Atomically tailoring synergistic active centers on molybdenum sulfide basal planes for alkaline hydrogen generation

doi:10.1016/S1872-2067(24)60034-3

Abstract

Abstract:

Alkaline water electrolysis allows the adoption of non-precious metal catalysts, but increases the challenge of cathodic hydrogen evolution reaction (HER) with the proton-deficient environment. Here we report an “all-in-one” design by atomic-level tailoring on molybdenum sulfide (MoS₂) basal planes with synergistic active centers to trigger water dissociation for proton supply and meanwhile improve proton adsorption for hydrogen evolution. The resultant Co/O-codoped MoS₂ (Co-O@MoS₂) catalyst shows superb alkaline HER activity with a small Tafel slope of 42 mV dec^-1 and an overpotential as low as 81 mV at 100 mA cm^-2, and considerable stability over 300 h even at industrial-grade high current density of 600 mA cm^-2, which are among the best records for precious-metal-free HER catalysts in alkaline media. The markedly enhanced alkaline HER performance is attributed to the synergistic effect from atomically constructed O-Co-S₂ motifs with local electronic interactions, in which Co sites promote the premier water dissociation, and S sites facilitate proton transition to generate hydrogen, respectively. This work presents an atomic-scale structural modification to create synergistic active sites for alkaline HER and provides insights into the atomic activation engineering towards advanced catalysts.

Key words: Alkaline water electrolysis, Hydrogen evolution reaction, Molybdenum sulfide, Atomic-scale activation, Synergistic active center

Xuyu Luo, Ying Wang, Guang Yang, Lu Liu, Shiying Guo, Yi Cui, Xiaoyong Xu. Atomically tailoring synergistic active centers on molybdenum sulfide basal planes for alkaline hydrogen generation[J]. Chinese Journal of Catalysis, 2024, 61: 281-290.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60034-3

https://www.cjcatal.com/EN/Y2024/V61/I6/281

Figures/Tables 5

Fig. 1. Schematic diagram of atomic-level synergistic active ‘O-Co-S2’ motifs onto MoS2 basal planes with protrudent Co sites serving for favorable WD and OH* transition to provide proton supply and planar S sites serving for nearly optimal H* transition to evolve H2.

Fig. 2. Structure characterizations of Co-O@MoS2. (A) SEM image of Co-O@MoS2 nanosheets grown on CFC. (B) TEM image of Co-O@MoS2. Inset: the SAED pattern. (C) HRTEM image of Co-O@MoS2. Inset: the magnified lattice fringe in plane region. (D) HAADF-STEM image of Co-O@MoS2. (E) Aberration-corrected HAADF-STEM image with simulated hexagonal units of Co-O@MoS2. (F) Atomic intensity profiles along the three different colored lines labeled in (E). (G) EDX elemental mapping images of Co-O@MoS2.

Fig. 3. Coordination characterizations of atomic Co site. (A) High-resolution XPS spectrum of Co 2p in Co-O@MoS2. (B) Normalized Co K-edge XANES spectra and (C) Fourier-transformed k2-weighted Co K-edge EXAFS spectra of Co-O@MoS2, CoO, Co2O3, and Co foil. (D) Co K-edge EXAFS (points) and fit curve (line) for Co-O@MoS2. Inset: a configuration model of O-Co-S2 center. (E) Wavelet transform for the k2-weighted EXAFS spectra of Co-O@MoS2, Co2O3, and Co foil.

Fig. 4. HER performance of Co-O@MoS2 catalyst. LSV curves of MoS2, O@MoS2, Co-O@MoS2 and Pt/C catalysts on CFC substrates measured in 1.0 mol L-1 KOH at 5 mV s-1 scan rate (A), and the corresponding Tafel slopes (B). (C) In situ Raman spectra of Co-O@MoS2 with applied potentials in control. EIS Nyquist plots (D), Cdl (E), and TOF curves (F) of MoS2, O@MoS2, and Co-O@MoS2. (G) Stability test of Co-O@MoS2 for 300 h in CA model at -242 mV vs. RHE, with arrow marks for electrolyte adding.

Fig. 5. DFT Calculations on HER mechanism. (A) Charge density difference of MoS2 and Co-O@MoS2. The brown and green contours indicate electron accumulation and depletion, respectively. (B,C) PDOS for MoS2 and Co-O@MoS2. The insets show the unoccupied orbital distributions (purple contour) near Fermi level. (D) Gipps free energy for H* absorption at different sites. The inset shows the markers of different S sites on Co-O@MoS2. (E) Relative energy diagram along alkaline HER route on MoS2 and Co-O@MoS2. The inset shows the schematic of catalytic mechanism of alkaline HER with the absorption configurations of various intermediates.

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