By using the strategy of pre-assembly chlorosulfonation applied to a linker precursor, the first sulfonated zirconium metal–organic framework ( JUK-14 ) with two-dimensional (2D) structure, was synthesized. Single-crystal X-ray diffraction reveals that the material is built of Zr6O4(OH)4(COO)8 oxoclusters, doubly 4-connected by angular dicarboxylates, and stacked in layers spaced 1.5 nm apart by the presence of sulfonic groups. JUK-14 exhibits excellent hydrothermal stability, permanent porosity confirmed by gas adsorption studies, and shows high (>10−4 S/cm) and low (<10−8 S/cm) proton conductivity under humidified and anhydrous conditions, respectively. Post-synthesis inclusion of imidazole improves the overall conductivity increasing it to 1.7×10−3 S/cm at 60 °C and 90 % relative humidity, and by 3 orders of magnitude at 160 °C. The combination of 2D porous nature with robustness of zirconium MOFs offers new opportunities for exploration of the material towards energy and environmental applications. 相似文献
Among various two-dimensional (2D) materials, organic 2D polymers have attracted much attention, owing to their specific properties, such as lightweight, good flexibility, adjustable structure, and high adaptability. In recent years, more and more scientists have devoted to the research on their structural design, synthesis, characterization, and potential properties. However, in contrast to traditional one-dimensional (1D) and three-dimensional (3D) network macromolecules, the synthesis of 2D structures presents a challenge to polymer chemists, because polymerization usually takes place in a spatially random manner in solution-phase synthesis. In this review, we will focus on the synthesis methods of organic 2D materials, which have played a pivotal role since the beginning of the development of this field. We will highlight the representative examples according to the different types of polymers, including supramolecular organic 2D layers and covalent organic 2D polymers, and identify possible future research directions. 相似文献
The development of nonprecious metal–nitrogen–carbon (M-N-C) materials with efficient metal utilization and abundant active sites for the oxygen reduction reaction (ORR) is of great significance for fuel cells and metal–air batteries. Ultrasmall 2 D CoxZn2−x(benzimidazole)4 [CoxZn2−x(bim)4] bimetallic metal–organic framework (MOF) nanosheets (≈2 nm thick) are synthesized by a novel bottom-up strategy and then thermally converted into a core–shell structure of sub-5 nm Co nanodots (NDs) wrapped with 2 to 5 layers of Co,N-codoped graphene (Co@FLG). The size of the Co NDs in Co@FLG could be precisely controlled by the Co/Zn ratio in the CoxZn2−x(bim)4 nanosheet. As an ORR electrocatalyst, the optimized Co@FLG exhibits an excellent half-wave potential of 0.841 V (vs. RHE), a high limiting current density of 6.42 mA cm−2, and great stability in alkaline electrolyte. Co@FLG also has great ORR performance in neutral electrolyte, as well as in Mg–air batteries. The experimental studies and DFT calculations reveal that the high performance of Co@FLG is mainly attributed to its great O2 absorptivity, which is endowed by the abundant Co−Nx and pyridinic-N in the FLG shell and the strong electron-donating ability from the Co ND core to the FLG shell. This elevates the eg orbital energy of CoII and lowers the activation energy for breaking the O=O/O−O bonds. This work sheds light on the design and fabrication of 2 D MOFs and MOF-derived M-N-C materials for energy storage and conversion applications. 相似文献
Abstract This work describes the estimation of uncertainty following the “bottom‐up” and the “top‐down” approaches for the determination of several trace metals in seawater when using a classical 1‐pyrrolidinedithiocarbamate/diethyldithiocarbamate/freon extraction method followed by electrothermal atomic absorption spectrometry. A detailed analysis of the uncertainty sources of this method is included, which allows estimating the expanded uncertainties. The results show that the main contribution to the relative overall uncertainty is the extraction step. The estimation of the uncertainty components is shown to be a suitable tool for the experimental design in order to obtain a small uncertainty in the analytical result. 相似文献
Unprecedented double S2− templated Ag27 clusters have been stabilized by 5,10,15,20-tetra(4-pyridyl)porphyrin (TPyP-H2) ligands to afford a robust 2D metal–organic framework ( Ag27-MOF ). This silver cluster-assembled material serves as a highly efficient heterogeneous catalyst for the cyclization of both terminal and internal propargylamines with CO2 under atmospheric pressure. Density functional theory (DFT) calculations illustrate that the high catalytic activity and broad substrate scope are attributable to the saddle-shaped metallic node in Ag27-MOF , which features an accessible platform with high-density silver atoms as π-Lewis acid sites for activating C≡C triple bonds. As a result, different sterically hindered alkyne substrates can be effectively activated through π-interactions with these cationic silver centers. 相似文献
This review summarizes recent developments made in the incorporation of functional materials into organic polymer monoliths, together with new monolithic forms and formats, which enhance their application as supports and stationary phase materials for sample preparation and chromatographic separations. While polymer monoliths are well‐known supports for the separation of large molecules, recent developments have been made to improve their features for the separation of small molecules. The selectivity and performance of organic polymer monoliths has been improved by the incorporation of different materials, such as metal‐organic frameworks, covalent organic frameworks, or other types of nanostructured materials (carbon nanohorns, nanodiamonds, polyoxometalates, layered double hydroxides, or attapulgite). The surface area of polymer monoliths has been significantly increased by polymer hypercrosslinking, resulting in increased efficiency when applied to the separation of small molecules. In addition, recent exploration of less conventional supports for casting polymer monoliths, including photonic fibres and 3D printed materials, has opened new avenues for the applications of polymer monoliths in the field of separation science. Recent developments made in these topics are covered, focusing on the strategies followed by the authors to prepare the polymer monoliths and the effect of these modifications on the developed analytical applications. 相似文献
