10.1002/anie.201901695
Angewandte Chemie International Edition
COMMUNICATION
[1]
S. Singh, S. Jain, A. K. Tiwari, M. R. Nouni, J. K. Pandey, S. Goel,
Renewable Sustainable Energy Rev. 2015, 51, 623.
J. O’.M. Bockris, Science 1972, 176, 1323.
processes are unlikely in both the dehydrogenation and
hydrogenation processes (see SI). Thus, a reversible hydrogen
storage system on basis of hydrogenation of ethylene urea and
dehydrogenation of methanol and ethylenedimine was
established.
[2]
[3]
a) T. He, Q. Pei, P. Chen, J. Energy Chem. 2015, 24, 587; b) P. Preuster,
C. Papp, P. Wasserscheid, Acc. Chem. Res. 2017, 50, 74; c) R. H.
Crabtree, ACS Sustainable Chem. Eng. 2017, 5, 4491; d) E. Gianotti, M.
Taillades-Jacquin, J. Rozière, D. J. Jones, ACS Catal. 2018, 8, 4660; e)
K. Sordakis, C. Tang, L. K. Vogt, H. Junge, P. J. Dyson, M. Beller, G.
Laurenczy, Chem. Rev. 2018, 118, 372.
[4]
[5]
[6]
[7]
N. Armaroli, V. Balzani, Energy for a Sustainable World: From the Oil
Age to a Sun-Powered Future; Wiley-VCH, 2011.
D. Minic, (ed.) Hydrogen Energy—Challenges and Perspectives; InTech,
2012.
A. F. Dalebrook, W. Gan, M. Grasemann, S. Moret, G. Laurenczy, Chem.
Commun. 2013, 49, 8735.
a) S. Satyapal, J. Petrovic, C. Read, G. Thomas, G. Ordaz, Catal. Today
2007, 120, 246–256; b) T. He, P. Pachfule, H. Wu, Q. Xu, P. Chen, Nat.
Rev. Mater. 2016, 16059.
[8]
[9]
J. O’.M.Bockris, Int. J. Hydrogen Energy 2013, 38, 2579.
P. Makowsky, A. Thomas, P. Kuhn, F. Goetmann, Energy Environ. Sci.
2009, 2, 480.
[10]
[11]
D. Teichmann, K. Stark, K. Müller, G. Zöttl, P. Wasserscheid, W. Energy
Environ. Sci. 2012, 5, 9044.
Figure 2. a) Hydrogenation of DFA. b) Hydrogenation of the dehydrogenated
products. c) Interconversion between H2-rich compounds and H2-lean
compounds by dehydrogenation and hydrogenation.
a) M. Taube, D. W. T. Rippin, D. L. Cresswell, W. Knecht, Int. J.
Hydrogen Energy 1983, 8, 213; b) T. Schildhauer, E. Newson, S. Muller,
J. Catal. 2001, 198, 355; c) Y. Okada, T. Mikuriya, T. M. Yasui, Kemikaru
Enjiniyaringu 2015, 60, 187.
In conclusion, we have developed a new, rechargeable
hydrogen storage system, which is based on the unprecedented
hydrogenation of the ethylene urea, and its formation by
dehydrogenative coupling of the inexpensive and abundant
ethylenediamine and methanol, catalyzed by the same Ru-pincer
complex. The dehydrogenation could be achieved using a very
small amount of solvent. This LOHC system has a theoretically
high hydrogen capacity of 6.52 wt% and enjoys excellent yields
for both loading and unloading hydrogen. Mechanistic studies
demonstrated that N-(2-aminoethyl)formamide is one of the key
intermediate products, which could be converted to ethylene urea
or N,N'-(ethane-1,2-diyl)diformamide in the presence of [Ru]-1.
[12] G. P. Pez, A. R. Scott, A. C. Cooper, H. Cheng, 2006, US7101530B2.
[13] a) Y. Cui, S. Kwok, A. Bucholtz, B. Davis, R. A. Whitney, P. G. Jessop,
New J. Chem., 2008, 32, 1027; b) K. Fujita, Y. Tanaka, M. Kobayashi, R.
Yamaguchi, J. Am. Chem. Soc. 2014, 136, 4829; c) D. Forberg, T.
Schwob, M. Zaheer, M. Friedrich, N. Miyajima, R. Kempe, Nat. Commun.
2016, 7, 13201; d) K. Fujita, T. Wada, T. Shiraishi, Angew. Chem. Int. Ed.
2017, 56, 10886; e) J. Oh, K. Jeong, T. W. Kim, H. Kwon, J. W. Han, J.
H. Park, Y.-W. Suh, ChemSusChem 2018, 11, 661; f) M. Yang, G. Cheng,
D. Xie, T. Zhu, Y. Dong, H. Ke, H. Cheng, Int. J. Hydrogen Energy 2018,
43, 8868.
[14] P. Hu, E. Fogler, Y. Diskin-Posner, M. A. Iron D. Milstein, Nat. Commun.
2015, 6, 6859.
[15] a) P. Hu, Y. Ben-David, D. Milstein, Angew. Chem. Int. Ed. 2016, 55,
1061; b) J. Kothandaraman, S. Kar, R. Sen, A. Goeppert, G. A. Olah, G.
K. S. Prakash, J. Am. Chem. Soc. 2017, 139, 2549.
Acknowledgements
[16] A. Kumar, T. Janes, N. A. Espinosa-Jalapa, D. Milstein, J. Am. Chem.
Soc. 2018, 140, 7453.
This research was supported by the European Research Council
Advanced Grant (ERC AdG 692775). D. M. holds the Israel Matz
Professorial Chair of Organic Chemistry. Y. X. thanks the
Alternative Sustainability and Energy Research Initiative (SAERI)
and the Feinberg Graduate School of The Weizmann Institute of
Science for a Senior Postdoctoral Fellowship.
[17] J. Moran, A. Preetz, R. A. Mesch, M. J. Krische, Nat. Chem. 2011, 3, 287.
[18] a) E. Balaraman, Y. Ben-David, D. Milstein, Angew. Chem. Int. Ed. 2011,
50, 11702; b) for challenge levels in catalytic hydrogenation, see: M. Ito,
T. Ootsuka, R. Watari, A. Shiibashi, A. Himizu, T. Ikariya, J. Am. Chem.
Soc. 2011, 133, 4240
[19] a) J. Zhang, G. Leitus, Y. Ben-David, D. Milstein, J. Am. Chem. Soc.
2005, 127, 10840; b) E. Balaraman, B. Gnanaprakasam, L. J. W. D.
Shimon, D. Milstein, J. Am. Chem. Soc. 2010, 132, 16756; c) E. Fogler,
J. Garg, P. Hu, G. Leitus, L. J. W. Shimon, D. Milstein, Chem. Eur. J.
2014, 20, 15727.
Keywords: hydrogen storage • urea hydrogenation • ruthenium
pincer complex • methanol • ethylenediamine
This article is protected by copyright. All rights reserved.