Three-dimensional graphene nanosheets (3D-GNS) were used as cathode catalysts for microbial fuel cells (MFCs) operating in neutral conditions. 3D-GNS catalysts showed high performance towards oxygen electroreduction in neutral media with high current densities and low hydrogen peroxide generation compared to activated carbon (AC). 3D-GNS was incorporated into air-breathing cathodes based on AC with three different loadings (2, 6 and 10 mgcm-2). Performances in MFCs showed that 3D-GNS had the highest performances with power densities of 2.059 ± 0.003 Wm-2, 1.855 ± 0.007 Wm-2 and 1.503 ± 0.005 Wm-2 for loading of 10, 6 and 2 mgcm-2 respectively. Plain AC had the lowest performances (1.017 ± 0.009 Wm-2). The different cathodes were also investigated in supercapacitive MFCs (SC-MFCs). The addition of 3D-GNS decreased the ohmic losses by 14-25%. The decrease in ohmic losses allowed the SC-MFC with 3D-GNS (loading 10 mgcm-2) to have the maximum power (Pmax) of 5.746 ± 0.186 Wm-2. At 5 mA, the SC-MFC featured an apparent capacitive response that increased from 0.027 ± 0.007 F with AC to 0.213 ± 0.026 F with 3D-GNS (loading 2 mgcm-2) and further to 1.817 ± 0.040 F with 3D-GNS (loading 10 mgcm-2).

In this work, four different supercapacitive microbial fuel cells (SC-MFCs) with carbon brush as the anode and an air-breathing cathode with Fe-Aminoantipyrine (Fe-AAPyr) as the catalyst have been investigated using galvanostatic discharges. The maximum power (Pmax) obtained was in the range from 1.7 mW to 1.9 mW for each SC-MFC. This in-series connection of four SC-MFCs almost quadrupled Pmax to an operating voltage of 3025 mV and a Pmax of 8.1 mW, one of the highest power outputs reported in the literature. An additional electrode (AdHER) connected to the anode of the first SC-MFC and placed in the fourth SC-MFC evolved hydrogen. The hydrogen evolution reaction (HER) taking place at the electrode was studied on Pt and two novel platinum group metal-free (PGM-free) catalysts: Fe-Aminoantipyrine (Fe-AAPyr) and Fe-Mebendazole (Fe-MBZ). The amount of H2 produced was estimated using the Faraday law as 0.86 mMd-1cm-2 (0.132 L day-1) for Pt, 0.83 mMd-1cm-2 (0.127 L day-1) for Fe-AAPyr and 0.8 mMd-1cm-2 (0.123 L day-1) for Fe-MBZ. Hydrogen evolution was also detected using gas chromatography. While HER was taking place, galvanostatic discharges were also performed showing simultaneous H2 production and pulsed power generation with no need of external power sources.

The oxygen reduction reaction (ORR) is one of the major factors that is limiting the overall performance output of microbial fuel cells (MFC). In this study, Platinum Group Metal-free (PGM-free) ORR catalysts based on Fe, Co, Ni, Mn and the same precursor (Aminoantipyrine, AAPyr) were synthesized using identical sacrificial support method (SSM). The catalysts were investigated for their electrochemical performance, and then integrated into an air-breathing cathode to be tested in clean environment and in a working microbial fuel cell (MFC). Their performances were also compared to activated carbon (AC) based cathode under similar conditions. Results showed that the addition of Mn, Fe, Co and Ni to AAPyr increased the performances compared to AC. Fe-AAPyr showed the highest open circuit potential (OCP) that was 0.307 ± 0.001 V (vs. Ag/AgCl) and the highest electrocatalytic activity at pH 7.5. On the contrary, AC had an OCP of 0.203 ± 0.002 V (vs. Ag/AgCl) and had the lowest electrochemical activity. In MFC, Fe-AAPyr also had the highest output of 251 ± 2.3 μWcm-2, followed by Co-AAPyr with 196 ± 1.5 μWcm-2, Ni-AAPyr with 171 ± 3.6 μWcm-2, Mn-AAPyr with 160 ± 2.8 μWcm-2 and AC 129 ± 4.2 μWcm-2. The best performing catalyst (Fe-AAPyr) was then tested in MFC with increasing solution conductivity from 12.4 mScm-1 to 63.1 mScm-1. A maximum power density of 482 ± 5 μWcm-2 was obtained with increasing solution conductivity, which is one of the highest values reported in the field.

Iron aminoantipyrine (Fe-AAPyr), graphene nanosheets (GNSs) derived catalysts and their physical mixture Fe-AAPyr-GNS were synthesized and investigated as cathode catalysts for oxygen reduction reaction (ORR) with the activated carbon (AC) as a baseline. Fe-AAPyr catalyst was prepared by Sacrificial Support Method (SSM) with silica as a template and aminoantipyrine (AAPyr) as the organic precursor. 3D-GNS was prepared using modified Hummers method technique. The Oxygen Reduction Reaction (ORR) activity of these catalysts at different loadings was investigated by using rotating ring disk (RRDE) electrode setup in the neutral electrolyte. The performance of the catalysts integrated into air-breathing cathode was also investigated. The co-presence of GNS (2 mg cm-2) and Fe-AAPyr (2 mg cm-2) catalyst within the air-breathing cathode resulted in the higher power generation recorded in MFC of 235 ± 1 μW cm-2. Fe-AAPyr catalyst itself showed high performance (217 ± 1 μW cm-2), higher compared to GNS (150 ± 5 μW cm-2) while AC generated power of roughly 104 μW cm-2.