Hydroxide Ligands Cooperate with Catalytic Centers in Metal-Organic Frameworks for Efficient Photocatalytic CO2 Reduction

Article abstract of DOI:10.1021/jacs.7b10107

Converting CO₂ into fuels via photochemical reactions relies on highly efficient and selective catalysts. We demonstrate that the catalytic active metal center can cooperate with neighboring hydroxide ligands to boost the photocatalytic CO

Full text of DOI:10.1021/jacs.7b10107

Subscriber access provided by READING UNIV
Communication
Hydroxide Ligands Cooperate with Catalytic Centers in Metal-
Organic Frameworks for Efficient Photocatalytic CO2 Reduction
Yu Wang, Ning-Yu Huang, Jian-Qiang Shen, Pei-Qin Liao, Xiao-Ming Chen, and Jie-Peng Zhang
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b10107 • Publication Date (Web): 20 Dec 2017
Downloaded from http://pubs.acs.org on December 20, 2017
Just Accepted
“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Journal of the American Chemical Society is published by the American Chemical
Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the
course of their duties.

Page 1 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
Hydroxide Ligands Cooperate with Catalytic Centers in Metal‐
Organic Frameworks for Efficient Photocatalytic CO2 Reduction
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
Yu Wang, Ning-Yu Huang, Jian-Qiang Shen, Pei-Qin Liao*, Xiao-Ming Chen and Jie-Peng Zhang*
MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry, Sun Yat-Sen University, Guangzhou
510275, China.
Supporting Information Placeholder
comparing the photocatalytic CO2 reduction performances of a
series of cobalt-based MOFs possessing different coordination
environments, we demonstrate the cooperation effect between
catalytic active metal centers and their neighboring -OH− ligands,
and develop a new MOF with record catalytic performances to
date especially at low CO2 pressure.
ABSTRACT: Converting CO2 into fuels via photochemical
reactions relies on highly efficient and selective catalysts. We
demonstrate that the catalytic active metal center can cooperate
with neighboring hydroxide ligands to boost the photocatalytic
CO2 reduction. Six cobalt-based metal-organic frameworks
(MOFs) with different coordination environments are studied at
the same reaction condition (photosensitizer, electron donor,
water/organic mixed solvent, and visible light). In pure CO2 at 1.0
atm, the MOFs bearing -OH− ligands neighboring the open Co
centers showed CO selectivities and turnover frequencies (TOFs)
up to 98.2% and 0.059 s−1, respectively. More importantly, their
TOFs reduced only ca. 20% when the CO2 partial pressure was
reduced to 0.1 atm, while other MOFs reduced by at least 90%.
Periodic density functional theory calculations and isotope tracing
experiments showed that the -OH− ligands serve not only as
strong hydrogen-bonding donors to stabilize the initial Co−CO2
adduct, but also local proton sources to facilitate the C−O bond
breaking.
[Co2(-Cl)2(bbta)] (MAF-X27-Cl, H2bbta = 1H,5H-benzo(1,2-
d:4,5-d')bistriazole),40 [Co2(-OH)2(bbta)] (MAF-X27-OH)29 and
[Co2(dobdc)] (MOF-74-Co, H4dobdc
benzenedicarboxylic are
acid)41
=
2,5-dihydroxyl-1,4-
isostructural/isoreticular
honeycomb-like MOFs bearing OMSs with the same coordination
geometry (Figures S1). The main difference among these three
MOFs is their donor atoms. The metal azolate frameworks MAF-
X27-Cl/MAF-X27-OH are more stable than the metal carboxylate
framework MOF-74-Co.42 Further, all donor atoms in MOF-74-
Co are from the organic linkers, while isostructral MAF-X27-
Cl/MAF-X27-OH bear a pair of inorganic -OH−/-Cl− ligands at
the cis-positions of its OMS, which may cooperate with the OMS
to enhance the catalytic performance.
