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 sp 2 -hybridized, turbostratic free carbon. The samples exposed to 1300 °C revealed a specific surface area of 239 m 2 /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 ( E o ) and half-wave potential ( E 1/2 ) 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 ( I d ) of 3.7 mA/cm 2 were observed for this sample. The increase in E o 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 E 1/2 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 I d .