Figure 4. Various ways in which electron transfer to the anode can occur.
The focus is on natural ecosystems when choosing microorganisms for a PMFC system. Relatedly, bacteria inhabit the environment in the rhizosphere; they are anaerobes that produce protons and carbon dioxide and can transfer electrons to the anode during the oxidation of organic compounds. Table 1 presents a description of some rhizospheric bacteria.
Table 1.
Rhizospheric microorganisms capable of direct extracellular electron transfer.
The basic property of microorganisms that allows their use in bioelectric systems
[48,49,50][46][47][48] is their ability to produce electroactive compounds, as well as to use an anode as an electron acceptor. Moreover, the use of inorganic anions as an electron acceptor makes it possible to reduce the salinity of treated wastewater
[51[49][50],
52], for example, when using sulfate-reducing bacteria that are capable of the assimilatory reduction of sulfates to sulfides
[53][51].
PGPR (plant-growth-promoting rhizobacteria), which promote plant growth, play an important role in maintaining the vital activity of plants and are used for the development of PMFC. Such microorganisms include, for example, bacteria of the species
Bacillus thuringiensis, which are involved in nitrogen fixation processes, sulfur and phosphorus exchanges, and the synthesis of plant growth stimulants
[54][52]. Bacteria of the genus
Pseudomonas sp. can be also considered as a PGPR-group bacteria
[55][53]. Some species of
Pseudomonas sp. are capable of surfactant destruction
[56,57][54][55]; they can form biofilms on the surface of an anode and secrete compounds of the phenase-new series
[58][56]. These compounds play an important role both in protecting plants from pathogen infection
[59][57] and stimulating the growth of shoots
[60][58]. Moreover, phenazines act as mediators of the electronic transport between bacteria and an electrode
[61][59]. Bacteria of the family
Ruminococcaceae spp. are not electroactive but are capable of utilizing cellulose (35–50% of the dry plant weight) while producing organic substrates, which are additionally used by electroactive microorganisms as electron donors
[62][60]. Therefore, the use of PGPR-group bacteria can be used in PMFC systems to stimulate plant growth and protection, which theoretically can have a beneficial effect on electricity generation.
2.2. Electrodes in PMFC
It is important to choose the right electrode material for the efficient generation of electrical energy when creating PMFCs along with biological components
[63][61]. Generally, the electrode material should have high electrical conductivity, electrochemical stability, porosity, and biocompatibility
[64][62]. Metals (zinc
[65][63], stainless steel
[66][64], and platinum
[67][65]) and carbon materials
[68][66] are usually used as electrodes in bioelectrochemical systems. Despite the high electrical conductivity of metals in comparison with carbon materials, the use of stainless steel, for example, increases the period of microorganism adaptation on the metal anode surface
[68][66]. It causes a decrease in current generation at the initial stage of the PMFC operation, which is explained by the lower biocompatibility of stainless steel to microorganisms. Moreover, metals are subject to corrosion processes
[66][64] and have a high cost, thus limiting their use in PMFC development.
The geometric area of the electrodes affects the output of electricity—the larger the area, the more contact there is for electroactive microorganisms, which leads to an increase in current density
[69][67]. In turn, graphite electrodes (felt/fiber) have a developed surface that promotes the adhesion of microorganisms and the sorption of organic compounds. This material is not subject to corrosion; therefore, it is promising for the creation of PMFCs
[70][68]. The addition of granular graphite or activated carbon to the surface of the anode improves the adsorption of organic compounds and increases the specific surface area for colonization via bacteria. Electrode modification is used to improve the producible power of bioelectrochemical systems, which is described in detail in recent articles
[71,72,73,74,75][69][70][71][72][73]. The use of carbon materials produced from crop waste is also promising in this field
[76][74].
Thus, the choice of electrode material is the key element determining the efficiency of the entire PMFC system. Existing materials can be modified to reduce their internal resistance in order to increase the current output and power.
2.3. Application of Proton Exchange Membranes in PMFC System
Various PMFC configurations have been developed so far: sediment PMFCs, constructed-wetland MFCs, tubular PMFCs, floating-treatment wetland MFCs, flat plate PMFCs, and power-generating trees. The advantages and disadvantages of each model are detailed in the review
[24][75]. One of the components of bioelectrochemical systems for power generation is a proton exchange membrane, which allows the improvement of charge segregation and power performance
[77][76]. The most preferred proton exchange membrane is Nafion, but its use in BES significantly (by 40%) increases the cost of the device
[78][77]. Thus, the search for new membranes that will have a lower cost and provide high stability and efficiency in BES is currently underway.
