CN114965611A - Microbial fuel cell sensor - Google Patents
Microbial fuel cell sensor Download PDFInfo
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- CN114965611A CN114965611A CN202110219049.6A CN202110219049A CN114965611A CN 114965611 A CN114965611 A CN 114965611A CN 202110219049 A CN202110219049 A CN 202110219049A CN 114965611 A CN114965611 A CN 114965611A
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to the technical field of new energy and environmental engineering, and provides a microbial fuel cell sensor which comprises a hollow shell, a pretreatment layer, a micro motor, an anode, a reference electrode, a Rujin capillary tube, a data acquisition part and an energy acquisition part. The microbial fuel cell sensor is designed in an open circuit mode, gets rid of the ancient plate mode of the traditional microbial fuel closed loop, simplifies the structure of the sensor to the greatest extent, reduces the equipment cost, improves the sensitivity, shortens the response time, and better meets the requirements of practical application; the direct-current micro motor drives the anode to rotate, so that the sensitivity of the sensor can be prevented from being reduced due to the fact that the mixed bacterial film is too thick; the data acquisition part and the energy acquisition part can realize in-situ, on-line and real-time monitoring, and overcome the difficulty of field data remote transmission; the pretreatment layer can reduce the interference of other substances (such as heavy metals) to the sensor, ensure the stable operation of the sensor and realize the in-situ, rapid and real-time monitoring of the nitrate concentration in water.
Description
Technical Field
The invention belongs to the technical field of new energy and environmental engineering, and particularly relates to a microbial fuel cell sensor.
Background
Nitrate is one of the important existing forms of nitrogen element, widely exists in natural water, and the content of nitrate in water is higher and higher with the development of socioeconomic. Research shows that when the inorganic nitrogen content in the water body is more than 200mg/L, algal bloom phenomenon can be caused, red tide phenomenon is caused at estuaries and gulfs, the water body is lack of oxygen, a large amount of water body organisms die, and the ecological environment is seriously damaged. If humans drink water containing a large amount of nitrate for a long period of time, methemoglobinemia is caused. Although nitrate is not toxic to the human body itself, it can be reduced to nitrite in the human body, which has the ability to reduce the ferric iron in hemoglobin to ferrous iron and denature newly formed red blood cells to lose oxygen carrying capacity, at which time the patient's body appears blue or bluish purple, a condition known as blue baby disease in infants. In addition, nitrate may be accompanied with acute pollutants such as tetrafluoroethylene pesticides and the like in the water body, and the acute pollutants are stably existed through a series of biochemical actions, so that the normal operation of a drinking water treatment system is not facilitated, and the safety of drinking water is threatened. Therefore, nitrate in water needs to be monitored timely and effectively to maintain the stability of the ecosystem and ensure the drinking water safety of human beings.
At present, the method for monitoring nitrate in water is mainly a physical and chemical analysis method and depends on complex large-scale instruments and equipment, so the method is not suitable for developing an on-line water quality monitoring system, for example, ultraviolet spectroscopy and ion chromatography require complicated sample pretreatment processes and professional operation, and the monitoring hysteresis cannot quickly cope with water quality change and take effective measures. The portable ion selective electrode is produced to overcome the disadvantage of heavy weight of large-scale monitoring equipment, however, the permselective membrane used in the portable ion selective electrode is easily interfered by other ions, such as pH, which has a great influence on the device, and in addition, the reproducibility of the electrode is not strong, and the influence factors of the electrode life are many, so that the portable ion selective electrode still has many problems when being used for in-situ long-term monitoring. Although most researches are focused on the early warning of toxic substances, such as luminescent bacteria, algae and biological fish water environment early warning systems, methods and devices for detecting nitrate and other conventional pollutants have been developed, such as a biological enzyme sensor, which has high selectivity and low detection limit, but because the service life of the biological enzyme sensor is short (about 5 days), the activity of the biological enzyme sensor is greatly influenced by the environment, so that the biological enzyme sensor cannot be widely applied to the field of environmental monitoring.
Disclosure of Invention
The invention provides a microbial fuel cell sensor, which can quickly, accurately, in-situ, online and monitor the concentration of nitrate in a water body and simultaneously ensure the stability and sensitivity of the sensor, and aims to solve the problems that when the traditional closed-circuit microbial fuel cell sensor monitors nitrate in water, the response time of the device is relatively long, the device is easily interfered by other substances (such as heavy metals, ferric iron, sulfate and the like) in water to cause poor stability of the device, and the sensitivity of the sensor is reduced because an aged biological membrane cannot be updated timely.
