Titanium materials are excellent catalysts for a multitude of chemical and photochemical reactions. Specifically, Ti materials exhibit beneficial semiconductor properties making them ideal photocatalysts, and they can be easily activated by peroxides, thus making them versatile oxidation catalysts. When designing solid Ti-based catalysts, high surface area and accessible active sites are required for an active material. Metal-organic frameworks (MOFs) typically exhibit the former of these parameters due to their high crystallinity resulting in a microporous material. As a relevant example, the Ti-based MOFs MIL-125 and NH<sub>2</sub>-MIL-125 have been shown to be active catalysts for photocatalytic H<sub>2</sub> production via water splitting, various photocatalytic reductions, and various chemical oxidations. Due to their molecular dimensions however, the use of MOFs as catalysts has been limited to small reactants. In this work, through the utilization of a vapor-assisted crystallization technique in conjunction with a soft template, microporous MIL-125 exhibiting significant mesoporosity was synthesized (Scheme 1). The mesoporous MIL-125 was then shown as an active catalyst for oxidative desulfurization applications (of a substrate too large to fit into micropores), outperforming a strictly microporous MIL-125 material. The source of this activity was linked to an increase in accessible active sites.

Vapor-assisted crystallization synthesis of a microporous (Ti) MIL-125 exhibiting significant mesoporosity

249th National Meeting (2015)

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