This review presents comprehensively recent progress in metal-metalloporphyrin frameworks (MMPFs) with an emphasis on versatile functionalities. Following a brief introduction of basic concepts and the potential virtues of MMPFs, we give a snapshot of the historical perspective of MMPFs since 1991. We then summarize four effective strategies implemented frequently to construct prototypal MMPFs. MMPFs represent a resurging class of promising functional materials, highlighted with diverse applications including guest-molecule adsorption and separation, catalysis, nano-thin films and light-harvesting.
In this work, we demonstrate for the first time the introduction of π-complexation into a porous aromatic framework (PAF), affording significant increase in ethylene uptake capacity, as illustrated in the context of Ag(I) ion functionalized PAF-1, PAF-1-SO3Ag. IAST calculations using single-component-isotherm data and an equimolar ethylene/ethane ratio at 296 K reveal that PAF-1-SO3Ag shows exceptionally high ethylene/ethane adsorption selectivity (Sads: 27 to 125), far surpassing benchmark zeolite and any other MOF reported in literature. The formation of π-complexation between ethylene molecules and Ag(I) ions in PAF-1-SO3Ag has been evidenced by the high isosteric heats of adsorption of C2H4 and also proved by in situ IR spectroscopy studies. Transient breakthrough experiments, supported by simulations, indicate the feasibility of PAF-1-SO3Ag for producing 99.95%+ pure C2H4 in a Pressure Swing Adsorption operation. Our work herein thus suggests a new perspective to functionalizing PAFs and other types of advanced porous materials for highly selective adsorption of ethylene over ethane.
Contents 1. Introduction 2. Application of MFS-MOFs in catalysis 2.1 Multi-functional catalytic sites on both organic ligands and metal clusters 2.2 Multi-functional catalytic sites in organic ligands 2.3 Multi-functional catalytic sites in framework and guest moiety separately 2.4 Combine MFS of two guest components 3. Application of MFS-MOFs in gas adsorption/separation 3.1 CO 2 adsorption. 3.1.1 CO 2 adsorption by multifunctional non-metal sites. 3.1.2 CO 2 adsorption by combination of non-metal sites and open metal sites 3.2 Hydrocarbon separation. 4. Application of MFS-MOFs in optics. 5. Application of MFS-MOFs in proton conduction.
We report a strategy of combining a Brønsted acid metal-organic framework (MOF) with Lewis acid centers to afford a Lewis acid@Brønsted acid MOF with high catalytic activity, as exemplified in the context of MIL-101-Cr-SO3H·Al(III). Because of the synergy between the Brønsted acid framework and the Al(III) Lewis acid centers, MIL-101-Cr-SO3H·Al(III) demonstrates excellent catalytic performance in a series of fixed-bed reactions, outperforming two benchmark zeolite catalysts (H-Beta and HMOR). Our work therefore not only provides a new approach to achieve high catalytic activity in MOFs but also paves a way to develop MOFs as a new type of highly efficient heterogeneous catalysts for fixed-bed reactions.
An unprecedented nanoscopic polyhedral cage-containing metal-metalloporphyrin framework, MMPF-1, has been constructed from a custom-designed porphyrin ligand, 5,15-bis(3,5-dicarboxyphenyl)porphine, that links Cu(2)(carboxylate)(4) moieties. A high density of 16 open copper sites confined within a nanoscopic polyhedral cage has been achieved, and the packing of the porphyrin cages via an "ABAB" pattern affords MMPF-1 ultramicropores which render it selective toward adsorption of H(2) and O(2) over N(2), and CO(2) over CH(4).
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