Benefiting from the unique advantages of MOFs materials, efficient delivery of various kinds of drugs has been achieved in some MOF materials. However, it is only the outset of MOFs in drug delivery system, and numerous work need to be done before clinical applications, for example, studying their in vivo toxicity, exploring degradation mechanisms so as to establish real stability of MOFs in body's liquid, providing appropriated surface modification avenue for MOFs, and researching in vivo efficiency and pharmacokinetics of drug-loaded MOFs.
A rational synthetic strategy to construct two supramolecular isomers based on polyoxovanadate organic polyhedra with tetrahedral symmetries is presented. VMOP‐α, a low‐temperature product, has an extremely large cell volume (470 842 Å3), which is one of the top three for well‐defined MOPs. The corner‐to‐corner packing of tetrahedra leads to a quite low density of 0.174 g cm−3 with 1D channels (ca. 5.4 nm). The effective pore volume is up to 93.6 % of cell volume, nearly the largest found in MOPs. For the high‐temperature outcome, VMOP‐β, the cell volume is only 15 513 Å3. The packing mode of tetrahedra is corner‐to‐face, giving rise to a high‐density architecture (1.324 g cm−3; channel 0.8 nm). Supramolecular structural transformation between VMOP‐α and VMOP‐β can be reversibly achieved by temperature‐induced solvent‐mediated transformation. These findings give a good opportunity for understanding 3D supramolecular aggregation and crystal growth based on large molecular tectonics.
An all-inorganic perovskite (CsPbBr3) was introduced into g-C3N4 to fabricate the CsPbBr3@g-C3N4 photocatalyst for photochemical reduction in diluted CO2.
CO2 photoreduction is a promising avenue to alleviate
climate change and energy shortage, and highly active and selective
photocatalysts have been pursued. Discrete metal–organic cages
(MOCs) with tunable structures and dispersion not only render integration
of multiple functional moieties but also facilitate the accessibility
of catalytic sites, yet the studies of MOCs on CO2 reduction
are still underexplored. Herein, a single molecular cage of the Ir(III)
complex-decorated Zr-MOC (IrIII-MOC-NH2) is
proposed for CO2 photoreduction. IrIII-MOC-NH2 shows high reactivity and selectivity in converting CO2 into CO under visible light. The selectivity is of 99.5%
and the turnover frequency reaches ∼120 h–1 which is 3.4-fold higher than that of bulk IrIII-MOC-NH2 and two orders of magnitude higher than that of the classical
metal–organic framework counterpart (IrIII-Uio-67-NH2). The apparent quantum yield is up to 6.71% that ranks the
highest among the values reported for crystalline porous materials.
Moreover, aggregation-induced deactivation of the Ir(III) complex
is restrained after incorporating into MOC-NH2. The density
functional theory calculations and dedicated experiments including
cyclic voltammetry, mass spectrometry and in situ IR show that the
Ir(III) complex is the catalytic center, and −NH2 in the framework plays the synergetic role in the stabilization
of the transition state and CO2 adducts.
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