Graphene as Thinnest Coating on Copper Electrodes in Microbial Methanol Fuel Cells.

Dehydrogenation of methanol (CH3OH) into direct current (DC) in fuel cells can be a potential energy conversion technology. However, their development is currently hampered by the high cost of electrocatalysts based on platinum and palladium, slow kinetics, the formation of carbon monoxide intermediates, and the requirement for high temperatures. Here, we report the use of graphene layers (GL) for generating DC electricity from microbially driven methanol dehydrogenation on underlying copper (Cu) surfaces. Genetically tractable Rhodobacter sphaeroides 2.4.1 (Rsp), a nonarchetypical methylotroph, was used for dehydrogenating methanol at the GL-Cu surfaces. We use electrochemical methods, microscopy, and spectroscopy methods to assess the effects of GL on methanol dehydrogenation by Rsp cells. The GL-Cu offers a 5-fold higher power density and 4-fold higher current density compared to bare Cu. The GL lowers charge transfer resistance to methanol dehydrogenation by 4 orders of magnitude by mitigating issues related to pitting corrosion of underlying Cu surfaces. The presented approach for catalyst-free methanol dehydrogenation on copper electrodes can improve the overall sustainability of fuel cell technologies.

Oxygen Reduction Reaction with Manganese Oxide Nanospheres in Microbial Fuel Cells.

Operating microbial fuel cells (MFCs) under extreme pH conditions offers a substantial benefit. Acidic conditions suppress the growth of undesirable methanogens and increase redox potential for oxygen reduction reactions (ORRs), and alkaline conditions increase the electrocatalytic activity. However, operating any fuel cells, including MFCs, is difficult under such extreme pH conditions. Here, we demonstrate a pH-universal ORR ink based on hollow nanospheres of manganese oxide (h-Mn3O4) anchored with multiwalled carbon nanotubes (MWCNTs) on planar and porous forms of carbon electrodes in MFCs (pH = 3-11). Nanospheres of h-Mn3O4 (diameter ∼ 31 nm, shell thickness ∼ 7 nm) on a glassy carbon electrode yielded a highly reproducible ORR activity at pH 3 and 10, based on rotating disk electrode (RDE) tests. A phenomenal ORR performance and long-term stability (∼106 days) of the ink were also observed with four different porous cathodes (carbon cloth, carbon nanofoam paper, reticulated vitreous carbon, and graphite felt) in MFCs. The ink reduced the charge transfer resistance (R ct) to the ORR by 100-fold and 45-fold under the alkaline and acidic conditions, respectively. The current study promotes ORR activity and subsequently the MFC operations under a wide range of pH conditions, including acidic and basic conditions.

Electricity from methane by Methylococcus capsulatus (Bath) and Methylosinus trichosporium OB3b.

Given the difficulties valorizing methane (CH4) via catalytic routes, this study explores use of CH4-oxidizing bacteria ("methanotrophs") for generating electricity directly from CH4. A preconditioned methanotrophic biofilm on 3D nickel foam with reduced graphene oxide (rGO/Ni) was used as the anode in two-compartment microbial fuel cells (MFCs). This study demonstrates a proof of concept for turning CH4 into electricity by two model methanotrophs including Methylosinus trichosposium OB3b and Methylococcus capsulatus (Bath). Both OB3b (205 mW.m-2) and Bath (110 mW.m-2) strains yielded a higher electricity from CH4 when grown on rGO/Ni compared to graphite felt electrodes. Based on electrochemistry tests, molecular dynamics simulations, genome annotations and interaction analysis, a mechanistic understanding of reasons behind enhanced performance of methanotrophs grown on rGO/Ni are presented.

Valorization of methane from environmental engineering applications: A critical review.

Wastewater and waste management sectors alone account for 18% of the anthropogenic methane (CH4) emissions. This study presents a critical overview of methanotrophs ("methane oxidizing microorganisms") for valorizing typically discarded CH4 from environmental engineering applications, focusing on wastewater treatment plants. Methanotrophs can convert CH4 into valuable bioproducts including chemicals, biodiesel, DC electricity, polymers, and S-layers, all under ambient conditions. As discarded CH4 and its oxidation products can also be used as a carbon source in nitrification and annamox processes. Here we discuss modes of CH4 assimilation by methanotrophs in both natural and engineered systems. We also highlight the technical challenges and technological breakthroughs needed to enable targeted CH4 oxidation in wastewater treatment plants.

Vitamin-C-enabled reduced graphene oxide chemistry for tuning biofilm phenotypes of methylotrophs on nickel electrodes in microbial fuel cells.

This study reports the use of multi-layered reduced graphene oxide (rGO) coating on porous nickel foam (NF) electrodes for enhancing biofilm growth of Rhodobacter Sphaeroides spp fed with methanol in microbial fuel cells (CH3OH-MFCs). Electrochemical methods were used to assess the methylotrophic activity on rGO/NF electrodes. The power density and current density offered by rGO/NF (1200 mW m-2 and 680 mA m-2) were 220-fold and 540-fold higher compared to bare NF (5.50 mW m-2 and 1.26 mA m-2), respectively. Electrochemical impedance spectroscopy results show that rGO/NF suppresses charge transfer resistance to CH3OH oxidation by 40-fold compared to the control. This improved performance is due to the ability of rGO coatings to decrease the wetting contact angle (improve the hydrophilicity) of NF from 1280 to 00. A preliminary cost analysis was carried out to assess the viability of rGO/NF electrodes via vitamin-C-enabled graphene oxide chemistry for CH3OH-MFCs applications.