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Article

Sustainable Energy from Pickled Chili Waste in Microbial Fuel Cells

by
Rojas-Flores Segundo
1,*,
De La Cruz-Noriega Magaly
1,
Nélida Milly Otiniano
1,
Nancy Soto-Deza
1,
Nicole Terrones-Rodriguez
1,
De La Cruz-Cerquin Mayra
1,
Cabanillas-Chirinos Luis
2 and
Luis M. Angelats-Silva
3
1
Institutos y Centros de Investigación de la Universidad Cesar Vallejo, Universidad Cesar Vallejo, Trujillo 13001, Peru
2
Investigación Formativa e Integridad Científica, Universidad César Vallejo, Trujillo 13001, Peru
3
Laboratorio de Investigación Multidisciplinaria, Universidad Privada Antenor Orrego, Trujillo 13008, Peru
*
Author to whom correspondence should be addressed.
Processes 2024, 12(9), 2028; https://doi.org/10.3390/pr12092028
Submission received: 19 June 2024 / Revised: 26 July 2024 / Accepted: 15 August 2024 / Published: 20 September 2024
(This article belongs to the Special Issue Agricultural and Industrial Waste Recovery Technology and Process Optimization)
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Abstract

:
The amount of waste from agriculture has significantly increased in recent decades due to the growing demand for food. Meanwhile, providing electricity to remote areas remains a challenge due to the high installation costs. Single-chamber fuel cells offer a promising solution as they can effectively generate electric power and treat organic waste. For this reason, the main objective of this research is to utilize pickled chili waste as fuel in SC-MFCs (single-chamber fuel cells), using carbon and zinc electrodes to assess its potential as a sustainable alternative fuel source. The fuel cells exhibited a maximum electric current and voltage of 5.565 ± 0.182 mA with 0.963 ± 0.033 V of voltage, respectively, with a substrate electrical conductivity of 113.526 ± 6.154 mS/cm with a pH of 6.62 ± 0.42 on the twelfth day. The internal resistance measured was 46.582 ± 6.845 Ω, and the maximum power density reached 148.128 ± 8.914 mW/cm2 at a current density of 3.657 A/cm2. Additionally, the microorganisms Pseudomonas taiwanensis and Candida parapsilosis were identified with 100% identity in the anode electrode. This study demonstrates that pickled chili residues can successfully generate bioelectricity and light an LED bulb connected to MFCs in series with a voltage of 2.67 V.

