Non-noble metal catalyst for a future Pt free PEMFC

We have investigated the possibility of developing high-performance, cost-effective and durable non-noble Co metal electrocatalyst for PEMFC. In this work we applied electrodeposition process for PEMFC electrode preparation that is very efficient and far simpler than any other investigated method. The fuel cell with electrodeposited Co as anode catalyst has shown satisfying performance level. In determining FC’s operating conditions, subsequent electrochemical impedance and output power measurements were done, which enable the insight into the Co catalyst based anode behavior. Structure analysis of the electrodeposited anode layer was done by means of SEM and EDS technique. Although the Pt catalyst has higher efficiency, its cost performance ratio is significantly lower than for the Co catalyst, thus this investigation gives interesting possibilities in area of stationary fuel cell application.     

Surface states of titanium dioxide nanoparticles modified with enediol ligands

Control of surface states of titanium dioxide nanoparticles using 2-(3,4-dihydroxyphenyl)ethylamine (dopamine) and 3,4-dihydrophenylacetic acid, which act as ligands to the undercoordinated surface sites (carrier traps), is demonstrated by electrochemical techniques. The deepest traps were found to be most reactive and are selectively removed by the addition of the ligands which enhances the kinetics of electron accumulation in the film. Furthermore, a shift in the Fermi level to more positive potentials was detected for electrodes modified with the negatively charged ligand (3,4-dihydrophenylacetic acid) compared to that of electrodes modified with the positively charged ligand (dopamine). The presence of the negative charge on the ligand also contributed to the underpotential of hydrogen evolution on 3,4-dihydrophenylacetic acid-modified electrodes.     

Assembly and charge transfer in hybrid TiO(2) architectures using biotin-avidin as a connector

Exploiting the presence of undercoordinated surface Ti atoms at the tips of TiO2 nanorods and the dopamine selectivity for these Ti surface states, biotin was conjugated to TiO2 nanocrystallites using dopamine as a bridging linker. Using abiotin-avidin complex as a connector the "tip-to-tip" assembly of 400 nm elongated TiO2 rods was obtained. The photoexcitation of avidin-TiO2 hybrids resulted in the transfer of holes from nanocrystallites to protein and consequent oxidation of avidin, most probably at tyrosine 33.     

Charge separation and surface reconstruction: a Mn2+ doping study

Hydrothermal synthesis of Mn doped anatase (TiO2) nanoparticles using scrolled nanotubes of TiO2 and MnCl2 as the starting materials is described. Incorporation of Mn2+ ions on the substitutional sites was confirmed using X-ray absorption fine structure (FT-XAFS) while the oxidation state Mn(II) and coordination environment were determined using both electron paramagnetic resonance (EPR) and X-ray absorption near edge spectroscopy (XANES). Two different hyperfine couplings of 96 and 86 G were found using high-field (130 GHz) EPR reporting that Mn atoms occupy two distinct sites: one undercoordinated (reconstructed surface) and the other octahedral crystalline geometry (nanoparticle core), respectively. It was found that Mn atoms that occupy surface layers are weakly bound to the anatase lattice and can be easily leached using simple dialysis, while those incorporated in the nanoparticle core are bound more strongly and cannot be removed by dialysis. Light excitation EPR reveals that Mn ions incorporated in the surface layers participate in the charge separation, while those trapped deeply in the nanoparticle core do not show any photoactivity. Doping of the core of nanoparticles with Mn2+ ions, on the other hand, enables synthesis of optically transparent films having superparamagnetic behavior at room temperatures with a saturation magnetic moment of 1.23 microB per Mn atom.     

Complex and charge transfer between TiO2 and pyrroloquinoline quinone

Pyrroloquinoline quinone (PQQ) forms a tridentate complex with coordinatively unsaturated titanium atoms on the surface of approximately 4.5 nm TiO2 particles; an association constant of K = 550 M-1 per Ti(IV)surf has been determined. Low-temperature electron paramagnetic resonance was employed in identification of localized charges and consequently produced radicals and in determination of charge-transfer processes. The photoexcitation of the PQQ-TiO2 complex results in the transfer of conduction band electrons from TiO2 to bound PQQ and the formation of the semiquinone radical. Attaching dopamine (DA) as an electron donor and PQQ as an electron acceptor on the surface of TiO2 results in spatial separation of photogenerated charges; the holes localize on dopamine and electrons on PQQ, with higher yields than for each component separately. In this triad-type assembly (PQQ-TiO2/DA) the PQQ that is bound to the particles acts as a sink for electrons allowing their almost complete scavenging even at temperature as low as 4 K.