High-entropy alloy metallene for highly efficient overall water splitting in acidic media

doi:10.1016/S1872-2067(22)64166-4

Abstract

Abstract:

The preparation of stable and efficient acidic overall water splitting catalysts is crucial to advance the progress of proton exchange membrane water electrolyzers. Herein, we successfully prepared IrPdRhMoW HEA metallene with rich amorphous and crystalline structures. In 0.5 mol L^-1 H₂SO₄, the extraordinary catalytic performance (the overpotentials for hydrogen evolution (HER) and oxygen evolution (OER) of IrPdRhMoW/C at 10 mA cm^-2 are 15 mV and 188 mV, respectively) is far stronger than that of commercial catalysts (HER: Pt/C, 47 mV and OER: RuO₂, 305 mV) and even other reported noble metal-based catalysts. Using IrPdRhMoW/C for the overall water splitting, only a cell voltage of 1.48 V is required to achieve 10 mA cm^-2 and 1.59 V required to achieve 100 mA cm^-2, which is the best voltage under high current density reported so far. More importantly, the IrPdRhMoW/C still maintains excellent electroactivity and structural stability after 100 h of water splitting at 100 mA cm^-2. Theory calculations reveal the self-balanced effect of electronic structures in the HEA due to the co-existence of crystalline and amorphous lattice structures. The strong orbital couplings not only maximize the electroactivity towards both HER and OER but also stabilize the valence states of metal sites for durable electrocatalysis.

Key words: High-entropy alloy, Metallene, Crystalline/amorphous, Overall water splitting, Acidic media

Dan Zhang, Yue Shi, Xilei Chen, Jianping Lai, Bolong Huang, Lei Wang. High-entropy alloy metallene for highly efficient overall water splitting in acidic media[J]. Chinese Journal of Catalysis, 2023, 45: 174-183.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(22)64166-4

https://www.cjcatal.com/EN/Y2023/V45/I2/174

Figures/Tables 5

Fig. 1. TEM image (a), XRD pattern (b), HRTEM images (c,d), HAADF-STEM and corresponding EDX mapping images (e) of IrPdRhMoW/C.

Fig. 2. (a) HER polarization curves. (b) Overpotentials at 10 mA cm-2. (c) The corresponding Tafel plots. (d) Exchange current density. (e) TOF values. (f) Estimation of the ECSA using the Cu-UPD method of IrPdRhMoW/C and Pt/C.

Fig. 3. (a) OER polarization curves. (b) Overpotentials at 10 mA cm-2. (c) The corresponding Tafel plots. (d) TOF values. (e) Electrochemical impedance spectra of IrPdRhMoW/C. (f) Polarization curves of IrPdRhMoW/C before and after 10000 CV cycles.

Fig. 4. (a) The top view of the IrPdRhMoW structure. (b) 3D contour plot of electronic distribution near Fermi level of IrPdRhMoW. Dark green balls = Pd, purple balls = Rh, orange balls = Mo, pink balls = Ir and grey balls = W. Blue isosurface = bonding orbitals and green isosurface = anti-bonding orbitals. (c) The PDOS of IrPdRhMoW HEA. (d) The simulated RDF of IrPdRhMoW HEA. The inset is the RDF of crystalline IrPdRhMoW. The site-dependent PDOS of Ir-5d (e), Pd-4d (f), Rh-4d (g), Mo-4d (h) and W-5d (i). (j) The formation energy of different metal vacancies. (k) The energy change of OER at U = 0 V. (l) The energy change of OER at U = 1.23 V. (m) The binding energy comparisons of the proton.

Fig. 5. (a) The digital photo of two-electrode configuration with bubbles on both electrodes. (b) Polarization curves of the two-electrode overall water splitting cells. (c) The amount of H2 and O2 theoretically calculated and experimentally measured for IrPdRhMoW/CP||IrPdRhMoW/CP for 60 minutes. (d) Chronopotentiometry curve of IrPdRhMoW/CP||IrPdRhMoW/CP at 100 mA cm?2.

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