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In-situ activation of self-supported 3D hierarchically porous Ni3S2 films grown on nanoporous copper as excellent pH-universal electrocatalysts for hydrogen evolution reaction

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journal contribution
posted on 17.05.2017, 09:00 by C. Yang, M. Y. Gao, Q. B. Zhang, J. R. Zeng, X. T. Li, A. P. Abbott
The exploitation of low-cost, stable, and highly active electrocatalysts based on earth-abundant metals for hydrogen evolution reaction (HER) is crucial for developing renewable energy techniques. In this work, we report a facile synthesis strategy for in-situ fabrication of 3D hierarchically porous Ni3S2 films on a nanoporous copper substrate (Ni3S2@NPC) by unusual galvanic replacement reaction in the Ethaline-based deep eutectic solvent (DES) under a normal atmosphere. The self-supported nanoporous Ni3S2@NPC electrode is binder- free and exhibits good structural integrity with high conductivity. A mild evolution of bulk gas bubbles (H2-O2 gas mixture) is proved to drive an in-situ structure rearrangement process of the Ni3S2@NPC and results in substantial increases in the HER activity. The activated Ni3S2@NPC (a-Ni3S2@NPC) electrode can serve as a highly efficient and stable electrocatalyst for the HER in water over a wide pH range. Significantly, it displays high-performance HER catalytic activity in acidic media with robust durability over 111 h and functions well under alkaline and neutral conditions. Such a superior catalytic performance of the a-Ni3S2@NPC is mainly due to the unique hierarchically nanoporous architectures and the synergetic effects in it caused by the restructuring NPC skeletons and active components. Our work offers a generic strategy for design and fabrication of many other self-supported transition metal sulfide and phosphide based HER electrocatalysts, and uncovers a new O2-induced electrochemical self-activation mechanism for improving the activity of catalysts.


The authors gratefully acknowledge the financial support of the National Natural Science Foundation of China (51464028, 51204080, and 5177010886), the Application Foundation Research of Yunnan Province (2014FB125), and the Independent Research Funds for the State Key Laboratory (CNMRCUTS1601).



Nano Energy, 2017, 36, pp. 85-94

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/Organisation/COLLEGE OF SCIENCE AND ENGINEERING/Department of Chemistry


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Characterization details and computational methods are included as Supporting information.;The file associated with this record is under embargo until 12 months after publication, in accordance with the publisher's self-archiving policy. The full text may be available through the publisher links provided above.