The application of silicon-based preceramic polymers as precursors to advanced porous ceramics has gained increasing interest for prospective applications in chemical conversion processes, with a particular focus on catalysis and catalyst reactors. Here, a distinct control over size, morphology, and directionality of porosity from the macro- to the mesopore size range is of major relevance in order to provide both high interaction with catalytically active centers as well as suitable flow characteristics.

In this contribution, an overview of our work on the coupling of polymer-derived ceramic technology with photopolymerization-based structuring techniques towards parts with distinct pore morphologies will be given. By employing the distinct advantage of light in terms of spatial and temporal control of chemical reactions, complex microstructural features can be generated and/or retained, and subsequently utilized as pore templates.

The first example comprises the generation of 3D-structured hierarchically porous SiOC ceramics, exhibiting pore features ranging from the mm- down to the sub-µm domain, via a simultaneous use of vat photopolymerization and photopolymerization-induced phase separation. By exploiting the chemical modifiability of preceramic polymer systems, the resulting materials can be decorated by in-situ formed metal nanoparticles, resulting in a highly promising performance of the hierarchically porous monoliths as catalyst reactors in CO₂ methanation.

The second example includes the fabrication of macroporous polymer-derived ceramic scaffolds via a photopolymerization-assisted solidification templating concept, providing a straightforward methodology towards ceramic materials with highly controlled and oriented pore channels. The versatility of these monolithic materials is highlighted via various applications in CO₂ valorization processes, including their use as suitable supports for ionic liquid phases as catalysts for the production of cyclic carbonates using bio-based feedstocks.