Inducing porosity and growing carbon nanofibers in ferroin perchlorate: An example of morphological transitions in coordination complexes

Inducing porosity in solid coordination complex crystals, which are an important class of catalysts, is critical for many applications where a high surface area is required. However, unlike metal organic frameworks (MOFs), fabrication of porous coordination crystals remains a significant challenge. Here we demonstrate a simple method to produce and modulate porosity in coordination complex crystals using ferroin perchlorate, a model system that combines a common ionic complex with a very reactive counter-ion. Using thermal chemical vapor deposition (CVD), we show that by annealing ferroin perchlorate crystals at 350 °C under a flow of ethylene, hydrogen, argon, and oxygen, we induced pores in the crystal. We demonstrate that small amounts of oxygen, which may combine with hydrogen to form water, are essential for pore formation. We also demonstrate that pore size and density can be easily controlled by varying the ethylene flow. Upon raising the annealing temperature to 500 °C, we observed a second transition in which carbon nanofibers (CNFs) grew from the porous crystal. This approach represents a simple and effective method for the synthesis of porous materials with good control over pore size and density. It also enables the synthesis of complex networks of nanostructures (in our case CNFs) by simply varying process parameters such as temperature and gas flows. This represents an important advance for the fabrication of porous coordination complex crystals.