1. Introduction

The excessive energy demand that the world faces today due to the overuse of usual energy sources (coal, oil, gas, gasoline, etc.) to satisfy the requirements of urbanization and industrialization in recent decades has generated significant problems [1,2]. The current requirements for preserving the environment and human health have become a crisis [3,4]. Technological and population advancements continue to increase and aggravate the need to cover the current energy requirements [5]. On the other hand, the development of humanity has generated an increase in the demand for food, which has caused agroiokustry companies to make significant investments to increase food production [6]. This accelerated food production has increased waste during harvesting and the consumption of fruit and vegetables [7]. It has been reported that approximately 998 million tons of agricultural waste is produced worldwide; for example, it has been reported that 120, 529, 279, and 300 tons of rice husks, wheat straw, sugarcane bagasse, and corn cobs are discarded annually [8,9].
An innovative solution that has been intensively investigated in the last two decades is microbial fuel cells (MFCs) [10]. MFCs are a way for microbes present in waste as substrates (fuel) to be converted from organic matter into electrical energy, which originates through the generation of electrons that travel from the anodic chamber to the cathodic chamber through an external circuit [11,12,13]. This technology is based on the electrogenic oxidation process of different wastes used as substrates, which occurs in the anodic chamber where electrons and protons are generated by microorganisms [14,15]. This technology provides us with a sustainable development solution for electrical energy production, whereby environmental pollutants are transformed into usable products for society [16]. For example, Dragon fruit waste was used as fuel in SC-MFCs, where they managed to produce maximum levels of V (voltage) and I (electrical current) of 0.46 ± 0.03 V and 2.86 ± 0.07 mA, operating at a pH of 4.22 ± 0.09 with an Rint. (internal resistance) of 75.58 ± 5.89 Ω [17]. Zafar et al. (2023) used solid fruit waste as fuel in their MFCs, generating voltage peaks of 641 mV with a power density of 221 mW/m2, while managing to reduce chemical oxygen demand by 83% [18]. Likewise, Aleid et al. (2023) used fruit waste as a carbon source in single-chamber microbial fuel cells, generating a voltage of 102 mV on the thirteenth day and a power density of 0.060 mW/m2 [19]. Waste from tangerines was also used as fuel in MFCs operating for 30 days, with its maximum peak generation of voltage (1.191 ± 0.035 V) and electrical current (1.43973 ± 0.05568 mA) occurring on the 17th day, showing an Rint. of 65.378 ± 1.967 Ω [20].
In Peru, the production of pickled chili (Capsicum baccatum or Capsicum microcarpum) is used in a variety of traditional foods, and due to its great success, it has begun to be in demand internationally, a demand that has generated an increase in production in recent years [21,22]. It has been reported that Peru produces an average of 30 tons/hectares in each harvest, and in 2018, 5017 hectares were harvested, with an annual demand of 17 thousand tons per year and an export of 57% [23]. This high demand is due to the protein compounds such as calcium, phosphorus, iron, zinc, and vitamins (A, C, and B1) contained in the vegetable [24,25]. However, Peru is not the only producer of this vegetable; for example, Mexico leads exports with 1.007 million tons produced, covering 21% of world demand. Spain and the Netherlands are also some of the most prominent producers worldwide, estimating a growth of 7% annually in the demand for this vegetable [26,27]. However, there are no reports on the use of pickled chili waste in SC-MFCs as a potential alternative candidate for use in the sustainable generation of electrical energy; this article will be the first such report.
