•We prepared cobalt octaethylporphyrin (Co-OEP)-modified perovskite/carbon catalysts.•ORR activity of perovskite/carbon was enhanced by Co-OEP-modification.•RRDE measurements suggested that the 2 + 2 electron reduction of O2 is promoted.•The porphyrin plays a role as a two-electron O2 reduction catalyst to give HO2−.•HO2− is further reduced to OH− by the perovskite-type oxide.Perovskite-type oxide-carbon (Vulcan XC72) mixture (La0.6Sr0.4Mn0.6Fe0.4O3/C) was modified by a metalloporphyrin (cobalt octaethylporphyrin: Co-OEP) having two-electron O2 reduction activity, and its electrochemical reduction activity for O2 (ORR) was investigated in an alkaline solution by rotating ring disk electrode (RRDE) voltammetry. The Co-OEP/La0.6Sr0.4Mn0.6Fe0.4O3/C catalyst showed improved ORR activity, with a positive shift of the onset potential. In addition, a decreased ring current compared to Co-OEP/C suggested that the quasi-four-electron reduction of O2 was also enhanced. Further experiments showed that ORR activity was also enhanced by Co-OEP-modification of other types of carbon (Ketjenblack EC600JD, Denka Black) or perovskite-type oxide (La0.6Ca0.4Mn0.6Fe0.4O3, La0.8Sr0.2Co0.6Fe0.4O3). In the case of the addition of other porphyrin complexes (cobalt tetraphenylporphyrin (Co-TPP), iron octaethylporphyrin (Fe-OEP)) to a La0.6Sr0.4Mn0.6Fe0.4O3/C catalyst, the onset potential did not shift to the positive side due to the lower activity compared to Co-OEP.

Nonenzymatic glucose fuel cells were prepared by using a polymer electrolyte membrane and Pt-based metal catalysts. A fuel cell with a cation exchange membrane (CEM), which is often used for conventional polymer electrolyte fuel cells, shows an open circuit voltage (OCV) of 0.86 V and a maximum power density (Pmax) of 1.5 mW cm−2 with 0.5 M d-glucose and humidified O2 at room temperature. The performance significantly increased to show an OCV of 0.97 V and Pmax of 20 mW cm−2 with 0.5 M d-glucose in 0.5 M KOH solution when the electrolyte membrane was changed from a CEM to an anion exchange membrane (AEM). This is due to the superior catalytic activity for both glucose oxidation and oxygen reduction in alkaline medium than in acidic medium. The anodic reaction of the fuel cell can be estimated to be the oxidation of glucose to gluconic acid via a two-electron process under these experimental conditions. The crossover of glucose through an electrolyte membrane was negligibly small compared with methanol and may not represent a serious technical problem due to the cross-reaction.

Direct ethanol fuel cells (DEFCs) with a PtRu anode and a Pt cathode were prepared using an anion exchange membrane (AEM) as an electrolyte instead of a cation exchange membrane (CEM), as in conventional polymer electrolyte fuel cells. The maximum power density of DEFCs significantly increased from 6 mW cm−2 to 58 mW cm−2 at room temperature and atmospheric pressure when the electrolyte membrane was changed from CEM to AEM. The anode and cathode polarization curves showed a decrease in the anode potential and an increase in the cathode potential for AEM-type DEFCs compared to CEM-type. This suggests that AEM-type DEFCs have superior catalytic activity toward both ethanol oxidation and oxygen reduction in alkaline medium than in acidic medium. The product species from the exhausted liquid from DEFCs operated at a constant current density were identified by enzymatic analysis. The main product was confirmed to be acetic acid in AEM-type, while both acetaldehyde and acetic acid were detected in 1:1 ratio in CEM-type. The anodic reaction of AEM-type DEFCs can be estimated to be the oxidation of ethanol to acetic acid via a four-electron process under these experimental conditions.

l-Ascorbic acid (AA), also known as vitamin C, is an environmentally-benign and biologically-friendly compound that can be used as an alternative fuel for direct oxidation fuel cells. While direct ascorbic acid fuel cells (DAAFCs) have been studied experimentally, modelling and simulation of these devices have been overlooked. In this work, we develop a mathematical model to describe a DAAFC and validate it with experimental data. The model is formulated by integrating the mass and charge balances, and model parameters are estimated by best-fitting to experimental data of current–voltage curves. By comparing the transient voltage curves predicted by dynamic simulation and experiments, the model is further validated. Various parameters that affect the power generation are studied by simulation. The cathodic reaction is found to be the most significant determinant of power generation, followed by fuel feed concentration and the mass-transfer coefficient of ascorbic acid. These studies also reveal that the power density steadily increases with respect to the fuel feed concentration. The results may guide future development and operation of a more efficient DAAFC.

l-Ascorbic acid (AA) was directly supplied to polymer electrolyte fuel cells (PEFCs) as an alternative fuel. Only dehydroascorbic acid (DHAA) was detected as a product released by the electrochemical oxidation of AA via a two-electron transfer process regardless of the anode catalyst used. The ionomer in the anode may inhibit the mass transfer of AA to the reaction sites by electrostatic repulsion. In addition, polymer resins without an ionic group such as poly(vinylidene fluoride) and poly(vinyl butyral) were also useful for reducing the contact resistance between Nafion membrane and carbon black used as an anode, although an ionomer like Nafion is needed for typical PEFCs. A reaction mechanism at the two-phase boundaries between AA and carbon black was proposed for the anode structure of DAAFCs, since lack of the proton conductivity was compensated by AA. There was too little crossover of AA through a Nafion membrane to cause a serious technical problem. The best performance (maximum power density of 16 mW cm−2) was attained with a Vulcan XC72 anode that included 5 wt.% Nafion at room temperature, which was about one-third of that for a DMFC with a PtRu anode.

Electrochemical oxidation of fuel compounds in acidic media was examined on eight electrodes (Pt, Ru, PtRu, Rh, Ir, Pd, Au, and glassy carbon) simultaneously by multiple cyclic voltammetry (CV) with an electrochemical cell equipped with an eight-electrode configuration. Direct-type polymer electrolyte fuel cells (PEFCs), in which aqueous solutions of the fuel compounds are directly supplied to the anode, were also evaluated. The performances of direct PEFCs with various anode catalysts could be roughly estimated from the results obtained with multiple CV. This multiple evaluation may be useful for identifying novel fuels or electrocatalysts. Methanol, ethanol, ethylene glycol, 2-propanol, and d-glucose were oxidized selectively on Pt or PtRu, as reported previously. However, several compounds that are often used as reducing agents show electrochemical oxidation with unique characteristics. Large current was obtained for the oxidation of formic acid, hypophosphorous acid, and phosphorous acid on a Pd electrode. l-Ascorbic acid and sulfurous acid were oxidized on all of the electrodes used in the present study.