The present invention provides a microbial fuel cell sensor having features comprising: the shell is hollowed, the top of the shell is opened, and the interior of the shell is used as a reaction cavity; the pretreatment layer is arranged on the hollow shell, and a water body enters the reaction cavity after being pretreated by the pretreatment layer; the micro motor is arranged at the top end of the hollow shell; the anode is used for adsorbing the electrogenesis bacteria, is positioned in the reaction cavity, is connected with the output end of the micro motor through a conductive metal wire and is driven by the micro motor to rotate; the reference electrode is positioned in the reaction cavity and is arranged beside the anode; one end of the Rujin capillary is electrically connected with the reference electrode, and the other end of the Rujin capillary is away from the anode by a preset distance; the data acquisition part is electrically connected with the anode, the reference electrode and the micro motor and is used for measuring the voltage between the anode and the reference electrode and controlling the rotation frequency of the micro motor; and the energy acquisition part is electrically connected with the anode and the micro motor and is used for collecting the charges on the anode so as to supply power to the micro motor.
In the microbial fuel cell sensor provided by the present invention, the sensor may further have the following features: the data collection part comprises a micro control module, an analog-to-digital conversion module, a wireless communication module, a clock module and a data storage module, the micro control module sets the measuring frequency of the analog-to-digital conversion module according to the clock real-time module and the rotating frequency of the micro motor, the analog-to-digital conversion module measures the voltage between the anode and the reference electrode according to the measuring frequency, the micro control module calculates the concentration of nitrate in the water body according to the voltage, the clock module records the time corresponding to each concentration, the data storage module stores the concentration and obtains monitoring data at the time corresponding to each concentration, and the wireless communication module sends the monitoring data to an external coordinator.
In the microbial fuel cell sensor provided by the present invention, the sensor may further have the following features: the energy collection part comprises a charge pump, a super capacitor, a switch and a direct current converter, the charge pump is electrically connected with the anode, electric energy on the anode is collected to charge the super capacitor, the super capacitor is automatically charged and discharged under the control of the switch, and the direct current converter boosts the electric energy released by the super capacitor and provides the electric energy to the micro motor.
In the microbial fuel cell sensor provided by the present invention, the sensor may further have the following features: the hollow shell is a double-layer metal net, the pretreatment layer is formed by filling a cellulose cation adsorbent in the double-layer metal net, the thickness of the pretreatment layer is 0.5 cm-1.5 cm, and the surface of the cellulose cation adsorbent is provided with surface active groups.
In the microbial fuel cell sensor provided by the present invention, the sensor may further have the following features: wherein, the surface active group is any one or more of aldehyde group, amino group or sulfonic group.
The microbial fuel cell sensor provided by the invention can also have the following characteristics: wherein, the surface of the anode is pasted with tungsten carbide nano-particles, and the average load is 1.15mg/cm 2 。
In the microbial fuel cell sensor provided by the present invention, the sensor may further have the following features: wherein, the anode is made of conductive, corrosion-resistant and biocompatible material.
In the microbial fuel cell sensor provided by the present invention, the sensor may further have the following features: wherein the predetermined distance is less than or equal to the outer diameter of the thin end of the luggin capillary.
In the microbial fuel cell sensor provided by the present invention, the sensor may further have the following features: wherein, the cultivation of the electrogenesis bacteria on the anode comprises the following steps: step S1, constructing a typical double-chamber microbial fuel cell, wherein an anode chamber and a cathode chamber are separated by a cation exchange membrane; step S2, mixing the anode culture solution and inoculated anaerobic sludge according to the volume ratio of 4:1 to obtain a mixed solution, injecting the mixed solution into an anode chamber, and injecting the cathode culture solution into a cathode chamber; step S3, placing the anode into the anode chamber and connecting with the anode of the MFC, placing the counter electrode into the cathode chamber and connecting with the cathode of the MFC, and placing the Ag/AgCl reference electrode near the working electrode in the anode chamber; and step S4, starting the MFC by adopting a constant anode potential method intermittent feeding mode, regularly replacing the cathode culture solution and the mixed solution in the anode chamber, and taking out the anode when the MFC obtains constant voltage output, namely the maximum voltage of three continuous days is kept constant, so as to finish the culture of the electrogenic bacteria.
Action and Effect of the invention
According to the microbial fuel cell sensor provided by the invention, the anode, the reference electrode, the data acquisition part and the energy acquisition part are used for constructing a novel open-circuit microbial fuel cell nitrate sensor, nitrate is used as an electron acceptor, the voltage drop generated by competitive electrons of the biological anode is used as a sensitive signal, and the nitrate concentration in effluent can be monitored in situ and in real time after signal conversion and transmission. Compared with the traditional double-chamber or single-chamber closed loop sensor, the open-circuit design gets rid of the ancient plate mode of the traditional microbial fuel closed loop, the structure of the sensor is simplified to the greatest extent, the equipment cost is reduced, the sensitivity is improved, the response time is shortened, and the practical application requirements are better met; the direct-current micro motor drives the anode to rotate, so that the sensitivity of the sensor can be prevented from being reduced due to the fact that the mixed bacterial film is too thick; the data acquisition part and the energy acquisition part can realize in-situ, on-line and real-time monitoring, and overcome the difficulty of field data remote transmission; the pretreatment layer can reduce the interference of other substances (such as heavy metals) to the sensor and ensure the stable operation of the sensor.
