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The performance of Pd electrocatalysts for formic acid electrooxidation was improved by application of metal oxide-multiwall carbon nanotubes composites as a catalyst support. Hybrid oxides/MWCNTs were synthesized by two different methods: chemical reduction method and impregnation method. Pd based catalysts were synthesized by polyol method on the MWCNTs or oxide/MWCNTs composites. The In2O3 was deposited on MWCNTs by impregnation method (In2O3/MWCNTs-IM support) and in the presence of NaBH4 (In2O3/MWCNTs-NaBH4 support). The physical properties of the Pd/In2O3/MWCNTs-IM, Pd/In2O3/MWCNTs-NaBH4, Pd/SnO2/MWCNTs, and Pd/MWCNTs catalysts were characterized and their electrocatalytical performance in formic acid oxidation was compared. During Pd deposition on In2O3/MWCNTs-NaBH4 support, InPd2 structure was formed as observed by XRD. The electrochemical tests indicate that the two Pd/ In2O3/MWCNTs electrocatalysts have higher electrocatalytic activity than those of Pd/SnO2/MWCNTs and Pd/MWCNTs. The best performance was observed for the catalyst obtained by In2O3 impregnation of MWCNTs denoted by Pd/In2O3/MWCNTs-IM.

In the present work, the magnetron sputtering technique was used to prepare new catalysts of formic acid electrooxidation based on TiO2 nanotubes decorated with Pt (platinum), Pd (palladium) or Pd + Pt nanoparticles. TiO2 nanotubes (TiO2 NTs) with strictly defined geometry were produced by anodization of Ti foil and Ti mesh in a mixture of glycerol and water with ammonium fluoride electrolyte. The above mentioned catalytically active metal nanoparticles (NPs) were located mainly on the top of the TiO2 NTs, forming ‘rings’ and agglomerates. A part of metal nanoparticles decorated also TiO2 NTs walls, thus providing sufficient electronic conductivity for electron transportation between the metal nanoparticle rings and Ti current collector. The electrocatalytic activity of the TiO2 NTs/Ti foil, decorated by Pt, Pd and/or Pd + Pt NPs was investigated by cyclic voltammetry (CV) and new Pd/TiO2 NTs/Ti mesh catalyst was additionally tested in a direct formic acid fuel cell (DFAFC). The results so obtained were compared with commercial catalyst—Pd/Vulcan. CV tests have shown for carbon supported catalysts, that the activity of TiO2 NTs decorated with Pd was considerably higher than that one decorated with Pt. Moreover, for TiO2 NTs supported Pd catalyst specific activity (per mg of metal) was higher than that for well dispersed carbon supported commercial catalyst. The tests at DFAFC have revealed also that the maximum of specific power for 0.2 Pd/TiO2 catalyst was 70% higher than that of the commercial one, Pd/Vulcan. Morphological features, and/or peculiarities, as well as surface composition of the resulting catalysts have been studied by scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and chemical surface analytical methods (X-ray photoelectron spectroscopy—XPS; Auger electron spectroscopy—AES).