The photocatalytic CO2 reduction performances of MAF-X27-
Cl, MAF-X27-OH, and MOF-74-Co were studied under visible
light in pure CO2 at 1.0 atm in 4:1 CH3CN/H2O mixed solvent for
10 hours (Figures S2-4, Tables S1-3), using [Ru(bpy)3]Cl2 as the
photosensitizer, which is the typical reaction condition used in the
literature (Table S4).25,36 CO and H2 were detected as the main
product and by-product, respectively (Figure S5-9). As shown in
Figure 1, the quantity of CO increased along with the irradiation
time, but the production rates slowly decreased (consumption of
the photosensitizer), being similar to the reported examples.43,44
As calculated from the initial CO production rates (Figure 2 and
Table S1), the turnover frequency (TOF) for CO follows MAF-
X27-OH (28  10−3 s−1) > MOF-74-Co (13  10−3 s−1) > MAF-
X27-Cl (6.3  10−3 s−1). The CO selectivity (calculated as TOF
(CO)/TOF(CO+H2)) follows the same trend, i.e., MAF-X27-OH
Photocatalytic conversion of CO2 into fuels (such as CO,
HCOOH, CH4 etc.) under visible light is a promising approach to
achieve a carbon neutral economic.1-6 With outstanding structural
designability, metal-organic frameworks (MOFs) containing both
adsorption and catalyst sites, e.g. open metal sites (OMSs), are
emerging as potential catalysts.7-24 However, similar with
traditional homogeneous and heterogeneous catalysts, reported
MOF catalysts also suffer from poor water stability and low
catalytic activity/selectivity.4 Particularly, the reaction/conversion
performances at low CO2 pressure are generally very poor.25-27
It is well known that the activity and selectivity of catalysts are
mainly affected by the kind, the coordination geometry, and the
surrounding environment of the metal centers, cooperately.28-32
For example, coordination complexes of precious metals, such as
Ru, Re and Ir, are so far the most efficient catalysts for
photocatalytic CO2 reduction,33-35 while cobalt is one of the best
earth-abundant metal candidates.26,36 The amino acid residues and
supramolecular environments surrounding the active sites of metal
proteins play critical roles to cooperate with the catalytic metal
centers for binding and activating the reaction substrates.37
Nevertheless, such structure-property relationships and
cooperation roles have not been investigated for MOFs in the field
of photocatalytic CO2 reduction.
(97.2%)
> MAF-X27-Cl (63.6%) > MOF-74-Co (58.8%).
Obviously, the catalytic performance of MAF-X27-OH is much
higher than the other two MOFs, implying the usefulness of the -
OH− ligands. To verify these results, we also measured the
photochemical CO2 reduction performance of SOD-[Co(bim)2]
(Co-ZIF-9, Hbim = benzimidazole, Figures S2 and S3), which
holds the highest TOF value for this reaction among reported
MOF catalysts.36 The obtained TOF of 27  10−3 s−1 and
selectivity of 63.1% for Co-ZIF-9 are consistent with the reported
values (Table S2).
Considering the necessary participation of protons in most CO2
reduction processes, putting Brønsted-acid type functional groups
near the catalytic active metal center may improve the reaction
rate and selectivity.38,39 Nevertheless, there is no strategy for
designing and synthesizing such MOFs. In this work, by
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 2 of 5
1
2
3
4
5
6
7
8
9
(a)
(e)
(c)
8
6
4
2
0
1.0 bar
0.1 bar
1.0 bar
0.1 bar
1.0 bar
0.1 bar
4
3
2
1
0
8
6
4
2
0



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
MAF-X27-Cl
MAF-X27l-Cl
MOF-74-Co
0
2
4
6
8
10
0
2
4
6
8
10
0
2
4
6
8
10
Time (h)
Time (h)
Time (h)
(b)
(d)
(f)
1.0 bar
0.1 bar
20
15
10
5
1.0 bar
0.1 bar
1.0 bar
0.1 bar
40
30
20
10
0
15
10
5



Co-ZIF-9
MAF-X27-OH
MAF-X27l-OH
0
0
0
2
4
6
8
10
0
2
4
6
8
10
0
2
4
6
8
10
Time (h)
Time (h)
Time (h)
Figure 1. CO production rate of photocatalytic CO2 reduction by using catalyst (a) MAF-X27-Cl; (b) MAF-X27-OH; (c) MOF-74-Co; (d)
Co-ZIF-9; (e) MAF-X27l-Cl; and (f) MAF-X27l-OH. Reaction condition: [Ru(bpy)3]Cl2·6H2O (2 μmol), catalysts (30 nmol on the basis of
Co), solvent (5 mL, CH3CN/H2O = 4:1), Triethanolamine (TEOA, 0.1 mol), LED light (λ = 420 nm), 25 C, 1.0 atm (pure CO2 or 1:9
o
CO2/Ar mixture). Insets: Structures of the coordination framework and catalytic active sites.