In addition, compared with the traditional closed loop fuel cell sensor, the conditions of anode pH drop and cathode pH rise can not occur in the open circuit, and the pH of the solution is not required to be adjusted. And the open circuit does not need long-distance electron transmission, thereby reducing the electrode potential, improving the reaction rate of nitrate, further enhancing the sensitivity of the sensor and shortening the response time.
In addition, compare in traditional closed loop sensor, the open circuit voltage is difficult for influencing by organic matter concentration, has better stability. The pretreatment layer wrapped around the electrode forms a protective barrier, so that the hydraulic impact of the sensor in water can be reduced, a certain buffering effect is achieved, and a good environmental condition is created for microorganisms adsorbed on the surface of the electrode.
Therefore, when the microbial fuel cell sensor provided by the invention is used for monitoring nitrate in water, the sensor can be powered and operated by degrading substrates in water by electroactive microbes enriched by an anode, and no additional electric energy is required to be input, so that the sensor is energy-saving and environment-friendly; the water quality can be monitored and a certain purification effect can be achieved; the equipment maintenance is simple, and the operation cost is low; the water quality change is directly converted into an electric signal which is easy to measure, and the structure is simple; the raw water is used as a culture medium, so that the nitrate concentration in the water can be monitored in situ, rapidly and in real time.
Drawings
FIG. 1 is a schematic diagram of the structure of a microbial fuel cell sensor in an embodiment of the invention;
FIG. 2 is a schematic representation of the operation of a microbial fuel cell sensor in an embodiment of the invention;
FIG. 3 is a linear fit of pressure drop versus nitrate concentration for an example of the invention;
FIG. 4 is a graph showing the results of the removal rate of the cellulose cation adsorbent in the example of the present invention;
FIG. 5 is a graph comparing sulfate interference results in examples of the present invention; and
fig. 6 is a graph comparing interference results of ferric ions in examples of the present invention.
Detailed Description
In order to make the technical means, the creation features, the achievement objects and the effects of the invention easy to understand, a microbial fuel cell sensor of the invention is specifically described below with reference to the embodiments and the accompanying drawings.
Fig. 1 is a schematic structural view of a microbial fuel cell sensor in an embodiment of the present invention.
As shown in fig. 1, the microbial fuel cell sensor 100 includes a hollow housing 101, a pretreatment layer 102, a micro motor 103, an anode 104, a reference electrode 105, a luggin capillary 106, a data acquisition unit 107, and an energy acquisition unit 108.
The hollow shell 101 is a double-layer stainless steel metal net with an open top and is used as a reaction chamber inside. The volume of the reaction cavity is 10 ml-50 ml. In this embodiment, the hollow casing 101 has an inner diameter of 5cm and an outer diameter of 6 cm.
The pretreatment layer 102 is formed by filling cellulose cation adsorbent in the double-layer stainless steel metal net 101, and the thickness of the pretreatment layer 102 is 0.5 cm-1.5 cm. The surface of the selected cellulose cation adsorbent has surface active groups. The surface active group is any one or more of aldehyde group, amino group or sulfonic group. In the present embodiment, the thickness of the pretreatment layer 102 is 1.0 cm. The water body enters the reaction chamber after being pretreated by the pretreatment layer, so that the pretreatment layer 102 is used for removing heavy metal ions in the water and organic matters which can be adsorbed by the heavy metal ions.
The filling thickness of the cellulose cation adsorbent in the double-layer stainless steel net is required to ensure that the adsorbent is not lost from the stainless steel net, and meanwhile, enough gaps are also required to be reserved between the adsorbents to allow water to penetrate into the reaction cavity. The cellulose cation sorbent needs to be replaced periodically, typically over a period of two years, and can also be taken out and verified with a prepared nitrate-containing water body, and replaced when the detected nitrate concentration deviates from the actual concentration by more than 5%.
The micro motor 103 is a dc motor and is fixed to the top of the hollow housing 101 by a screw thread.
The anode 104 is used for adsorbing electrogenic bacteria, is located in the reaction chamber, is connected with the output end of the micro motor 103 through a conductive metal wire 109, for example, a titanium wire, and is driven by the micro motor 103 to rotate at regular time.
The anode 104 can be used as an anode material, and has the characteristics of electric conductivity, corrosion resistance and good biocompatibility. The anode 104 may be a graphite rod electrode (4 cm long, 2cm diameter) or a graphite felt electrode (1cm by 5cm by 0.2 cm).
The tungsten carbide nanoparticles are adhered to the surface of the anode 104 with 5 w% Nafion solution as a binder, and the average load is 1.15mg/cm 2 。
The anode 104 is washed by deionized water to remove surface impurities, then soaked for 1h by 1mol/L NaOH, washed by deionized water, dried in a 50 ℃ oven, then soaked for 1h by 1mol/L HCl, washed by deionized water and dried for later use.