Non-noble metal-based bifunctional electrocatalysts are highly desired for water electrolysis. However, constructing a water electrolyzer using a sole catalyst without compromising either its oxygen evolution reaction (OER) or hydrogen evolution reaction (HER) performance is still challenging. In this study, a simple strategy is developed to integrate 2 D and 0 D CoP in the same metal–organic framework precursor-derived hollow N-doped carbon nanotube-assembled polyhedron (HNCNP). The unique hierarchical structure endows the resulting nanocomposite with both the advantages of more exposed active sites for 2 D and large surface-to-volume ratio for 0 D materials, whereas the hollow interior could benefit the charge and mass transfer properties. Thus, CoP/HNCNP@2 D CoP exhibits outstanding OER and HER activity and a low cell voltage when employed as both the anode and cathode in a two-electrode water electrolyzer. The approach of integrating the same metal phosphide phase with diverse dimensions may inspire new ways to design hierarchical nanostructures for advanced energy conversion applications. 相似文献
Metal–organic frameworks (MOFs) are among the most attractive porous materials known today, exhibiting very high surface areas, tuneable pore sizes and shapes, adjustable surface functionality, and flexible structures. Advances in the formation of MOF crystals, and in their subsequent assembly into more complex and/or composite superstructures, should expand the scope of these materials in many applications (e.g., drug delivery, chemical sensors, selective reactors and removal devices, etc.) and facilitate their integration onto surfaces and into devices. This Concept article aims to showcase recently developed synthetic strategies to control the one‐, two‐ and three‐dimensional (1‐, 2‐ and 3D) organisation of MOF crystals. 相似文献
Synthesizing 2D metal–organic frameworks (2D MOFs) in high yields and rational tailoring of the properties in a predictable manner for specific applications is extremely challenging. Now, a series of porphyrin‐based 2D lanthanide MOFs (Ln‐TCPP, Ln=Ce, Sm, Eu, Tb, Yb, TCPP=tetrakis(4‐carboxyphenyl) porphyrin) with different thickness were successfully prepared in a household microwave oven. The as‐prepared 2D Ln‐TCPP nanosheets showed thickness‐dependent photocatalytic performances towards photooxidation of 1,5‐dihydroxynaphthalene (1,5‐DHN) to synthesize juglone. Particularly, the Yb‐TCPP displayed outstanding photodynamic activity to generate O2? and 1O2. This work not only provides fundamental insights into structure designing and property tailoring of 2D MOFs nanosheets, but also pave a new way to improve the photocatalytic performance. 相似文献
Force‐field based grand‐canonical Monte Carlo simulations are employed to predict the hydrogen adsorption properties of seven structurally different MOFs. The performance of different parameter sets is assessed by comparison with experimental data, and the capabilities and limitations of the methodology are critically discussed, with a particular emphasis on systems with unsaturated metal sites. In addition to adsorption isotherms and isosteric heats of adsorption, the preferred adsorption sites are obtained from a detailed analysis of the calculated hydrogen density fields. Where possible, these positions are compared to the results of neutron diffraction experiments. This study highlights the capabilities of computational methods to identify the structural features which are most favourable for hydrogen adsorption, providing valuable implications for the synthesis of novel MOFs.相似文献
Metal‐organic frameworks (MOFs), which are known as a class of porous coordination polymers, have proven to be of great significance to manifold applications, owing to their fascinating topology, ultrahigh porosity, enormous internal surface area, and the combination of being as rigid as inorganic materials and as flexible as organic materials . In this review, we give a concise history of the development of MOFs as functional materials prior to our entry into this area in 2006, then a summary of our road to participate in and extend the outline of the research in MOFs chemistry, as well as the challenge in further designing applicable functional materials. We describe not only the road of evolution from the past, present, and future of this chemistry, but also the road to finalize a functional material from the desire to the design, synthesis, and postmodification of a MOF. Throughout the review, we particularly emphasize the improvements in the application of MOFs as heterogeneous catalysts, such as employing MOFs as one component for the construction of composites, and their extended scope in tough catalytic reactions. Examples of applications in gas storage and separation, small molecular sensing, and our perspectives for future applications triggered by MOFs, are also introduced.
Recording the evolution of concentration profiles in nanoporous materials opens a new field of diffusion research with particle ensembles. The technique is based on the complementary application of interference microscopy and IR micro‐imaging. Combining the virtues of diffusion measurements with solids and fluids, it provides information of unprecedented wealth and visual power on transport phenomena in molecular ensembles. These phenomena include the diverging uptake and release patterns for concentration‐dependent diffusivities, the mechanisms of mass transfer at the fluid–solid interface and opposing tendencies in local and global concentration evolution.相似文献