MAF-X27l-OH
To understand the roles of the -OH ligands, we used periodic
density functional theory (PDFT) to simulate the CO2 binding
structures of the reduced forms of MAF-X27-OH and MAF-X27-
Cl (Figures 3 and S10-12). For the computational simulation, a
host-guest binding structure was built by connecting a V-shaped
CO2 molecule with the Co(I) ion of the MOF via a Co−C bond,
according to the reported single-crystal structures of the
metal−CO2 adducts.45,46 The structure was then optimized by
PDFT without any restriction, and the results showed that the CO2
binding strength of MAF-X27-OH (208 kJ mol−1) is 167 kJ mol−1
stronger than for MAF-X27-Cl (41 kJ mol−1). In the optimized
structures, the Co−C bond (1.91 Å) of MAF-X27-OH is obviously
shorter than that for MAF-X27-Cl (1.96 Å). More importantly, for
MAF-X27-OH, the CO2 molecule formed two strong hydrogen
bonds (O−H···O = 2.68 Å, H···O = 1.82 Å, O−H···O = 138.4o)
with the two -OH– ligands neighboring the cobalt center. In
contrast, the -Cl– ligands in MAF-X27-Cl provided electrostatic
repulsive forces to the CO2 molecule. To attain a reasonable
separation between the electronegative O and Cl atoms (3.17 Å),
the molecular plane of CO2 was obviously deviated from the
Cl−Co−Cl chain. For comparison, the molecular plane of CO2 and
the OH−Co−OH chain are parallel. We also simulated the H2O
binding structures (Figure S10). Interestingly, the H2O binding of
MAF-X27-OH is significantly weaker (104 kJ mol−1) than its CO2
binding, while MAF-X27-Cl showed 35 kJ mol−1 stronger H2O
binding than its CO2 binding (Figure 3). In principle, a strong CO2
binding affinity can stabilize the initial Co−CO2 adduct to
promote the CO2 reduction, and a weak H2O binding affinity can
reduce the undesired Co−H2O adduct which lead to the H2
byproduct.
60
50
40
30
20
10
0
MAF-X27-OH
Co-ZIF-9
MOF-74-Co
MAF-X27l-Cl
MAF-X27-Cl
Figure 2. Comparison of the TOF values for the photocatalytic
reduction of CO2 to CO under 1.0 atm (blue) and 0.1 atm (orange).
The photocatalytic CO2 reduction experiments of MAF-X27-
Cl, MAF-X27-OH, MOF-74-Co, and Co-ZIF-9 were further
conducted in 1:9 CO2/Ar at 1.0 atm (Figures 1 and 2).25-27 Notably,
MAF-X27-OH maintains a high TOF of 23  10−3 s−1 (ca. 80%
that at 1.0 atm CO2) and an unchanged CO selectivity of 97.2%.
Importantly, these values are even better than for the best
homogeneous catalysts (TOF of 16.7  10−3 s−1, selectivity of
100%) working under the same condition.27 On the other hand,
the TOFs of the other three MOFs were reduced significantly by
more than 90% (Figure 2). Generally, the different catalytic
performances of MOFs is difficult to explain, because metal
coordination mode and surround environment, framework/pore
structure, and porosity, in principle, can all affect their properties.
Nevertheless, the isostructural frameworks MAF-X27-Cl and
MAF-X27-OH are only different at the -Cl/-OH ligands,
highlighting the importance of the -OH ligands again, so that the
-OH ligands should be critical for the superb catalytic
performances of MAF-X27-OH.
