Synthesis And Properties Of Cluster-Based Chalcogenide Framework Materials Containing Indium

In recent years,the metal chalcogenide open-framework materials(MCOFMs)have been widely studied because of its unique properties such as semiconductor,photoelectric properties,ion exchange,photoelectric catalysis and thermoelectric.Most metal chalcogenide crysallize materials reported currently are formed by the self-assembly of transition metals or main group metal cations and chalcogenide actions in the control of organic amine templates.For main-group metals,indium plays an important role in synthesis of cluster-based chalcogenide framework because it can forms a variety of stable open-framework structure.For three-dimension framework materials with regular channel,it is expected to be as a new type of multifunction materials because of good application in ion exchange and to construct hybrid materials.Although a variety of three-dimensional materials were successfully synthesized,they can not completely meet the need for some extended applications.Therefore,it is still necessary to synthesize novel and stable three-dimensional chalcogenide framework materials by adjusting organic amine templates and synthetic conditions.The novel three-dimensional materials not only inject new vitality for this field but also enrich the type of such materials,which can be applied into the fields of catalysis and solar cells.Based on this,we did the following works:(1)An infinite extented open-framework metal chalcogenide assembled by T5-Cu-In-S supertetrahedral cluster with vertex-edge connection mode was prepared under solvothermal condition by using 3,5-dimethylpiperidine(C7NHi5)as template.Such vertex-edge connection mode was reported for the first time among the cluster-based chalcogenide open ftamework.We studied the effect of connection mode and framework topology on the optical band gap.(2)Under the control of mixed amine,hexahydropyridine(PR)and 1,8-diazabicyclo[5.4.0]undec-7-ene(DBU),a unique non-interpenetrated Mn-In-S open framework with large cavity was built from different size supertetrahedral clusters(T4 and T5).Given the large porosity,we studied the ion exchange to open the hole and CO2 adsorption property of ion-exchanged sample.In addition,we also studied the Mn2+-realted photoluminescent properties.(3)Using 1,5-diazabicyclo[4.3.0]non-5-ene(DBN)and N,N,N’,N’-tetramethyl ethylenediamine(TMED)as templates,we got a Cu-In-Sn-S open framework chalcogenide built from the largest penta-supertetrahedral,(Cu5In12Sn9S42]7-).Because its composition was different from the reported one with the similar structure,we studied the effect of composition of framework on the optical band gap.The project realizes the diversity of the connection mode of indium chalcogenides framework materials and enrichs the secondary structure unit assembly by large sized hybrid clusters,which provides the basic theoretical guidance for synthesis and properties study of indium chalcogenide framework materials.