The objective of this research is to observe the potential of pickled chili as a generative source of electrical energy, using it as fuel in single-chamber MFCs. The parameters of power density (PD), current density (CD), electric current (I), electrical conductivity (EC), voltage, chemical oxygen demand (COD), oxidation–reduction potential (ORP), pH, and internal resistance (Rint.) of the MFCs will be monitored. Anodic microbes of biofilm from the MFCs will also be molecularly identified. This research presents the first report on using pickled chili waste as fuel to generate electrical energy sustainably with the environment unaffected. The companies that harvest these products will benefit shortly when they can scale to larger sizes because they can generate their electricity using their waste.

2. Materials and Methods

  • Manufacturing of the anode electrode
Three circular electrodes made of granulated activated carbon (GAC) were carefully fabricated, each weighing 26.00 ± 2.5 g, with a diameter of 10.6 ± 1.2 cm and a thickness of 0.5 ± 0.1 cm. These electrodes were then connected to a 1 mm thick copper wire. The process started with 200 g of GAC (plate number 1) being ground to a fine powder and continued with a mixture of 50 g of sucrose and 60 mL of distilled water. This was thoroughly mixed to ensure a uniform blend. A circular mold measuring 10.8 cm in diameter and 1.1 cm thick was carefully prepared and covered with aluminum foil. The mold was then put into an electric oven for 30 min at a temperature of 350 °C.
b.
Preparation of the single-chamber fuel cells
Polyethylene was used in the shape of a rectangular prism as the MFC; a circular hole was made on one of the faces to place the cathode electrode (zinc), which had an area of 230 cm2, and the carbon anode electrode was placed in the center of the container, which had an area of 105 cm2. The proton exchange membrane/Nafion 117 (Wilmington, DE, USA) was attached to the cathode electrode, and, using an external resistance of 100 Ω, the MFC circuit was made (Figure 1). Three MFCs were made in total.
c.
Obtaining samples used as substrates
The substrate was collected from waste from Huanchaco, Trujillo, La Libertad, Peru. Carefully selected samples from the soil were taken to the laboratory at Cesar Vallejo University, which is a key player in our research. The 3 kg of pickled chili residues collected was washed several times to remove all impurities acquired from the environment. Then, the residues were left to dry at 28 ± 1 °C for 48 h. Finally, with the help of an extractor, a liquid solution of 950 mL was obtained. This solution was used as a substrate in the MFCs.
d.
Obtaining the parameters of the SC-MFCs
The electrical values of voltage and current were obtained from a digital multimeter (830-Truper MUT, Mexico, Jilotepec), using an external resistance of approximately 100 Ω. The COD parameters were obtained using the closed reflux colorimetric method [28]. A multimeter (HI98194) was also used to obtain the ORP, pH, and EC parameters. The Rint. was calculated using Ohm’s law and an energy sensor (±1000 mA and ±30 V—Vernier). The PD and CD values were calculated using the formulas PD = V2cell/(Rext.A) and CD = Vcell/(Rext.A), where Vcell is the voltage of the MFC and Rext takes the values used in previous work [28].
e.
Molecular process
Microbiological techniques of swabbing and streaking on plates with nutrient agar and Mac Conkey were used to isolate the energy-generating bacteria. These were incubated at 36 °C × 48 h, where colonies developed on the surface of the agar. The isolated colonies were classified macroscopically and microscopically before being replicated in nutrient agar to be sent to the external laboratory ECOBOTECH LAB SAC, where molecular characterization was carried out by studying the 16S rRNA gene.

