Study On Ru(Ⅲ) Surface Imprinted Polymers Based On Porous Materials

Ruthenium is a precious metal with excellent physical and chemical properties,which plays a crucial role in aerospace,medicine,catalytic,electronics,and other fields.As a member of platinum group metals,it not only has the excellent properties of other platinum group metal elements,but also has a low price,and has an irreplaceable position in the high-tech field.Due to its non-concentrated distribution,it is difficult to mine ore,and the ore grade is low,it needs to invest a lot of manpower and material resources to screen ruthenium ore particles from metal ore.The ruthenium waste produced in various high-tech fields constitutes the secondary resources of ruthenium,such as sputtering target materials,abandoned ruthenium catalysts,retired high temperature alloy and other wastes,the content of ruthenium is high,and the form of existence is relatively single.Recycling ruthenium from secondary resources is a good way to alleviate the current tight supply and demand in the market.Therefore,it is urgent to prepare a suitable material to effectively enrich and recover ruthenium in secondary resources.In this thesis,using surface imprinting technology and reversible addition-fragmentation chain transfer polymerization,the imprinting system is coated on the surface of the substrate,two kinds of ruthenium ion-imprinted polymers based on porous materials are prepared,their morphology and structure are characterized,and their adsorption,desorption,and other properties are explored.The research results are as follows:1)Firstly,introduction of nitro and reduction to amino for functionalized modification of polystyrene resin RL without active functional groups.Through the amidation reaction,the RAFT reagent is grafted on the substrate,and then the thermosensitive functional monomer N,N-diethylacrylamid(DEA)is polymerized on the surface of the substrate by reversible addition-fragmentation chain transfer polymerization(RAFT).Used Ru(ⅠⅠⅠ)as template ion,acrylamide(AM)and acrylic acid(AA)as functional monomers,N,N-methylenediacrylamide(NMBA)as crosslinker,and ammonium persulfate/N,N,N,N-tetramethylenediamine(AP-TEMED)as compound initiator,preparing a kind of intelligent Ru(ⅠⅠⅠ)surface imprinted polymer(RL@Ru(ⅠⅠⅠ)-SIP)based on RL resin.Characterized RL@Ru(ⅠⅠⅠ)-SIP morphology and structure,and its adsorption property to Ru(ⅠⅠⅠ)was investigated.The results showed that RL@Ru(ⅠⅠⅠ)-SIP was successfully prepared through FTIR characterization.SEM,BET and other characterization methods confirmed that the imprinted layer on the surface of RL@Ru(ⅠⅠⅠ)-SIP had a loose and porous structure.Adsorption was carried out by controlling the single factor variable method,the result indicated that the best adsorption conditions was at 33~oC and p H=2.0.And 33~oC is the temperature slightly higher than the LCST temperature of PDEA.The adsorption conformed to the pseudo-first-order kinetic model and the Langmuir model.The optimal mass ratio of the imprinting system to the matrix was 1:20,and the optimal adsorption capacity was 0.031 mmol/g.2)In order to optimize the synthesis route of Ru(ⅠⅠⅠ)surface imprinted polymer and improve the adsorption effect,on the basis of the above work,the YL resin with its own primary amine group was selected as the matrix.RAFT reagent was introduced into the matrix through amidation reaction,and the temperature-sensitive monomer DEA was polymerized on the surface of the matrix by RAFT polymerization method to prepare the Ru(ⅠⅠⅠ)surface imprinted polymer YL@Ru(ⅠⅠⅠ)-SIP.Its structure and morphology were characterized by SEM,FTIR,BET etc.And its adsorption properties and optimal conditions were investigated,as well as its application to high-temperature alloy electrolytes and evaluation of its performance.The results showed that the successful preparation of YL@Ru(ⅠⅠⅠ)-SIP can be confirmed by the characterization,microscopic morphology presents a penetrating pore structure and cross-linked network structure.The adsorption study showed that the adsorption effect is the best at 33~oC and p H=2.0.The adsorption conformed to the pseudo-first-order kinetic model and Langmuir model.And the highest adsorption capacity was 0.042 mmol/L when the mass ratio of the imprinting system to the matrix was 1:10,which was higher than the optimal adsorption capacity of RL@Ru(ⅠⅠⅠ)-SIP prepared with RL matrix.In its application to high-temperature alloy electrolyte,after a single adsorption-desorption,the concentration of precious metals in the solution is successfully increased,and the sieving of base metal ions such as Fe and Al was achieved.