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COMMUNICATION
Chemical Communications
14. M. L. Helm, M. P. Stewart, R. M. Bullock, M. R. DuBois aVnidewDA.rLti.clDeuOBnolinise,
these CPE measurements and the TON and TOF (Table S12)
confirm that 6a remains active for electrocatalytic H+ reduction
under almost neutral, saline aqueous conditions containing
Na+ or K+, even when mercury electrodes are used to suppress
the activity of nanomaterials.
Science, 2011, 333, 863-866.
DOI: 10.1039/C5CC09456A
15. R. M. Bullock, A. M. Appel and M. L. Helm, Chem. Commun., 2014, 50,
3125-3143.
16. G. M. Jacobsen, J. Y. Yang, B. Twamley, A. D. Wilson, R. M. Bullock, M. R.
DuBois and D. L. DuBois, Energy Environ. Sci., 2008, 1, 167-174.
17. M.-H. Ho, M. O'Hagan, M. Dupuis, D. L. DuBois, R. M. Bullock, W. J.
Shaw and S. Raugei, Dalton T, 2015.
18. N. M. Muresan, J. Willkomm, D. Mersch, Y. Vaynzof and E. Reisner,
Angew. Chem., Int. Ed., 2012, 124, 12921-12925.
Conclusions
19. M. J. Rose, H. B. Gray and J. R. Winkler, J. Am. Chem. Soc., 2012, 134,
8310-8313.
20. D. P. Estes, D. C. Grills and J. R. Norton, J. Am. Chem. Soc., 2014, 136,
We have prepared new mononuclear Ni complexes with
salicylaldimine ligands that can be used as electrocatalysts for
the production of H2 in both neutral and acidic aqueous
17362-17365.
solutions. The chelating ether groups in the structure can bind 21. S. Mandal, S. Shikano, Y. Yamada, Y.-M. Lee, W. Nam, A. Llobet and S.
alkali metal cations to form Lewis acids and promote the H+
reduction efficiency. Future studies will focus on modification
Fukuzumi, J. Am. Chem. Soc., 2013, 135, 15294-15297.
22. G. Connor, K. Mayer, C. Tribble and W. McNamara, Inorg. Chem., 2014,
53, 5408–5410.
of the Ni complexes with electron withdrawing substituents to
23. P. Du and R. Eisenberg, Energy Environ. Sci., 2012, 5, 6012-6021.
reduce the overpotential, applying 6a in photocatalytic units
for H2 evolution, and grafting the molecules on
semiconductors for artificial photosynthesis.47, 48
24. T. R. Simmons, G. Berggren, M. Bacchi, M. Fontecave and V. Artero,
Coord. Chem. Rev., 2014, 270–271, 127-150.
25. C. S. Letko, J. A. Panetier, M. Head-Gordon and T. D. Tilley, J. Am. Chem.
Soc., 2014, 136, 9364-9376.
26. L. Gan, T. L. Groy, P. Tarakeshwar, S. K. Mazinani, J. Shearer, V. Mujica
and A. K. Jones, J. Am. Chem. Soc., 2015, 137, 1109-1115.
27. D. J. Graham and D. G. Nocera, Organometallics, 2014, 33, 4994-5001.
28. H. I. Karunadasa, C. J. Chang and J. R. Long, Nature, 2010, 464, 1329-
1333.
29. W. M. Singh, T. Baine, S. Kudo, S. Tian, X. A. N. Ma, H. Zhou, N. J.
DeYonker, T. C. Pham, J. C. Bollinger and D. L. Baker, Angew. Chem., Int.
Ed., 2012, 124, 6043-6046.
HSS is supported by a NTU start-up grant (M4081012), the Nanyang
Assistant Professorship (M4081154), and an MOE Tier 1 grant
(M4011154). The authors acknowledge the funding support from
the Singapore-Berkeley Research Initiative for Sustainable Energy
(SinBeRISE) CREATE Programme. The authors also thank Asst. Prof.
Jason Xu Zhichuan from the NTU Solar Fuels Laboratory for support
in electrochemistry and both Dr. Li Yongxin and Dr. Rakesh Ganguly
for solving and refining the crystal structures in the ESI.
30. L. Chen, M. Wang, K. Han, P. Zhang, F. Gloaguen and L. Sun, Energy
Environ. Sci., 2014, 7, 329-334.
31. H. Chen, Z. Sun, S. Ye, D. Lu and P. Du, J. Mater. Chem. A, 2015, 3,
15729-15737.
Notes and references
32. C. Floriani and G. Fachinetti, J. Chem. Soc., Chem. Commun., 1974, 615-
616.
33. O. F. Schall, K. Robinson, J. L. Atwood and G. W. Gokel, J. Am. Chem.
Soc., 1993, 115, 5962-5969.
† The onset overpotential is defined as the difference between
the reversible potential of the H+/H2 redox couple of neutral DI
water (-0.46 V vs. NHE at pH 7.6) and the potential at which 10%
of the current value at the peak potential was reached.
