Surveying Iron–Organic Framework TAL-1-Derived Materials in Ligandless Heterogeneous Oxidative Catalytic Transformations of Alkylarenes

Abstract

The use of carbonized materials derived from metal–organic frameworks (MOFs) in catalytic organic transformations is less well explored than is the use of MOFs. Here, we survey the oxidative performance of heterogeneous catalyst materials derived from the polycrystalline iron–organic framework TAL-1.

Multi-purpose heterogeneous catalyst material from an amorphous cobalt metal–organic framework

“…30 Typically, Co-N-C catalysts are used for reduction reactions (nitroarenes, 31,32 N-heterocycles, 33 and hydrocarbons 34 ), reductive aminations 35 and alkylations, 36,37 while the oxidative esterification of benzyl alcohols were done under dioxygen. [38][39][40] Overall, the cobalt materials outperformed the three previously reported related Fe-N-C systems (TAL-1-900, TAL-6-900, TAL-7-900), 22,23 and importantly, they sustained their activity over a larger number of cycles (Fig. 2A and B; Tables S6 and S7, ESI †).…”

“…The de novo Co-N-C catalysts were screened against oxidative transformations with tert-butyl peroxide (TBHP) as terminal oxidant at a considerably low catalyst loadings, namely, that of 5 mg mmol À1 . While TBHP-driven oxidations of arylmethanes have been reported to be catalyzed by Fe-N-C materials effectively, 23,[27][28][29] the cobalt corresponding Co-N-C catalysts were not. 30 Typically, Co-N-C catalysts are used for reduction reactions (nitroarenes, 31,32 N-heterocycles, 33 and hydrocarbons 34 ), reductive aminations 35 and alkylations, 36,37 while the oxidative esterification of benzyl alcohols were done under dioxygen.…”

“…During the pyrolysis, however, MOFs undergo drastic molecular rearrangements; hence, amorphous MOFs can be used as the precursors. 20,21 To this end, we recently assessed iron-based catalysts derived from polycrystalline metal-organic framework precursors (TAL-1-900, TAL-6-900, TAL-7-900), 22,23 which were based on carbon-rich 24 organic linkers. Even the slightest variations around the benzimidazole core have led to alterations in the performance of the materials as bifunctional oxygen electrocatalysts 22 and in heterogeneous catalysis.…”

“…Even the slightest variations around the benzimidazole core have led to alterations in the performance of the materials as bifunctional oxygen electrocatalysts 22 and in heterogeneous catalysis. 23 Herein, we report a unique amorphous cobalt-based MOF-derived multifunctional material, which acts as an efficient trifunctional electrocatalyst 25,26 and as a robust heterogeneous catalyst.…”

Iron Triad-Based Bimetallic M–N–C Nanomaterials as Highly Active Bifunctional Oxygen Electrocatalysts

“…Bimetallic M–N–C catalysts were synthesized by carbonizing metal organic materials containing Fe and Co, or Fe and Ni, or Co and Ni. Initially, the organic ligand solutions were mixed with corresponding metal chlorides to form MOMs. − Upon carbonization and acid etching of these MOMs, the resulting bimetallic M–N–C catalysts were obtained, as depicted in Scheme .…”