Communication
catalyst (Mo
ChemComm
3
S
13@EB-COF) with excellent catalytic performance and Conflicts of interest
enhanced cycling stability.
There are no conflicts to declare.
Furthermore, we investigated the reaction mechanism of the
Ru(bpy) Cl /Mo S @EB-COF/L-Vc photocatalytic system. Visible
3
2
3 13
Notes and references
light is first absorbed by Ru(bpy) Cl to generate photoelectrons,
3
2
+
2
and the ground state of Ru(bpy)
3
transitions to excited state
1
2
3
4
X. Y. Dong, M. Zhang, R. B. Pei, Q. Wang, D. H. Wei, S. Q. Zang,
Y. T. Fan and T. C. W. Mak, Angew. Chem., Int. Ed., 2016, 55, 2073.
X. Z. Fang, Q. C. Shang, Y. Wang, L. Jiao, T. Yao, Y. F. Li, Q. Zhang,
Y. Luo and H. L. Jiang, Adv. Mater., 2018, 30, 1705112.
R. Wang, X. Y. Dong, J. Du, J. Y. Zhao and S. Q. Zang, Adv. Mater.,
2018, 30, 1703711.
2
+
29–31
2+
[
Ru(bpy)
quenched by L-Vc reductively or Mo
we acquired the fluorescence emission spectra of Ru(bpy)
the presence of L-Vc and Mo 13@EB-COF, respectively (Fig. S29a
and S30a, ESI†). A linear fitting of the Stern–Volmer curve yielded
3
]*.
To evaluate the excited state, [Ru(bpy)
13@EB-COF oxidatively, and
Cl in
3
]* was
3
S
3
2
3
S
L. Zhao, J. W. Wei, J. Zhang, C. He and C. Y. Duan, Angew. Chem., Int.
Ed., 2017, 56, 15284.
4
À1
a rate constant (k ) of 2.58 Â 10 M for the oxidative quenching
sv
5 X. B. Chen, S. H. Shen, L. J. Guo and S. S. Mao, Chem. Rev., 2010,
110, 6503.
6 Z. Z. Gu, L. Y. Chen, H. F. Wang, Y. T. Guo, M. L. Xu, Y. Y. Zhang and
C. Y. Duan, Int. J. Hydrogen Energy, 2017, 42, 26713.
resulting from Mo S @EB-COF (Fig. S29b, ESI†), whereas the k
3
13
sv
À1
obtained by the reduction quenching of L-Vc was 2.18 M
(
Fig. S30b, ESI†), i.e., more than 4 orders of magnitude lower
than the oxidation quenching constant. Thus, we concluded
that the photocatalytic HER in Mo 13@EB-COF occurred via
3 13
photoelectron transfer from the [Ru(bpy) ]* to Mo S @
7
8
9
K. Li, M. Han, R. Chen, S. L. Li, S. L. Xie, C. Y. Mao, X. H. Bu, X. L. Cao,
L. Z. Dong, P. Y. Feng and Y. Q. Lan, Adv. Mater., 2016, 28, 8906.
J. D. Xiao, L. L. Han, J. Luo, S. H. Yu and H. L. Jiang, Angew. Chem.,
Int. Ed., 2018, 57, 1103.
D. Y. Shi, R. Zheng, M. J. Sun, X. R. Cao, C. X. Sun, C. J. Cui, C. S. Liu,
J. W. Zhao and M. Du, Angew. Chem., Int. Ed., 2017, 56, 14637.
3
S
2
+
3
EB-COF. L-Vc apparently consumed the photogenerated holes
of the photosensitizer, and the protons were reduced to H2
1
0 L. Jiao, Y. Wang, H. L. Jiang and Q. Xu, Adv. Mater., 2018,
30, 1703663.
by accepting the photoelectrons from the Mo S @EB-COF
3
13
11 X. Tang, J. H. Zhao, Y. H. Li, Z. J. Zhou, K. Li, F. T. Liu and Y. Q. Lan,
3
2,33
(
Scheme 2).
We also measured the oxidative quenching rate (ksv) values
of MS-c and Mo 13@MIL-100(Fe), and they were determined to
be 2.97 Â 10 and 6.48 Â 10 M , respectively (Fig. S31b and
S32b, ESI†). The ksv of Mo 13@EB-COF was found to be nearly
the same as that of MS-c, but the ksv of Mo S @MIL-100(Fe)
Dalton Trans., 2017, 46, 10553.
2 B. Ma, P. Y. Guan, Q. Y. Li, M. Zhang and S. Q. Zang, ACS Appl.
Mater. Interfaces, 2016, 8, 26794.
3 J. D. Ran, J. Zhang, J. G. Yu, M. Jaroniec and S. Z. Qiao, Chem. Soc.
Rev., 2014, 43, 7787.
4 T. T. Jia, M. M. J. Li, L. Ye, S. Wiseman, G. L. Liu, J. Qu, K. Nakagawa
and S. C. E. Tsang, Chem. Commun., 2015, 51, 13496.
