Electrochemically deposited Pd-Pt and Pd-Au codeposits on graphite electrodes for electrocatalytic H2O2 reduction.

Improved electrocatalytic activity and selectivity for the reduction of H2O2 were obtained by electrodepositing Pd-Pt and Pd-Au on spectrographic graphite from solutions containing salts of the two metals at varying ratio. The electrocatalytic activity of the resulting binary codeposits for H2O2 reduction was evaluated by means of the redox-competition mode of scanning electrochemical microscopy (SECM) and voltammetric methods. In a potential range from 0 to -600 mV (vs. Ag/AgCl/3 M KCl) at pH 7.0 in 0.1 M phosphate citrate buffer, the electrocatalytic activity of both Pd-Pt and Pd-Au codeposits was substantially improved as compared with the identically deposited single metals suggesting an electrocatalytic synergy of the codeposits. Pd-Pt and Pd-Au codeposits were characterized by X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM). Codepositing with Au caused a change of hedgehog-like shaped Pd nanoparticles into cauliflower-like nanoparticles with the particle size decreasing with increasing Au concentration. Codepositing Pd with Pt caused the formation of oblong structures with the size initially increasing with increasing Pt content. However, the particle size decreases with further increase in Pt concentration. The improved electrocatalytic capability for H2O2 reduction of the Pd-Pt electrodeposits on graphite was further demonstrated by immobilizing glucose oxidase as a basis for the development of an interference-free amperometric glucose biosensor.

Metal-free and electrocatalytically active nitrogen-doped carbon nanotubes synthesized by coating with polyaniline.

Nitrogen doping of multi-walled carbon nanotubes (CNTs) was achieved by the carbonization of a polyaniline (PANI) coating. First, the CNTs were partially oxidized with KMnO4 to obtain oxygen-containing functional groups. Depending on the KMnO4 loading, thin layers of birnessite-type MnO2 (10 wt% and 30 wt%) were obtained by subsequent thermal decomposition. CNT-supported MnO2 was then used for the oxidative polymerization of aniline in acidic solution, and the resulting PANI-coated CNTs were finally heated at 550 degrees C and 850 degrees C in inert gas. The samples were characterized by transmission electron microscopy and X-ray photoelectron spectroscopy. A thin layer of carbonized PANI was observed on the CNT surface, and the surface nitrogen concentration of samples prepared from 30% MnO2 was found to amount to 7.6 at% and 3.8 at% after carbonization at 550 degrees C and 850 degrees C, respectively. These CNTs with nitrogen-containing shell were further studied by electrochemical impedance spectroscopy and used as catalysts for the oxygen reduction reaction. The sample synthesized from 30 wt% MnO2 followed by carbonization at 850 degrees C showed the best electrochemical performance indicating efficient nitrogen doping.

Pt-Ag catalysts as cathode material for oxygen-depolarized electrodes in hydrochloric acid electrolysis.

Pt-Ag nanoparticles were prepared on a glassy carbon (GC) surface by pulsed electrodeposition and tested using cyclic voltammetry and scanning electrochemical microscopy (SECM) with respect to their possible use as catalyst material for oxygen reduction in 400 mM HCl solution. For comparison, a Pt catalyst was investigated under similar conditions. The redox competition mode of scanning electrochemical microscopy (RC-SECM) was adapted to the specific conditions caused by the presence of Cl(-) ions and used to visualize the local catalytic activity of the Pt-Ag deposits. Similarly prepared Pt deposits were shown to dissolve underneath the SECM tip. Pt-Ag composites showed improved long-term stability toward oxygen reduction as compared with Pt even under multiple switching off to open-circuit potential in 400 mM HCl.