Soc. 2009, 131, 9492; (f)Dybtsev, D. N.; Chun, H.; Kim, K.
Angew. Chem. Int. Ed. 2004, 43, 5033.
CONCLUSIONS
In summary, we present a comprehensive study on the linker inꢀ
stallation method. First, kinetic analysis is adopted to construct a
MOF with inherent missing linker sites, namely PCNꢀ700. Twelve
linkers with different substituents are designed to study the size
effect of functional groups on the linkers. Guided by the geometꢀ
rical analysis, linkers with different lengths and combinations
thereof were sequentially installed into a parent PCNꢀ700, giving
rise to eleven new MOFs, and each bearing up to three different
functional groups in predefined positions. The pore environments
of the PCNꢀ700 system were engineered by tuning the sizes and
functionalities of installed linkers. Systematic variation of the pore
volume and decoration of pore environment resulted in synergistic
effects including an enhancement of H2 uptake to 57%. Besides, a
sizeꢀselective catalytic system for aerobic alcohol oxidation is built
in PCNꢀ700 through linker installation, which shows high activity
and tunable sizeꢀselectivity. These results highlight the unique poꢀ
tential of the linker installation method to decorate pore environꢀ
ment of MOF with multiple functional groups in a highly designed
manner. In light of the ubiquity of ZrꢀMOFs with coordinately
unsaturated Zr6 clusters, we believe that linker installation is a verꢀ
satile strategy to synthesize stable MOFs with unprecedented mulꢀ
tiꢀfunctionality.
(3) (a)Makal, T. A.; Li, J.ꢀR.; Lu, W.; Zhou, H.ꢀC. Chem. Soc. Rev.
2012, 41, 7761; (b)Ma, L.; Abney, C.; Lin, W. Chem. Soc. Rev. 2009,
38, 1248; (c)Li, J. R.; Kuppler, R. J.; Zhou, H. C. Chem. Soc. Rev.
2009, 38, 1477; (d)Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald,
T. M.; Bloch, E. D.; Herm, Z. R.; Bae, T. H.; Long, J. R. Chem. Rev.
2012, 112, 724; (e)Suh, M. P.; Park, H. J.; Prasad, T. K.; Lim, D. W.
Chem. Rev. 2012, 112, 782; (f)Li, J.ꢀR.; Sculley, J.; Zhou, H.ꢀC. Chem.
Rev. 2011, 112, 869.
(4) (a)Cavka, J. H.; Jakobsen, S.; Olsbye, U.; Guillou, N.; Lamberti, C.;
Bordiga, S.; Lillerud, K. P. J. Am. Chem. Soc. 2008, 130, 13850; (b)Bai,
Y.; Dou, Y.; Xie, L.ꢀH.; Rutledge, W.; Li, J.ꢀR.; Zhou, H.ꢀC. Chem. Soc.
Rev. 2016, 45, 2327; (c)Feng, D.; Gu, Z.ꢀY.; Li, J.ꢀR.; Jiang, H.ꢀL.; Wei,
Z.; Zhou, H.ꢀC. Angew. Chem. Int. Ed. 2012, 51, 10307; (d)Lin, Q.;
Bu, X.; Kong, A.; Mao, C.; Zhao, X.; Bu, F.; Feng, P. J. Am. Chem. Soc.
2015, 137, 2235; (e)Liu, T.ꢀF.; Feng, D.; Chen, Y.ꢀP.; Zou, L.; Bosch,
M.; Yuan, S.; Wei, Z.; Fordham, S.; Wang, K.; Zhou, H.ꢀC. J. Am.
Chem. Soc. 2015, 137, 413; (f)Morris, W.; Volosskiy, B.; Demir, S.;
Gándara, F.; McGrier, P. L.; Furukawa, H.; Cascio, D.; Stoddart, J. F.;
Yaghi, O. M. Inorg. Chem. 2012, 51, 6443; (g)Schaate, A.; Roy, P.;
Preuße, T.; Lohmeier, S. J.; Godt, A.; Behrens, P. Chem. Eur. J. 2011,
17, 9320; (h)Wu, H.; Chua, Y. S.; Krungleviciute, V.; Tyagi, M.; Chen,
P.; Yildirim, T.; Zhou, W. J. Am. Chem. Soc. 2013, 135, 10525;
(i)Mondloch, J. E.; Bury, W.; FairenꢀJimenez, D.; Kwon, S.; DeMarco,
E. J.; Weston, M. H.; Sarjeant, A. A.; Nguyen, S. T.; Stair, P. C.; Snurr,
R. Q.; Farha, O. K.; Hupp, J. T. J. Am. Chem. Soc. 2013, 135, 10294;
(j)Yuan, S.; Chen, Y.ꢀP.; Qin, J.; Lu, W.; Wang, X.; Zhang, Q.; Bosch,
ASSOCIATED CONTENT
Supporting Information. Experimental details, figures, tables and crysꢀ
tallographic data. This material is available free of charge via the Interꢀ
M.; Liu, T.ꢀF.; Lian, X.; Zhou, H.ꢀC. Angew. Chem. Int. Ed. 2015, 54
,
14696; (k)Cliffe, M. J.; Wan, W.; Zou, X.; Chater, P. A.; Kleppe, A. K.;
Tucker, M. G.; Wilhelm, H.; Funnell, N. P.; Coudert, F.ꢀX.; Goodwin,
A. L. Nat. Commun. 2014, 5, 4176.
(5) (a)Furukawa, H.; Gándara, F.; Zhang, Y.ꢀB.; Jiang, J.; Queen, W.
L.; Hudson, M. R.; Yaghi, O. M. J. Am. Chem. Soc. 2014, 136, 4369;
(b)Katz, M. J.; Brown, Z. J.; Colon, Y. J.; Siu, P. W.; Scheidt, K. A.;
AUTHOR INFORMATION
Corresponding Author
*zhou@chem.tamu.edu
Author Contributions
Snurr, R. Q.; Hupp, J. T.; Farha, O. K. Chem. Commun. 2013, 49
,
9449; (c)Schaate, A.; Roy, P.; Godt, A.; Lippke, J.; Waltz, F.; Wiebcke,
M.; Behrens, P. Chem. Eur. J. 2011, 17, 6643.
‡These authors contributed equally.
(6) Yamada, T.; Kitagawa, H. J. Am. Chem. Soc. 2009, 131, 6312.
(7) (a)Tanabe, K. K.; Cohen, S. M. Chem. Soc. Rev. 2011, 40, 498;
(b)Kim, M.; Cohen, S. M. CrystEngComm 2012, 14, 4096; (c)Nickerl,
G.; Senkovska, I.; Kaskel, S. Chem. Commun. 2015, 51, 2280;
(d)Kandiah, M.; Usseglio, S.; Svelle, S.; Olsbye, U.; Lillerud, K. P.;
Tilset, M. J. Mater. Chem. 2010, 20, 9848; (e)Wang, T. C.; Vermeulen,
N. A.; Kim, I. S.; Martinson, A. B. F.; Stoddart, J. F.; Hupp, J. T.; Farha,
ACKNOWLEDGMENT
The gas adsorptionꢀdesorption studies of this research was supported
by the Center for Gas Separations Relevant to Clean Energy Technolꢀ
ogies, an Energy Frontier Research Center funded by the U.S. Departꢀ
ment of Energy, Office of Science, Office of Basic Energy Sciences
under Award Number DEꢀSC0001015. Structural analyses were supꢀ
ACS Paragon Plus Environment