Cryoplasma-mediated fabrication of Au-TiO₂ composite film using freezing ice front templated structures

Ice-templating is a powerful technique that exploits self-organized ice structures formed during the freezing of colloidal suspensions as templates to fabricate microstructured materials. However, the active introduction of reactivity to the ice-templating process remains limited. In this study, a Au-TiO₂ composite film composed of gold and titanium oxide (TiO₂) was fabricated on a frozen aqueous colloidal suspension, using cryoplasma to introduce reactive species to the frozen suspension. Auric ions and TiO₂ nanoparticles were segregated on the ice body by one-directional freezing of the aqueous colloidal suspension from the lower side. Meanwhile, a cryoplasma, in which the gas temperature was controlled to be lower than the melting point of water, was irradiated onto the frozen aqueous colloidal suspension to facilitate the chemical reduction of gold ions and the formation of gold bridges between TiO₂ nanoparticles. The face of the fabricated Au-TiO₂ composite film that had been adjacent to the ice structure during its formation was shown to possess both greater roughness and higher photocatalytic activity for methylene blue degradation when the aqueous colloidal suspension was frozen at a higher temperature during the fabrication of the composite film. The temperature dependence of the roughness and photocatalytic activity indicates a potential of the combination of cryoplasma irradiation and ice-templating processes for structure-controlled fabrication of composite film materials, suggesting that alterations in the structure of the freezing ice front that occur with changes in temperature can be harnessed.