The Thermodynamic Study Of The Synthesis And Modified Process Of Prussian Blue Analogous

Calorimetry is a non-specific method,so all processes which include heat change can be detected.And isothermal titration calorimetry(ITC)is able to record the thermal signal of the process continuously.Hence,isothermal titration calorimetry technology has gained wide attention.In order to discover the influencing factors on the catalytic properties of Prussian blue analogue(PBA)from the point of view of thermodynamic,we focused on the thermodynamics studies of the synthesis process of seven kinds of Prussian blue analogues,and the modified process of Fe CoPBA by using TAM 2277 calorimeter in this thesis.1.Seven kinds of PBAs(FeCoPBA,Cu Co PBA,NiCo PBA,ZnCoPBA,CdCoPBA,CoCo PBA and MnCo PBA)nanoparticles were prepared,characterized and used to catalyze the epoxidation of styrene,respectively.Then the synthesis processes of these PBAs were studied by using ITC.The results indicated that the formation of these PBAs were all exothermic.The synthesis of ZnCo PBA was both entropy-driven and enthalpy-driven process as the ?S was positive,other processes were all enthalpy-driven reaction except Mn Co PBA,which was not suitable for single-affinity binding site model.It was found that Cu Co PBA which had the highest catalytic performance had the smallest dimension,enthalpy change and Gibbs free energy change,while the ZnCo PBA which had the lowest catalytic performance had the largest dimension,enthalpy change and Gibbs free energy change.2.The Fe Co PBAs modified by alkali metal ion,cesium ion or rubidium ion,were prepared and applied to catalyze the epoxidation of styrene,respectively.Then the synthesis processes of FeCoPBAs modified by cesium ion or rubidium ion were studied by using ITC.It was obtained that the formation of these FeCo PBAs were all exothermic and these processes were enthalpy-driven reaction.With the increase of cesium ion or rubidium ion,the catalytic properties of FeCoPBAs were enhanced significantly,whilst the sizes,the enthalpy change and Gibbs free energy change were decreased.3.FeCo PBA was modified by four kinds of organic ligands,methyl alcohol,ethyl alcohol,tertiary butanol and DMF,and applied to catalyze the epoxidation of styrene,respectively.Then the synthesis processes of FeCoPBAs modified by four kinds of organic ligands were studied by using ITC.The results declared that the formation of these FeCoPBAs were all exothermic.The synthesis processes of FeCo PBA? methyl alcohol,FeCoPBA?ethyl alcohol,Fe Co PBA?tertiary butanol were enthalpy-driven reaction,however that of FeCoPBA?DMF was both entropy-driven and enthalpy-driven process.Compared to FeCo PBA,the catalytic efficiency of FeCo PBA? methyl alcohol was decreased because the binding of methyl alcohol with FeCo PBA was too strong.But the catalytic property of Fe Co PBA?DMF was increased obviously for the weakest binding with FeCoPBA.