In
[79][78], modified Nafion 117 proton exchange membranes were tested. The modification included the treatment of the membrane with solutions of polyvinylidene difluoride (PVDF) and sulfonated PVDF with the addition of silicon oxide (SiO
2). The third modification involved the polymerization of a Nafion membrane in a methyl methacrylate (MMA) solution with the addition of sodium sulfite as an initiator. According to the results obtained, all three methods increase the power generation parameters of MFC systems. The highest increase in current density, from 0.81 mA/m
2 to 18.82 mA/m
2, was demonstrated using the modification of Nafion with MMA.
In
[80][79], a proton exchange membrane based on agar and polyvinyl alcohol (PVA) with the addition of vermiculite nanoparticles was tested. According to the results obtained, the proton exchange properties of the tested membranes were 216% higher than those of the commercial Nafion membrane. In addition, the MFC current density increased (from 605 mA/m
2 to 1515 mA/m
2) when agar and PVA-based membranes were used. A low cost and environmental safety, in combination with the increased efficiency of MFC energy generation, allow the use of agar and PVA-based membranes as an alternative to expensive Nafion membranes.
Ceramic membranes based on clay, bentonite, coal ash, Na
2CO
3, Na
2SiO
3, and H
3BO
3 were considered in
[81][80]. The use of hybrid ceramic membranes with the addition of different compounds contributed to the increase in PMFC power density by 78% (up to 22.38 mW/m
2) compared to the control (100% clay membrane). There was a decrease in internal resistance from 346 Ω (control) to 234 Ω. The addition of bentonite, coal ash, Na
2CO
3, Na
2SiO
3, and H
3BO
3 improved the membrane’s cation transport, reducing oxygen diffusion to the anode chamber. The membrane demonstrated high stability during 6 months of PMFC operation. In addition, the ceramic membrane is significantly cheaper than the Nafion membrane.
Thus, one of the important aspects of PMFC operation, power increase, and internal resistance reduction is the use of proton exchange membranes. At the same time, for the commercialization of PMFC systems, it is necessary to take into account the cost of the production of such membranes and the expenses associated with the complication of the design when using membranes.
2.4. The Influence of Environmental Factors on the Electricity Generation in a PMFC
The metabolic activity of exoelectrogenic microorganisms, which play an important role in BES functioning and electricity generation, depends on the temperature, the pH, and the rate of organic substrates’ receipt. Thus, the work
[82][81] showed that, when the air temperature rises to 30 °C, the voltage of the bioelectrochemical system increases from 100 to 150 mV, which may be due to an increase in the metabolic rate of exoelectrogenic microorganisms. The pH value affects the development of microorganisms. pH of 6–9 is mostly suitable for the functioning of BES
[83][82]. The power decreases to 158 mW/m
2 at a pH value of 6.0 for the MFC system
[84][83], while the power value is 600 mW/m
2 at a pH of 8.0. The inhibition of the metabolic activity of exoelectrogenic microorganisms is observed with a decrease in pH, which contributes to a decrease in the BES power
[85][84].
Periodic watering is necessary for the normal functioning of plants since soil moisture affects the generated potential in a PMFC system. The article
[86][85] states that, in the absence of irrigation, the soil dries up, which leads to a two-fold decrease in the PMFC potential, but after watering (60–70% of the soil moisture capacity), the potential is restored. Thus, energy generation changes depending on the time of day
[87][86]. An increase in electrogenic activity is observed after sunrise due to the launch of photosynthesis processes, the peak of which is observed from 14 to 15 h. Depending on the system under study, the open circuit potential is 600–700 mV at the specified time. Then, the photosynthetic activity of plants decreases at nightfall, which leads to a decrease in electricity generation to 300–400 mV.
The rate of photosynthesis is affected by the concentration of carbon dioxide in the atmosphere
[88][87]. The trend towards carbon dioxide emissions increases every year and is 390 ppmv, according to the latest data (mass fractions of a percent per volume), which is 30% more than the CO
2 concentration in the early twentieth century
[89][88]. The increasing CO
2 concentration and climate warming significantly affect plant growth
[90][89]. The work
[91][90], using agricultural plants (
Saccharum officinarum and
Sorghum bicolor), showed that the rate of photosynthesis grows significantly with an increase in the CO
2 concentration, which in theory can have a positive effect on the power produced via a PMFC. It should be noted that plants with the C
3 and C
4 types of photosynthesis react differently to an increase in the carbon–acid gas concentration. C
4 plants attach CO
2 to phosphoenolpyruvate
[86][85], resulting in the formation of oxalic acid containing four carbon atoms. The photosynthesis efficiency of C
4 plants is significantly higher since the C
4 pathway is an extra pump that supplies additional portions of CO
2, increasing its concentration in the plant since the CO
2 concentration in the assimilation chamber is lower than in the air, which is a limiting factor of photosynthesis.
It should be noted that the countries with warm climates and high solar insolation, as well as “green roofs” cities, have the greatest potential for the PMFC technology’s implementation to reduce the concentration of carbon dioxide in the air
[92][91].