3. Results and Discussion

The voltage values increased from the first day (0.103 ± 0.005 V) to the twelfth day (0.963 ± 0.033 V), and then a decrease was observed until the thirtieth day (0.546 ± 0.105 V), as seen in Figure 2a. Voltage values show an increase in the first days because the organic matter is oxidized through the metabolism of the microbes present in the used substrate, producing electrons and protons [29,30]. However, there are potential losses in this process primarily due to thermodynamics due to reduction–oxidation reactions [31]. By comparison, the decrease in voltage values is due to a loss of organic matter, which, by not recirculating or being changed, loses the ability to provide new compounds to generate new oxidation reactions [32]. Banana peels have been used as substrates in SC-MFCs, generating a maximum voltage of 602 ± 1.5 mV; as their substrates were not recharged, the voltage did not recover its initial maximum value, and the increase in voltage initially was due to the growth of indigenous microbes [33]. Lemon peels have also been used as fuel in MFCs with stainless-steel mesh electrodes, showing a voltage of 792.33 ± 1.53 mV; their decrease in voltage values was because the microorganisms consumed the entire carbon source present in the waste [34]. Yaakop et al. (2023) used food waste from a university campus kitchen as a substrate in SC- MFCs with carbon electrodes, generating 110 mV; they mentioned that through introducing inoculum again, the MFC recovered its voltage values but not its initial value [35]. The electric current showed a value of 0.860 ± 0.004 mA on the first day, then increased until the twelfth day (5.565 ± 0.182 mA), and then decreased until the last day (3.033 ± 0.891 mA) of monitoring; see Figure 2b. The generation of electrons depends on the ability of the microbes to generate them by metabolizing and by releasing electrons that are adhered through the anodic biofilms to the same electrode, which generate an electric current through their ability to transport these electrons through the external circuit to the cathodic electrode [36,37]. Latuihamallo et al. (2023) used vegetable waste as fuel in SC-MFCs with aluminum electrodes, generating a maximum electrical current of 9.48 mA on the seventh day. The production of electrons was due to two microbial groups (the fermentative group and the electrifying microbial group), where those of the fermentative group had the function of converting glucose into short-chain organic acids (hydrogen and carbon dioxide), and the electrifying group acquired electrons from the redox reactions that occurred on the anode surface [38]. Coriander waste has been used as a substrate in SC-MFCs with Zn and Cu electrodes, generating electric current peaks of 2.287 ± 0.072 mA on the 10th day, where adequate biofilm formation was found to optimize electron adhesion, improving the MFC’s effectiveness [39].
Figure 3a shows the monitored pH values, observing an increase from the modernly acidic level to slightly alkaline, with an optimal pH for the MFCs of 6.62 ± 0.42 on the twelfth day. Banerjee et al. (2023), in their research on the influence of pH in microbial fuel cells, mention that excessively acidic or alkaline waste inhibits the activity of microbes in the anodic chamber and that the effectiveness of microbial fuel cell technology is determined by the kinetics and speed of the biochemical reactions that also occur in the anodic chamber [40]. Gul et al. (2021) mention that potential losses are also due to differences in pH when microbial fuel cells operate, with the acidity of the electrolyte influencing the performance of electron-generating microbes in the MFC [41]. Kebaili et al. (2021) used lychee fruit waste as a substrate in their MFCs, managing to generate voltage peaks of 140 mV using graphite electrodes with an operating pH of 4; they mention that electroactive bacteria produced a more significant number of electrons in anaerobiosis [42]. Potato, tomato, and pineapple waste have been used as substrates in MFCs, generating maximum voltage values of 0.348 ± 0.003, 0.318 ± 0.013, and 0.432 ± 0.013 V, respectively, with the researchers mentioning that the pH values are specific for each type of substrate because waste has microorganisms with different nutrients and these microorganisms grow at specific pH values [43]. The EC values increased from the first day (47.142 ± 1.732 mS/cm) to the twelfth day (113.526 ± 6.154 mS/cm), and then showed continuous decreases until the thirtieth day (63.044 ± 9.735 mS/cm), as shown in Figure 3b. The low conductivity of the substrates in MFCs directly affects the performance values (power density) of the cells, demonstrating that values greater than 30 mS/cm are considered optimal [44]. Showing that the relationship between electrical conductivity and ionic strength is essential for the generation of desirable electricity in MFCs; an explanation accepted by researchers is that a low ionic strength will limit the transport of ions and generate an Ohmic resistance in the cells and that this resistance will have approximately 60% of the total internal resistance of the MFC [45]. In their research, Obileke et al. (2021) reported that the presence of glucose in waste used as substrates improves the values of electrical conductivity, thus improving the power density values in MFCs [46]. Dwivedi et al. (2022) reported that a decrease in resistance can be achieved by improving the electrolytic substrate’s electrical conductivity or the distance between the anodic and cathodic electrodes [47]. COD values decreased by 84.88% (124.35 ± 18.61 mg/L) compared to the initial value (802.38 ± 5.52 mg/L); see Figure 3c. Barakat et al. (2024) managed to reduce the amount of COD by 85% and generate maximum values of 0.75 V using mango waste as a substrate, deducing that the decrease in COD can be attributed to the metabolic activity of the microbes during the operation of the MFCs [48]. Zonfa et al. (2023) used cheese whey as fuel in their MFC, managing to reduce the COD by 86 ± 8% and generating a maximum electrical current of 1.6 mA; they mention that, although the organic matter decreased the current values after 509 h, it was