Study on Performance of Copper Doped Carbon Nitride Electrocatalyzing Nitrate to Produce Ammonia

doi:10.6023/A23110508

Abstract

As the increasing demand for ammonia in other industries such as energy, the ammonia production now available can no longer meet the needs of industrial production, and the existing Haber-Bosch process for the production of NH₃ will cause harm to the atmospheric environment. Therefore, there is an urgent need to find a new method that is compatible with or can replace the existing ammonia production process. Nitrate wastewater contains a large amount of nitrogen, and NH₃ is one of the nitrate reduction products, the reduction of nitrate into ammonia can not only reduce the environmental pollution of nitrate nitrogen, but also alleviate the industrial demand for ammonia, nitrate wastewater treatment methods are generally physical, chemical and biological, but there are shortcomings of long cycle time and high cost. The electrocatalytic method is convenient, safe and can catalyze the synthesis of NH₃ at room temperature and pressure, which makes the electrocatalytic synthesis of NH₃ become a hot research topic in recent years. In this experiment, 3-amino-1,2,4-triazole was loaded into alumina crucible and used as the precursor to synthesize C₃N₅ by pyrolysis method in Muffle furnace, and then Cu-C₃N₅ was synthesized under calcination conditions by modulating the ratio of copper elements, which resulted in a series of C₃N₅-based catalysts with differences in material morphology, crystal conformation, and chemical valence state, including five catalysts of different proportions were synthesized. These catalysts were tested, then their electrochemical performance and electrocatalytic reduction of nitrate to produce ammonia performance were evaluated, and it was found that the ammonia yield and Faraday efficiency could reach 0.541 mmol•h⁻¹•mg_cat⁻¹ and 87.79% by 1 h electrolysis experiments in a mixed electrolyte solution of 0.1 mol/L KOH＋0.1 mol/L KNO₃, which are much higher than that of C₃N₅, and the catalyst has good activity and stability in cyclic and long time experiments, indicating that it has some research value in the field of electrocatalytic nitrate.

Key words: electrocatalytic reduction, NH₃ yield rate, Faraday efficiency, C₃N₅-based catalysts, nitrate

Cite this article

Jing Han, Runhua Liao, Wenqiang Deng, Boyu Liang, Yuqing Zhou, Shuai Ren, Yan Hong. Study on Performance of Copper Doped Carbon Nitride Electrocatalyzing Nitrate to Produce Ammonia[J]. Acta Chimica Sinica, 2024, 82(3): 295-302.

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Fig. & Tab. 9

Figure 1. The XRD patterns obtained from the composite materials with different doping amounts of copper

Figure 2. (a) FTIR comparison of C3N5 and composite materials; (b) FTIR magnification comparison of C3N5 and Cu-C3N5-1

Figure 3. (a) XPS full spectra of C3N5, Cu-C3N5-1 and Cu-C3N5-3; (b) XPS full spectra of C3N5-5, Cu-C3N5-7 and Cu-C3N5-9; (c) C1s spectra of C3N5, Cu-C3N5-1 and Cu-C3N5-5; (d) N1s spectra of C3N5, Cu-C3N5-1 and Cu-C3N5-5; (e) Cu2p spectra of Cu-C3N5-1 and Cu-C3N5-5; (f) XPS full spectra of Cu-C3N5-9

Figure 4. (a) Scanning electron microscope image of C3N5; (b) scanning electron microscope image of Cu-C3N5-9; (c) copper element distribution of Cu-C3N5-9

Figure 5. LSV diagram of each sample obtained after the experiment

Figure 6. (a, b) NH3 yield rate and Faraday efficiency plots of each catalyst at -0.5~-1.0 V (vs. RHE) potentials; (c) NH3 yield rate of the catalyst at -0.8 V (vs. RHE) potential

Figure 7. (a) LSV diagram of Cu-C3N5-9 at -1.0 V (vs. RHE) potential test for 5 times; (b) NH3 yield rate and Faraday efficiency of Cu-C3N5-9 at -1.0 V (vs. RHE) potential cycle for 5 times

Figure 8. (a) Comparison of LSV before and after 12 h of electrolysis of Cu-C3N5-9 performed at -1.0 V (vs. RHE) potential; (b) comparison of NH3 yield rate and Faraday efficiency of Cu-C3N5-9 before and after 12 h electrolysis at -1.0 V (vs. RHE) potential

Figure 9. NH4Cl standard mass concentration profile

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