Preparation Of The Ternary Solid Supramolecular Recognition Materials And Their Fundamental Adsorption Characteristics

90Sr and 137Cs are so-called heat emitting nuclides.It is harmful for the vitrified-highly active liquid waste(HLW)in final geological disposal.They are considered to be one of the most contributors of the radioactivity in HLW.Another long-lived isotope,137Cs,has the long-termed potential risk on environment due to its mobility in final repository.lt is said that they can pose a serious radiation hazard to health and environment.Their separation from HLW is therefore significant.However,remove Sr and Cs from HLW has always been one of the most challenging works that have not been solved yet.In the present work,some ternary solidsupramolecular recognition materials were prepared based on calixcrown and crown ether derivatives,the adsorption behavior of Cs,Sr and some typical elements onto the materials was studied.It provides theoretical and experimental basis for application of the materials in separating Cs and Sr simultaneously.The main results showed as follows:1.Calix[4]BisCrown-6(BC6),Calix[4]BisCrown-5(BC5),nProCalix[4]-Mono-Crown-6(BnPC6),iProCalix[4]MonoCrown-6(BiPC6),nonyloxyCalix[4]-Mono-Crown-6(NoNC6),dodecyloxyCalix[4]MonoCrown-6(DoDC6)were synthesized and characterized by 1H NMR,ESI-MS,elemental analysis and SEM.2.A series of novel ternary solid supramolecular adsorbents,Calix[4]crown/Crown-ether/XAD-7 such as BnPDTX7,DoDDTX7,BC6DCX7,BnPDCX7,NoNDTX7,BC5DTX7 and BC6DCX7 were prepared based on vacuum sucking technology.4’,4,"(5")-di-tert-butyldicyclohexano-18-crown-6(DtBuCH18C6,DT)and dicyclohexyl-18-crown-6(DCH18C6,DC)as two representative crown-ether derivatives were used.It was synthesied by impregnating and immbolizating supramolecular hosts,Calix[4]crowns and Crown-ether derivatives,into polymeric carrier XAD-7.The characterization of SEM,BET,XRD and TG-DSC demonstrated that Calix[4]Crown/Crown-ether/XAD-7 was a mesoporous material combined with XAD-7 through intermolecular interactions in physical pathway.3.The adsorption of 20 typical metal ions onto Calix[4]Crown/Crown-ether/XAD-7 was studied.The effect of HNO3 concentration,contact time,temperature and pH value on the adsorption was studied.The results show that the adsorption of Calix[4]Crown/Crown-ether/XAD-7 strongly depended on the change of HNO3 concentration and pH value.BnPDTX7,DoDDTX7,BC6DCX7,BnPDCX7,NoNDTX7 and BC6DCX7 had significant adsorption behavior for Cs,Sr,Rb,Ba and K.While K and Rb were adsorbed by BC5DTX7.In addition,other tested ions exhibited weak or almost no adsorption onto Calix[4]Crowns/Crown-ethers/XAD-7.4.The adsorption isotherm,kinetics and thermodynamic behavior of Calix[4]Crown/Crown-ether/XAD-7 were studied.The experimental data fitted with Langmuir model well rather than Freundlich,and fitted with pseudo-second-order model,indicative of the monolayer and chemical adsorption mechanism.