zero. [49]. Adegunloye et al. (2023) used cow manure as a substrate in their MFC, managing to reduce the COD by approximately 50%, determining that temperature is an essential factor in the reduction in COD and the generation of voltage and electric current due to the dependence of microbial activity on temperature [50]. The ORP values increased progressively from the first day (155.857 ± 1.210 mV) to the twelfth (406.112 ± 10.412 mV) day, and then, successive losses were observed until the thirtieth day (69.439 ± 18.519 mV); see Figure 3d. The positive ORP values show that the system is found in an oxidative environment, where the organic matter present in the substrate was oxidized by anaerobic microbes generating electrons and protons [51]. It has been reported that redox power values greater than 100 mV ORP should be considered anaerobic environments, while ORP values less than 100 mV should be considered aerobic [52]. Agüero et al. (2023) managed to generate maximum ORP values of 378 mV; they mention that an oxidizing environment facilitates electroactive species to thrive, resulting in a more significant number of electrons favoring electrical energy generation [53].
The maximum power density (PDmax.) observed was 148.128 ± 8.914 mW/cm2 for a current density (CD) of 3.657 A/cm2 with a peak voltage of 834.928 ± 16.847 V; Figure 4a. Sayed et al. (2024) mention in their research that increasing the concentration of organic matter in a substrate tends to increase the power density values of the MFC because it serves as fuel for the microbes that metabolize the compounds in the anodic chamber. However, this increase in organic matter is up to the saturation point of the electrode capacity; if that saturation point is passed, the PD values begin to decrease [54]. Yaqoob et al. (2022) used potato waste as a substrate in their MFCs, managing to generate power density peaks of 2.3 × 10−5 mW/m2. They mention that the PD values they obtained were due to the oxygen present in the substrate, which helped promote kinetic and cathodic reactions, and this led to stabilizing the power generation. They also mention that the equity of internal and external resistance stabilizes the PD values [55]. Kumar et al. (2021) showed a power density of 2.23 mW/m2 using tomato waste as a substrate in their single-chamber microbial fuel cells, mentioning that the nature of each electrode used in the MFCs has importance in the obtained PD values, as well as the electrode size, which should be considered because this is where the biofilm adheres [56]. Avocado waste has also been used as substrates in single-chamber MFCs, generating a maximum power density of 566.80 ± 13.48 mW/cm2; the researchers mention that the amount of electrogenic electron-generating microorganisms enhances the PD values but that when the choice of electrodes is not appropriate, the electrons generated will not be fully used [57].
A linear adjustment of Ohm’s law (V = IR) was used to obtain the value of the Rint of the MFC, where the values of the electric potential were adjusted to the “y” axis and those of the electric current to the “x” axis, whose slope is the value of the internal resistance (Rint.). The value of the Rint. found was 46.582 ± 6.845 Ω; see Figure 4b. Lawson et al. (2020), in their MFC using wastewater, calculated an internal resistance of 62 ± 4 Ω, mentioning that the Rint of the MFC depends on several variables, but mainly on the substrate, biofilm, and electrode used [58]. The use of papaya waste as a substrate in MFCs with zinc and copper electrodes showed an Rint. of 195.2 ± 2.14 Ω, with the researchers deducing that the decomposition of the organic matter used as a substrate depended on the resistance of the MFCs, because when an Rint is shown at low temperatures, electrons can be transported more freely, generating higher electrical current values, which may affect the anodic biofilm’s microorganisms [59]. Likewise, Rincón et al. (2022) managed to calculate an Rint. of 580.99 Ω using banana waste as a substrate in their single-chamber MFCs; they mention that the presence of inorganic salts in the substrate improves electron transfer by improving the output potential, reducing the internal resistance of the MFC and shortening the time of treatment processing for the organic substances [60]. In another study, food waste in MFCs has shown an internal resistance of 813.78 Ω, with the researchers mentioning that to obtain stability of electrical values, the internal and external resistances in an MFC must be equal for stable electron transport [61].
The extraction of the genetic material was carried out at the ECOBIOTECH LA SAC Laboratory using MEGA bioinformatics software. X was used for sequencing, and the bases of the genomic material were compared with the BLAST bioinformatics program to obtain the microorganisms’ identity percentage. Two microorganisms were identified from the anodic chamber with a percentage of identity of 100% corresponding to Pseudomonas taiwanensis and 100% to the species Candida parapsilosis (Table 1). The results obtained in the present investigation coincide with those reported by Benites et al. (2020), who observed more excellent voltage production with Zn-Cu electrodes, reaching a maximum peak of 0.761 volts, when using a culture of Saccharomyces cerevisiae [62]. It has also been reported that using redox mediators such as phenanthrenequinone facilitates the transfer of electrons to the electrode through the cell membrane and the yeast’s cell wall without decreasing these yeasts’ viability [63]. On the other hand, it was found that species of the genus Pseudomonas that were isolated from the MFCs gave maximum values of 6.04414 ± 0.2145 mA and 0.77328 ± 0.213 V for current and voltage [64]. This is supported by the fact that the genus Pseudomonas produces the pigment pyocyanin, which is responsible for its electrochemical activity [65]. The microbial fuel cells used in this research were connected in series, showing a voltage of 2.67 V, enough to light an LED light bulb; see Figure 5. Effectively using this technology will shortly allow us to bring these results to the laboratory and the field, where we can use it to benefit the environment and society.

