传感器类型
电化学生物传感器
检测对象
乙酸(acetate)、挥发性脂肪酸(VFAs)、可生物降解有机物/COD(chemical oxygen demand);样品基质:厌氧消化液/循环液(anaerobic digestion leachate/recirculation stream)、人工OECD废水、马铃薯水解液
检测原理
该传感器以电活性生物膜作为生物识别与催化元件。厌氧消化液中的乙酸等可生物降解有机物进入阳极室后,被生物膜中的电活性微生物氧化,电子经直接电子传递途径转移到石墨阳极,同时产生质子。质子通过Nafion 117质子交换膜迁移至阴极室,电子经外电阻流向石墨阴极,并在阴极参与氧还原反应,形成闭合回路。外电阻上的电位U被数据采集系统记录,电流I按U=IR计算。被测物浓度升高时,微生物氧化底物速率增加,阳极电子通量增大,MFC电位/电流信号随之增强;在优化条件下信号与COD呈Monod型关系,低浓度段近似线性。该装置无需外加电子媒介体,信号发生器与换能器一体化。
检测灵敏度
线性范围: 0–200 mg COD L⁻¹(原文:sensor signals rose linearly with substrate concentration up to 200 mg COD l⁻¹)
效应效果
6个月运行中,生物膜MFC对负荷变化响应明显:离散加料时电位由20–30 mV升至45–60 mV,沼气流量由0–3升至20–30 mL/h,甲烷由65%升至75%;负荷升至2.52 g COD/(L·d)时电位达80 mV,气体流量75 mL/h,pH降至7.3。对照MFC信号弱且无宽峰,降负荷时约25 mV。MFC信号与pH、沼气流量、COD及VFA/HPLC相关,作者认为其比离线COD更敏感反映乙酸动态。系统采样频率1 min,便携、低成本、可原位兼容;负荷超过3 g COD/(L·d)时信号饱和。
传感器的构成
- 基底/换能器电极:石墨卷电极(Spektralkolstav, ISOAB),阳极有效面积6.28 cm²、阴极有效面积5.78 cm²,用于电子收集与传递
- 离子交换层:Nafion 117质子交换膜(Dupont),分隔阴阳极并允许H⁺迁移
- 结构支撑层:塑料网(plastic net)、O形圈(O-ring)和螺丝夹持,固定膜/电极并形成壁式射流流道
- 识别元件:电活性生物膜(electroactive biofilm, EAB),固定于阳极,氧化乙酸等有机物并直接传递电子
- 阴极反应层:石墨阴极与阴极液(60 mM磷酸盐缓冲液+50 mM NaCl),维持阴极还原反应和溶解氧
- 电子供体:厌氧消化液中的乙酸/可生物降解有机物(acetate/COD),作为微生物电子供体
- 信号读出:外电阻(在线200 Ω)与数据采集系统(DAQ),测量闭合回路电位U并计算电流I
中文摘要
本研究开发了一种壁式射流型微生物燃料电池(MFC)生物传感器,用于原位监测厌氧消化(AD)过程。该传感器以固定化电活性生物膜为识别元件,具有便携、样品流通水力停留时间短、便于连续运行等特点。MFC被安装于小型上流式厌氧固定床(UAFB)反应器的循环回路中,与pH探头和沼气流量计联用,实时监测发酵液pH和沼气流量。实验通过改变进料浓度和工艺构型人为施加外部扰动,考察传感器响应。在6个月运行中,MFC电位信号与在线参数(pH、气体流量)及离线分析(COD)具有良好相关性。结果表明,MFC信号能够反映厌氧消化过程的动态变化,可作为生物过程监测与控制的潜在工具。
英文摘要
A wall-jet microbial fuel cell (MFC) was developed for the monitoring of anaerobic digestion (AD). This biofilm based MFC biosensor had a character of being portable, short hydraulic retention time (HRT) for sample flow through and convenient for continuous operation. The MFC was installed in the recirculation loop of an upflow anaerobic fixed-bed (UAFB) reactor in bench-scale where pH of the fermentation broth and biogas flow were monitored in real time. External disturbances to the AD were added on purpose by changing feedstock concentration, as well as process configuration. MFC signals had good correlations with online measurements (i.e. pH, gas flow rate) and offline analysis (i.e. COD) over 6-month operation. These results suggest that the MFC signal can reflect the dynamic variation of AD and can potentially be a valuable tool for monitoring and control of bioprocess.