We constructed highly oriented and ordered macropores within metal-organic framework (MOF) single crystals, opening up the area of three-dimensional–ordered macro-microporous materials (that is, materials containing both macro- and micropores) in single-crystalline form. Our methodology relies on the strong shaping effects of a polystyrene nanosphere monolith template and a double-solvent–induced heterogeneous nucleation approach. This process synergistically enabled the in situ growth of MOFs within ordered voids, rendering a single crystal with oriented and ordered macro-microporous structure. The improved mass diffusion properties of such hierarchical frameworks, together with their robust single-crystalline nature, endow them with superior catalytic activity and recyclability for bulky-molecule reactions, as compared with conventional, polycrystalline hollow, and disordered macroporous ZIF-8.

Carbon-based nanomaterials have been widely used as catalysts or catalyst supports in the chemical industry or for energy or environmental applications due to their fascinating properties. High surface areas, tunable porosity, and functionalization are considered to be crucial to enhance the catalytic performance of carbon-based materials. Recently, the newly emerging metal−organic frameworks (MOFs) built from metal ions and polyfunctional organic ligands have proved to be promising self-sacrificing templates and precursors for preparing various carbon-based nanomaterials, benefiting from their high BET surface areas, abundant metal/organic species, large pore volumes, and extraordinary tunability of structures and compositions. In comparison with other carbon-based catalysts, MOF-derived carbon-based nanomaterials have great advantages in terms of tailorable morphologies and hierarchical porosity and easy functionalization with other heteroatoms and metal/metal oxides, which make them highly efficient as catalysts directly or as catalyst supports for numerous important reactions. In this perspective, we intend to give readers a survey of the research advances in the use of MOFs as self-sacrificing templates and precursors to prepare carbon-based nanomaterials, mainly including heteroatom-doped porous carbons and metal/metal oxide decorated porous carbons for applications as catalysts in energy and environment-related electrocatalysis and traditional heterogeneous catalysis. Finally, some perspectives are provided for future developments and directions of MOF-derived carbon-based materials for catalysis.

Redox-inactive metal ions play pivotal roles in regulating the reactivities of high-valent metal-oxo species in a variety of enzymatic and chemical reactions. A mononuclear non-heme Mn(IV)-oxo complex bearing a pentadentate N5 ligand has been synthesized and used in the synthesis of a Mn(IV)-oxo complex binding scandium ions. The Mn(IV)-oxo complexes were characterized with various spectroscopic methods. The reactivities of the Mn(IV)-oxo complex are markedly influenced by binding of Sc(3+) ions in oxidation reactions, such as a ~2200-fold increase in the rate of oxidation of thioanisole (i.e., oxygen atom transfer) but a ~180-fold decrease in the rate of C-H bond activation of 1,4-cyclohexadiene (i.e., hydrogen atom transfer). The present results provide the first example of a non-heme Mn(IV)-oxo complex binding redox-inactive metal ions that shows a contrasting effect of the redox-inactive metal ions on the reactivities of metal-oxo species in the oxygen atom transfer and hydrogen atom transfer reactions.

A mononuclear non-heme manganese(IV)-oxo complex has been synthesized and characterized using various spectroscopic methods. The Mn(IV)-oxo complex shows high reactivity in oxidation reactions, such as C-H bond activation, oxidations of olefins, alcohols, sulfides, and aromatic compounds, and N-dealkylation. In C-H bond activation, the Mn(IV)-oxo complex can activate C-H bonds as strong as those in cyclohexane. It is proposed that C-H bond activation by the non-heme Mn(IV)-oxo complex does not occur via an oxygen-rebound mechanism. The electrophilic character of the non-heme Mn(IV)-oxo complex is demonstrated by a large negative ρ value of -4.4 in the oxidation of para-substituted thioanisoles.