Dark formation of hydroxyl radical upon oxidation of reduced iron minerals plays an important role in the degradation and transformation of organic and inorganic pollutants.Herein,we compared the hydroxyl radical form...Dark formation of hydroxyl radical upon oxidation of reduced iron minerals plays an important role in the degradation and transformation of organic and inorganic pollutants.Herein,we compared the hydroxyl radical formation from various reduced iron minerals at different redox conditions.·OH production was generally observed from the oxidation of reduced iron minerals,following the order:mackinawite(FeS)>reduced nontronite(iron-bearing smectite clay)> pyrite(FeS2)> side rite(FeCO3).Structural Fe^2+ and dissolved O2 play critical roles in ·OH production from reduced iron minerals.·OH production increases with decreasing pH,and Cl^-has little effect on this process.More importantly,dissolved organic matter significantly enhances ·OH production,especially under O2 purging,highlighting the importance of this process in ambient environments.This sunlight-independent pathway in which ’OH forms during oxidation of reduced iron minerals is helpful for understanding the degradation and transformation of various inorganic and organic pollutants in the redox-fluctuation environments.展开更多
The dark oxidation reactions of ethers including aether, isopropyl ether, phenyl isopropyl ether, and benzyl isopropyl ether have been studied by using density functional theory calculations. The structures of initial...The dark oxidation reactions of ethers including aether, isopropyl ether, phenyl isopropyl ether, and benzyl isopropyl ether have been studied by using density functional theory calculations. The structures of initial Contact charge transfer complexes （CCTCs）, transition states and caged radical intermediates have been located at the B3LYP/6-31G （d） level, The bonding nature of ethers with triplet 02 in CCTCs has been analyzed, and the detailed mechanism of dark oxidation reactions of ether is presented clearly.展开更多
基金financially supported by the National Natural Science Foundation of China (No.21777178)Key Projects for Frontier Sciences of the Chinese Academy of Sciences (No.QYZDBSSWDQC018)+2 种基金the CAS Interdisciplinary Innovation Team (No. JCTD-2018-04)supports from the National Young Top-Notch Talents (No.W03070030)Youth Innovation Promotion Association of the Chinese Academy of Sciences (No. 2016037)
文摘Dark formation of hydroxyl radical upon oxidation of reduced iron minerals plays an important role in the degradation and transformation of organic and inorganic pollutants.Herein,we compared the hydroxyl radical formation from various reduced iron minerals at different redox conditions.·OH production was generally observed from the oxidation of reduced iron minerals,following the order:mackinawite(FeS)>reduced nontronite(iron-bearing smectite clay)> pyrite(FeS2)> side rite(FeCO3).Structural Fe^2+ and dissolved O2 play critical roles in ·OH production from reduced iron minerals.·OH production increases with decreasing pH,and Cl^-has little effect on this process.More importantly,dissolved organic matter significantly enhances ·OH production,especially under O2 purging,highlighting the importance of this process in ambient environments.This sunlight-independent pathway in which ’OH forms during oxidation of reduced iron minerals is helpful for understanding the degradation and transformation of various inorganic and organic pollutants in the redox-fluctuation environments.
基金Project supported by the National Natural Science Foundation of China (No. 20473047) and the Major State Basic Research Development Program of China (973 Program, No. 2004CB719902)
文摘The dark oxidation reactions of ethers including aether, isopropyl ether, phenyl isopropyl ether, and benzyl isopropyl ether have been studied by using density functional theory calculations. The structures of initial Contact charge transfer complexes （CCTCs）, transition states and caged radical intermediates have been located at the B3LYP/6-31G （d） level, The bonding nature of ethers with triplet 02 in CCTCs has been analyzed, and the detailed mechanism of dark oxidation reactions of ether is presented clearly.
