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

Kousik Papakollu; Aman Bhardwaj; Emanuel Ionescu; Sanjay Mathur; Ravi Kumar

doi:10.1021/acsami.3c05449

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

ACS Appl Mater Interfaces. 2023 Jul 26;15(29):34895-34908. doi: 10.1021/acsami.3c05449. Epub 2023 Jul 13.

Authors

Kousik Papakollu^{1

2}, Aman Bhardwaj³, Emanuel Ionescu^{2

4}, Sanjay Mathur^{5

3}, Ravi Kumar^{1

5}

Affiliations

¹ Laboratory for High Performance Ceramics, Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras (IIT Madras), Chennai 600036, India.
² Institut für Materialwissenschaft, Technische Universität Darmstadt, Darmstadt 64287, Germany.
³ Institute of Inorganic Chemistry, University of Cologne, Cologne 50939, Germany.
⁴ Fraunhofer Research Institution for Materials Recycling and Resource Strategies (Fraunhofer IWKS), Brentanostr. 2a, D-63755 Alzenau, Germany.
⁵ Ceramic Technologies for Futuristic Mobility, Indian Institute of Technology Madras (IIT Madras), Chennai 600036, India.

PMID: 37439783
DOI: 10.1021/acsami.3c05449

Abstract

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 (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/cm² 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.

Keywords: free carbon; nanocomposites; oxygen reduction reaction; polymer-derived ceramics; silicon oxycarbide; vanadium carbide.