Citation: Zunjie Zhang, Mengran Liu, Bingcheng Ge, Tianfang Yang, Shuaitong Wang, Yang Liu, Shuyan Gao. In-situ reconstructed Cu/NiO nanosheets synergistically boosting nitrate electroreduction to ammonia[J]. Chinese Chemical Letters, ;2025, 36(8): 110657. doi: 10.1016/j.cclet.2024.110657 shu

In-situ reconstructed Cu/NiO nanosheets synergistically boosting nitrate electroreduction to ammonia

a.
School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, China
b.
School of Materials Science and Engineering, Henan Normal University, Xinxiang 453007, China

shuyangao@htu.cn

Received Date: 14 June 2024
Revised Date: 30 October 2024
Accepted Date: 19 November 2024
Available Online: 21 November 2024

Figures(4)

Electrochemical reduction of nitrate (NO₃⁻) serves as an eco-friendly friendly alternative to the conventional Haber-Bosch ammonia (NH₃) synthesis process. The Cu electrocatalyst is widely recognized for its strong adsorption capacity towards nitrate, but its limited H adsorption and slow hydrogenation of oxynitride intermediates hinder the efficiency of converting NO₃⁻ into NH₃. Herein, a series of nanocomposite catalysts composed of CuO nanostructure with low NiO content that grow in-situ on carbon paper (CuO/NiO_x-CP) were synthesized via hydrothermal method and calcination for enhanced nitrate electroreduction utilizing the strong nitrate adsorption capacity of copper and excellent water dissociation ability of NiO to supply hydrogen free radicals (^•H). In-situ Raman spectroscopy reveals dynamic reconstruction of Cu/NiO_x during the electrochemical nitrate reduction process from CuO/NiO_x. Due to the synergistic effect of Cu and NiO, a high Faradaic efficiency (FE, ~97.9%) and yield rate (YR, 391.5 µmol h⁻¹ cm⁻²) of ammonia are achieved on CuO/NiO_2.3%-CP. Electron paramagnetic resonance (EPR) proves that the presence of NiO enhances the generation of ^•H, which can be rapidly consumed during nitrate reduction process. Density functional theory (DFT) calculations indicate that the activation energy of NiO (0.57 eV) is much lower than Cu (0.84 eV) for water splitting to generate ^•H, thus facilitating ^*NO hydrogenations. This drives us to create more effective catalysts for nitrate reduction under neutral conditions by promoting H₂O dissociation.
- Nitrate reduction,
- Ammonia synthesis,
- Synergistic effect,
- Hydrogenation,
- Water dissociation
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