Mn-triggered dynamic phase transition in NiSe2 catalyst via doping engineering for boosted urea electrolysis

doi:10.1016/S1872-2067(26)65138-8

Abstract

Abstract:

Understanding and guiding the dynamic structural evolution of electrocatalysts under operating conditions is essential for advancing high-performance energy conversion systems. Herein, we report manganese-doped nickel selenide (Mn/NiSe₂) as a model platform to elucidate that dopant-induced reversible phase transitions suppress the irreversible over-oxidation of γ-phase nickel oxyhydroxide (γ-NiOOH), thereby achieving superior urea oxidation reaction (UOR) performance (with a low onset potential of 1.26 V vs. RHE) and accelerating urea-electrolysis hydrogen generation (284.8 μmol h^-1, 3.9 times that of pristine NiSe₂). In-situ Raman spectroscopy reveals that Mn acts as a dynamic phase-transition trigger, modulating the local electronic structure of NiSe₂ to promote its electrochemical reconstruction into highly active γ-NiOOH, and inducing a reversible γ-β structural regeneration during UOR. Density functional theory calculations further show that Mn doping optimizes the electronic state distribution of nickel sites, significantly strengthens urea adsorption (adsorption energy increases from -2.09 to -4.66 eV), and lowers the energy barrier for N-H bond cleavage in the key CO(NH₂·NH₂)* intermediate (from 3.45 to 3.11 eV). This work establishes a dopant-triggered dynamic phase regulation paradigm, and provides a novel strategy for designing self-adaptive electrocatalysts for complex energy conversion reactions.

Key words: Urea oxidation reaction, Hydrogen, NiOOH, Doping, Dynamic phase-transition

Yingzhen Zhang, Wei Zhang, Zhangzheng Huang, Weilong Cai, Yun Hau Ng, Jianying Huang, Yuekun Lai. Mn-triggered dynamic phase transition in NiSe₂ catalyst via doping engineering for boosted urea electrolysis[J]. Chinese Journal of Catalysis, 2026, 88: 335-346.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)65138-8

https://www.cjcatal.com/EN/Y2026/V88/I9/335

Figures/Tables 6

Fig. 1. (a) Schematic illustration of Mn/NiSe2. SEM images of NF (b), Mn (c), NiSe2 (d), Mn/NiSe2 (e). HR-TEM images of NiSe2 (f) and Mn/NiSe2 (g). (h) EDS spectrum of Mn/NiSe2.

Fig. 2. High-resolution XPS spectra of Ni 2p (a), Se 3d (b), and Mn 2p (c) of NiSe2 and Mn/NiSe2, respectively. (d) Normalized XANES spectra near Ni K-edge of Ni foil, NiO, NiSe2 and Mn/NiSe2. WT-EXAFS spectra of NiSe2 (e) and Mn/NiSe2 (f) at the Ni K-edge. (g) FT-EXAFS spectra. Structural models of NiSe2 (h) and Mn/NiSe2 (i).

Fig. 3. (a) UOR performance of Mn/NiSe2 prepared at different etching times. E100, Eonset (b), and Ea (c) of NF, Mn, NiSe2, and Mn/NiSe2 for UOR. (d) Pulsed i-t curves recorded at alternating potentials of 1.35 V vs. RHE (oxidation) and 0.90 V vs. RHE (reduction) in 1.0 mol L-1 KOH for NiSe2 and Mn/NiSe2. (e) EIS spectra. (f) Differential pulse voltammetry curves of NiSe2 and Mn/NiSe2 towards UOR. (g) Comprehensive performance comparison of different catalysts. LSV curves (h) and Ea (i) of Mn/NiSe2 for UOR and OER.

Fig. 4. In-situ Raman spectra. NiSe2 for the OER (a) and UOR (b). Mn/NiSe2 for OER (c) and UOR in 1.0 mol L-1 KOH with 0.33 (d), 0.165 (e), and 0.0825 mol L-1 (f) urea. UOR on γ-Mn/NiOOH, in 1.0 mol L-1 KOH with 0.0825 (g) and 0.165 mol L-1 (h) urea.

Fig. 5. (a) Adsorption energy of CO(NH2)2 and H2O on NiOOH and Mn/NiOOH. Charge density difference of CO(NH2)2 adsorbed on NiOOH (b) and Mn/NiOOH (c). (d) The projected COHP of Mn/NiOOH and NiOOH for N-H interaction, respectively. (e) The calculated d-band center of Mn/NiOOH and NiOOH. (f) UOR pathways on NiOOH and Mn/NiOOH.

Fig. 6. (a) Schematic illustration of the urea-assisted water electrolysis for H2 production. Polarization curves (b) and time-dependent H2 production (c) of Mn/NiSe2||Mn/NiSe2 and NiSe2||NiSe2 in 1.0 mol L-1 KOH with 0.33 mol L-1 urea. Polarization curves (d) and H2 generation rate (e) of Mn/NiSe2||Mn/NiSe2 in 1.0 mol L-1 KOH with and without urea. (f) Comparison of cell voltage and H2 production rate for Mn/NiSe2 with other reported electrocatalysts.

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Mn-triggered dynamic phase transition in NiSe₂ catalyst via doping engineering for boosted urea electrolysis

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