Polymer-derived Ni/SiOC materials structured by vat-based photopolymerization with catalytic activity in CO₂ methanation

Abstract

A new concept for the additive manufacturing of nickel-modified polymer-derived ceramics via vat-based photopolymerization is presented. A photoactive polysiloxane resin system modified by nickel nitrate via methacrylic acid complexation was developed and modified to facilitate vat-based photopolymerization. Through pyrolysis of the Ni-modified preceramic polymer at temperatures between 600 and 800 °C, amorphous SiOC components with well-dispersed Ni nanoparticles can be obtained. The modified polymer and the fabricated structures were characterized by photorheology, thermal analysis, scanning and transmission electron microscopy, optical coherence tomography, and powder X-ray diffraction. In addition, the effect of pyrolysis temperature on specific surface area, crystallinity, and shrinkage was investigated. The developed material systems enable additive manufacturing of porous SiOC structures containing crystalline, uniformly distributed, and bimodally sized Ni nanoparticles, exhibiting catalytic activity suitable for CO₂ methanation. The developed printable SiOC/Ni materials represent a promising approach for combining metal-modified polymer-derived ceramic systems and additive manufacturing for prospective catalysis applications.