Homojunction-driven d-band engineering in NiMoO4 for selective electrochemical nitrogen reduction to ammonia

doi:10.1016/S1872-2067(26)64978-9

Abstract

Abstract:

The selectivity of the electrochemical nitrogen reduction reaction (eNRR) is predominantly influenced by the d-band electronic structure of the catalyst. An effective catalyst requires d-band electrons at appropriate energy levels to activate N₂ while simultaneously suppressing the competitive hydrogen evolution reaction (HER). In this study, an α/β-NiMoO₄ heterophase homojunction with tailored d-band was constructed by a facile temperature-controlled strategy for selective electrochemical N₂ to NH₃ conversion. Experimental and theoretical results demonstrate that forming an α/β-NiMoO₄ heterophase homojunction induced moderate downshift of the d-band center and weakened the metal-hydrogen interaction, thereby effectively suppressing the competitive HER. Electrochemical measurements reveal that the optimized NMO-500 catalyst exhibits a boosted ammonia yield rate (63.9 μg h^-1 mg^-1) with a high efficiency of 33.5% at -1.1 V vs. Ag/AgCl under ambient conditions, outperforming its single-phase NiMoO₄ counterpart. Homojunction-driven d-band engineering stands out as a facile, effective, and rational strategy for developing high-performance eNRR catalysts.

Key words: Electrocatalysis, Heterophase homojunction, d-Band modification, Suppress hydrogen evolution reaction, Nitrogen fixation

Yuxi Ren, Baorong Xu, Yu Jin, Hang Xiao, Ranran Niu, Wei Liu, Honghui Ou, Guidong Yang. Homojunction-driven d-band engineering in NiMoO₄ for selective electrochemical nitrogen reduction to ammonia[J]. Chinese Journal of Catalysis, 2026, 85: 216-225.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64978-9

https://www.cjcatal.com/EN/Y2026/V85/I6/216

Figures/Tables 5

Fig. 1. (a) Schematic diagram of the temperature-controlled strategy to construct α/β-NiMoO4 heterophase homojunction. TEM images of NMO-450 (b), NMO-500 (c), and NMO-600 (d). The corresponding HRTEM images of NMO-450 (e), NMO-500 (f), and NMO-600 (g).

Fig. 2. XRD patterns (a) and Raman spectra (b) of NMO-450, NMO-500, and NMO-600. (c) Detail information of the NMO-450 in (b). (d) FTIR spectra of NMO-pre, NMO-450, NMO-500, and NMO-600. XPS spectra of Mo 3d (e) and Ni 2p (f) of NMO-450, NMO-500, and NMO-600.

Fig. 3. (a) UV-vis absorption spectra of electrolyte obtained before test, and after 1-hour test under N2/Ar condition. Ammonia yield rate (b) and corresponding FE (c) of NMO-450, NMO-500, and NMO-600 at different potentials. Chronoamperometry test for NMO-500 under N2 condition at 1.1 V for 6 cycles (d) and the corresponding activity (e). (f) NRR performance comparison with a series of reported catalyst.

Fig. 4. The work functions of α-NiMoO4 (a) and β-NiMoO4 (b). (c) Schematic diagram of the work function-driven electrons transfer. UPS spectra corresponding to the work function of NMO-450 (d) and NMO-500 (e). (f) FE of HER at -0.35 mA cm-2 on NMO-450 and NMO-500. (g) Schematic diagram of the HER suppression by d-band modulation. (h) In-situ FTIR spectra of NMO-500 at 1.1 V under N2 atmosphere.

Fig. 5. Charge density differences (Blue region represents charge depletion, while yellow region represents accumulation. Sphere represents atoms: Purple represents Mo, red represents O, light grey represents Ni and light blue represents N) (a) and electronic location function (ELF) (b) of the adsorbed N2 on NMO-500. (c) The pCOHP of the free N2 and the adsorbed N2 on NMO-500. (d) Gibbs free energy for N2 reduction pathway on NMO-500.

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Homojunction-driven d-band engineering in NiMoO₄ for selective electrochemical nitrogen reduction to ammonia

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