Hydrothermal Synthesized Nickel Copper Composite Phosphides as Bifunctional Electrocatalysts for Hydrogen Evolution and Hydrazine Oxidation

doi:10.15541/jim20190640

Abstract

Abstract:

Herein, we report a kind of NiCu-based composite phosphides electrocatalyst(NiCuP/NM), which was prepared in situ on nickel mesh substrate by one-step hydrothermal method with NaH₂PO₂, CuSO₄, NiSO₄as initial materials. The morphology, crystal structure, composition, and electrocatalytic performance of NiCuP/NM were characterized. Under the optimal preparation conditions of Ni, Cu and P(molar ratio 8 : 1 : 20), hydrothermal synthesis at 140 ℃ for 24 h, the obtained composite electrocatalyst displayed three-level micro-nanostructure with Ni₂P and Cu₃P as main crystal phases. At the current density of 10 mA·cm ^-2, the required HER (Hydrogen Evolution Reaction) overpotential and HzOR (Hydrazine Oxidation Reaction) potential of NiCuP/NM were 165 and 49 mV, respectively. In the two-electrode system, the decomposition tank pressure for the NiCuP/NM cell at the same current density was only 0.750 V which remained substantially unchanged for 24 h catalysis, exhibiting excellent catalytic stability. NiCuP/NM displays prominent electrocatalytic performances towards HER or HzOR in both three-electrode and two-electrode systems, which can be ascribed to two aspects. On the one hand, the 14-fold electrochemical active surface area compared with original nickel mesh enables NiCuP/NM expose huge number of catalytic active sites in both HER and HzOR. On the other hand, the electronic structure modification of Ni and Cu atoms induced by doping P atom brings great improvement of intrinsic HzOR activity of electrode materials. This study provides a new perspective for nanoscale synthesis and promotes the development of novel nanopores in fuel cell and energy conversion applications.

Key words: nickel copper-based phosphides, hybrid water electrolysis, hydrogen evolution reaction, hydrazine oxidation

CLC Number:

O611

LI Zhao, SUN Qiangqiang, CHEN Suoqian, ZHOU Chunsheng, CAO Jing, WANG Yongfeng, WANG Yanan. Hydrothermal Synthesized Nickel Copper Composite Phosphides as Bifunctional Electrocatalysts for Hydrogen Evolution and Hydrazine Oxidation[J]. Journal of Inorganic Materials, 2020, 35(10): 1149-1156.

Figures/Tables 9

Fig. 1 (a-c) FESEM images, (d) EDX spectra and (e) element mappings of NiCuP/NM electrode

Fig. 2 (a) HRTEM image and (b) XRD pattern of NiCuP/NM electrocatalyst

Fig. 3 (a, c) LSV polarization curves and (b, d) Tafel curves of NiCuP/NM composite electrode towards HER (a, b) and HzOR (c, d)

Fig. 4 (a) LSV polarization curves, (b) stability test by chronopotentiometry, (c) SEM image after 24 h hybrid electrolysis, (d) gas chromatography (GC) spectra of gas products for NiCuP/NM in the two-electrode system, and (e) the amount comparison of calculated H2 and measured H2

Fig. 5 (a) CV curves at different scan rates (5, 10, 25, 50, 100, 200 mV?s-1), (b) Coulomb curves of charge double-layer capacitance, (c) Nyquist plots, and (d) LSV curves by ECSA normalization of NiCu/NM towards HER

Fig. S1 SEM images of composite electrocatalysts with different ratios of Ni to Cu (a) 2 : 1; (b) 4 : 1; (c) 6 : 1; (d) 8 : 1; (e) 10 : 1

Fig. S2 SEM images of composite electrocatalysts prepared by different P doping concentrations (a) 10 mmol·L-1; (b) 20 mmol·L-1; (c) 30 mmol·L-1; (d)40 mmol·L-1

Fig. S3 SEM images of composite electrocatalysts prepared at different hydrothermal temperatures (a) 100 ℃; (b) 120 ℃; (c) 140 ℃; (d) 160 ℃; (e)180 ℃

Fig. S3 SEM images of composite electrocatalysts prepared with different hydrothermal time (a) 12 h; (b) 18 h; (c) 24 h; (d) 30 h

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