铜掺杂氮化碳电催化硝酸盐产氨性能研究

doi:10.6023/A23110508

摘要/Abstract

NH₃是硝酸盐还原产物之一, 不仅在工业中需要大量应用, 在清洁生产过程中也是一种非常有前途的能源载体, 现有的哈伯-博施(Haber-Bosch)工艺生产NH₃会对大气环境造成危害, 而电催化法由于便捷、安全且能够在常温和常压下催化合成NH₃成为最近研究的热点. 本实验以3-氨基-1,2,4三唑为前驱体, 利用热解法先合成C₃N₅, 再通过调控铜元素的比例在煅烧条件下合成Cu-C₃N₅, 合成一系列材料形貌、晶体构相、化学价态存在差异的C₃N₅基催化剂, 并评价这些催化剂的电化学性能以及电催化硝酸盐还原产氨性能, 通过在0.1 mol/L KOH＋0.1 mol/L KNO₃混合电解液中进行1 h电解实验后发现, 氨气产量和法拉第效率可以达到0.541 mmol•h⁻¹•mg_cat⁻¹和87.79%, 远远高于C₃N₅, 且该催化剂在循环试验和长时间实验中具有良好的活性和稳定性, 表明在电催化硝酸盐领域中具有一定的研究价值.

关键词: 电催化还原, 氨产率, 法拉第效率, C₃N₅基催化剂, 硝酸盐

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

引用此文

韩晶, 廖润华, 邓文强, 梁博宇, 周雨晴, 任帅, 洪燕. 铜掺杂氮化碳电催化硝酸盐产氨性能研究[J]. 化学学报, 2024, 82(3): 295-302.

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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图/表 9

图1. 不同掺杂量的铜所合成材料得到的XRD图

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

图2. (a) C3N5与复合材料的红外对比图; (b) C3N5与Cu-C3N5-1两者红外放大对比图

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

图3. (a) C3N5、Cu-C3N5-1和Cu-C3N5-3的XPS全谱图; (b) C3N5-5、Cu-C3N5-7和Cu-C3N5-9的XPS全谱图; (c) C3N5、Cu-C3N5-1和Cu-C3N5-5的C1s图; (d) C3N5、Cu-C3N5-1和Cu-C3N5-5的N1s图; (e) Cu-C3N5-1和Cu-C3N5-5的Cu2p图; (f) Cu-C3N5-9 XPS图

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

图4. (a) C3N5扫描电镜图; (b) Cu-C3N5-9扫描电镜图; (c) Cu-C3N5-9铜元素分布图

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

图5. 各样品在进行实验后所得到的LSV图

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

图6. (a), (b)各催化剂在-0.5~-1.0 V (vs. RHE)电位下的产氨速率和法拉第效率图; (c)催化剂在-0.8 V (vs. RHE)电位下的NH3产率

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

图7. (a) Cu-C3N5-9在-1.0 V (vs. RHE)电势试验5次时的LSV图; (b) Cu-C3N5-9在-1.0 V (vs. RHE)电势循环试验5次时的产氨速率和法拉第效率图

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

图8. (a) Cu-C3N5-9在-1.0 V (vs. RHE)电势进行的电解12 h前后的LSV对比图; (b) Cu-C3N5-9在-1.0 V (vs. RHE)电势进行的电解12 h前后的产氨速率和法拉第效率对比图

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

图9. 氯化铵标准质量浓度曲线图

Figure 9. NH4Cl standard mass concentration profile

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