Bifunctional electrocatalysis of hydrazine oxidation and hydrogen evolution reactions on 2D CoX (X = P, S, As, Se): Insights from DFT calculations

doi:10.1016/S1872-2067(25)64884-4

Abstract

Abstract:

Producing high-purity hydrogen through water electrolysis offers a promising eco-friendly alternative to fossil fuels. However, the anodic oxygen evolution reaction (OER) poses significant challenges in practical applications due to its sluggish kinetics. In contrast, the hydrazine oxidation reaction (HzOR), which operates at a much lower theoretical potential (−0.33 V vs. RHE) compared to OER (1.23 V vs. RHE), has emerged as an attractive substitute for more energy-efficient hydrogen production. Developing efficient bifunctional electrocatalysts for both HzOR and hydrogen evolution reaction (HER) is critical for scaling up energy-efficient hydrazine-hydrate-assisted hydrogen production. Nevertheless, the lack of viable catalyst design strategies has hindered their widespread applications. In this study, comprehensive density functional theory calculations were employed to explore the catalytic potential of defect-engineered and Pt-doped CoX (X = P, S, As, Se) materials. Our results reveal that several modified CoX materials exhibit exceptional catalytic activity for HzOR. Notably, CoSe-v-Pt stands out with an ultralow ΔG_PDS of 0.24 eV for HzOR along with excellent HER performance, demonstrating its potential as a highly effective bifunctional catalyst. The enhanced catalytic activity is attributed to electronic reconfiguration induced by structural modification, which optimizes the adsorption and reaction dynamics of N₂H_y intermediates and hydrogen at the Co active sites. This study provides a new avenue for designing high-performance HzOR and HER catalysts, paving the way for an energy-efficient, environmentally friendly, and highly effective electrocatalytic hydrogen production.

Key words: Hydrogen production, Electrocatalysis, Hydrazine oxidation reaction, Bifunctional catalyst, Density functional theory

Runlin Ma, Xiandi Ma, Hejing Wang, Xu Zhang, Yongzheng Fang, Menggai Jiao, Zhen Zhou. Bifunctional electrocatalysis of hydrazine oxidation and hydrogen evolution reactions on 2D CoX (X = P, S, As, Se): Insights from DFT calculations[J]. Chinese Journal of Catalysis, 2026, 82: 115-124.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(25)64884-4

https://www.cjcatal.com/EN/Y2026/V82/I3/115

Figures/Tables 6

Fig. 1. Top view (a) and side view (c) of the 3×3 CoP supercell structure. Top view (b) and side view (d) of optimized N2H4 adsorption configurations on 2D CoP. (e) Schematic illustration of possible reaction mechanisms during N2H4 oxidation.

Fig. 2. (a) Structural evolution of intermediates and free energy profile for the hydrazine oxidation reaction on CoSe-v. (b) Free energy profile (ΔG, eV) of potential-determining step (ΔGPDS), hydrazine adsorption (ΔG*N2H4), and nitrogen desorption steps for four anion-defect types in CoX-v (X = P, S, As, Se). (ΔG*N2 represents the adsorption free energy for nitrogen adsorption, thus ?ΔG*N2 indicates the free energy change for nitrogen desorption).

Fig. 3. Free energy diagram of CoSe-v and CoSe-v-Pt (a) and CoS-v and CoS-v-Pt (b) via alternating pathway. (c) Top views of the configurations of all intermediates during the HzOR progress on 2D CoSe-v-Pt.

Fig. 4. Free energy profile for the PDS (*N2H2 → *N2H) of CoSe-v (a) and the PDS (*N2H3 → *N2H2) of CoSe-v-Pt (b). With variation in CV, key N-H bond lengths are shown as yellow dashed lines. (c) Snapshots of key structures from AIMD simulations in the *N2H3 dehydrogenation to form *N2H2 catalyzed by CoSe-v-Pt. The snapshots for initial, transitional, and final states. Purple-colored H atoms indicate H transferred via the hydrogen-bond network.

Fig. 5. Adsorption free energy for H atom (a) and adsorption energy for H2O (b) on CoSe-v, CoSe-v-Pt, CoS-v, CoS-v-Pt. (c) Snapshots of key structures during the AIMD simulation of Volmer step catalyzed by CoSe-v-Pt. Free energy profile for Volmer step of CoSe-v (d) and CoSe-v-Pt (e). With variation in CV, key O-H bond lengths are shown as yellow dashed lines.

Fig. 6. Deformation charge density plots for CoSe (a), CoSe-v (b), and CoSe-v-Pt (c). (d) The d-band density of states (DOS) at the Co site in CoSe and at the active Co sites in CoSe-v and CoSe-v-Pt. The red line represents the d-band center, while the black dashed line indicates the Fermi level (EF). (e) Adsorption energies of each adsorbed intermediate on CoSe-v and CoSe-v-Pt. (f) Crystal orbital Hamilton populations (COHPs) of N2H2 on CoSe-v and CoSe-v-Pt.

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