Sadia Kabir

Air breathing cathodes for Microbial Fuel Cell using Mn-, Fe-, Co- and Ni-containing platinum group metal-free catalysts

Graphical abstract

Three-dimensional graphene nanosheets as cathode catalysts in standard and supercapacitive microbial fuel cell

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).

Co-generation of hydrogen and power/current pulses from supercapacitive MFCs using novel HER iron-based catalysts

Highlights • Supercapacitive MFC boosted up power/current pulses.• In-series connection of 4 microbial fuel cells quadrupled voltage and power output.• Fe-catalysts showed high hydrogen evolution reaction rate in neutral media.• Co-generation of electricity and hydrogen using SC-MFCs is here demonstrated.

Platinum group metal-free NiMo hydrogen oxidation catalysts: high performance and durability in alkaline exchange membrane fuel cells

We introduce a new platinum group metal-free (PGM-free) hydrogen oxidation electrocatalyst with superior performance in anodes of alkaline exchange membrane fuel cells (AEMFCs). A carbon-supported bimetallic nickel–molybdenum catalyst was synthesized by thermal reduction of transition metal precursors on the surface of a carbon support (KetjenBlack 600J). The mass-weighted activity of 4.5 A gMe−1 determined in a liquid electrolyte 0.1 M NaOH using a rotating disk electrode (RDE) technique is comparable to the value reported for Pd/C with a comparable particle size under similar conditions. This NiMo/KB catalyst was integrated in a membrane electrode assembly (MEA) using an alkaline exchange membrane and ionomer. Single AEMFC tests performed in a H2/O2 configuration resulted in a record power density output of 120 mW cm−2 at 0.5 V, the MEA was found to be durable under the conditions of potential hold of 0.7 V for 115 h. For the first time, operando X-ray computed tomography (CT) experiments were performed demonstrating liquid water formation at the PGM-free anode during cell operation, and in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) and X-ray absorption spectroscopy (APXAS) were used to study the role of molybdenum in hydrogen adsorption.

Role of Nitrogen Moieties in N-Doped 3D-Graphene Nanosheets for Oxygen Electroreduction in Acidic and Alkaline Media

This study elucidates the synthesis-structure-property correlations of nitrogen moieties present in nitrogen-functionalized graphene nanomaterials toward oxygen reduction reactions (ORRs) and their electrochemical pathways in acidic and alkaline electrolytes. Porous three-dimensional nitrogen-doped graphene nanosheets (N/3D-GNSs) were fabricated using the sacrificial support method and doped with nitrogen using 10 atom % NH3 under thermal pyrolysis at T = 650, 850, and 1050 °C for evaluating the nitrogen species formed under different temperatures. The abundances of the various nitrogen species formed under pyrolytic conditions were evaluated with X-ray photoelectron spectroscopy. Using rotating ring-disk electrode, we analyzed the role played by the nitrogen moieties influencing the electrochemical activity of the N/3D-GNS supports for oxygen reduction reactions (ORRs) in both acidic and alkaline media. It was demonstrated that the concentrations of the nitrogen moieties: graphitic-N, quaternary, hydrogenated-N (hydrogenated nitrogen combined pyrrolic nitrogen and hydrogenated pyridine) and pyridinic-N varied considerably with pyrolysis temperatures. A decrease in graphitic-N content and an increase in the ratio of hydrogenated-N/pyridinic-N significantly improved the activity of the material. The half-wave and onset potentials as well as the current densities and hydrogen peroxide (H2O2)/(HO2-) yields of the N/3D-GNS materials also varied between acidic and alkaline electrolytes but followed the general trend in terms of pyrolysis temperatures and abundance of the nitrogen moieties. Among the synthesized materials, the 3D-graphene nanosheets that were doped with nitrogen at 850 °C, optimized to have the highest hydrogenated-N and lowest pyridinic-N as well as better catalyst-ionomer integration, showed the highest ORR performance. This strategy for the tunable synthesis of nitrogen-doped graphene materials with controlled nitrogen functionalization offers a platform for developing active supports or catalytic nanomaterials for fuel cell applications.

Enhancement of microbial fuel cell performance by introducing a nano-composite cathode catalyst

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.

Anodic materials for electrooxidation of alcohols in alkaline media

Recent achievements in the development of platinum and platinum group metals (PGMs) electrocatalysts for oxidation of alcohols in alkaline media has been summarized and critically reviewed. The mechanistic aspects of current state-of-the-art mono-, bi- and tri-metallic Pt and Pd based alloys/compounds towards the electrooxidation of alcohols – in particular ethanol, methanol, ethylene glycol and glycerol in alkaline media were discussed in detail. The main emphasis of the present chapter was targeted fig towards elucidating the correlations between structure, chemical composition, and physicochemical properties of the catalysts and their electrochemical activities. Finally, the effect of structure–property relationships towards selectivity and tolerance towards CO poisoning in alcohol oxidation reactions were also summarized.