Eu（ Ⅲ ） can be utilized as an indirect electrochemical probe to investigate the interaction of bio-molecules such as DOPA and Dopamine with Ca（ Ⅱ ） in vitro. The interaction of DOPA and Dopamine with Eu（ Ⅲ ）...Eu（ Ⅲ ） can be utilized as an indirect electrochemical probe to investigate the interaction of bio-molecules such as DOPA and Dopamine with Ca（ Ⅱ ） in vitro. The interaction of DOPA and Dopamine with Eu（ Ⅲ ）-Eu（ Ⅱ ） redox pair was investigated by electrochemical techniques. Both the neurotransmitters are structurally related and undergo interaction with Eu （Ⅲ ）. Eu （ Ⅲ ） coordinates with DOPA and Dopamine through five-member chelate tings via carboxylic oxygen and amino nitrogen. The electrode kinetic parameters viz, transfer coefficient （αna）, diffusion coefficient （D）, forward heterogeneous rate constant （ k^0 fh） were evaluated for Eu（ Ⅲ ）-DOPA/Eu（ Ⅲ ）-Dopamine. The results obtained were used to investigate the nature of interaction of Eu （Ⅲ） with muhi-donor biomolecules. The possible mechanism was also proposed.展开更多
Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electr...Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.展开更多
To explore the kinetic adsorption under continuous and nonequilibrium states, an integration of continuous measurement and adsorption platform kinetics method was proposed, which was initially called the ICM-AP kineti...To explore the kinetic adsorption under continuous and nonequilibrium states, an integration of continuous measurement and adsorption platform kinetics method was proposed, which was initially called the ICM-AP kinetics method, and a corresponding kinetic adsorption experimental method was developed. Adsorption experiments of europium(Eu) on Ca-bentonite,Na-bentonite, and the D231 cation exchange resin were performed using the ICM-AP kinetics method and continuous measurements. Because the kinetic experimental results observed in this study were different from those of traditional batch adsorption data, pseudo-first-order or pseudo-second-order kinetic models were unsuitable for fitting the experimental data.Hence, a liquid membrane diffusion(LMD) model was developed based on the assumption of simultaneous adsorption/desorption to discuss the mechanism of kinetic adsorption. The kinetic adsorption mechanism was also studied by using XPS.The results indicated that the proposed adsorption model can fit the experimental data more suitably, and the adsorption/desorption behaviors of Eu on bentonite and the D231 resin were simultaneously observed, suggesting that the adsorption kinetics of Eu(Ⅲ) was mainly dominated by hydrated Eu(Ⅲ) ions on the liquid membrane.展开更多
基金Foundation ite m:Project supported by DST(SP/S1/F03/98)
文摘Eu（ Ⅲ ） can be utilized as an indirect electrochemical probe to investigate the interaction of bio-molecules such as DOPA and Dopamine with Ca（ Ⅱ ） in vitro. The interaction of DOPA and Dopamine with Eu（ Ⅲ ）-Eu（ Ⅱ ） redox pair was investigated by electrochemical techniques. Both the neurotransmitters are structurally related and undergo interaction with Eu （Ⅲ ）. Eu （ Ⅲ ） coordinates with DOPA and Dopamine through five-member chelate tings via carboxylic oxygen and amino nitrogen. The electrode kinetic parameters viz, transfer coefficient （αna）, diffusion coefficient （D）, forward heterogeneous rate constant （ k^0 fh） were evaluated for Eu（ Ⅲ ）-DOPA/Eu（ Ⅲ ）-Dopamine. The results obtained were used to investigate the nature of interaction of Eu （Ⅲ） with muhi-donor biomolecules. The possible mechanism was also proposed.
基金supported by the Science and Technology Foundation of Guizhou Province,China(No.[2020]1Y163)the National Natural Science Foundation of China(No.41827802).
文摘Fe(Ⅲ)has been proved to be a more eff ective oxidant than dissolved oxygen at ambient temperature,however,the role of Fe(Ⅲ)in pyrite acidic pressure oxidation was rarely discussed so far.In this paper,in-situ electrochemical investigation was performed using a flow-through autoclave system in acidic pressure oxidation environment.The results illustrated that increasing Fe(Ⅲ)concentrations led to raising in redox potential of the solution,and decreased passivation of pyrite caused by deposition of elemental sulfur.Reduction of Fe(Ⅲ)at pyrite surface was a fast reaction with low activation energy,it was only slightly promoted by rising temperatures.While,the oxidation rate of pyrite at all investigated Fe(Ⅲ)concentrations increased obviously with rising temperatures,the anodic reaction was the rate-limiting step in the overall reaction.Activation energy of pyrite oxidation decreased from 47.74 to 28.79 kJ/mol when Fe(Ⅲ)concentration was increased from 0.05 to 0.50 g/L,showing that the reaction kinetics were limited by the rate of electrochemical reaction at low Fe(Ⅲ)concentrations,while,it gradually turned to be diffusion control with increasing Fe(Ⅲ)concentrations.
基金This work was supported by the Natural Science Foundation of the Jiangxi Province,China(No.20202BABL203004)Opening Project of the State Key Laboratory of Nuclear Resources and Environment(East China University of Technology)(No.2022NRE23)Opening Project of the Jiangxi Province Key Laboratory of Polymer Micro/Nano Manufacturing and Devices(No.PMND202101).
文摘To explore the kinetic adsorption under continuous and nonequilibrium states, an integration of continuous measurement and adsorption platform kinetics method was proposed, which was initially called the ICM-AP kinetics method, and a corresponding kinetic adsorption experimental method was developed. Adsorption experiments of europium(Eu) on Ca-bentonite,Na-bentonite, and the D231 cation exchange resin were performed using the ICM-AP kinetics method and continuous measurements. Because the kinetic experimental results observed in this study were different from those of traditional batch adsorption data, pseudo-first-order or pseudo-second-order kinetic models were unsuitable for fitting the experimental data.Hence, a liquid membrane diffusion(LMD) model was developed based on the assumption of simultaneous adsorption/desorption to discuss the mechanism of kinetic adsorption. The kinetic adsorption mechanism was also studied by using XPS.The results indicated that the proposed adsorption model can fit the experimental data more suitably, and the adsorption/desorption behaviors of Eu on bentonite and the D231 resin were simultaneously observed, suggesting that the adsorption kinetics of Eu(Ⅲ) was mainly dominated by hydrated Eu(Ⅲ) ions on the liquid membrane.
基金supported by the National Natural Science Foundation of China(20972015)the Natural Science Foundation of Beijing(Grant2082016)a joint project of Beijing Municipal Education Commission(China)