The reference electrode 105 is an Ag/AgCl electrode, located within the reaction chamber, and disposed beside the anode 104.
One end of the luggin capillary 106 is electrically connected to the reference electrode 105 through a titanium wire, and the other end is spaced apart from the surface of the anode 104 by a predetermined distance. The predetermined distance is less than or equal to the outer diameter of the thin end of the luggin capillary tube. In this example, the predetermined distance is 3 mm.
The tip of the thin end of the luggin capillary 106 should be as close as possible to the surface of the study electrode to minimize ohmic potential drop. But not too close, which would otherwise have a significant shielding effect on the electrode surface and affect the current distribution. In order to reduce the ohmic drop of the solution without generating significant shielding effect and improve the accuracy of the potentiometric data, the distance of the luggin capillary 106 from the surface of the electrode should be no less than the outer diameter of the thin end of the luggin capillary.
The data acquisition unit 107 and the energy acquisition unit 108 are hermetically sealed with the micro motor 103.
The anode 104 and the reference electrode 105 are electrically connected to the data acquisition unit 107 via a titanium wire, and the voltage between the anode and the reference electrode is measured. Meanwhile, the data acquisition part 107 is also electrically connected with the micro motor 103 to control the rotation frequency of the micro motor.
The anode 104 is electrically connected to the energy collection unit 108 through a titanium wire, and the micro motor 103 is also electrically connected to the energy collection unit 108, so that the energy collection unit 108 collects electric charges from the anode 104 and supplies the electric charges to the micro motor 103.
Fig. 2 is a schematic diagram of the operation of a microbial fuel cell sensor in an embodiment of the invention.
As shown in fig. 2, the working flow of the microbial fuel cell sensor 100 is as follows:
the data acquisition unit 107 includes a micro control module, an analog-to-digital conversion module, a wireless communication module, a clock module, and a data storage module. The microcontroller sets the measuring frequency of the analog-digital conversion module and the rotating frequency of the micro motor according to the clock real-time module, the analog-digital conversion module measures the voltage between the anode 104 and the reference electrode 105 according to the measuring frequency, the microcontroller calculates the concentration of nitrate in the water body according to the voltage, the clock module records the time corresponding to each concentration, the data storage module stores the concentration and the time corresponding to each concentration to obtain monitoring data, and the wireless communication module sends the monitoring data to an external coordinator.
Specifically, the analog-to-digital conversion module is electrically connected with the anode 104 and the reference electrode 105 through titanium wires, and the micro control module is electrically connected with the micro motor 103. The micro-control module is a microcontroller and is used for controlling and coordinating the operation of the whole equipment and setting the voltage data to be acquired every 1 min. The analog-to-digital conversion module is an analog-to-digital converter, converts the acquired voltage into a digital signal, and obtains the nitrate concentration by an internal program of the microcontroller. The clock module is a real-time clock and records the time corresponding to each datum; and a metric. The data storage module stores the monitoring data, and the monitoring data before one month can be automatically cleared in order to ensure sufficient storage space. The wireless communication module adopts a Zigbee wireless sensing technology, has the characteristics of short distance, low speed and high efficiency, and sends real-time monitoring data to an external Zigbee coordinator to realize the remote monitoring of the nitrate.
For further optimization, the microcontroller employs a 16-bit ultra-low power hybrid signal processor MSP430F149, available from texas instruments. It integrates many analog circuit peripherals (such as ADC, DAC, analog comparator, etc.) and common digital modules (such as SCI, SPI, PC, PWM, CAP, timer/timer) inside the chip.
For further optimization, the digital-to-analog converter adopts AD7194, which is a low-noise complete analog front end suitable for high-precision measurement application. It integrates a low noise 24-bit sigma-delta analog-to-digital converter (ADC), with low noise gain stage on-chip meaning that small signals can be directly input.
The energy collection unit 108 includes a charge pump, a super capacitor, a switch, and a dc converter. The charge pump is electrically connected with the anode 104, collects the electric energy on the anode 104 to charge the super capacitor, the super capacitor is automatically charged and discharged under the control of the switch, and the direct current converter boosts the electric energy released by the super capacitor and provides the electric energy to the load micro motor 103 and elements in the data acquisition part 107.
Specifically, the charge pump collects the electrical energy of the anode 104, and the super capacitor stores the electrical energy as an energy storage capacitor. When the voltage value at the two ends of the energy storage capacitor reaches the threshold value, the capacitor starts to discharge under the control of the switch, and the voltage is boosted to 5V through the direct current converter to supply power to a load, namely the micro motor 103; when the voltage of the super capacitor is reduced to the threshold value, the switch is switched off, and the super capacitor starts the charging process again. The energy storage capacitor is automatically charged and discharged, the system operates circularly, and the micro motor 103 works intermittently.
