Carlo Santoro

Microbial fuel cells: From fundamentals to applications. A review

In the past 10–15 years, the microbial fuel cell (MFC) technology has captured the attention of the scientific community for the possibility of transforming organic waste directly into electricity through microbially catalyzed anodic, and microbial/enzymatic/abiotic cathodic electrochemical reactions. In this review, several aspects of the technology are considered. Firstly, a brief history of abiotic to biological fuel cells and subsequently, microbial fuel cells is presented. Secondly, the development of the concept of microbial fuel cell into a wider range of derivative technologies, called bioelectrochemical systems, is described introducing briefly microbial electrolysis cells, microbial desalination cells and microbial electrosynthesis cells. The focus is then shifted to electroactive biofilms and electron transfer mechanisms involved with solid electrodes. Carbonaceous and metallic anode materials are then introduced, followed by an explanation of the electro catalysis of the oxygen reduction reaction and its behavior in neutral media, from recent studies. Cathode catalysts based on carbonaceous, platinum-group metal and platinum-group-metal-free materials are presented, along with membrane materials with a view to future directions. Finally, microbial fuel cell practical implementation, through the utilization of energy output for practical applications, is described.

Cathodic and anodic biofilms in single chamber microbial fuel cells

The oxygen reduction due to microaerophilic biofilms grown on graphite cathodes (biocathodes) in Single Chamber Microbial Fuel Cells (SCMFCs) is proved and analysed in this paper. Pt-free cathode performances are compared with those of different platinum-loaded cathodes, before and after the biofilm growth. Membraneless SCMFCs were operating in batch-mode, filled with wastewater. A substrate (fuel) of sodium acetate (0.03 M) was periodically added and the experiment lasted more than six months. A maximum of power densities, up to 0.5 W m(-2), were reached when biofilms developed on the electrodes and the cathodic potential decreased (open circuit potential of 50-200 mV vs. SHE). The power output was almost constant with an acetate concentration of 0.01-0.05 M and it fell down when the pH of the media exceeded 9.5, independently of the Pt-free/Pt-loading at the cathodes. Current densities varied in the range of 1-5 Am(-2) (cathode area of 5 cm(2)). Quasi-stationary polarization curves performed with a three-electrode configuration on cathodic and anodic electrodes showed that the anodic overpotential, more than the cathodic one, may limit the current density in the SCMFCs for a long-term operation.

Parameters characterization and optimization of activated carbon (AC) cathodes for microbial fuel cell application.

Activated carbon (AC) is employed as a cost-effective catalyst for cathodic oxygen reduction in microbial fuel cells (MFC). The fabrication protocols of AC-based cathodes are conducted at different applied pressures (175-3500 psi) and treatment temperatures (25-343°C). The effects of those parameters along with changes in the surface morphology and chemistry on the cathode performances are comprehensively examined. The cathodes are tested in a three-electrode setup and explored in single chamber membraneless MFCs (SCMFCs). The results show that the best performance of the AC-based cathode is achieved when a pressure of 1400 psi is applied followed by heat treatment of 150-200°C for 1h. The influence of the applied pressure and the temperature of the heat treatment on the electrodes and SCMFCs is demonstrated as the result of the variation in the transfer resistance, the surface morphology and surface chemistry of the AC-based cathodes tested.

Iron based catalysts from novel low-cost organic precursors for enhanced oxygen reduction reaction in neutral media microbial fuel cells

Two iron-based platinum group metal-free catalysts for the oxygen reduction reaction (ORR) were synthesized from novel and low cost organic precursors named niclosamide and ricobendazole. These catalysts have been characterized, incorporated in a gas diffusional electrode and tested in “clean” conditions as well as in operating microbial fuel cell (MFC) for 32 days. Both catalysts demonstrated unprecedented performance yielding a power density 25% higher than that of platinum (Pt) and roughly 100% higher than activated carbon (AC) used as a control. Durability tests were performed and showed that Pt-based cathodes lost their activity within the first week of operation, reaching the level of the supporting AC-based electrode. Fe–ricobendazole, however, demonstrated the highest performance during the long-term study with a power density of 195 ± 7 μW cm−2 (day 2) that slightly decreased to 186 ± 9 μW cm−2 at day 29. Fe–niclosamide also outperformed Pt and AC but the power density roughly decreased with 20% for the 32 days of the study. Accelerated poisoning test using S2− as pollutant showed high losses in activity for Pt. Fe–niclosamide suffered higher losses compared to Fe–ricobendazole. Importantly, Fe–ricobendazole represents a 55-fold cost reduction compared to platinum.

Double‐Chamber Microbial Fuel Cell with a Non‐Platinum‐Group Metal Fe–N–C Cathode Catalyst

Non-Pt-group metal (non-PGM) materials based on transition metal-nitrogen-carbon (M-N-C) and derived from iron salt and aminoantipyrine (Fe-AAPyr) of mebendazole (Fe-MBZ) were studied for the first time as cathode catalysts in double-chamber microbial fuel cells (DCMFCs). The pH value of the cathode chamber was varied from 6 to 11 to elucidate the activity of those catalysts in acidic to basic conditions. The Fe-AAPyr- and Fe-MBZ-based cathodes were compared to a Pt-based cathode used as a baseline. Pt cathodes performed better at pH 6-7.5 and had similar performances at pH 9 and a substantially lower performance at pH 11 at which Fe-AAPyr and Fe-MBZ demonstrated their best electrocatalytic activity. The power density achieved with Pt constantly decreased from 94-99 μW cm(-2) at pH 6 to 55-57 μW cm(-2) at pH 11. In contrast, the power densities of DCMFs using Fe-AAPyr and Fe-MBZ were 61-68 μW cm(-2) at pH 6, decreased to 51-58 μW cm(-2) at pH 7.5, increased to 65-75 μW cm(-2) at pH 9, and the highest power density was achieved at pH 11 (68-80 μW cm(-2) ). Non-PGM cathode catalysts can be manufactured at the fraction of the cost of the Pt-based ones. The higher performance and lower cost indicates that non-PGM catalysts may be a viable materials choice in large-scale microbial fuel cells.

