Syntheses,Structures And Properties Of Main Group Oxysulfide Open-framework Materials

Inorganic open-framework materials have attracted great attention due to their unique structural properties such as ordered channels and high surface area,which were widely used in catalysis,ion-exchange,adsorption and separation,luminescence.They play an important role in environment,chemical engineering,electronic industries,agriculture and medicine.Specific functions oriented,the rational design and synthesis of new inorganic open-framework is one of the hotsports.Based on the relationship between structure and functional properties,the aim of this work is to explor the main group oxysulfide open-framework material.We design and synthesis of novel oxysulfide,and research their significant applications in ion-exchange,photocatalysis,and optics.The main contents and results are as follows:1.A series of pseudo-T4 supertetrahedral [In₄Sn₁₆O₁₀S₃₄]12-clusters have been synthesized under solvothermal conditions,in which organic amines as template and counterions reside in the channel.The incorporation of oxygen gives new clusters and allows for a different construction principle.Specifically,the coordination polyhedra of the metals in the oxysulfide clusters are no longer limited to tetrahedra.There exist SnS₄O₂ octahedra and InS₃O₃ octahedra.The large continuous void space in the compound favors the fast movement of counterions in and out of the structure.Because of the selective bonding interactions of the soft Lewis basic（S2-）sites to heavy metal ions,this material selectively sequesters heavy metal ions from aqueous solutions including ones with heavy concentrations of sodium,calcium,ammonium,magnesium,zinc,carbonate,phosphate,and acetate ions.The removal of heavy metal ions showed highly ion exchange efficiency at p H 2-10.In contrast to chalcogenide clusters,oxychalcogenide clusters can increase the stability of large clusters due to incorporation of oxygen anions.Oxysulfide open-framework materials can combine the semiconductor properties of chalcogenide materials and good stability of oxide materials.2.Oxysulfide open-framework based on pseudo-T4 supertetrahedral [In₄Sn₁₆O₁₀S₃₄]12-cluster exhibits an efficient decomposition of organic pollutants（Methyl Orange,Methylene Blue and Rhodanmine B）under visible-light irradiation.The geometric structure of opened,distorted tetrahedral SnS₄ and distorted octahedral In O₃S₃,SnO₂S₄ play an important role in the photocatalysis.Together with highly dispersive of hybridized valence band and conduction band and well positioned band edges co-contribute to the high performance photocatalytic effectiveness.3.A novel 2-D organic templated bismuth-oxide compound（H₂en）0.5[Bi O（OH）₂（H₂O）]（en=ethylenediamine）has been synthesized in the presence of ethylenediamine acting as a template under mild hydrothermal conditions.In the compound,the Bi atom is coordinated by eight oxygen atoms.The BiO₈ polyhedra share edges or corners with their neighbors to result in an anionic inorganic layer with protonated ethylenediamine cations occupied between layers.Upon excitation at 320 nm,strong fluorescent emission at 476 nm is observed.4.An alkali metal-alkaline earth metal borate Ba3 Li O[B₉O16][B（OH）₃] has been synthesized under a facile hydrothermal condition.The compound contain a 3D B₉O₁₆ network which is constructed by B₉O₁₉（9:3Δ+6T）fundamental building block.The anionic framework can be reduced into an acs topology.The B（OH）₃ locates in the channels.UV-Vis diffuse reflectance spectroscopy demonstrates that the compound has a cutoff edge about 230 nm.Second-harmonic generation（SHG）test shows that the compound is phase matchable and the powder SHG effect is approximately 0.8 times that of KDP.The SHG response of the compond mainly originates from the cooperative action of BO₃,BO₄ and the distorted BaO₉,LiO₇ polyhedra.