ACS Paragon Plus Environment

Page 3 of 5
Journal of the American Chemical Society
1
2
3
4
5
6
7
8
9
300
250
200
150
100
50
1.0 bar CO2
0.1 bar CO2
24
18

12
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
6
0
0
O
O
O
O
F
··C
··C
··H
··H
A
1
2
3
Run
4
5
·
l
H·
H·
·
l
C
C
-
O
-
7
-
O
7
-
7
2
7
2
2
X
2
X
-
X
-
X
-
F
-
F
A
F
A
A
M
M
M
M
Figure 4. CO production amounts of repeated photocatalytic CO2
reduction reactions by using MAF-X27-OH as catalyst. After each
10 h of reaction, a fresh crop of 2 μmol of [Ru(bpy)3]Cl2 was
injected into the reaction mixture with subsequent purging of pure
CO2 or 1:9 CO2/Ar at 1.0 atm.
Figure 3. Comparison of the CO2 and H2O binding structures and
energies of reduced MAF-X27-Cl and MAF-X27-OH.
The direct precipitation of the -OH– proton was demonstrated
by isotope tracing experiments (Figure S9). The infrared
stretching vibration of OD– of MAF-X27-OD at 2671 cm–1 almost
disappeared after a photocatalytic CO2 reduction reaction for 1
hour, accompanying with the appearance of the stretching
vibration of OH– at 3616 cm–1. In the same environment, the
stretching vibration of OD– was almost unchanged for 2 hours
without light irradiation. These observations demonstrated the
direct participation of the hydrogen atom of the -OH– ligand
during the photocatalytic process (Figure S14 and Table S4). With
similar acidity of a phenolic hydroxyl group (pKa ≈ 20),47,48 the
-OH– ligand should be sufficient to donate a proton to participate
the photocatalytic reaction.38 The important roles of the -OH–
ligands for promoting the photocatalytic CO2 reduction
performance were further confirmed by a series of control
experiments (eg. anhydrous condition, kinetic isotope effect, CO
inhibition and so on, see detail in Table S4), and a catalytic
mechanism based on the hydrogen-bonding and proton donor can
be proposed (Figure S14).
Inspired by the above discovery, we further synthesized a new
MOF [Co2(-OH)2(btdd)] (MAF-X27l-OH, H2btdd = bis(1H-
1,2,3-triazolo-[4,5-b],[4’,5’-i])dibenzo[1,4]dioxin),
by
ion
exchange treatment of [Co2(-Cl)2(btdd)] (MAF-X27l-Cl)
(Figures S1-S4). MAF-X27l-Cl and MAF-X27l-OH are the
expanded version of MAF-X27-Cl and MAF-X27-OH,
respectively.40,51 In pure CO2 at 1.0 atm, MAF-X27l-Cl and MAF-
X27l-OH showed CO selectivities of 66.7% and 98.2% and TOFs
of 0.012 s−1 and 0.059 s−1, respectively (Figure 1 and Table S1).
In 0.1 atm CO2, MAF-X27l-OH also maintained ca. 80% TOF
(0.049 s−1) and unchanged selectivity (Figure 2). As the CO2
binding affinities of MAF-X27-Cl/MAF-X27-OH and MAF-
X27l-Cl/MAF-X27l-OH should be similar, the higher catalytic
activities of MAF-X27l-OH/MAF-X27l-Cl can be attributed to
their larger pore sizes (Figures S1),51 which could allow quicker
diffusion of the reactants/products.52,53 To the best of our
knowledge, the overall catalytic performances (in terms of TOF
and CO selectivity) of MAF-X27l-OH, in both 1.0 and 0.1 atm
CO2, are much higher than for all reported heterogeneous
catalysts working at similar reaction conditions (Tables S2 and
S3).1,2,4
Considering that durability is also an important factor for
evaluating catalysts, we carried out consecutive runs of
photocatalytic CO2 reduction experiments for MAF-X27-OH
under reaction conditions in both 1.0 and 0.1 atm CO2. As shown
in Figure 4, after 5 runs, the TOF and CO selectivity in 1.0/0.1
atm remained 25/21  10−3 s−1 and 95.6%/95.1%, respectively.
