Controlled Architectures in Supported Photocatalysis: Exploring the Potential of Cold Plasma Discharge, Additive Manufacturing, and Fractal Geometry to Form Hierarchically Immobilized Ni-MOF/BiOI/AgVO 3 .

Herein, we explore the potential of innovative manufacturing techniques based on green chemistry principles, for the fabrication of convenient, performant, and stable supported photocatalysts to be used for water depollution. After giving some insight into the use of fractal geometry for the fabrication of tunable polymer supports for photocatalysts, we investigated the use of liquid crystal display (LCD) 3D printing to generate the fractal resin substrates to be used for the immobilization of semiconductor photocatalysts. Notably, confocal laser imaging was used as a first attempt for assessing the surface area of the fractal substrate. Immobilization methods based on cold plasma discharge (CPD) were employed to modify the surface of the polymer substrates and permanently anchor three different phases, namely, nickel-based metal-organic framework (Ni-MOF), BiOI, and AgVO ₃ , in a hierarchical configuration. Herein, for the first time, we developed a plasma-initiated condensed in situ complexation-assisted precipitation (c-ISCAP) method that allowed 2D Ni-MOF to be synthesized directly onto the surface of a polymer substrate, in a single step. Not only this MOF coating was found to be strongly bound to the surface of the polymer substrate but also very uniform and fully functional, even when other inorganic phases were immobilized on the top of this layer. This chemical approach opens the way for the fabrication of hybrid materials with complex polymer substrates and MOF coatings that could be used in a range of possible applications, for instance as chemical sensors, electrodes, adsorbents, optical devices, etc. Our hybrid photocatalysts were tested via photodegradation of Rhodamine B (RhB) dye upon visible light activation, with recycling runs to assess their durability. It was found that the hierarchical heterojunction Ni-MOF/BiOI/AgVO ₃ showed an outstanding ability for the removal of RhB dye, owing to the activity of the Ni-MOF layer in terms of charge transfer, and also partly because of its adsorbing potential. The three photoactive phases demonstrated a strong synergistic effect through coupling. However, more importantly, our findings show that their immobilization itself, regardless of the method used, significantly modified their optoelectronic properties, hence most likely changing the overall mechanism of charge transfer in the heterojunction. The Ni-MOF phase, notably, was found to display a reduced bandgap when obtained by c-ISCAP, which contributed to enhance its activation by visible light irradiation. Finally, it was established that the fractal geometry had a significant impact on the efficiency of the supported catalysts, probably thanks to an increased immobilization ratio of photocatalyst mostly, owing to the larger surface area available.