Air-breathing cathodes for microbial fuel cells based on iron-nitrogen-carbon electrocatalysts.

This work reports the development of an iron-nitrogen-carbon electrocatalyst (Fe-N-C) synthesized by functionalization of carbon support using low-cost Fe- and N-based precursors in a wet impregnation procedure followed by a pyrolysis treatment under an inert atmosphere. Structure and surface chemistry were investigated by Raman and X-ray photoelectron spectroscopy (XPS), which indicated an efficient interaction of precursors with the carbon support during the wet-impregnations step, which allows obtaining a carbonized material with a high content of active sites based on Fe-Nx moieties. This led to Fe-N-C materials with high catalytic activity towards oxygen reduction at neutral pH, as demonstrated by cyclic voltammetry (CV) and hydrodynamic linear sweep voltammetry with rotating ring disk electrode (LSV-RRDE). The Fe-N-C electrocatalyst was incorporated in air-breathing cathodes and performance was optimized in terms of oxygen reduction activity and stability. Such cathodes were assembled in single-chamber microbial fuel cell prototypes, and electrical power and voltage generation were evaluated over time.

Oxygen Reduction Reaction Electrocatalysts Derived from Iron Salt and Benzimidazole and Aminobenzimidazole Precursors and Their Application in Microbial Fuel Cell Cathodes.

In this work, benzimidazole (BZIM) and aminobenzimidazole (ABZIM) were used as organic-rich in nitrogen precursors during the synthesis of iron-nitrogen-carbon (Fe-N-C) based catalysts by sacrificial support method (SSM) technique. The catalysts obtained, denoted Fe-ABZIM and Fe-BZIM, were characterized morphologically and chemically through SEM, TEM, and XPS. Moreover, these catalysts were initially tested in rotating ring disk electrode (RRDE) configuration, resulting in similar high electrocatalytic activity toward oxygen reduction reaction (ORR) having low hydrogen peroxide generated (<3%). The ORR performance was significantly higher compared to activated carbon (AC) that was the control. The catalysts were then integrated into air-breathing (AB) and gas diffusion layer (GDL) cathode electrode and tested in operating microbial fuel cells (MFCs). The presence of Fe-N-C catalysts boosted the power output compared to AC cathode MFC. The AB-type cathode outperformed the GDL type cathode probably because of reduced catalyst layer flooding. The highest performance obtained in this work was 162 ± 3 µWcm-2. Fe-ABZIM and Fe-BZIM had similar performance when incorporated to the same type of cathode configuration. Long-term operations show a decrease up to 50% of the performance in two months operations. Despite the power output decrease, the Fe-BZIM/Fe-ABZIM catalysts gave a significant advantage in fuel cell performance compared to the bare AC.

Design of Iron(II) Phthalocyanine-Derived Oxygen Reduction Electrocatalysts for High-Power-Density Microbial Fuel Cells.

Iron(II) phthalocyanine (FePc) deposited onto two different carbonaceous supports was synthesized through an unconventional pyrolysis-free method. The obtained materials were studied in the oxygen reduction reaction (ORR) in neutral media through incorporation in an air-breathing cathode structure and tested in an operating microbial fuel cell (MFC) configuration. Rotating ring disk electrode (RRDE) analysis revealed high performances of the Fe-based catalysts compared with that of activated carbon (AC). The FePc supported on Black-Pearl carbon black [Fe-BP(N)] exhibits the highest performance in terms of its more positive onset potential, positive shift of the half-wave potential, and higher limiting current as well as the highest power density in the operating MFC of (243±7) µW cm-2 , which was 33 % higher than that of FePc supported on nitrogen-doped carbon nanotubes (Fe-CNT(N); 182±5 µW cm-2 ). The power density generated by Fe-BP(N) was 92 % higher than that of the MFC utilizing AC; therefore, the utilization of platinum group metal-free catalysts can boost the performances of MFCs significantly.

Carbon-Supported Zirconium Oxide as a Cathode for Microbial Fuel Cell Applications.

Cost-effective electrode materials to be used as cathodes in lab-scale prototype microbial fuel cells (MFCs) were prepared from mixtures of carbon black (C) and zirconium oxide (ZrO2 ) of different composition. The catalytic activity of these cathodes in the oxygen reduction reaction (ORR) and their stability toward poisoning in typical MFC operative conditions were assessed by using electrochemical techniques. Scanning electron microscopy and Brunauer-Emmett-Teller measurements gave insights into sample morphology and surface area. The results indicated that the C/ZrO2 sample with a ZrO2 loading of 25 wt % (C/ZrO2 _25) represents the best compromise in terms of ORR activity and stability. C/ZrO2 _25 was assembled into cathodes of a prototype single-chamber MFC, which produced a maximum power density of 600 mW m-2 . A comparative cost analysis of energy production indicated that the cost of energy delivered by MFCs assembled with a C/ZrO2 cathode was more than 15 times lower than that of MFCs assembled with a reference Pt/C cathode.

Vertical TiO2 Nanorods as a Medium for Stable and High-Efficiency Perovskite Solar Modules.

