Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic–hydrophobic metal–organic framework
M. Infas H. MohideenBo XiaoPaul WheatleyAlistair C. McKinlayYang LiAlexandra M. Z. SlawinD.W. AldousNaomi F. CessfordTina DürenXuebo ZhaoRachel GillK. Mark ThomasJohn M. GriffinSharon E. AshbrookRussell E. Morris
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Metal–organic frameworks (MOFs) are nanoporous materials composed of organic linkers and inorganic nodes. The large variety of linkers and nodes and the multiple ways to combine them make MOFs highly tunable materials, which are thoroughly studied for their use in, e.g., catalysis, gas capture, and separation. The chemistry of MOFs is further enriched by defects, e.g., missing linker defects, which provide active sites for catalysis or anchoring sites for introducing new functionalities. A commonly reported method to quantify linker defects assumes the presence of one type of linker and the complete removal of capping agents, solvents, and other impurities upon activation at high temperature, e.g., 400 °C (M-400). However, attempts to use this method for MOFs containing different types of linkers, also called multivariate MOFs (MTV-MOFs), or capping agents that are not completely removed at 400 °C, give inaccurate results and hamper comparing results from different publications. In this work, we have developed a new procedure to compute missing linker defects in Zr-based MOFs using standard analytical techniques to quantify the capping agents that remain in the MOF upon activation at 200 °C (M-200). This method, which has been tested in UiO-66/67 based MOFs, should be applicable to any MOF that (1) has known decomposition products, (2) has no missing cluster defects, (3) has empty pores or contain species that can be quantified after activation, and (4) has a known node composition at 200 °C.
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We report a topology-guided, precise insertion of three distinct secondary linkers into a zirconium-based metal–organic framework, NPF-300. Constructed from a tetratopic linker L and Zr6 cluster, NPP-300 exhibits a unique scu topology and certain flexibility along the crystallographic a axis, and in conjunction with the conformation change of the primary ligand, is able to accommodate the stepwise insertion of three different secondary linkers along the a and c axes. Size-matching and mechanic strain of the resulting framework are two important factors that determine the chemical stability of the inserted linkers. Secondary linker insertion in NPF-300 significantly enables not only its porosity but also potentials to install up to three different functional groups for the construction of multivariate MOFs with homogeneity.
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In this work, we introduce a novel enantiopure chiral spiro bistriazolate linker molecule (H 2-bibta ) and the corresponding first enantiopure bistriazolate-based metal–organic framework, CFA-18 (Coordination Framework Augsburg-18 ).
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Metal-organic framework MOF-5 (i.e. IRMOF-1) with the chemical structure of Zn4O(BDC)3 were successfully synthesized using room temperature synthesis approach of direct-mixing method ans liquid-crystal templating method. The metal clusters organic linker used was benzenedicarboxylic acid (BDC). Direct-mixing approach resulted in MOF-5 with tetragonal cell while the liquid-crystal templating method resulted in cubic structure. The metal/linker ratios were varied from 0.1 to 1 to study the effect of metal linker on the formation of MOF-5 materials and their characteristics. The crystallinity of the evacuated framework MOF-5 materials were increased when the metal/organic linker ratios were increased from 0.3 to 0.5. However, the cubic structure of the evacuated framework was relatively disrupted at metal/linker ratio 0.7.
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For the application of high-surface-area nanoporous platinum (Pt) to catalytic device, electrodes and sensors, dealloying technique, which can synthesize nanoporous Pt, was combined with surface alloying technique. As a result, nanoporous structure with ligament and pore sizes below 10 nm was successfully fabricated on the Pt plate surface. Cyclic voltammetry in H2SO4 indicated that the nanoporous structure increases the true surface area by 170 times. The approximation by spherical pore model suggested that the nanoporous surface layer has a thickness of 200 nm.
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This work reports the effects of metallic glass precursors on the catalytic performance of nanoporous metals. Pd-based multicomponent nanoporous metals with similar nanoporous structure were successfully fabricated by electrochemically dealloying the Pd20Ni60P17B3 and Pd20Ni20Cu40P17B3 metallic glass precursors at the critical dealloying potentials. It was found that the glassy precursors with different chemical compositions result in different doping elements in the as-obtained nanoporous metals and thus lead to different catalytic activities.
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A series of metal–organic frameworks (MOFs) (PCN-606-OH-TPDC, PCN-606-OMe-TPDC, PCN-606-OH-EDDB, and PCN-606-OMe-EDDB) are synthesized through linker installation onto open sites of 8-connected Zr6 clusters in PCN-606-R (where R = −OH or −OMe) parent frameworks of differing flexibilities. The two postsynthetically installed linear linkers possess slight differences in length and bulk, which result in a noticeable difference in the installation temperatures, reflective of a different thermodynamic barrier to incorporation into PCN-606-R. The X-ray crystallographic data as well as the N2 adsorption properties of these four newly produced MOFs are explored and compared to gain a more comprehensive understanding of the implications that this difference in linker size and bulk have during insertion into flexible MOFs.
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3D nanoporous graphene shows excellent physics and electrochemical performance in the fields of energy storage and conversion due to its high-quality and unique interconnected structure. Nanoporous metals, especially nanoporous Ni and nanoporous Cu, have high catalysis for the synthesis of high-quality 3D nanoporous graphene. This chapter presents an overview of the most recent research about the 3D nanoporous graphene, heteroatoms-doped nanoporous graphene, and the nanoporous graphene-based composite materials synthesized by using nanoporous Ni and nanoporous Cu.
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