氮掺杂稻壳生物炭阴极微生物燃料电池处理含Cr（Ⅵ）废水

doi:10.19965/j.cnki.iwt.2025-0361

摘要/Abstract

摘要：

制备氮掺杂稻壳热解材料（NDK）作为双室MFC（Microbial fuel cell，MFC）阴极催化剂，对碳纸表面进行修饰，探究了NDK对MFC还原Cr（Ⅵ）和产电性能的影响，同时对阳极细菌多样性进行分析。结果表明，经氮掺杂后，材料表面孔隙度明显增大，氮元素原子数分数达到6.75%，与未进行氮掺杂材料相比提升了4.35%。电极的电化学性能分析表明，经生物质热解材料修饰后，碳纸电极的电化学活性有大幅提高，NDK修饰电极的电子转移电阻为238.9 Ω，较未修饰电极下降了74.08%。以NDK修饰碳纸为阴极的双室MFC（NDK-MFC）具有最佳性能，当装置内Cr（Ⅵ）初始质量浓度为200 mg/L时，NDK-MFC运行90 h时Cr（Ⅵ）去除率达87.02%，是未修饰电极MFC的3.38倍，获得的平均输出电压和最大功率密度分别为86.21 mV和1.53 mW/m²，并在连续运行第二周期时仍保持优良的性能。细菌群落分布及功能基因分析表明，MFC装置阳极富集了有机物降解和产电相关的优势菌群，同时微生物繁殖与新陈代谢的相关基因表达十分活跃。

关键词: 微生物燃料电池, 高浓度Cr（Ⅵ）废水, 氮掺杂, 细菌多样性, 代谢组学

Abstract:

A nitrogen-doped rice-husk pyrolysis material(NDK) was prepared to modify the surface of carbon paper,as a cathode catalyst of two-compartment MFC (Microbial Fuel Cell, MFC). The effects of NDK on Cr(Ⅵ) reduction and MFC power-generation performance were investigated, and the diversity of anodic bacteria was also analyzed. The results showed that after nitrogen doping, the surface porosity of the material increased significantly, and the elemental nitrogen content reached 6.75%, which was enhanced by 4.35% compared with the non-nitrogen doped material. The electrochemical performance analysis of the electrodes showed that the electrochemical activity of the carbon paper electrodes was substantially improved after modification with biomass pyrolysis materials. And the electron transfer resistance of the NDK-modified electrode was 238.9 Ω, which was 74.08% lower than that of the unmodified electrode. The two-compartment MFC with NDK-modified carbon paper(NDK-MFC) as the cathode had the best performance. When the initial Cr(Ⅵ) concentration in the device was 200 mg/L,the NDK-MFC was operated for 90 h to achieve Cr(Ⅵ) removal rate of 87.02%, which was 3.38 times higher than that of the MFC of the unmodified electrode. Average output voltage and maximum power density reached 86.21 mV and 1.53 mW/m² respectively. The excellent performance was maintained at the second cycle of continuous operation. The analysis of bacterial communities and functional genes showed that the anode of the MFC device was enriched with dominant flora related to organic matter degradation and electricity production, while the expression of genes related to microbial reproduction and metabolism was highly active.

Key words: microbial fuel cell, high-concentration Cr(Ⅵ) wastewater, nitrogen doping, bacterial diversity, metabolomics

中图分类号:

TM911.45

吴卿, 刘睿怡, 张颖, 彭森. 氮掺杂稻壳生物炭阴极微生物燃料电池处理含Cr（Ⅵ）废水[J]. 工业水处理, 2026, 46(4): 173-183.

Qing WU, Ruiyi LIU, Ying ZHANG, Sen PENG. Nitrogen-doped rice husk biochar cathode microbial fuel cell for Cr(Ⅵ) wastewater treatment[J]. Industrial Water Treatment, 2026, 46(4): 173-183.

https://gyscl.magtechjournal.com/CN/Y2026/V46/I4/173

图/表 12

表1 营养液成分

Table 1 List of nutrient solution ingredients

试剂	质量浓度/ （g·L^-1）	试剂	质量浓度/ （g·L^-1）
C₆H₁₂O₆	1.000 0	CaCl₂·2H₂O	0.198 7
NH₄Cl	0.310 0	K₂HPO₄·3H₂O	6.567 0
MgCl₂·6H₂O	0.219 9	KH₂PO₄	2.415 0
KCl	0.130 0

图1 DK和NDK的SEM

Fig.1 SEM images of DK and NDK

图2 DK和NDK的XPS

Fig.2 XPS images of DK and NDK

图3 不同电极的电化学性能

Fig.3 Electrochemical performance of different electrodes

图4 使用不同阴极电极的MFC连续运行两周期的Cr（Ⅵ）去除率

Fig.4 Cr（Ⅵ） removal rate of MFCs with different cathodes operating continuously for two cycles

图5 MFC连续运行两周期后电极的Nyquist曲线

Fig.5 Nyquist plot of electrodes after two consecutive cycles of MFC operation

图6 使用不同阴极电极的MFC连续运行两周期的输出电压

Fig.6 Output voltage of MFC with different cathodes operating continuously for two cycles

图7 使用不同阴极电极的MFC连续运行两周期的产电性能

Fig.7 Power production of MFC with different cathodes operating continuously for two cycles

表2 生物炭修饰阴极MFC中重金属去除性能的研究比较

Table 2 A comparative study of heavy metal removal performance in biochar-modified cathode MFC

MFC阴极材料	重金属种类及初始质量浓度	去除率	最大功率密度/（mW·m^-2）	参考文献
石墨负载玉米芯生物炭	300 mg/L Pb²⁺	7 h内降解29.7%	5.76	〔36〕
石墨负载玉米芯生物炭	20 mg/L Cr（Ⅵ）	8 h内降解41.9%	5.94	〔37〕
碳毡负载磁性玉米秸秆生物炭	20 mg/L Cr（Ⅵ）	6 d内降解98.19%	8.285	〔38〕
导电炭黑复合花生壳生物炭	50 mg/L Cu²⁺	5 d内降解95%	22.88	〔39〕
碳纸负载氮掺杂稻壳生物炭	200 mg/L Cr（Ⅵ）	90 h内降解87.02%	1.53	本研究

图8 运行结束后阴极电极SEM图和Cr元素分布

Fig.8 SEM images and Cr elements distribution of cathode at the end of operation

图9 不同装置阳极液细菌群落分布

Fig.9 Distribution of bacterial community in anode liquid of different devices

图10 DK-MFC和NDK-MFC样品间COG差异分析

Fig.10 Analysis of COG differences between DK-MFC and NDK-MFC samples

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