These catalytic stabilities are significantly higher than for the
most stable homogeneous catalysts (20-50% reduction of TOF
In summary, we demonstrated that -OH– ligands can
cooperate with catalytic active metal centers in MOFs, serving as
hydrogen-bonding donors and local proton sources to improve the
performance of photocatalytic CO2 reduction, particularly at low
CO2 pressure. Moreover, following this stragtegy, we synthesized
a
new MOF and achieved extraordinarily high catalytic
after
3
runs),44 and comparable with the most durable
performances, in both pure CO2 and 0.1 atm CO2. These strategy
and results may open up new possibilities for CO2 reduction
catalysts and related materials.
catalysts.36,49,50 After the aforementioned reactions, the MAF-
X27-OH catalyst was recovered from the reaction mixture and
found to be almost unchanged according to PXRD patterns and N2
sorption isotherms (Figures S15 and S16). Further, inductively
coupled plasma–mass spectrometry showed that, just 0.2% of Co
ion in MAF-X27-OH was leached into the reaction solution after
the reaction, and the filtrate showed negligible catalytic activity
(Table S4), which confirmed the heterogeneous nature and the
stability of the catalyst.
ASSOCIATED CONTENT
Supporting Information
Experimental details, additional figures/tables in PDF. This mate-
rial is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
liaopq3@mail.sysu.edu.cn; zhangjp7@mail.sysu.edu.cn
ACS Paragon Plus Environment

Journal of the American Chemical Society
Page 4 of 5
1
2
3
4
5
6
7
8
9
(31) Perman, J. A.; Chen, M.; Mikhail, A. A.; Niu, Z.; Ma, S.
CrystEngComm 2017, 19, 4171.
(32) Xia, Q.; Li, Z.; Tan, C.; Liu, Y.; Gong, W.; Cui, Y. J. Am. Chem. Soc.
2017, 139, 8259.
(33) Ueda, Y.; Takeda, H.; Yui, T.; Koike, K.; Goto, Y.; Inagaki, S.;
Ishitani, O. ChemSusChem 2015, 8, 439.
(34) Choi, K. M.; Kim, D.; Rungtaweevoranit, B.; Trickett, C. A.;
Barmanbek, J. T. D.; Alshammari, A. S.; Yang, P.; Yaghi, O. M. J. Am.
Chem. Soc. 2017, 139, 356.
(35) Wang, C.; Xie, Z.; deKrafft, K. E.; Lin, W. J. Am. Chem. Soc. 2011,
133, 13445.
(36) Wang, S.; Yao, W.; Lin, J.; Ding, Z.; Wang, X. Angew. Chem. Int. Ed.
2014, 53, 1034.
(37) Krishnamurthy, V. M.; Kaufman, G. K.; Urbach, A. R.; Gitlin, I.;
Gudiksen, K. L.; Weibel, D. B.; Whitesides, G. M. Chem. Rev. 2008, 108,
946.
(38) Costentin, C.; Drouet, S.; Robert, M.; Savéant, J.-M. Science 2012,
338, 90.
(39) Chapovetsky, A.; Do, T. H.; Haiges, R.; Takase, M. K.; Marinescu, S.
C. J. Am. Chem. Soc. 2016, 138, 5765.
(40) Liao, P.-Q.; Li, X.-Y.; Bai, J.; He, C.-T.; Zhou, D.-D.; Zhang, W.-X.;
Zhang, J.-P.; Chen, X.-M. Chem. Eur. J. 2014, 20, 11303.
(41) Dietzel, P. D. C.; Morita, Y.; Blom, R.; Fjellvåg, H. Angew. Chem.
Int. Ed. 2005, 117, 6512.
(42) Zhang, J.-P.; Zhang, Y.-B.; Lin, J.-B.; Chen, X.-M. Chem. Rev. 2012,
112, 1001.
