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    Home > Research group of Liming associate professor of Hubei University: preparation of two-dimensional phosphorous materials in a two-dimensional nano reactor based on organometallic framework

    Research group of Liming associate professor of Hubei University: preparation of two-dimensional phosphorous materials in a two-dimensional nano reactor based on organometallic framework

    • Last Update: 2018-07-08
    • Source: Internet
    • Author: User
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    Since the discovery of graphene, two-dimensional materials have been widely concerned by scientists The synthesis of two-dimensional materials has always been the forefront of material chemistry However, its synthesis strategy is very limited, mainly including micelle template method, lamellar crystal stripping method and interface method, which have some limitations Therefore, it is very necessary to develop a practical, economical and simple method to prepare two-dimensional materials Susumu Kitagawa, a professor at Kyoto University in Japan, proposed the use of a cylindrical layered metal organic framework (MOFs) with two-dimensional channels as a nano reactor to synthesize two-dimensional polymers, which has the advantage that the products can be released after the framework is disassembled However, due to the lack of appropriate MOFs, this synthesis strategy has not been applied Recently, liming associate professor research group of College of chemistry and chemical engineering of Hubei University has developed a new strategy for the preparation of two-dimensional materials This work was published in Chemical Science (DOI: 10.1039 / c8sc01439f) with the title of "synthesis of a 2D phosphorus material in a MOF based 2D nano reactor" A new type of column layered MOF was prepared by assembling ligand and CO 2 + to construct a two-dimensional nano reactor Butylene, which has a smaller skeleton, was selected as the pillar unit (bottom of Fig 1a) It was covalently bound to the layer unit (isophthalic acid) by ether bond Due to the kink of bond, the ligand could be bent into a suitable conformation with gap (height ~ 0.7nm, FIG 1b) The length of the extended ligand is ~ 2 nm (Fig 1b, right) The gap of the two-dimensional nano reaction vessel is very suitable for the absorption of white phosphorus (P4), so the author prepared two-dimensional phosphorous materials with P4 as the single system P 4 is confined to the internal two-dimensional space, and a polyphosphate network is generated after radiation-induced polymerization A two-dimensional phosphorus material with self-supporting structure can be obtained by disassembling MOF (Fig 1c) Its structure is shown in Fig 1D, wherein the phosphorus atom is bound by covalent bond, and the ligand runs through the two-dimensional network The author describes the work as an industrial process: "our method is similar to casting iron in a mold The two-dimensional nano reactor is a mold with two-dimensional cavities, in which white phosphorus is polymerized After the resolution of the two-dimensional nano reactor, a separate two-dimensional phosphorous sheet is obtained " Fig 1 (a) the columnar MOF is assembled by ligands and CO 2 +; (b) the structure of ligands; (c) 2D phosphorous materials were prepared in 2D nano reactor; (d) the structure of 2D phosphorous materials (picture source: Chemical Science) Firstly, the ligands were prepared under mild conditions, and then the ligands and CO 2 + were complexed in DMF / ethanol solution under heating conditions to form MOF Crystal, observed by optical microscope, the results show that: MOF is purple red, crystal size is greater than 0.1 mm (Fig 2a) The void height is ~ 0.72 nm If the van der Waals radius is taken into account, the void height is ~ 0.36 nm, indicating that the void of MOF is enough to hold P4 molecule (Fig 2b) The m-phthalic acid group is coordinated with CO 2 + to form a close coordination layer (Fig 2c, d) There is a two-dimensional nano reactor between the layers (Fig 2e) In the compact layer, adjacent ligands are not from the same two-dimensional nanoreactor, but from the top or bottom nanoreactor (Figure 2C) The results show that: (1) P4 molecules can not penetrate the tight layer but stay in a separate 2D nano reactor; (2) stacking 2D nano reactor filled with 2D polyphosphate network can be decomposed by breaking the coordination Fig 2 (a) optical microscope image of MOF crystal; (b) coordination map of adjacent ligands; (c) ball bar model of coordination tight layer; (d) space filling model of coordination tight layer; (E) column distance between two-dimensional nano reactor and two-dimensional nano reactor in MOF (photo source: Chemical Science) In a word, the author developed a new strategy to prepare two-dimensional materials: polymerization in two-dimensional nano reactor A new type of column layer MOF was prepared by assembling ligands and CO2 +, and MOF was polymerized to form a two-dimensional nano reactor The two-dimensional nano reactor has air and humidity stability and can be used to synthesize a variety of two-dimensional materials This study not only provides a new method for the preparation of two-dimensional materials, but also provides a simple method for the safe storage and transportation of highly spontaneous combustion materials Correspondence Professor: Li Ming, associate professor of chemistry and chemical engineering, Hubei University, mainly engaged in two-dimensional polymer film materials, two-dimensional supramolecular membrane materials and their applications in electronics, energy and environmental protection In addition, they are also involved in polymer hydrogel materials and pharmaceutical industry.
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