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.

SEM characterization and ageing analysis on two generation of invisible aligners.

BACKGROUND: The purpose of the in vitro study is to investigate and compare the morphological features and the chemical stability in weight of two different polyurethane-based blends, Smart Track (LD30) and Exceed30 (EX30), used for orthodontic aligners manufacture before and after the oral usage. METHODS: Twenty orthodontic aligners were randomly selected: 10 LD30 and 10 EX30, each group was divided in two subgroups, never used and intra-orally aged. By the employment of a Stereomicroscope, a section of 5 × 5 mm was cut from the buccal surface of the incisal region of each aligner. All samples were subjected to Scanning Electron Microscopy and Ageing tests in different solutions to simulate the hostility of the oral environment. The statistical method used was t-test. RESULTS: At SEM images, LD30 appears more homogeneous in texture respect to EX30. However, after clinical usage, both materials show significant structural alterations: findings have been supported by higher magnifications at SEM, by which it is clearly to observe many superficial cracks cross through the polymer structures of LD30U, absent in never used samples. LD30U surface becomes also smoother due to the disappearance of most of the conglomerates, but at the same time also rougher while EX30U shows a greater irregularity and porosity in which large and deep cracks are also highlighted. Although these changes occur persistently, in the aging tests no significant weight loss from both materials has been found, confirming the initial hypothesis of a good chemical stability and safety of both polyurethane mixtures even in conditions of severe hostility. CONCLUSION: LD30 is the expression of the technological evolution of EX30, this is made evident above all by its morphological architecture, more homogeneous and defined but also by the chemical stability that can be appreciated even in evident critic situations.

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.

Mechanical properties of "two generations" of teeth aligners: Change analysis during oral permanence.

Aim of this in vitro study was to analyze structural properties of two different polymeric orthodontic aligners, Exceed30 (EX30) and Smart Track (LD30), before and after use. Forty patterns of aligners were randomly selected: 20 LD30 and 20 EX30, worn intra-orally for 14±3 days, 22 h/day. From each aligner, 10 specimens were prepared from buccal surfaces of the incisor region by the cutting of samples 5×5 mm under a stereomicroscope. All samples were subjected to Fourier transform infrared spectroscopy, micro-Raman spectroscopy, X-ray diffraction, tensile and indentation strength test. LD30 appeared more homogeneous, with a crystalline fraction lower than EX30 and exhibited a higher elastic behavior and a lower tendency to warp after use than EX30. LD30 demonstrated better adaptability to the dental arch and greater consistency of application of orthodontic forces than produced with EX30. However, both materials showed structural modifications that resulted in increased sample hardness and hyper-plasticity.

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.

Tuning Structural Changes in Glucose Oxidase for Enzyme Fuel Cell Applications.

Stabilization and electrical contacting of redox enzymes with electrodes are fundamental requirements for bioelectronics devices, including biosensors and enzyme fuel cells (EFCs). In this study, we show increased glucose oxidase (GOx) stability by immobilization with Nafion. The immobilization process affected GOx conformation but was not detrimental to its activity, which was maintained for more than 120 days. The GOx/Nafion system was interfaced to a carbon cloth electrode and assembled in a prototypal EFC fed with glucose. Polarization and power density curves demonstrated that GOx/Nafion system was able to generate power, exploiting a Nafion-assisted electron transfer process to the electrode. Our findings are consistent with the onset of pH-dependent conformational equilibrium for the enzyme secondary structure and its active site. Significantly, the protective effect exerted by Nafion on the enzyme structure may be tuned by varying parameters such as the pH to fabricate durable EFCs with good electrocatalytic performance.

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.

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.

Thick soft tissue reconstruction on highly perfusive biodegradable scaffolds.

The lack of a vascular network and poor perfusion is what mostly prevents three-dimensional (3D) scaffolds from being used in organ repair when reconstruction of thick tissues is needed. Highly-porous scaffolds made of poly(L-lactic acid) (PLLA) are prepared by directional thermally induced phase separation (dTIPS) starting from 1,4-dioxane/PLLA solutions. The influence of polymer concentration and temperature gradient, in terms of imposed intensity and direction, on pore size and distribution is studied by comparison with scaffolds prepared by isotropic TIPS. The processing parameters are optimized to achieve an overall porosity for the 3D scaffolds of about 93% with a degree of interconnectivity of 91%. The resulting pore network is characterized by the ordered repetition of closely packed dendrite-like cavities, each one showing stacks of 20 microm large side lamellar branches departing from 70 microm diameter vertical backbones, strongly resembling the vascular patterns. The in vitro biological responses after 1 and 2 weeks are evaluated from mesenchymal (bone marrow stromal) cells (MSC) static culturing. A novel vacuum-based deep-seeding method is set up to improve uniform cell penetration down to scaffold thicknesses of over 1 mm. Biological screenings show significant 3D scaffold colonization even after 18 h, while cellular retention is observed up to 14 d in vitro (DIV). Pore architecture-driven cellular growth is accompanied by cell tendency to preserve their multi-potency towards differentiation. Confluent tissues as thick as 1 mm were reconstructed taking advantage of the large perfusion enhanced by the highly porous microstructure of the engineered scaffolds, which could successfully serve for applications aimed at vascular nets and angiogenesis.