In use, the microbial fuel cell sensor 100 is placed in a body of water to be monitored. The water body is a water body with more stable microorganism and organic matter conditions, such as a drinking water source place, a pond and a lake with little fluctuation of the water body conditions and the like. Heavy metal ions (Cu) in water before water sample enters sensor 2+ 、Hg 2+ 、Cr 6+ Etc.) and part of suspended organic matters are firstly adsorbed by a cellulose cation adsorbent wrapped around an electrode, a pretreated water sample enters a reaction chamber, microorganisms gradually gather on an anode 104 to form an electrogenesis bacterial film 200, electrons generated by the organic matters degraded by the microorganisms and entering the reaction chamber accumulate on the electrode in the formation process of the electrogenesis bacterial film 200, the electrode potential finally tends to be stable, and the organic matters in the water body continue to enter the organic matters in the reaction chamber and do not influence the potential change of the organic matters in the reaction chamber to form the maximum open-circuit potential. When Nitrate (NO) appears in water 3 - ) In this case, a bioelectrochemical denitrification reaction can be carried out:
the reduction of dissimilated nitrate to ammonium (DNRA) may also occur, and it is not currently predictable how nitrate reacts, but both reactions consume electrons that accumulate on the electrodes and thus create a voltage drop. Through the early-stage linear fitting experiment, the concentration of the nitrate in the water can be calculated according to the pressure drop, and the purpose of monitoring the nitrate in the water body is achieved.
In the early stage linear fitting experiment, nitrate with different concentrations is added to an in-situ water source (which is also a water source of a place to be monitored) respectively, and then pressure drop and concentration tests are carried out. The experimental process specifically comprises the following steps: when the sensor is in stable operation in a simulated water sample, nitrate solutions of 1mg/L, 5mg/L, 10mg/L, 20mg/L, 30mg/L and 40mg/L are respectively prepared and introduced into the sensor at the flow rate of 5ml/min, a voltage data acquisition system is used for recording the change condition of voltage, after each concentration is introduced, the voltage of the sensor is recovered to a stable state for 30min, and then the next nitrate concentration experiment is carried out. The test results are shown in FIG. 3.
FIG. 3 is a linear fit of pressure drop versus nitrate concentration for examples of the invention.
As shown in FIG. 3, the nitrate concentration in the range of 1mg/L to 40mg/L showed a good linear relationship between the pressure drop and the nitrate concentration (R) 2 0.9844), so the nitrate concentration in the water can be calculated by the feedback of the voltage signal, and the purpose of monitoring the nitrate in the water body is achieved. When the nitrate concentration is lower than 1mg/L or higher than 40mg/L, the pressure drop is not obvious, and a large deviation exists.
When the water quality of the water body has no large fluctuation, chemical energy in the water is converted into electric energy through the electricity generating bacteria on the surface of the anode, the whole sensor is in a stable electricity storage state, when the electrode voltage is equal to the maximum open-circuit voltage value and is maintained for 5min, the charge pump starts to charge the super capacitor, and if the open-circuit voltage is reduced and changed, the charging is immediately suspended, so that the accuracy of voltage drop data is ensured. When the voltage at two ends of the capacitor reaches the threshold value during charging, the capacitor starts to discharge, and the voltage is converted into 5V to be supplied to a load through direct current conversion. Under the condition of sufficient current, the super capacitor can be fully charged within dozens of seconds, automatic cyclic charge and discharge are easy to realize, and the load operates once every a period of time.
The micro direct current motor is started to drive the anode below to rotate, and a biological membrane (namely an electrogenesis bacterial membrane) on the surface of the anode and water generate shearing force in the tangential direction, so that the falling of an aging biological membrane is accelerated, the updating of the biological membrane is promoted, and the sensitivity of the sensor is ensured; the real-time clock enables all monitoring data to have corresponding time, the data which cannot be sent in time are stored, and when the super capacitor discharges, the data are transmitted to the coordinator through a Zigbee wireless communication technology, so that the monitoring problem of remote areas is solved.
In order to verify the adsorption rate of the pretreatment layer to heavy metal ions in water, a removal rate experiment was performed. Separately prepared Cu of 1mg/L 2+ 、Hg 2+ 、Cr 6+ And (3) respectively passing the solution of the heavy metal ions through three identical home-made filter membranes filled with a cellulose cation adsorbent with the thickness of 1cm at the flow rate of 5ml/min, and detecting the concentration of the metal ions in the water by using ICP-MS (inductively coupled plasma-mass spectrometry), thereby obtaining the removal effect of the adsorbent on various heavy metal ions. The test results are shown in FIG. 4.
Fig. 4 is a graph showing the results of the removal rate of the cellulose cation adsorbent in the example of the present invention.
As can be seen from FIG. 4, after the water sample passes through the pretreatment layer 102, the heavy metal ions Cu in the water 2+ 、Hg 2+ 、Cr 6+ The removal rate of the catalyst reaches 87%, 84% and 85% respectively, and the removal efficiency is good.
