Effect of Structural Changes at Various Length Scales in SiVOC Ceramic Nanocomposites on Electrocatalytic Performance for the Oxygen Reduction Reaction

Polymer-derived processing of ceramics (PDC) is an efficient technique to prepare porous nanocomposites with precise control over their phase composition and in relation to the Si-based ceramic matrix containing free carbon. The microstructure of these nanocomposites can be fine-tuned at the molecular scale for obtaining necessary properties by tailoring the chemical configuration of the preceramic polymer. In the present work, vanadium-based nanocomposites were synthesized as oxygen reduction reaction (ORR) catalysts with the objective of elucidating the effect of microstructure changes on catalytic efficiency. For this purpose, a single-source precursor (SSP) was synthesized by crosslinking phenyl- and hydrido-substituted polysiloxane and vanadium acetylacetonate followed by pyrolysis at 1100 °C. The resulting solid was composed of sparsely distributed nanodomains of vanadium carbide (VC) crystals precipitated within an amorphous silicon oxycarbide (-Si-O-C-) matrix. High-temperature treatment of the pyrolyzed samples beyond 1300 °C induced the crystallization of β-SiC as well as VC. Furthermore, Raman spectroscopy confirmed the segregation of sp2-hybridized, turbostratic free carbon. The samples exposed to 1300 °C revealed a specific surface area of 239 m2/g. The electrocatalytic activity of the sample heat-treated at 1300 °C showed the best performance with respect to the ORR performance with onset potential (Eo) and half-wave potential (E1/2) values of 0.81 and 0.72 V, respectively. In addition, improved kinetics with a Tafel slope of 57 mV/dec and enhanced current density in the diffusion-controlled region (Id) of 3.7 mA/cm2 were observed for this sample. The increase in Eo was attributed to the optimal interfacial characteristics between the VC and SiOC matrix with better embedment of VC with free carbon through V-C bonds. The higher E1/2 and faster kinetics are because of the higher electronic conductivity caused by the free carbon effectively connecting metallic VC crystallites. Besides, the higher specific surface area of this sample enhanced Id.