ChemComm
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DOI: 10.1039/C5CC00242G
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layer deposition (ALD) method to have largely improved the 4. J. J. Concepcion, J. W. Jurss, J. L. Templeton and T. J. Meyer, J. Am.
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device stability. Following a similar idea, we have here
introduced a protection layer of polypyrrole to prevent the
catalyst from dissociation. This protection layer was simply
achieved by further electroꢀpolymerization on the catalyst
modified electrode in a pyrrole solution. As shown in Figure 5,
under this protection, the stability in the late phase was improved
significantly as expected. CVs of the electrode show tiny
changes before and after electrolysis (Figure S13), indicating a
Chem. Soc., 2008, 130, 16462ꢀ16463.
L. Duan, F. Bozoglian, S. Mandal, B. Stewart, T. Privalov, A. Llobet
and L. Sun, Nat Chem, 2012, , 418ꢀ423.
L. Wang, L. Duan, B. Stewart, M. Pu, J. Liu, T. Privalov and L. Sun,
J. Am. Chem. Soc., 2012, 134, 18868ꢀ18880.
M. D. Kärkäs, T. Åkermark, H. Chen, J. Sun and B. Åkermark,
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5
.
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6
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7
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good stability of the immobilized catalyst on the surface. A 8. R. Zong and R. P. Thummel, J. Am. Chem. Soc., 2005, 127, 12802ꢀ
possible reason for the lower initial current density is the 12803.
coverage of the Ru catalyst by polypyrrole which blocks the 9. D. J. Wasylenko, C. Ganesamoorthy, M. A. Henderson, B. D.
access of water to the catalyst. This problem needs further
verification and as predicated can be solved by introducing
materials with a high porousity, and the relative work is
undergoing.
Koivisto, H. D. Osthoff and C. P. Berlinguette, J. Am. Chem. Soc., 2010,
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32, 16094ꢀ16106.
0. J. R. McKone, N. S. Lewis and H. B. Gray, Chemistry of Materials
013, 26, 407ꢀ414.
,
In summary, we have successfully immobilized our molecular
water oxidation catalysts in situ on the conductive carbon
surfaces via polymerization. This design by enriching the
catalysts on the electrode surface allows certain possibility for
the radical coupling process in water oxidation and also greatly
improves the catalytic efficiency. The length of the linkage
doesn’t have to be very long by comparing 1@BPG and
1. J. D. Blakemore, A. Gupta, J. J. Warren, B. S. Brunschwig and H. B.
Gray, J. Am. Chem. Soc., 2013, 135, 18288ꢀ18291.
2. Z. Chen, J. J. Concepcion, J. W. Jurss and T. J. Meyer, J. Am. Chem.
Soc., 2009, 131, 15580ꢀ15581.
3. F. Li, B. Zhang, X. Li, Y. Jiang, L. Chen, Y. Li and L. Sun, Angew.
Chem., Int. Ed., 2011, 50, 12276ꢀ12279.
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@BPG. The TON over 30000 of 1@BPG was obtained by 1 14. K. S. Joya, N. K. Subbaiyan, F. D'Souza and H. J. M. de Groot,
hour bulk electrolysis at 700 mV overpotential. To the best of Angew. Chem., Int. Ed., 2012, 51, 9601ꢀ9605.
–
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our knowledge, TOF of 10.47 s (ƞ = 0.77 V) is a very high 15. F. M. Toma, A. Sartorel, M. Iurlo, M. Carraro, P. Parisse, C.
number ever reported on the electrode surface. This high
efficiency provides an opportunity for light driven water splitting
with a high quantum yield. In principle this immobilization
method is generally applicable for tunable catalysts structures
and more importantly won’t affect the existing catalytic property
of the catalyst. Application of this method in the lightꢀdriven
water oxidation setup is undergoing in our group. Such work will
encouragingly provide candidates for solar–driven water–
splitting devices and help to accelerate the transition to future
sustainable energy systems.
Maccato, S. Rapino, B. R. Gonzalez, H. Amenitsch, T. Da Ros, L.
Casalis, A. Goldoni, M. Marcaccio, G. Scorrano, G. Scoles, F. Paolucci,
M. Prato and M. Bonchio, Nat Chem, 2010,
2, 826ꢀ831.
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6. L. Tong, M. Gothelid and L. Sun, Chem. Commun., 2012, 48, 10025ꢀ
0027.
7. Z. Fang, S. Keinan, L. Alibabaei, H. Luo, A. Ito and T. J. Meyer,
Angew. Chem., Int. Ed., 2014, 53, 4872ꢀ4876.
8. T. R. O'Toole, B. P. Sullivan, M. R. M. Bruce, L. D. Margerum, R.
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W. Murray and T. J. Meyer, Journal of Electroanalytical Chemistry and
Interfacial Electrochemistry, 1989, 259, 217ꢀ239.
We thank the Swedish Research Council, K & A Wallenberg
Foundation, Swedish Energy Agency, China Scholarship Council 19. P. Denisevich, H. D. Abruna, C. R. Leidner, T. J. Meyer and R. W.
(
(
(
CSC), National Natural Science Foundation of China Murray, Inorg. Chem., 1982, 21, 2153ꢀ2161.
21120102036) and the National Basic Research Program of China
2014CB239402) for financial support of this work.
2
0. D. L. Ashford, A. M. Lapides, A. K. Vannucci, K. Hanson, D. A.
Torelli, D. P. Harrison, J. L. Templeton and T. J. Meyer, J. Am. Chem.
Soc., 2014, 136, 6578ꢀ6581.
Notes and references
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a
Department of Chemistry, KTH Royal Institute of Technology, 10044
b
2
Department of Physics and Astronomy, Uppsala University, Box 516,
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c
51 20, Uppsala, Sweden
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State Key Laboratory of Fine Chemicals, DUT–KTH Joint Education
and Research Center on Molecular Devices, Dalian University of
Technology (DUT), Dalian 116024, P. R. China
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