‡ The charge passed during CPE were 38 and 94 C at 1 and 2.5 h
respectively, in excess of the charge needed to reduce Ni2+ to Ni+
(0.12 and 0.26 C for 10% and 22% 6a respectively).
34. S. T. Meally, C. McDonald, P. Kealy, S. M. Taylor, E. K. Brechin and L. F.
Jones, Dalton T, 2012, 41, 5610-5616.
35. B. Choudary, T. Ramani, H. Maheswaran, L. Prashant, K. Ranganath and
K. V. Kumar, Adv. Synth. Catal., 2006, 348, 493-498.
36. A. Schepartz and J. P. McDevitt, J. Am. Chem. Soc., 1989, 111, 5976-
5977.
1. Z. Han and R. Eisenberg, Acc. Chem. Res., 2014, 47, 2537-2544.
2. N. S. Lewis and D. G. Nocera, Proc. Natl. Acad. Sci. U.S.A., 2006, 103,
15729-15735.
3. D. G. Nocera, Acc. Chem. Res., 2012, 45, 767-776.
4. P. D. Tran, L. H. Wong, J. Barber and J. S. C. Loo, Energy Environ. Sci.,
2012, 5, 5902-5918.
5. D. Merki, H. Vrubel, L. Rovelli, S. Fierro and X. Hu, Chem. Sci., 2012, 3,
2515-2525.
6. Y. Sun, C. Liu, D. C. Grauer, J. Yano, J. R. Long, P. Yang and C. J. Chang, J.
Am. Chem. Soc., 2013, 135, 17699-17702.
7. Y. Zheng, Y. Jiao, M. Jaroniec and S. Z. Qiao, Angew. Chem. Int. Ed.,
2015, 54, 52-65.
8. W.-F. Chen, C.-H. Wang, K. Sasaki, N. Marinkovic, W. Xu, J. Muckerman,
Y. Zhu and R. Adzic, Energy Environ. Sci., 2013, 6, 943-951.
9. J. Kibsgaard and T. F. Jaramillo, Angew. Chem. Int. Ed., 2014, 53, 14433-
14437.
10. E. J. Popczun, C. G. Read, C. W. Roske, N. S. Lewis and R. E. Schaak,
Angew. Chem., Int. Ed., 2014, 126, 5531-5534.
37. C. Costentin, M. Robert and J.-M. Saveant, Chem. Soc. Rev., 2013, 42,
2423-2436.
38. C. Costentin, H. Dridi and J.-M. Savéant, J. Am. Chem. Soc., 2014, 136,
13727-13734.
39. C. Costentin, S. Drouet, M. Robert and J.-M. Savéant, J. Am. Chem. Soc.,
2012, 134, 11235-11242.
40. J. B. Geri and N. K. Szymczak, J. Am. Chem. Soc., 2015, 137, 12808-
12814.
41. D. W. Shaffer, S. I. Johnson, A. L. Rheingold, J. W. Ziller, W. A. Goddard,
R. J. Nielsen and J. Y. Yang, Inorg. Chem., 2014, 53, 13031-13041.
42. E. S. Rountree, B. D. McCarthy, T. T. Eisenhart and J. L. Dempsey, Inorg.
Chem., 2014, 53, 9983-10002.
43. B. H. Solis, A. Maher, T. Honda, D. C. Powers, D. G. Nocera and S.
Hammes-Schiffer, ACS Catal., 2014, 4, 4516-4526.
44. J. S. Kanady, E. Y. Tsui, M. W. Day and T. Agapie, Science, 2011, 333,
733-736.
45. S. Bang, Y.-M. Lee, S. Hong, K.-B. Cho, Y. Nishida, M. S. Seo, R. Sarangi, S.
Fukuzumi and W. Nam, Nat. Chem., 2014, 6, 934-940.
46. T. D. Harris, H. S. Soo, C. J. Chang and J. R. Long, Inorg. Chim. Acta, 2011,
369, 91-96.
47. C. A. Caputo, M. A. Gross, V. W. Lau, C. Cavazza, B. V. Lotsch and E.
Reisner, Angew. Chem., Int. Ed., 2014, 126, 11722-11726.
48. S. K. Muduli, S. Wang, S. Chen, C. F. Ng, C. H. A. Huan, T. C. Sum and H.
S. Soo, Beilstein J. Nanotechnol., 2014, 5, 517-523.
11. M. Ledendecker, S. Krick Calderón, C. Papp, H. P. Steinrück, M.
Antonietti and M. Shalom, Angew. Chem., Int. Ed., 2015, 127, 12538-
12542.
12. Y. F. Xu, M. R. Gao, Y. R. Zheng, J. Jiang and S. H. Yu, Angew. Chem. Int.
Ed., 2013, 52, 8546-8550.
13. Z. Zhang, R. Dua, L. Zhang, H. Zhu, H. Zhang and P. Wang, ACS Nano,
2013, 7, 1709-1717.
4 | Chem. Commun., 2015, 00, 1-3
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