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Effective Electrochemical Nitrogen Reduction through π Back-donation Process in Mn3+ of Mn-doped g-C3N4

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Abstract

Ammonia (NH3) synthesis via nitrogen reduction reaction under mild conditions is challenging due to the difficulty of activating nitrogen. Herein, Mn-doped g-C3N4 (x-Mn-CN, x = 5, 10, and 15) catalysts with efficiency NRR performance were synthesized. The resulting 5-Mn-CN exhibits higher NRR performance (NH3 yield rate: 15.2 μg h−1 mgcat−1, Faradaic efficiency: 7.1%) at -0.4 V (vs. RHE) than others. It is found that the active sites of Mn3+ are generated by electron transfer from Mn2+ to the N of g-C3N4, and active N2 through the π back-donation process. This is evidenced by the experimental result that the NH3 yield rate of 5-Mn-CN significantly decreases from 15.2 μg h−1 mgcat−1 to 2.6 μg h−1 mgcat−1 after lowering the concentration of Mn3+. The concentration of Mn3+ is reduced by treating the catalyst in the ethylenediaminetetraacetic acid disodium salt (EDTA-2Na) solution. This study enhances the understanding of N2 activation and provides insights into the transition metal-doped g-C3N4 as NRR catalysts.

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Authors and Affiliations

  1. Key Laboratory of Superlight Materials & Surface Technology of Ministry of Education, Harbin Engineering University, Harbin, 150001, PR China

    Yi** Ma, Yinpeng Lu, Chang Li, Liangqing Hu, Hexin Zhang & **g Feng

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  1. Yi** Ma
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  2. Yinpeng Lu
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  3. Chang Li
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  4. Liangqing Hu
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Correspondence to Hexin Zhang or **g Feng.

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Highlights

1. The Mn3+ were formed by electron transfer from Mn2+ to N of g-C3N4

2. Mn3+ were verified as the active sites of NRR using EDTA-2Na.

3. Mn-doped g-C3N4 exhibited a high NH3 yield rate: 15.2 μg mgcat-1 h-1

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Ma, Y., Lu, Y., Li, C. et al. Effective Electrochemical Nitrogen Reduction through π Back-donation Process in Mn3+ of Mn-doped g-C3N4. Catal Lett (2024). https://doi.org/10.1007/s10562-024-04772-1

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