TiO₂-Containing Carbon Derived from a Metal–Organic Framework Composite: A Highly Active Catalyst for Oxidative Desulfurization

A new metal-organic framework (MOF) composite consisting of Ti- and Zn-based MOFs (ZIF-8(x)@H₂N-MIL-125; in brief, ZIF(x)@MOF) was designed and synthesized. The pristine MOF [H₂N-MIL-125 (MOF)]- and an MOF-composite [ZIF(30)@MOF]-derived mesoporous carbons consisting of TiO₂ nanoparticles were prepared by pyrolysis (named MDC-P and MDC-C, respectively). MDC-C showed a higher surface area, larger pore sizes, and larger mesopore volumes than MDC-P. In addition, the TiO₂ nanoparticles on MDC-C have more uniform shapes and sizes and are smaller than those of MDC-P. The obtained MDC-C and MDC-P [together with MOF, ZIF(30)@MOF, pure/nanocrystalline TiO₂, and activated carbon] were applied in the oxidative desulfurization reaction of dibenzothiophene in a model fuel. The MDC-C, even with a lower TiO₂ content than that of MDC-P, showed an outstanding catalytic performance, especially with a very low catalyst dose (i.e., a very high quantity of dibenzothiophene was converted per unit weight of the catalyst), fast kinetics (∼3 times faster than that for MDC-P), and a low activation energy (lower than that for any reported catalyst) for the oxidation of dibenzothiophene. The large mesopores of MDC-C and the well-dispersed/small TiO₂ might be the dominant factors for the superior catalytic conversions. The oxidative desulfurization of other sulfur-containing organic compounds with various electron densities was also studied with MDC-C to understand the mechanism of catalysis. Moreover, the MDC-C catalyst can be reused many times in the oxidative desulfurization reaction after a simple washing with acetone. Finally, composing MOFs and subsequent pyrolysis is suggested as an effective way to prepare a catalyst with well-dispersed active sites, large pores, and high mesoporosity.