This example also examines the effect of different concentrations of sulfate and ferric ions, which are commonly used as electron acceptors, on the conventional closed circuit and the sensor of this example, and the results are shown in fig. 5 and 6.
FIG. 5 is a graph comparing sulfate interference results in examples of the present invention; fig. 6 is a graph comparing interference results of ferric ions in examples of the present invention.
Sulfate interference protocol: 0.3698g, 0.4438g, 0.5177g and 0.5917g of sodium sulfate are respectively weighed and dissolved in 1L of simulated water (equivalent to 250mg/L, 300mg/L, 350mg/L and 400mg/L of SO) 4 2- ) The sensor of the embodiment and a common commercial closed circuit sensor are sequentially fed at the flow rate of 5ml/min, the voltage change of the two sensors is recorded by a voltage acquisition system, and after the voltage of the sensor is recovered to a stable state for 30min after each concentration is fed, the next concentration experiment is carried out.
Ferric ion interference experimental protocol: 0.0014g, 0.0019g, 0.0024g and 0.0029g of ferric trichloride are respectively weighed and dissolved in 1L of simulated water (equivalent to 0.3mg/L, 0.4mg/L, 0.5mg/L, C),0.6mg/L Fe 3+ ) The operation is identical to that of the sulphate described above.
From the experimental results of fig. 5 and 6, it can be seen that the stability of the sensor of the present embodiment is very little affected by interfering ions, and the stability is better than that of the conventional closed-loop sensor.
When the sensor of the embodiment is used, the sensor can be placed in a water body to be monitored to culture the electrogenic bacteria in situ, and can also be used for quickly culturing the electrogenic bacteria in a laboratory. The time for culturing the electrogenic bacteria in situ is long, and the electrogenesis can be monitored and used after about 2 months. And the laboratory can cultivate the electrogenesis bacteria for about 2 weeks, the sensor cultivated with the electrogenesis bacteria is put into the water body to be monitored, and the sensor can be normally monitored and used for about 1 to 2 days.
The cultivation of the electrogenic bacteria on the anode comprises the following steps:
step S1, constructing a typical double-chamber microbial fuel cell, wherein an anode chamber and a cathode chamber are separated by a cation exchange membrane;
step S2, injecting a mixed solution obtained by mixing an anode culture solution and inoculated anaerobic sludge according to the volume ratio of 4:1 into the anode chamber, and injecting a cathode culture solution into the cathode chamber;
a step S3 of placing the anode in the anode chamber and connecting to an anode of an MFC, placing a counter electrode in the cathode chamber and connecting to a cathode of the MFC, and placing an Ag/AgCl reference electrode in the vicinity of the working electrode in the anode chamber;
and step S4, starting the MFC by adopting a constant anode potential method intermittent feeding manner, regularly replacing the cathode culture solution and the mixed solution in the anode chamber, and taking out the anode when the MFC obtains constant voltage output, namely the maximum voltage of three continuous days is kept constant, so as to finish the culture of the electrogenic bacteria.
Specifically, the preparation steps of the anode mixed mycoderm laboratory in the laboratory are as follows: a typical two-compartment microbial fuel cell was constructed from plexiglass with anode and cathode compartment liquid volumes of 50mL and 50mL respectively, separated by a cation exchange membrane. The anode graphite rod was fixed to the top of the reactor (MFC, common commercial fuel cell sensor) by a titanium wire. The cathode (counter electrode) is a carbon fiber brush with the length of 3cm and the diameter of 2cm, surface impurities are washed away by deionized water, the carbon fiber brush is soaked in acetone for 24 hours, then the carbon fiber brush is placed in a muffle furnace, is burnt for 30min at the temperature of 400-600 ℃, is washed in the deionized water, and is placed in a 50 ℃ drying oven for later use. An Ag/AgCl electrode was inserted as a reference electrode near the anode. The anode culture solution simulates the water quality of natural water and comprises the following components:
TABLE 1 ingredient Table of anode culture solution
| Composition (I) | Concentration (g/L) |
| CH 3 COONa | 1.64 |
| NH 4 Cl | 0.31 |
| CaCl 2 · |
0.1 |
| MgCl 2 ·6H 2 O | 0.1 |
| KH 2 PO 4 | 4.4 |
| K 2 HPO 4 ·3H 2 O | 3.4 |
| Mineral substance solution | 12.5mL/L |
| Vitamin solution | 5mL/L |
The catholyte composition was as follows:
TABLE 2 catholyte ingredients Table
| Composition (I) | Concentration (g/L) |
| K 3 [Fe(CN) 6 ] | 16.64 |
| KH 2 PO 4 | 4.4 |
| K 2 HPO 4 ·3H 2 O | 3.4 |
The anode culture solution and inoculated anaerobic sludge are mixed and injected into the anode chamber according to the proportion of 4:1, and the anaerobic sludge is taken from the residual sludge of an anaerobic tank of a certain sewage treatment plant. Catholyte is directly injected into the cathode chamber, and the magnetic stirrers are used at the bottoms of the two chambers to ensure that the reaction is uniform.
