We synthesized a two-dimensional (2D) crystalline covalent organic framework (spc-COF) that was designed to be fully π-conjugated and constructed from all sp carbons by C=C condensation reactions of tetrakis(4-formylphenyl)pyrene and 1,4-phenylenediacetonitrile. The C=C linkages topologically connect pyrene knots at regular intervals into a 2D lattice with π conjugations extended along both and directions and develop an eclipsed layer framework rather than the more conventionally obtained disordered structures. The spc-COF is a semiconductor with a discrete band gap of 1.9 electron volts and can be chemically oxidized to enhance conductivity by 12 orders of magnitude. The generated radicals are confined on the pyrene knots, enabling the formation of a paramagnetic carbon structure with high spin density. The sp carbon framework induces ferromagnetic phase transition to develop spin-spin coherence and align spins unidirectionally across the material.
Three thermally and chemically stable isoreticular covalent organic frameworks (COFs) were synthesized via room-temperature solvent-free mechanochemical grinding. These COFs were successfully compared with their solvothermally synthesized counterparts in all aspects. These solvent-free mechanochemically synthesized COFs have moderate crystallinity with remarkable stability in boiling water, acid (9 N HCl), and base [TpBD (MC) in 3 N NaOH and TpPa-2 (MC) in 9 N NaOH]. Exfoliation of COF layers was simultaneously observed with COF formation during mechanochemical synthesis. The structures thus obtained seemed to have a graphene-like layered morphology (exfoliated layers), unlike the parent COFs synthesized solvothermally.
Many methods have been proposed for efficient storage of molecular hydrogen for fuel cell applications. However, despite intense research efforts, the twin U.S. Department of Energy goals of 6.5% mass ratio and 62 kg͞m 3 volume density has not been achieved either experimentally or via theoretical simulations on reversible model systems. Carbon-based materials, such as carbon nanotubes, have always been regarded as the most attractive physisorption substrates for the storage of hydrogen. Theoretical studies on various model graphitic systems, however, failed to reach the elusive goal. Here, we show that insufficiently accurate carbon-H 2 interaction potentials, together with the neglect and incomplete treatment of the quantum effects in previous theoretical investigations, led to misleading conclusions for the absorption capacity. A proper account of the contribution of quantum effects to the free energy and the equilibrium constant for hydrogen adsorption suggest that the U.S. Department of Energy specification can be approached in a graphite-based physisorption system. The theoretical prediction can be realized by optimizing the structures of nano-graphite platelets (graphene), which are lightweight, cheap, chemically inert, and environmentally benign. equilibrium constants ͉ hydrogen storage ͉ quantum effects A recent report on hydrogen clathrate hydrate (1) shows that under high pressure, molecular hydrogen can be trapped in the clathrate cavities reaching a mass ratio close to that defined by the U.S. Department of Energy (DOE) (2). However, the hydrogen clathrate is only stable under high pressure or at very low temperature. Simple sterical considerations suggest that the use of a ''help gas'' to stabilize the clathrate hydrate under less severe thermodynamic conditions would lead to the deterioration of the hydrogen storage mass ratio and may not be viable for mobile applications. On the other hand, there have also been numerous experimental studies on the binding capacity of molecular hydrogen with graphitic substrates (3, 4). At technologically viable conditions, reliably reproducible results are still far from the DOE goal (3, 4). In the attempt to understand and improve the storage capacity of graphitic materials, calculations have been made on many models. Some of the calculations were based on empirical interaction potentials (5-9), and the others used potentials derived from quantum mechanical calculations (10-16). The role of quantum behavior of molecular hydrogen at low temperatures has also been investigated (6,8,(17)(18)(19). Unfortunately, the binding capacity for hydrogen at near-ambient conditions has not been calculated, including the quantum effects and accurate, ab initio-based interaction potentials. To date, there has not been a reliable theoretical study indicating that the DOE goal of 6.5% mass ratio can or cannot be achieved in pure graphitic materials.The interaction of nonpolar H 2 molecules with physisorption substrates in graphitic system is mainly the London dispersion. Accurate...
Highly luminescent covalent organic frameworks (COFs) are rarely achieved because of the aggregation-caused quenching (ACQ) of π-π stacked layers. Here, we report a general strategy to design highly emissive COFs by introducing an aggregation-induced emission (AIE) mechanism. The integration of AIE-active units into the polygon vertices yields crystalline porous COFs with periodic π-stacked columnar AIE arrays. These columnar AIE π-arrays dominate the luminescence of the COFs, achieve exceptional quantum yield via a synergistic structural locking effect of intralayer covalent bonding and interlayer noncovalent π-π interactions and serve as a highly sensitive sensor to report ammonia down to sub ppm level. Our strategy breaks through the ACQ-based mechanistic limitations of COFs and opens a way to explore highly emissive COF materials.
We propose a two-dimensional crystal which possesses low indirect band gaps of 0.55 eV (monolayer) and 0.43 eV (bilayer) and high carrier mobilities similar to those of phosphorene: GeP3. GeP3 has a stable three-dimensional layered bulk counterpart which is metallic and is known from experiment since 1970. GeP3 monolayer has a calculated cleavage energy of 1.14 J m -2 , which suggests exfoliation of bulk material as viable means for the preparation of mono-and few-layer materials. The material shows strong interlayer quantum confinement effects, resulting in a band gap reduction from mono-to bilayer, and then to a semiconductor-metal transition between bi-and triple layer. Under biaxial strain, the indirect band gap can be turned into a direct one. Pronounced light absorption in the spectral range from ~600 to 1400 nm is predicted for monolayer and bilayer and promises applications in photovoltaics.
Two water-stable covalent organic frameworks (COFs) named NUS-2 and NUS-3 having two-dimensional (2D) layered structures with different pore sizes were synthesized. These COFs were exfoliated into nanosheets and even monolayers with high aspect ratio. They were subsequently blended with commercial polymers poly(ether imide) (Ultem) or polybenzimidazole (PBI) into mixed matrix membranes (MMMs) exhibiting highly homogeneous textures due to the excellent compatibility between COF fillers and polymer matrixes. Thanks to the selective gas sorption properties of the porous COF fillers, the prepared MMMs exhibited increased gas permeabilities with NUS-2@PBI demonstrating an excellent H2/CO2 permselectivity that exceeded the 2008 Robeson upper bound. Our approach of using exfoliated 2D COFs as porous fillers in MMMs paves a novel way toward the tailored synthesis of advanced composite membrane materials for clean energy and environmental sustainability.
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