用于海水微生物燃料电池原位监测的新型伏安式pH传感器

doi:10.3976/j.issn.1002-4026.2025026

摘要/Abstract

摘要：

微生物燃料电池在生物电产生和生物修复方面应用前景广阔,其工作过程对酸碱度变化十分敏感。因此,在线pH监测对于优化微生物燃料电池的性能至关重要,现有的pH计难以满足这一特殊需求。设计了一种基于电化学原位合成石墨烯修饰丝网印刷电极的新型伏安式pH传感器。通过表面偶联氢键载体茜素番红花醇SE,可在pH4.0~9.0的范围内实现良好的pH传感线性度,灵敏度每pH单位的电极电位变化达70.7 mV。读数周期可控制在15 s内。该研究成功演示了在利用近海活性污泥构建的海水基微生物燃料电池中的原位长时pH动态监测,并获得理想结果。特别地,通过氢键载体的掺杂提高了石墨烯界面上的质子扩散速率,从而实现了伏安式pH传感器性能的改善。同时,研究发现该策略在参比系统的改进方面存在巨大空间,有望进一步改善该技术的长时传感性能。该方法为微生物燃料电池的未来开发提供了一种长时原位在线pH监测的新思路。

关键词: 微生物燃料电池, 海洋环境监测, 伏安式pH传感器, 原位连续监测

Abstract:

Microbial fuel cells (MFCs) hold considerable potential in bioelectricity generation and bioremediation, and their operational processes are highly sensitive to pH fluctuations. Therefore, online pH monitoring is crucial for optimizing the performance of MFCs. Existing pH meters often fall short in meeting the specific demands associated with online pH monitoring. In this study, we designed a novel voltammetric pH sensor based on electrochemically in situ-synthesized graphene-modified screen-printed electrodes. By surface coupling with the hydrogen-bond carrier alizarin safirol SE, the sensor achieves excellent linearity in pH detection within the range of 4.0 to 9.0, with a sensitivity of 70.7 mV per pH unit. The measurement cycle could be controlled within 15 s. This study successfully demonstrated in situ long-term pH dynamic monitoring in a seawater-based MFC constructed using coastal activated sludge, yielding ideal results. Notably, the incorporation of the aforementioned hydrogen-bond carrier enhanced the proton diffusion rate at the graphene interface, thereby improving the performance of the voltammetric pH sensor. Furthermore, this study revealed the considerable potential of this strategy for improving the reference system, which is expected to further substantially enhance the long-term sensing performance of this strategy. In addition, this strategy provides a new approach for long-term in situ online pH monitoring and thereby contribues to the future development of MFCs.

Key words: microbial fuel cell, marine environment monitoring, voltammetric pH sensor, in situ continuous monitoring

中图分类号:

TM911.45

李一苇, 宋瑾, 厉运周, 王军成. 用于海水微生物燃料电池原位监测的新型伏安式pH传感器[J]. 山东科学, 2025, 38(3): 72-83.

LI Yiwei, SONG Jin, LI Yunzhou, WANG Juncheng. A novel voltammetric pH sensor for in situ monitoring of seawater microbial fuel cell[J]. Shandong Science, 2025, 38(3): 72-83.

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干扰源	质量浓度/(g·L^-1)	pH₀	pH_int	pH漂移
盐度	20	8.18	8.12	-0.06±0.08
	30	8.12	8.11	-0.01±0.03
	40	8.14	8.07	-0.07±0.06
	50	8.09	8.13	0.04±0.02
	60	8.17	8.11	-0.06±0.11
DO	5.0	8.16	8.15	-0.01±0.04
	7.5	8.21	8.13	-0.08±0.04
	10.0	8.17	8.22	0.05±0.05
	12.5	8.11	8.14	0.03±0.09
	15.0	8.19	8.14	-0.05±0.02
NaS	0.02	8.07	8.17	0.1±0.07
	0.05	8.09	8.17	0.08±0.03
	0.10	8.16	8.06	-0.1±0.06
	0.25	8.11	8.09	-0.02±0.06
	0.50	8.18	8.13	-0.05±0.12
pAP	0.010	8.13	8.23	0.1±0.07
	0.025	8.08	8.19	0.11±0.04
	0.050	8.17	8.14	-0.03±0.11
	0.075	8.16	8.20	0.04±0.09
	0.100	8.13	8.11	-0.02±0.05