The MFC (fuel cell sensor) is started by adopting a constant anode potential method intermittent feeding mode, the anode of the MFC is connected with a working electrode (anode graphite rod), the cathode of the MFC is connected with a counter electrode, and the anode potential is kept at-290 mv relative to an Ag/AgCl reference electrode (relative to SHE +197 mv). The dual chamber solution was replaced with a syringe each day. When the MFC achieves a constant voltage output, i.e. the maximum voltage for three consecutive days remains substantially constant, the anode mix biofilm culture is complete by removing the anode from the MFC and placing it in the sensor reaction chamber, which may take approximately two weeks.
In the fuel cell sensor of the present embodiment, in order to omit the cathode, the proton exchange membrane and the external loop, and in order to be an open-circuit sensor, the electrode reaction equation is as follows:
①CH 3 COO - +2H 2 O→2CO 2 +7H + +8e -
②
therefore, compared with the traditional closed loop fuel cell sensor, the pH value of the anode does not drop and the pH value of the cathode does not rise when the fuel cell is opened, and the pH value of the solution does not need to be adjusted.
Effects and effects of the embodiments
According to the microbial fuel cell sensor provided by the embodiment, the anode, the reference electrode, the data acquisition part and the energy acquisition part are used for constructing the novel open-circuit microbial fuel cell nitrate sensor, nitrate is used as an electron acceptor, the voltage drop generated by competitive electrons of the biological anode is used as a sensitive signal, and the nitrate concentration in effluent can be monitored in situ and in real time after signal conversion and transmission. Compared with the traditional double-chamber or single-chamber closed loop sensor, the open-circuit design gets rid of the ancient plate mode of the traditional microbial fuel closed loop, the structure of the sensor is simplified to the greatest extent, the equipment cost is reduced, the sensitivity is improved, the response time is shortened, and the practical application requirements are better met; the direct-current micro motor drives the anode to rotate, so that the sensitivity of the sensor can be prevented from being reduced due to the fact that the mixed bacterial film is too thick; the data acquisition part and the energy acquisition part can realize in-situ, on-line and real-time monitoring, and overcome the difficulty of field data remote transmission; the cellulose adsorbent pretreatment layer on the outer layer can reduce the interference of other substances (such as heavy metals) to the sensor and ensure the stable operation of the sensor.
In addition, compared with the existing microbial fuel cell sensor, the present embodiment has the following advantages:
(1) compared with the traditional closed loop fuel cell sensor, the open circuit can not cause the conditions of anode pH drop and cathode pH rise, and the pH of the solution is not required to be adjusted.
(2) The open circuit does not need long-distance electron transmission, thus reducing the electrode potential, improving the reaction rate of nitrate, further enhancing the sensitivity of the sensor and shortening the response time;
(3) compared with the traditional closed loop sensor, the open-circuit voltage is not easily influenced by the concentration of organic matters, and the stability is better;
(4) heavy metal ions in water are removed through the cellulose cation adsorbent, so that the stability of the sensor is improved; the adsorbent wrapped around the electrode forms a protective barrier, so that the hydraulic impact of the sensor in water can be reduced, a certain buffering effect is achieved, and good environmental conditions are created for microorganisms adsorbed on the surface of the electrode.
(5) The micro direct current motor can accelerate the updating of the biological membrane on the surface of the electrode, so that a thicker biological membrane is not formed, the activity of microorganisms is effectively kept, and the sensitivity of the sensor is ensured;
(6) carry out wireless signal transmission through Zigbee, can fine adaptation field wireless sensor monitoring task.
Therefore, when the microbial fuel cell sensor provided by the embodiment monitors nitrate in water, the sensor can be powered and operated by an electroactive microbe enriched by an anode to degrade a substrate in water, no additional electric energy is needed to be input, and the sensor is energy-saving and environment-friendly; the water quality can be monitored and a certain purification effect can be achieved; the equipment maintenance is simple, and the operation cost is low; the water quality change is directly converted into an electric signal which is easy to measure, and the structure is simple; the raw water is used as a culture medium, so that the nitrate concentration in the water can be monitored in situ, rapidly and in real time.
The above embodiments are preferred examples of the present invention, and are not intended to limit the scope of the present invention.
In practical application, the data acquisition part and the energy acquisition part can be packaged in a shell, and then a display screen is arranged outside the shell and used for displaying the monitoring result and real-time.