Perovskite solar cells employing CH3NH3PbI3-xClx active layers show power conversion efficiency (PCE) as high as 20% in single cells and 13% in large area modules. However, their operational stability has often been limited due to degradation of the CH3NH3PbI3-xClx active layer. Here, we report a perovskite solar module (PSM, best and av. PCE 10.5 and 8.1%), employing solution-grown TiO2 nanorods (NRs) as the electron transport layer, which showed an increase in performance (∼5%) even after shelf-life investigation for 2500 h. A crucial issue on the module fabrication was the patterning of the TiO2 NRs, which was solved by interfacial engineering during the growth process and using an optimized laser pulse for patterning. A shelf-life comparison with PSMs built on TiO2 nanoparticles (NPs, best and av. PCE 7.9 and 5.5%) of similar thickness and on a compact TiO2 layer (CL, best and av. PCE 5.8 and 4.9%) shows, in contrast to that observed for NR PSMs, that PCE in NPs and CL PSMs dropped by ∼50 and ∼90%, respectively. This is due to the fact that the CH3NH3PbI3-xClx active layer shows superior phase stability when incorporated in devices with TiO2 NR scaffolds.

Composite polymer electrolytes for fuel cell applications: filler-induced effect on water sorption and transport properties.

Nafion- and sulfonated polysulfone (SPS)- based composite membranes were prepared by incorporation of SnO2 nanoparticles in a wide range of loading (0${ \div }$35 wt. %). The composites were investigated by differential scanning calorimetry, dynamic vapor sorption and electrochemical impedance spectroscopy to study the filler effect on water sorption, water mobility, and proton conductivity. A detrimental effect of the filler was observed on water mobility and proton conductivity of Nafion-based membranes. An increase in water mobility and proton conductivity was instead observed in SPS-based samples, particularly at low hydration degree. Analysis of the water sorption isotherms and states of water revealed that the presence of SnO2 in SPS enhances interconnectivity of hydrophilic domains, while not affecting the Nafion microstructure. These results enable the design of suitable electrolyte materials that operate in proton exchange membrane fuel cell conditions.

Using olive mill wastewater to improve performance in producing electricity from domestic wastewater by using single-chamber microbial fuel cell.

Improving electricity generation from wastewater (DW) by using olive mill wastewater (OMW) was evaluated using single-chamber microbial fuel cells (MFC). Doing so single-chambers air cathode MFCs with platinum anode were fed with domestic wastewater (DW) alone and mixed with OMW at the ratio of 14:1 (w/w). MFCs fed with DW+OMW gave 0.38 V at 1 kΩ, while power density from polarization curve was of 124.6 mW m(-2). The process allowed a total reduction of TCOD and BOD5 of 60% and 69%, respectively, recovering the 29% of the coulombic efficiency. The maximum voltage obtained from MFC fed with DW+OMW was 2.9 times higher than that of cell fed with DW. DNA-fingerprinting showed high bacterial diversity for both experiments and the presence on anodes of exoelectrogenic bacteria, such as Geobacter spp. Electrodes selected peculiar consortia and, in particular, anodes of both experiments showed a similar specialization of microbial communities independently by feeding used.

High proton conduction in grain-boundary-free yttrium-doped barium zirconate films grown by pulsed laser deposition.

Reducing the operating temperature in the 500-750 °C range is needed for widespread use of solid oxide fuel cells (SOFCs). Proton-conducting oxides are gaining wide interest as electrolyte materials for this aim. We report the fabrication of BaZr(0.8)Y(0.2)O(3-δ) (BZY) proton-conducting electrolyte thin films by pulsed laser deposition on different single-crystalline substrates. Highly textured, epitaxially oriented BZY films were obtained on (100)-oriented MgO substrates, showing the largest proton conductivity ever reported for BZY samples, being 0.11 S cm(-1) at 500 °C. The excellent crystalline quality of BZY films allowed for the first time the experimental measurement of the large BZY bulk conductivity above 300 °C, expected in the absence of blocking grain boundaries. The measured proton conductivity is also significantly larger than the conductivity values of oxygen-ion conductors in the same temperature range, opening new potential for the development of miniaturized SOFCs for portable power supply.

Composite Nafion/sulfonated zirconia membranes: effect of the filler surface properties on proton transport characteristics.

Due to their strong acidity and water affinity, sulfated zirconia nanoparticles were evaluated as inorganic additives in the formation of composite Nafion-based membranes. Two types of sulfated zirconia were obtained according to the preparation experimental conditions. Sulfated zirconia-doped Nafion membranes were prepared by a casting procedure. The properties of the composite membranes were compared with those of an unfilled Nafion membrane obtained by the same preparation method. The water uptake, measured at room temperature in a wide relative humidity range, was higher for the composite membranes, this confirming the hydrophilic nature of the selected additives. The membrane doped by zirconia particles having the highest sulphate group concentration showed the highest water diffusion coefficient in the whole range of temperature and relative humidity investigated due to the presence of SO(4) (2-) providing extra acid sites for water diffusion. The proton diffusivity calculated from impedance spectroscopy measurements was compared with water self diffusion coefficients measured by NMR Spectroscopy. The difference between proton and water diffusivity became significant only at high humidification levels, highlighting the role of water in the intermolecular proton transfer mechanism. Finally, great improvements were found when using the composite membrane as electrolyte in a fuel cell working at very low relative humidity.