1
1
1
3
S
4
3
À1
3
S
3
13
15 J. Kibsgaard, T. F. Jaramillo and F. Besenbacher, Nat. Chem., 2014,
6, 248.
was significantly lower than that of MS-c. This result can also be
attributed to EB-COF having been better than MIL-100(Fe) at
anchoring MS-c in the framework, since the cationic EB-COF
framework had almost no limiting effect on the catalytic activity
16 Y. G. Lei, M. Q. Yang, J. H. Hou, F. Wang, E. T. Cui, C. Kong and
S. A. Min, Chem. Commun., 2018, 54, 603.
1
7 T. Q. Ma, E. A. Kapustin, S. X. Yin, L. Liang, Z. Y. Zhou, J. Niu,
L. H. Li, Y. Y. Wang, J. Su, J. Li, X. G. Wang, W. D. Wang, W. Wang,
J. L. Sun and O. M. Yaghi, Science, 2018, 361, 48.
2À
of the [Mo
In summary, we prepared an excellent HER photocatalyst
Mo
3
S
13
]
anion, allowing it to play a catalytic role.
1
8 S. Wang, L. Ma, Q. Y. Wang, P. P. Shao, D. Ma, S. Yuan, P. Lei,
P. F. Li, X. Feng and B. Wang, J. Mater. Chem. C, 2018, 6, 5369.
(
3
S
13@EB-COF) by anchoring MS-c in the cationic EB-COF. 19 V. S. Vyas, V. W. H. Lau and B. V. Lotsch, Chem. Mater., 2016, 28, 5191.
2
2
2
2
0 G. G. Zhang, Z. A. Lan and X. C. Wang, Angew. Chem., Int. Ed., 2016,
5, 15712.
1 S. Wang, Q. Y. Wang, P. P. Shao, Y. Z. Han, X. Gao, L. Ma, S. Yuan, X. J. Ma,
J. W. Zhou, X. Feng and B. Wang, J. Am. Chem. Soc., 2017, 139, 4258.
2 T. Banerjee, K. Gottschling, G. Savasci, C. Ochsenfeld and
B. V. Lotsch, ACS Energy Lett., 2018, 3, 400.
Taking advantage of the well-defined COF structure and strong
interaction between COF and MS-c, the homogeneous molecular
MS-c completely converted to the heterogeneous Mo S @
5
3
13
EB-COF catalyst, with an accompanying significantly enhanced
stability and recyclability. Investigation of the visible-light-
3 P. Pachfule, S. Kandambeth, D. D. D ´ı az and R. Banerjee, Chem.
Commun., 2014, 50, 3169.
driven hydrogen evolution of Mo
3
S
13@EB-COF indicated a high
À1 À1
24 P. Pachfule, M. K. Panda, S. Kandambeth, S. M. Shivaprasad,
HER rate of 13 215 mmol g
h , superior to those of most
D. D. D ´ı az and R. Banerjee, J. Mater. Chem. A, 2014, 2, 7944.
reported COF-based photocatalytic HER systems, even many
systems containing noble-metal co-catalysts. Furthermore,
the photocatalytic activity of Mo S @EB-COF remained
2
2
2
5 D. Mullangi, D. Chakraborty, A. Pradeep, V. Koshti, C. P. Vinod,
S. Panja, S. Nair and R. Vaidhyanathan, Small, 2018, 14, 1801233.
6 H. P. Ma, B. L. Liu, B. Li, L. M. Zhang, Y. G. Li, H. Q. Tan, H. Y. Zang
and G. S. Zhu, J. Am. Chem. Soc., 2016, 138, 5897.
3
13
unchanged after four HER cycles. More importantly, the atom-
7 J. Gao and D. L. Jiang, Chem. Commun., 2016, 52, 1498.
ically precisely controllable COF structure and versatile guest 28 P. Horcajada, S. Surbl ´e , C. Serre, D. Y. Hong, Y. K. Seo, J. S. Chang,
J. M. Gren `e che, I. Margiolaki and G. F ´e reya, Chem. Commun., 2007,
molecules may pave the way for developing additional novel
photocatalysts.
2820.
2
9 L. Zhao, J. W. Wei, F. L. Zhang, C. He, S. J. Zheng and C. Y. Duan,
This work was supported by the National Science Fund for
Distinguished Young Scholars (No. 21825106), the National
Natural Science Foundation of China (No. 21671175), the Program
for Science & Technology Innovation Talents in Universities of
Henan Province (164100510005), the Program for Innovative
Research Team (in Science and Technology) in Universities of
Henan Province (19IRTSTHN022) and Zhengzhou University.
RSC Adv., 2017, 7, 48989.
3
3
0 T. S. Teets and D. G. Nocera, Chem. Commun., 2011, 47, 9268.
1 S. Y. Han, D. L. Pan, H. Chen, X. B. Bu, Y. X. Gao, H. Gao, Y. Tian,
G. S. Li, G. Wang, S. L. Cao, C. Q. Wan and G. C. Guo, Angew. Chem.,
Int. Ed., 2018, 57, 9864.
2 R. Chen, K. Li, X. S. Zhu, S. L. Xie, L. Z. Dong, S. L. Li and Y. Q. Lan,
CrystEngComm, 2016, 18, 1446.
3
3
3 Z. Han, W. R. McNamara, M. E. Eum, P. L. Holland and
R. Eisenberg, Angew. Chem., Int. Ed., 2012, 51, 1667.
13566 | Chem. Commun., 2018, 54, 13563--13566
This journal is ©The Royal Society of Chemistry 2018