Claims (10)
1. A microbial fuel cell sensor for monitoring the concentration of nitrate in a body of water, comprising:
the shell is hollowed out, the top of the shell is opened, and the interior of the shell is used as a reaction cavity;
the pretreatment layer is arranged on the hollow shell, and the water enters the reaction cavity after being pretreated by the pretreatment layer;
the micro motor is arranged at the top end of the hollow shell;
the anode is used for adsorbing electrogenesis bacteria, is positioned in the reaction cavity, is connected with the output end of the micro motor through a conductive metal wire and is driven by the micro motor to rotate;
a reference electrode positioned within the reaction chamber and disposed adjacent to the anode;
one end of the Rujin capillary is electrically connected with the reference electrode, and the other end of the Rujin capillary is away from the anode by a preset distance;
the data acquisition part is electrically connected with the anode, the reference electrode and the micro motor and is used for measuring the voltage between the anode and the reference electrode and controlling the rotation frequency of the micro motor; and
and the energy acquisition part is electrically connected with the anode and the micro motor and is used for collecting the charges on the anode so as to supply power to the micro motor.
2. The microbial fuel cell sensor of claim 1, wherein:
wherein the data collection part comprises a micro control module, an analog-to-digital conversion module, a wireless communication module, a clock module and a data storage module,
the micro-controller sets the measuring frequency of the analog-digital conversion module and the rotating frequency of the micro motor according to the clock real-time module, the analog-digital conversion module measures the voltage between the anode and the reference electrode according to the measuring frequency, the micro-control module calculates the concentration of nitrate in the water body according to the voltage, the clock module records the time corresponding to each concentration, the data storage module stores the concentration and the time corresponding to each concentration to obtain monitoring data, and the wireless communication module sends the monitoring data to an external coordinator.
3. The microbial fuel cell sensor of claim 2, wherein:
wherein the energy collecting part comprises a charge pump, a super capacitor, a switch and a DC converter,
the charge pump is electrically connected with the anode and used for collecting electric energy on the anode to charge the super capacitor, the super capacitor is automatically charged and discharged under the control of the switch, and the direct current converter boosts the electric energy released by the super capacitor and provides the electric energy to the micro motor.
4. The microbial fuel cell sensor of claim 1, wherein:
the hollow shell is a double-layer metal net, the pretreatment layer is formed by filling a cellulose cation adsorbent into the double-layer metal net, the thickness of the pretreatment layer is 0.5 cm-1.5 cm, and the surface of the cellulose cation adsorbent is provided with surface active groups.
5. The microbial fuel cell sensor of claim 4, wherein:
wherein, the surface active group is any one or more of aldehyde group, amino group or sulfonic group.
6. The microbial fuel cell sensor of claim 1, wherein:
wherein, the surface of the anode is pasted with tungsten carbide nano particles, and the average load is 1.15mg/cm 2 。
7. The microbial fuel cell sensor of claim 1, wherein:
the anode is made of a conductive material, corrosion-resistant material and good in biocompatibility.
8. The microbial fuel cell sensor of claim 1, wherein:
wherein the volume of the reaction cavity is 10 ml-50 ml.
9. The microbial fuel cell sensor of claim 1, wherein:
wherein the predetermined distance is less than or equal to the outer diameter of the thin end of the luggin capillary.
10. The microbial fuel cell sensor of claim 1, wherein:
wherein the cultivation of the electrogenic bacteria on the anode comprises the following steps:
step S1, constructing a typical double-chamber microbial fuel cell, wherein an anode chamber and a cathode chamber are separated by a cation exchange membrane;
step S2, injecting a mixed solution obtained by mixing an anode culture solution and inoculated anaerobic sludge according to the volume ratio of 4:1 into the anode chamber, and injecting a cathode culture solution into the cathode chamber;
a step S3 of placing the anode in the anode chamber and in connection with an anode of an MFC, placing a counter electrode in the cathode chamber and in connection with a cathode of the MFC, and placing an Ag/AgCl reference electrode in the vicinity of the working electrode in the anode chamber;
and step S4, starting the MFC by adopting a constant anode potential method intermittent feeding manner, regularly replacing the cathode culture solution and the mixed solution in the anode chamber, and taking out the anode when the MFC obtains constant voltage output, namely the maximum voltage of three continuous days is kept constant, so as to finish the culture of the electrogenic bacteria.
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| US20050211569A1 (en) * | 2003-10-10 | 2005-09-29 | Botte Gerardine G | Electro-catalysts for the oxidation of ammonia in alkaline media |
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| CN110398529A (en) * | 2018-04-25 | 2019-11-01 | 浙江自常环保技术有限公司 | A kind of BOD water quality monitoring method |
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| US3960673A (en) * | 1970-06-09 | 1976-06-01 | Fischer & Porter Co. | Technique for continuously analyzing the concentration of ozone dissolved in water |
| US20050211569A1 (en) * | 2003-10-10 | 2005-09-29 | Botte Gerardine G | Electro-catalysts for the oxidation of ammonia in alkaline media |
| CN207623276U (en) * | 2017-12-29 | 2018-07-17 | 环境保护部南京环境科学研究所 | Utilize the device of microbiological fuel cell evaluating water quality organic contamination situation |
| CN110398529A (en) * | 2018-04-25 | 2019-11-01 | 浙江自常环保技术有限公司 | A kind of BOD water quality monitoring method |
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