4. Conclusions

Bioelectricity was successfully generated using pickled chili waste as a substrate, which will provide a new opportunity for the potential use of this waste in the field of microbial fuel cells, offering a novel way to generate sustainable electric current and ecosystem-friendly alternatives. The microbial fuel cells showed maximum values of 0.963 V for voltage and 5.565 mA for electric current. These values are influenced by the pH of the environment in which the microorganisms metabolize, with the optimal pH being reported as 6.62. Additionally, electrical conductivity was measured at 113.526 mS/cm, and the oxidation–reduction potential (ORP) was 406.112 mV.
The study found that microorganisms in the substrate exhibited excellent electron generation, resulting in the flow of electrons with low resistance (46.582 ± 6.845 Ω). Furthermore, there was an 84.88% decrease in chemical oxygen demand (COD), indicating a substantial reduction in organic matter by the end of the MFCs’ operational period. The maximum power density observed was 148.128 mW/cm2, with a current density of 3.657 A/cm2 and a maximum voltage of 834.928 V. Microbial analysis revealed the presence of Pseudomonas taiwanensis and Candida parapsilosis species, which adhered to the biofilm of the anode electrode. Finally, the study demonstrated the capability of the MFCs to generate bioelectricity by connecting three MFCs in series, successfully lighting an LED bulb with a potential of 2.67 V.
In future studies, it is recommended to use biocatalysts (microorganisms) to improve the performance of MFCs. Additionally, incorporating metal nanoparticles into the electrodes can help enhance electron transport efficiency. Standardizing the pH value to the optimal level identified in this research is also advisable. Using an Arduino equipped with appropriate chemical compounds can help ensure the parameters influencing MFC performance are adequately standardized. It is important to consider the distance between the electrodes, as research has shown that this factor significantly influences power density values.

Author Contributions

Conceptualization, R.-F.S.; methodology, C.-C.L.; validation, N.M.O. and N.S.-D.; formal analysis, R.-F.S. and D.L.C.-N.M.; investigation, R.-F.S. and D.L.C.-C.M.; data curation, D.L.C.-N.M. and L.M.A.-S.; writing—original draft preparation, N.T.-R. and C.-C.L.; writing—review and editing, R.-F.S.; project administration, R.-F.S. and C.-C.L. All authors have read and agreed to the published version of the manuscript.

Funding

This research was financed by the Universidad Cesar Vallejo, project code No. P-2023-113.

Data Availability Statement

The original contributions presented in the study are included in the article, further inquiries can be directed to the corresponding author.

Conflicts of Interest

The authors declare no conflicts of interest.

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Processes 12 02028 g001
Figure 1. Schematization of the microbial fuel cell design.
Figure 1. Schematization of the microbial fuel cell design.
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Figure 2. Values obtained from (a) voltage vs. time and (b) current vs. time.
Figure 2. Values obtained from (a) voltage vs. time and (b) current vs. time.
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Figure 3. Obtaining parameters of (a) pH, (b) conductivity, (c) COD, and (d) ORP.
Figure 3. Obtaining parameters of (a) pH, (b) conductivity, (c) COD, and (d) ORP.
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Figure 4. Obtaining parameters of (a) PD vs. CD and (b) Rint.
Figure 4. Obtaining parameters of (a) PD vs. CD and (b) Rint.
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Figure 5. Recovery scheme for pickled waste for the generation of bioelectricity.
Figure 5. Recovery scheme for pickled waste for the generation of bioelectricity.
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Table 1. Electrogenic microorganisms from the MFC anode containing pickled chili residues.
Table 1. Electrogenic microorganisms from the MFC anode containing pickled chili residues.
Identified SpeciespbBLAST
Identity (%)Accession Number
Pseudomonas taiwanensis1443100.00%NR_116172.1
Candida parapsilosis523100.00%NR_130673.1
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Segundo, R.-F.; Magaly, D.L.C.-N.; Otiniano, N.M.; Soto-Deza, N.; Terrones-Rodriguez, N.; Mayra, D.L.C.-C.; Luis, C.-C.; Angelats-Silva, L.M. Sustainable Energy from Pickled Chili Waste in Microbial Fuel Cells. Processes 2024, 12, 2028. https://doi.org/10.3390/pr12092028

AMA Style

Segundo R-F, Magaly DLC-N, Otiniano NM, Soto-Deza N, Terrones-Rodriguez N, Mayra DLC-C, Luis C-C, Angelats-Silva LM. Sustainable Energy from Pickled Chili Waste in Microbial Fuel Cells. Processes. 2024; 12(9):2028. https://doi.org/10.3390/pr12092028

Chicago/Turabian Style

Segundo, Rojas-Flores, De La Cruz-Noriega Magaly, Nélida Milly Otiniano, Nancy Soto-Deza, Nicole Terrones-Rodriguez, De La Cruz-Cerquin Mayra, Cabanillas-Chirinos Luis, and Luis M. Angelats-Silva. 2024. "Sustainable Energy from Pickled Chili Waste in Microbial Fuel Cells" Processes 12, no. 9: 2028. https://doi.org/10.3390/pr12092028

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