The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of in...The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite （FeSe2） by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by： FeSe2 ＋ 2Fe3＋ = 2Se^0 ＋ 3Fe2＋. Kinetic studies indicated that the reaction can be described by second-order rate law, with rate constants of 0.49±0.01, 0.85±0.02, 1.84±0.04, and 3.29±0.13 L mol^-1 s^-1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3＋ oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe^3＋ suggests that ferric iron may play a significant role in FeSe2 oxidation process （e.g., by Se^4＋, 02, etc.） and Se^0 should be the first reaction product. Also, it was shown that the reduction rate of Fe^3＋ or Se^4＋ by pyrite （FeS2） can be significantly increased in the presence of FeSe2, suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium （i.e., selenite and selenate） in the Se-rich environment.展开更多
Fe3 O4 has attracted tremendous interest in vast areas of biomedicine and catalysis as well as environment engineering.However,it is highly desired to fully understand the chemical kinetic process and propose a genera...Fe3 O4 has attracted tremendous interest in vast areas of biomedicine and catalysis as well as environment engineering.However,it is highly desired to fully understand the chemical kinetic process and propose a general,surfactantfree,large-scale synthesis approach for Fe3 O4 spheres.Herein,we developed a facile scalable solvothermal method in the absence of surfactants to produce Fe3 O4 spheres with the yield of 5.1 g,which present tunable sizes from 107 to 450 nm by modulated molar ratio of Fe3+/COO-in the solution.Particularly,it is observed that the reactants undergo a redox process,composed of a precipitation-dissolution equilibrium combined with a coordination reaction(termed as RPC),to the final product based on the LaMer model.It is worth noting that the generation of di-carboxyl group and its coordination with iron cations determine the formation of Fe3 O4 spheres.This work not only offers a strategy to precisely tailor the particle size in scalable synthesis process,but also gives the insight on the role of dihydric alcohol in the formation mechanism of Fe3 O4 spheres in the absence of surfactants.展开更多
In recent years, visible light photoredox catalysis has emerged as an important research area in synthesis. In this review, we describe the recent progress in the visible light induced cycloaddition reactions, includi...In recent years, visible light photoredox catalysis has emerged as an important research area in synthesis. In this review, we describe the recent progress in the visible light induced cycloaddition reactions, including [2+2], [3+2], [4+2] and [2+2+2] cycloadditions, for the construction of four-, five- or six-membered cycles and polycycles. Furthermore, the mechanisms for these transformations are also discussed, in which the formation of the radicals is initiated by a visible light photoredox catalysis process.展开更多
基金supported by the Special Foundation for High-Level Radioactive Waste Disposal(2007-840,2012-851)the National Natural Science Foundation of China(11075006,91026010)+1 种基金the China Postdoctoral Science Foundation Project(2013M530013)the Collaborative Project from the Key Laboratory of Mineralogy and Metallogeny,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences(KLMM20120203)
文摘The mobility and bioavailability of selenium is a major health and environmental issue and a main concern for geological disposal of high-level radioactive waste. Chemically and/or microbially mediated oxidation of insoluble Se-bearing particulate, such as iron selenides, to dissolved and mobile phases controls the transport and distribution of Se in the environment. The oxidation of ferroselite （FeSe2） by ferric iron was investigated in anoxic conditions. The redox reaction can be represented by： FeSe2 ＋ 2Fe3＋ = 2Se^0 ＋ 3Fe2＋. Kinetic studies indicated that the reaction can be described by second-order rate law, with rate constants of 0.49±0.01, 0.85±0.02, 1.84±0.04, and 3.29±0.13 L mol^-1 s^-1 at pH 1.62, 1.87, 2.23, and 2.49, respectively. The positive correlation between reaction rate and pH implies that diffusion of Fe3＋ oxidant to the mineral surface is the rate-determining step. The strong reactivity of FeSe2 towards Fe^3＋ suggests that ferric iron may play a significant role in FeSe2 oxidation process （e.g., by Se^4＋, 02, etc.） and Se^0 should be the first reaction product. Also, it was shown that the reduction rate of Fe^3＋ or Se^4＋ by pyrite （FeS2） can be significantly increased in the presence of FeSe2, suggesting a stronger reactivity of FeSe2 compared with pyrite. The results obtained extend our knowledge about the subtle interaction between Se, pyrite and iron selenides in the environment, and give insight into the transfer of selenium from iron selenides to bio-available selenium （i.e., selenite and selenate） in the Se-rich environment.
基金financially supported by the National Natural Science Foundation of China(51631001,51672010 and81421004)the National Key R&D Program of China(2017YFA0206301 and 2016YFA0200102)
文摘Fe3 O4 has attracted tremendous interest in vast areas of biomedicine and catalysis as well as environment engineering.However,it is highly desired to fully understand the chemical kinetic process and propose a general,surfactantfree,large-scale synthesis approach for Fe3 O4 spheres.Herein,we developed a facile scalable solvothermal method in the absence of surfactants to produce Fe3 O4 spheres with the yield of 5.1 g,which present tunable sizes from 107 to 450 nm by modulated molar ratio of Fe3+/COO-in the solution.Particularly,it is observed that the reactants undergo a redox process,composed of a precipitation-dissolution equilibrium combined with a coordination reaction(termed as RPC),to the final product based on the LaMer model.It is worth noting that the generation of di-carboxyl group and its coordination with iron cations determine the formation of Fe3 O4 spheres.This work not only offers a strategy to precisely tailor the particle size in scalable synthesis process,but also gives the insight on the role of dihydric alcohol in the formation mechanism of Fe3 O4 spheres in the absence of surfactants.
基金supported by the National Natural Science Foundation of China(2140204621172060+2 种基金21472039)the Specialized Research Fund for the Doctoral Program of Higher Education(20120161110041)the Hunan Provincial Natural Science Foundation of China(13JJ2018)
文摘In recent years, visible light photoredox catalysis has emerged as an important research area in synthesis. In this review, we describe the recent progress in the visible light induced cycloaddition reactions, including [2+2], [3+2], [4+2] and [2+2+2] cycloadditions, for the construction of four-, five- or six-membered cycles and polycycles. Furthermore, the mechanisms for these transformations are also discussed, in which the formation of the radicals is initiated by a visible light photoredox catalysis process.
