CoWO<sub>4</sub> nanoparticles with dual active sites for highly efficient ammonia synthesis

Lian Duan; Zhencong Huang; Gen Chen; Min Liu; Xiaohe Liu; Renzhi Ma; Ning Zhang

doi:10.1039/d5nh00120j

Journal article CoWO₄ nanoparticles with dual active sites for highly efficient ammonia synthesis

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Lian Duan, Zhencong Huang, Gen Chen, Min Liu, Xiaohe Liu, Renzhi Ma, Ning Zhang. CoWO₄ nanoparticles with dual active sites for highly efficient ammonia synthesis. Nanoscale Horizons. 2025, 10 (6), 1096-1106. https://doi.org/10.1039/d5nh00120j

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The electrochemical reduction of NO3⁻ (NO3RR) represents a promising green technology for ammonia (NH3) synthesis. Among various electrocatalysts, Co-based materials have demonstrated considerable potential for NO3RR. However, the NH3 yield efficiency of Co-based materials is still limited due to challenges in competitive hydrogen evolution reaction (HER) and hydrogenating oxynitride intermediates (*NOx). In this study, elements of tungsten (W) and cobalt (Co) are coincorporated to form cobalt tungstate (CoWO4) nanoparticles with dual active sites, which are applied to optimize the hydrogenation of NOx and decrease HER, thereby achieving highly efficient NO3RR to NH3. Theoretical calculations indicate that Co sites in CoWO4 facilitate the adsorption and hydrogenation of *NOx intermediates, while W sites suppress the competitive HER. These dual active sites work synergistically to enhance NH3 production from NO3RR. Inspired by these calculations, CoWO4 nanoparticles are synthesized using a simple ion precipitation method, with sizes ranging from 10 to 30 nm. Electrochemical performance demonstrates that CoWO4 nanoparticles exhibit a high Faradaic efficiency of 97.8 ± 1.5% and an NH3 yield of 13.2 mg h−1 cm−2. In situ Fourier transform infrared spectroscopy characterizes the enhanced adsorption and hydrogenation behaviors of *NOx as well as minimized HER on CoWO4, which contributes to the high efficiency and selectivity to NH3. This work introduces a CoWO4 nanoparticle electrocatalytic material with dual active sites, which contribute to the design of electrocatalysts for synthesizing NH3.

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