Work function-induced spontaneous built-in electric field in Ir/MoSe2 for efficient PEM water electrolysis

doi:10.1016/S1872-2067(25)64685-7

Abstract

Abstract:

Bifunctional Ir catalysts for proton exchange membrane (PEM) water electrolysis offer transformative potential by streamlining electrolyzer while achieving efficient performance remains challenging due to the distinct conditions required for oxygen and hydrogen evolution reaction (OER and HER). Herein, we propose a theory-directed design of Ir-based bifunctional catalysts, Ir nanoparticles supported on mesoporous carbon spheres embedded with MoSe₂ (Ir/MoSe₂@MCS), leveraging a work function (WF)-induced spontaneous built-in electric field to enhance catalytic performance. They demonstrate exceptional kinetics for both OER and HER, and potential application in the practical PEM electrolyzer, showcasing the effectiveness of this innovative approach. Low overpotentials of 252 mV for OER and 28 mV for HER to drive 10 mA cm^-2 were observed, and the PEM electrolyzer showed the current density of 2 A cm^-2 at 1.87 V and maintained stable activity at 1.65 V for over 30 h to deliver 1 A cm^-2. Density functional theory calculations reveal that the WF difference at Ir/MoSe₂ interface induces a spontaneous built-in electric field with asymmetric charge distributions, that modulate the electronic environment and d-band center of Ir promoting bifunctional active phase formation. This significantly lowers reaction barriers for water splitting by balancing intermediate adsorption, endowing the bifunctional activity.

Key words: Proton exchange membrane water electrolysis, Built-in electric field, Work function, Bifunctional electrocatalyst, Iridium catalyst

Zhang Bingjie, Wang Chunyan, Yang Fulin, Wang Shuli, Feng Ligang. Work function-induced spontaneous built-in electric field in Ir/MoSe₂ for efficient PEM water electrolysis[J]. Chinese Journal of Catalysis, 2025, 75: 95-104.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64685-7

https://www.cjcatal.com/EN/Y2025/V75/I8/95

Figures/Tables 5

Fig. 1. (a) WF of Ir and MoSe2. (b) Electron transfer diagram. (c) Planar average potential along z direction at the Ir/MoSe2 interface. (d) The DOS diagram of bulk Ir, MoSe2 and Ir/MoSe2. (e) The DOS diagram of Ir and Ir in Ir/MoSe2. (f) COHP curves for O* intermediate adsorption on Ir active site for Ir and Ir/MoSe2.

Fig. 2. Fabrication procedure and structural characterization. (a) Schematic for MCS, MoSe2@MCS and Ir/MoSe2@MCS fabrication. (b-d) TEM images of the Ir/MoSe2@MCS. (e) SAED pattern. (f) HRTEM image. (g) STEM and corresponding elemental mapping images of the Ir/MoSe2@MHCS catalyst. (h) XRD patterns of MoSe2, MoSe2@MCS and Ir/MoSe2@MCS. XPS spectra of Ir 4f for Ir/MoSe2@MCS (i) and Mo 3d for MoSe2@MCS and Ir/MoSe2@MCS (j).

Fig. 3. Acidic OER and HER performance of Ir/MoSe2@MCS and other samples. (a) OER polarization curves (5 mV s-1). (b) Mass activity comparison. (c) Tafel slopes. (d) Nyquist plots. (e) HER polarization curves. (f) Mass activity comparison. (g) Tafel slopes. (h) Nyquist plots. (i) The Cdl values. (j) Polarization curves of the two-electrode electrolyzer. (k) CA curve for the Ir/MoSe2@MCS||Ir/MoSe2@MCS electrolyzer at 1.525 V and Pt/C||IrO2 electrolyzer at 1.623 V (inset: Schematic diagram of the device). (l)The collected H2 and O2 volumes as a function of operation time.

Fig. 4. Elemental mapping of Ir/MoSe2@MCS after 40 h of OER (a) and HER (b) stability test. The content change of Ir0 and Ir4+ (c) and Mo4+ and Mo6+ (d) after the stability test. (e) Schematic illustration of a PEMWE cell and components. (f) Performance curve of the PEM electrolyzer. (g) Chronoamperometric measurement of the PEMWE at 1.65 V using Ir/MoSe2@MCS as a bifunctional electrocatalyst (inset: photograph of the assembled cell). (g) PEMWE working at 1.65 V with Ir/MoSe2@MCS and Pt/C||IrO2 at 2.00 V for 30 h (inset: photograph of the assembled cell).

Fig. 5. (a) The PDOS diagram of IrO2/MoSe2 and IrO2. (b) Downshift of εd lowers the corresponding antibonding orbits. (c) The free energy diagrams for OER on the IrO2/MoSe2@MCS and IrO2 surface, showing the adsorption of oxygen intermediates (*O, *OH, and *OOH). (d) Gibbs free energy of the decision step of OER process. (e) HER on the Ir/MoSe2@MCS, Pt/C, Ir/C, and MoSe2 surface. (f) Schematic diagram of the Ir/MoSe2 adsorption/desorption intermediate process.

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Work function-induced spontaneous built-in electric field in Ir/MoSe₂ for efficient PEM water electrolysis

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