(43) Fei, H.; Sampson, M. D.; Lee, Y.; Kubiak, C. P.; Cohen, S. M. Inorg.
Chem. 2015, 54, 6821.
(44) Thoi, V. S.; Kornienko, N.; Margarit, C. G.; Yang, P.; Chang, C. J. J.
Am. Chem. Soc. 2013, 135, 14413.
(45) Fujita, E.; Creutz, C.; Sutin, N.; Brunschwig, B. S. Inorg. Chem.
1993, 32, 2657.
(46) Fujita, E.; Furenlid, L. R.; Renner, M. W. J. Am. Chem. Soc. 1997,
119, 4549.
Notes
The authors declare no competing financial interests.
ACKNOWLEDGMENT
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
This work was supported by the “973 Project” (2014CB845602)
and NSFC (21290173, 21473260, and 21701193).
REFERENCES
(1) White, J. L.; Baruch, M. F.; Pander, J. E.; Hu, Y.; Fortmeyer, I. C.;
Park, J. E.; Zhang, T.; Liao, K.; Gu, J.; Yan, Y.; Shaw, T. W.; Abelev, E.;
Bocarsly, A. B. Chem. Rev. 2015, 115, 12888.
(2) Li, K.; Peng, B.; Peng, T. ACS Catal. 2016, 6, 7485.
(3) Morris, A. J.; Meyer, G. J.; Fujita, E. Acc. Chem. Res. 2009, 42, 1983.
(4) Maina, J. W.; Pozo-Gonzalo, C.; Kong, L.; Schutz, J.; Hill, M.; Dumee,
L. F. Mater. Horiz. 2017, 4, 345.
(5) Ola, O.; Maroto-Valer, M. M. J. Photochem. Photobiol., C 2015, 24,
16.
(6) Wang, H.; Zhu, Q.-L.; Zou, R.; Xu, Q. Chem 2017, 2, 52.
(7) Chen, Y.; Wang, D.; Deng, X.; Li, Z. Catal. Sci. Technol. 2017, 7,
4893.
(8) Trickett, C. A.; Helal, A.; Al-Maythalony, B. A.; Yamani, Z. H.;
Cordova, K. E.; Yaghi, O. M. Nat. Rev. Mater. 2017, 2, 17045.
(9) Li, J.-R.; Ma, Y.; McCarthy, M. C.; Sculley, J.; Yu, J.; Jeong, H.-K.;
Balbuena, P. B.; Zhou, H.-C. Coord. Chem. Rev. 2011, 255, 1791.
(10) Zhang, T.; Lin, W. Chem. Soc. Rev. 2014, 43, 5982.
(11) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.; Hupp,
J. T. Chem. Soc. Rev. 2009, 38, 1450.
(12) He, H.; Perman, J. A.; Zhu, G.; Ma, S. Small 2016, 12, 6309.
(13) Li, S.-L.; Xu, Q. Energy. Environ. Sci. 2013, 6, 1656.
(14) Xiao, D. J.; Bloch, E. D.; Mason, J. A.; Queen, W. L.; Hudson, M. R.;
Planas, N.; Borycz, J.; Dzubak, A. L.; Verma, P.; Lee, K.; Bonino, F.;
Crocellà, V.; Yano, J.; Bordiga, S.; Truhlar, D. G.; Gagliardi, L.; Brown,
C. M.; Long, J. R. Nat. Chem. 2014, 6, 590.
(15) Kornienko, N.; Zhao, Y.; Kley, C. S.; Zhu, C.; Kim, D.; Lin, S.;
Chang, C. J.; Yaghi, O. M.; Yang, P. J. Am. Chem. Soc. 2015, 137, 14129.
(16) Xu, H.-Q.; Hu, J.; Wang, D.; Li, Z.; Zhang, Q.; Luo, Y.; Yu, S.-H.;
Jiang, H.-L. J. Am. Chem. Soc. 2015, 137, 13440.
(17) Lee, Y.; Kim, S.; Fei, H.; Kang, J. K.; Cohen, S. M. Chem. Commun.
2015, 51, 16549.
