In-situ electrochemical impedance analysis of a commercial SOFC stack fueled by real wood gas.

The combination of solid oxide fuel cells (SOFCs) and wood gasification has the potential to significantly increase renewable electricity production and decrease emissions. Depending on the quality of the wood gas, degradation processes have a significant impact on the reliability and lifetime of the SOFC. Using electrochemical impedance spectroscopy (EIS) and subsequent distribution of relaxation times (DRT) analysis, the impact on the degradation of coupling wood gasification with a commercial SOFC stack is determined in this study. The thermal behavior of the SOFC stack under various operating conditions, as well as various synthetic wood gas mixtures classified by their hydrogen-to-carbon (H/C) ratio, was assessed. The decrease in the H/C ratio from 8 to 1, observed during syngas and real wood gas operation, leads to a rightward shift in the Nyquist plots, suggesting an increase in the SOFC stack's impedance. Correlations between variations in the H/C ratio and their effects on anodic electrooxidation, ionic conduction, gas transport, and diffusion were identified using DRT analysis to interpret the EIS results. By incorporating an upstream desulfurization system and ensuring an H/C ratio greater than 2, the coupling of biomass gasification with the SOFC stack was stable to degradation issues.

Magnetically induced enzymatic cascades - advancing towards multi-fuel direct/mediated bioelectrocatalysis.

A generic method to magnetically assemble enzymatic cascades on electrode surfaces is introduced. The versatile method enables the simultaneous activation of both direct and mediated electron transfer bioelectrocatalysis to harness different substrates, which can serve as multiple fuels and oxidizers in biofuel cells generating clean energy.

Switchable aerobic/anaerobic multi-substrate biofuel cell operating on anodic and cathodic enzymatic cascade assemblies.

Enzymatic fuel cells may become more accessible for applications powering portable electronic devices by broadening the range of potentially usable fuels and oxidizers. In this work we demonstrate the operation of an integrated, yet versatile multi-substrate biofuel cell utilizing either glucose, fructose, sucrose or combinations of thereof as biofuels, and molecular oxygen originating from solution phase and/or an internal chemical source, as the oxidizer. In order to achieve this goal we designed an enzymatic cascade-functionalized anode consisting of invertase (INV), mutarotase (MUT), glucose oxidase (GOX), and fructose dehydrogenase (FDH), deposited on top of a mesoporous carbon nanoparticle matrix, in which electron relay molecules had been entrapped. The anode was then conjugated to a compatible enzymatic cathode that employs a cascade of catalase (CAT) and bilirubin oxidase (BOD), allowing the cell to operate in an aerobic environment and/or to utilize, under anaerobic conditions for instance, hydrogen peroxide as a source for the oxygen oxidizer. While operated in the presence of the sugar mixture and hydrogen peroxide, the power output of the dually cascaded biofuel cell reaches a peak power density of 0.25 mW cm-2 and demonstrates an open circuit potential of 0.65 V. To our knowledge this is the first reported biofuel cell that discharges with both anodic and cathodic enzymatic cascade architectures and the first biofuel cell that is repeatedly switched between aerobic and anaerobic conditions without any significant decrease in the discharge performance.

Domination of volumetric toughening by silver nanoparticles over interfacial strengthening of carbon nanotubes in bactericidal hydroxyapatite biocomposite.

In order to address the problem of bacterial infections in bone-substitution surgery, it is essential that bone replacement biomaterials are equipped with bactericidal components. This research aims to optimize the content of silver (Ag), a well-known antibacterial metal, in a multiwalled carbon nanotube (CNT) reinforced hydroxyapatite (HA) composite, to yield a bioceramic which can be used as an antibacterial and tough surface of bone replacement prosthesis. The bactericidal properties evaluated using Escherichia coli and Staphylococcus epidermidis indicate that CNT reinforcement supports growth of Gram negative E. coli bacteria (~8.5% more adhesion than pure HA); but showed a strong decrease of Gram positive S. epidermidis bacteria (~diminished to 66%) compared to that of pure HA. Small amounts of silver (2-5wt.%) already show a severe bactericidal effect when compared to that of HA-CNT (by 30% and ~60% respectively). MTT assay confirmed enhanced biocompatibility of L929 cells on HA-4wt.% CNT (~121%), HA-4wt.% CNT-1wt.% Ag (~124%) sample and HA-4wt.% CNT-2wt.% Ag (~100%) when compared to that of pure HA. The samples with higher silver content showed decreased biocompatibility (77% for HA-4wt.% CNT-5wt.% Ag sample and 73% for HA-4wt.% CNT-10wt.% Ag). Though reinforcement of 4wt.% CNT has shown an increase of fracture toughness by ~62%, silver reinforcement has shown enhancement of up to 244% (i.e. 3.43 times). Accordingly, isolation of toughening contribution indicates that volumetric toughening by silver dominates over interfacial strengthening contributed by CNTs towards enhanced fracture toughness of potential HA-Ag-CNT biocomposites.

Enzyme-capped relay-functionalized mesoporous carbon nanoparticles: effective bioelectrocatalytic matrices for sensing and biofuel cell applications.

The porous high surface area and conducting properties of mesoporous carbon nanoparticles, CNPs (<500 nm diameter of NPs, pore dimensions ∼6.3 nm), are implemented to design electrically contacted enzyme electrodes for biosensing and biofuel cell applications. The relay units ferrocene methanol, Fc-MeOH, methylene blue, MB(+), and 2,2'-azinobis(3-ethylbenzothiazoline-6-sulfonic acid), ABTS(2-), are loaded in the pores of the mesoporous CNPs, and the pores are capped with glucose oxidase, GOx, horseradish peroxidase, HRP, or bilirubin oxidase, BOD, respectively. The resulting relay/enzyme-functionalized CNPs are immobilized on glassy carbon electrodes, and the relays encapsulated in the pores are sufficiently free to electrically contact the different enzymes with the bulk electrode supports. The Fc-MeOH/GOx CNP-functionalized electrode is implemented for the bioelectrocatalyzed sensing of glucose, and the MB(+)/HRP-modified CNPs are applied for the electrochemical sensing of H2O2. The ABTS(2-)/BOD-modified CNPs provide an effective electrically contacted material for the bioelectrocatalyzed reduction of O2 (kcat = 94 electrons·s(-1)). Integration of the Fc-MeOH/GOx CNP electrode and of the electrically wired ABTS(2-)/BOD CNP electrode as anode and cathode, respectively, yields a biofuel cell revealing a power output of ∼95 µW·cm(-2).