A metal-organic nanotube (MONT) was synthesized by linking up the bent organic ligands and the tetra-coordinated zinc cations under mild conditions. Structural analysis revealed that the MONT has a very large exterior wall diameter of 4.91 nm and an interior channel diameter of 3.32 nm. Interlocking of the nanotubes gives rise to a 3D chiral framework containing 1D helical cylindered channels with diameter of 2.0 nm. The MONT has very interesting property by synergizing the functionality of nanotubes, metal-organic frameworks (MOFs), and N-heterocyclic carbenes (NHCs). The dye adsorption experiments demonstrate that the channels of the MONTs are accessible to large reagents typically used for catalysis. The postmodification of the MONT can be easily operated by unmarking the imidazolium moieties in the channel walls, which was conducted as a highly active heterogeneous catalyst for Suzuki-Miyaura and Heck coupling reactions, hydrogenation of olefins and nitrobenzene, while the constituent elements are less efficient for these reactions under the same conditions.
Four porous metalloporphyrinic framework materials, [(CH3)2NH2][Zn2(HCOO)2(Mn(III)-TCPP)]·5DMF·2H2O (1; H6TCPP = tetrakis(4-carboxyphenyl)porphyrin), [(CH3)2NH2][Cd2(HCOO)2(Mn(III)-TCPP)]·5DMF·3H2O (2), [Zn2(HCOO)(Fe(III)(H2O)-TCPP)]·3DMF·H2O (3), and [Cd3(H2O)6(μ2-O)(Fe(III)-HTCPP)2]·5DMF (4) were synthesized by heating a mixture of M(III)Cl-H4TCPP (M = Mn and Fe) and M' (M' = Zn or Cd) nitrate in a mixed solvent of DMF and acetic acid. Compounds 1-3 are built up from M'2(COO)4 paddle-wheel subunits bridged by M(III)-TCPP and formate ligands to form their 3D connections. The formate pillar heterogeneously connects with M and M' cations in 1 and 2 and homogeneously joins M' cations in 3. The μ2-O bridged Fe(III)-HTCPP dimer performs as a decadentate ligand to link 10 cadmium cations for the formation of an interesting 3D coordination network of 4. The four porphyrinic frameworks present interesting catalytic properties in the selective epoxidation of olefins, oxidation of cyclohexane, and intermolecular aldol reaction of aldehydes and ketones.
A new bifunctional N-heterocyclic carbene (NHC) precursor was used to construct two metal-organic frameworks, which can anchor palladium(II) sites by post-modification, presenting remarkable framework dependent catalytic activities.
Abstract:Since the weight of overburden is sustained by both the backfill body and the unmined solid coal in coal mining with compacted backfilling (CMCB) panels, the stress and deformation characteristics of the surrounding rocks in coal mining are radically changed. The overburden movement control mechanism by coordinating with backfill body and shield in CMCB was studied systematically in this paper. Based on the analysis of deformational and structural characteristics of surrounding rock in CMCB panels, the methods of theoretical analysis, numerical simulation and engineering test are employed. The results show that the fracture of the main roof is mainly controlled by the filling ratio ϕ and is non-correlated to the shield supporting pressure p. However, p has a significant control effect on the deflection of roof within the shield canopy length, and adversely affects the filling ratio. With the increase of the filling ratio of the gob, the maximum sagging of the immediate and the main roofs, the peak front and the influence range of the abutment pressures are gradually reduced. Correspondingly, the stable period of internal pressure of backfill body in the gob is shortened. Engineering practice shows that the sagging of the gob roof, the distribution of the abutment pressure, the distribution of the internal pressure in the backfill body, and the ground surface sagging results obtained by the in-situ measurement are approximately corresponding to the theoretical analysis and numerical simulation results.
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