(18) Zhang, S.; Li, L.; Zhao, S.; Sun, Z.; Hong, M.; Luo, J. J. Mater.
Chem. A 2015, 3, 15764.
(19) Xiao, D. J.; Oktawiec, J.; Milner, P. J.; Long, J. R. J. Am. Chem. Soc.
2016, 138, 14371.
(20) Uemura, T.; Ono, Y.; Hijikata, Y.; Kitagawa, S. J. Am. Chem. Soc.
2010, 132, 4917.
(21) Wang, X.; Lu, W.; Gu, Z.-Y.; Wei, Z.; Zhou, H.-C. Chem. Commun.
2016, 52, 1926.
(22) Hod, I.; Sampson, M. D.; Deria, P.; Kubiak, C. P.; Farha, O. K.;
Hupp, J. T. ACS Catal. 2015, 5, 6302.
(23) Fu, Y.; Sun, D.; Chen, Y.; Huang, R.; Ding, Z.; Fu, X.; Li, Z. Angew.
Chem. Int. Ed. 2012, 51, 3364.
(24) Das, M. C.; Xu, H.; Wang, Z.; Srinivas, G.; Zhou, W.; Yue, Y.-F.;
Nesterov, V. N.; Qian, G.; Chen, B. Chem. Commun. 2011, 47, 11715.
(25) Kajiwara, T.; Fujii, M.; Tsujimoto, M.; Kobayashi, K.; Higuchi, M.;
Tanaka, K.; Kitagawa, S. Angew. Chem. Int. Ed. 2016, 55, 2697.
(26) Ouyang, T.; Huang, H.-H.; Wang, J.-W.; Zhong, D.-C.; Lu, T.-B.
Angew. Chem. Int. Ed. 2017, 56, 738.
(27) Nakajima, T.; Tamaki, Y.; Ueno, K.; Kato, E.; Nishikawa, T.;
Ohkubo, K.; Yamazaki, Y.; Morimoto, T.; Ishitani, O. J. Am. Chem. Soc.
2016, 138, 13818.
(47) Zheng, H.; Zang, Y.; Dong, Y.; Young, V. G.; Que, L. J. Am. Chem.
Soc. 1999, 121, 2226.
(48) Jover, J.; Bosque, R.; Sales, J. QSAR Comb. Sci. 2007, 26, 385.
(49) Zhang, H.; Wei, J.; Dong, J.; Liu, G.; Shi, L.; An, P.; Zhao, G.; Kong,
J.; Wang, X.; Meng, X.; Zhang, J.; Ye, J. Angew. Chem. Int. Ed. 2016, 55,
14310.
(50) Lee, Y.; Kim, S.; Kang, J. K.; Cohen, S. M. Chem. Commun. 2015,
51, 5735.
(51) Rieth, A. J.; Tulchinsky, Y.; Dincă, M. J. Am. Chem. Soc. 2016, 138,
9401.
(52) Cai, G.; Jiang, H.-L. Angew. Chem. Int. Ed. 2017, 56, 563.
(53) Armel, V.; Hindocha, S.; Salles, F.; Bennett, S.; Jones, D.; Jaouen, F.
J. Am. Chem. Soc. 2017, 139, 453..
(28) Wang, D.; Huang, R.; Liu, W.; Sun, D.; Li, Z. ACS Catal. 2014, 4,
4254.
(29) Lu, X.-F.; Liao, P.-Q.; Wang, J.-W.; Wu, J.-X.; Chen, X.-W.; He, C.-
T.; Zhang, J.-P.; Li, G.-R.; Chen, X.-M. J. Am. Chem. Soc. 2016, 138,
8336.
(30) Shen, J.-Q.; Liao, P.-Q.; Zhou, D.-D.; He, C.-T.; Wu, J.-X.; Zhang,
W.-X.; Zhang, J.-P.; Chen, X.-M. J. Am. Chem. Soc. 2017, 139, 1778.
ACS Paragon Plus Environment

Page 5 of 5
Journal of the American Chemical Society
1
2
3
4
5
TOC
6
7
8
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
ACS Paragon Plus Environment