Facile construction of 3D integrated nickel phosphide composite as wide pH-tolerant electrode
for hydrogen evolution reaction
Xiaoguang Wang, Wei Li, Dehua Xiong, Lifeng Liu*
International Iberian Nanotechnology Laboratory (INL), 4715-330 Braga, Portugal
Contact@E-mail: lifeng.liu@inl.int
Abstract
Hydrogen, H2, has been proposed to be a clean and carbon-neutral fuel to replace the fossil fuels.
Compared with steam reforming of natural gas, water electrolysis represents a much cleaner and more
sustainable approach to H2 generation, but is underdeveloped. Platinum (Pt) has so far been the most
efficient and commonly used electrocatalysts for hydrogen evolution reaction (HER). But it is not
practical and economically viable to use Pt on a large scale because of its high cost and scarcity in the
earth crust. To deploy electrolyzers widely and to make the electrolyzed H2 fuel economically
competitive, it is important to develop inexpensive, earth-abundant electrocatalysts to promote the HER.
Transition metal carbides, sulfides, selenides, and nitrides have triggered a worldwide investigation on
their electrocatalytic performance towards HER, due to their unique electronic configuration similar to
that of Pt near the Fermi level [1,2]. Very recently, transition metal phosphides (TMPs), such as Ni2P [3],
Ni5P4 [4], CoP [5], FeP [6], Fe2P [7], MoP [8], Cu3P [9], etc, have emerged as a new class of catalysts
which have shown sufficiently high electrocatalytic activity and excellent stability toward the HER in
acidic electrolytes.
Here, we report a facile route to construct integrated 3D nickel phosphide composite electrodes using
gas-solid reaction between phosphorous vapor and nickel deposit. This contributes to the architecture of
nanostructured nickel phosphide uniformly supported onto a 3D conductive network electrode. In acid
solution (pH=0), to afford a cathodic current density of 10, 20, 100 mA cm-2 overpotentials as small as
98, 116 and 162 mV are needed, respectively, for this novel 3D nickel phosphide composite electrode.
In alkaline solution (pH=14), to afford a cathodic current density of 10, 20, 100 mA cm-2 only
overpotentials of 117, 150 and 250 mV are required. In addition, the integrated electrode also exhibits
excellent long-term stability and durability, retaining its microstructure even after extended
electrocatalytic tests. Therefore, this integrated 3D nickel phosphide composite electrode will find
promising prospects in actual large scale application for electrochemical hydrogen production.
References
[1] X. X. Zou, Y. Zhang, Chem. Soc. Rev., 44 (2015) 5148-5180.
[2] C. G. Morales-Guio, L. A. Stern, X. L. Hu, Chem. Soc. Rev., 43 (2014) 6555-6569.
[3] X. G. Wang, Y. V. Kolen’ko, L. F. Liu, Chem. Commun., 51 (2015) 6738-6741.
[4] X. G. Wang, Y. V. Kolen’ko, X. Q. Bao, K. Kovnir, L. F. Liu, Angew. Chem. Int. Ed., 54 (2015) 81888192.
[5] E. J. Popczun, C. G. Read, C. W. Roske, N. S. Lewis, R. E. Schaak, Angew. Chem. Int. Ed., 126
(2014) 5531-5534.
[6] ) P. Jiang, Q. Liu, Y. H. Liang, J. Q. Tian, A. M. Asiri, X. P. Sun, Angew. Chem. Int. Ed., 53 (2014) 16.
[7] Z. P. Huang, C. C. Lv, Z. Z. Chen, Z. B. Chen, F. Tian, C. Zhang, Nano Energy, 12 (2015) 666-674.
[8] P. Xiao, M. A. Sk, L. Thia, X. M. Ge, R. J. Lim, J. Y. Wang, K. H. Lim, X. Wang, Energy Environ. Sci.,
7 (2014) 2624-2629.
[9] J. Q. Tian, Q. Liu, N. Y. Cheng, A. M. Asiri, X. P. Sun, Angew. Chem. Int. Ed., 53 (2014) 9577-9581.