High catalytic activity and pollutants resistivity using Fe-AAPyr cathode catalyst for microbial fuel cell application.

For the first time, a new generation of innovative non-platinum group metal catalysts based on iron and aminoantipyrine as precursor (Fe-AAPyr) has been utilized in a membraneless single-chamber microbial fuel cell (SCMFC) running on wastewater. Fe-AAPyr was used as an oxygen reduction catalyst in a passive gas-diffusion cathode and implemented in SCMFC design. This catalyst demonstrated better performance than platinum (Pt) during screening in “clean” conditions (PBS), and no degradation in performance during the operation in wastewater. The maximum power density generated by the SCMFC with Fe-AAPyr was 167 ± 6 μW cm−2 and remained stable over 16 days, while SCMFC with Pt decreased to 113 ± 4 μW cm−2 by day 13, achieving similar values of an activated carbon based cathode. The presence of S2− and showed insignificant decrease of ORR activity for the Fe-AAPyr. The reported results clearly demonstrate that Fe-AAPyr can be utilized in MFCs under the harsh conditions of wastewater.

Self-powered supercapacitive microbial fuel cell: The ultimate way of boosting and harvesting power

In this work, for the first time, we demonstrate a supercapacitive microbial fuel cell which integrates the energy harvesting function of a microbial fuel cell (MFC) with the high-power operation of an internal supercapacitor. The pursued strategies are: (i) the increase of the cell voltage by the use of high potential cathodes like bilirubin oxidase (BOx) or iron-aminoantipyrine (Fe-AAPyr); (ii) the use of an additional capacitive electrode (additional electrode, AdE) which is short-circuited with the MFC cathode and coupled with the MFC anode (MFC-AdE). The high working potential of BOx cathode and the low impedances of the additional capacitive electrode and the MFC anode permitted to achieve up to 19 mW (84.4 Wm(-2), 152 Wm(-3)), the highest power value ever reported for MFCs. Exploiting the supercapacitive properties of the MFC electrodes allows the system to be simpler, cheaper and more efficient without additional electronics management added with respect to an MFC/external supercapacitor coupling. The use of the AdE makes it possible to decouple energy and power and to achieve recharge times in the order of few seconds making the system appealing for practical applications.

Influence of anode surface chemistry on microbial fuel cell operation

Self-assembled monolayers (SAMs) modified gold anodes are used in single chamber microbial fuel cells for organic removal and electricity generation. Hydrophilic (N(CH3)3(+), OH, COOH) and hydrophobic (CH3) SAMs are examined for their effect on bacterial attachment, current and power output. The different substratum chemistry affects the community composition of the electrochemically active biofilm formed and thus the current and power output. Of the four SAM-modified anodes tested, N(CH3)3(+) results in the shortest start up time (15 days), highest current achieved (225 μA cm(-2)) and highest MFC power density (40 μW cm(-2)), followed by COOH (150 μA cm(-2) and 37 μW cm(-2)) and OH (83 μA cm(-2) and 27 μW cm(-2)) SAMs. Hydrophobic SAM decreases electrochemically active bacteria attachment and anode performance in comparison to hydrophilic SAMs (CH3 modified anodes 7 μA cm(-2) anodic current and 1.2 μW cm(-2) MFCs power density). A consortium of Clostridia and δ-Proteobacteria is found on all the anode surfaces, suggesting a synergistic cooperation under anodic conditions.

A family of Fe-N-C oxygen reduction electrocatalysts for microbial fuel cell (MFC) application: Relationships between surface chemistry and performances

Graphical abstract Several organic precursors have been used to fabricate Fe-based catalysts using sacrificial support method. Those catalysts were then included in air breathing cathodes for microbial fuel cells working at neutral environment. Electrochemical performances and surface chemistry were measured and related.

Miniaturized supercapacitors: Key materials and structures towards autonomous and sustainable devices and systems

Supercapacitors (SCs) are playing a key role for the development of self-powered and self-sustaining integrated systems for different fields ranging from remote sensing, robotics and medical devices. SC miniaturization and integration into more complex systems that include energy harvesters and functional devices are valuable strategies that address system autonomy. Here, we discuss about novel SC fabrication and integration approaches. Specifically, we report about the results of interdisciplinary activities on the development of thin, flexible SCs by an additive technology based on Supersonic Cluster Beam Deposition (SCBD) to be implemented into supercapacitive electrolyte gated transistors and supercapacitive microbial fuel cells. Such systems integrate at materials level the specific functions of devices, like electric switch or energy harvesting with the reversible energy storage capability. These studies might open new frontiers for the development and application of new multifunction-energy storage elements.